Polarizer and image display device

Abstract

To provide a polarizer having a high degree of orientation and an image display device having the polarizer. The polarizer of the present application is formed from a composition for forming a polarizer containing a liquid crystalline compound, a first dichroic substance, and a second dichroic substance, and has an alignment structure formed from the first dichroic substance and an alignment structure formed from the second dichroic substance.

Description

[0001] This application is a divisional application of the invention patent application filed on June 17, 2019, with application number 201980042963.9 and entitled "Polarizer and Image Display Device". Technical Field

[0002] This invention relates to a polarizer and an image display device. Background Technology

[0003] Previously, when functions such as attenuation, polarization, scattering, or light blocking of laser or natural light were required, devices were used that operated on different principles for each function. Therefore, products corresponding to these functions were manufactured through different manufacturing processes for each function.

[0004] For example, in image display devices (e.g., liquid crystal displays), linear polarizers or circular polarizers are used to control optical rotation or birefringence in the display. Furthermore, in organic light-emitting diodes (OLEDs), circular polarizers are also used to prevent reflection of external light.

[0005] In the past, iodine has been widely used as a dichroic material in these polarizers, but research is also underway to use organic pigments instead of iodine as the dichroic material in polarizers.

[0006] For example, Patent Document 1 discloses a polarizer forming composition containing a polymeric liquid crystal compound and a dichroic material.

[0007] Previous technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2017 / 154907 Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] In this case, the inventors, referring to the embodiment of Patent Document 1, fabricated a polarizer and evaluated its orientation degree. As a result, it became clear that considering the expected performance improvement of future image display devices, etc., it is expected that the orientation degree can be further improved.

[0012] Therefore, in view of the above-mentioned actual situation, the objective of the present invention is to provide a polarizer with high orientation and an image display device having the above-mentioned polarizer.

[0013] means for solving technical problems

[0014] Through in-depth research on the above-mentioned issues, the inventors discovered that if a polarizer formed from a polarizer forming composition containing a liquid crystal compound, a first dichroic substance, and a second dichroic substance has an arrangement structure formed by the first dichroic substance and an arrangement structure formed by the second dichroic substance, the orientation degree is improved, and the present invention is realized.

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

[0016] [1] A polarizer formed from a polarizer forming composition comprising a liquid crystal compound, a first dichroic material, and a second dichroic material.

[0017] The polarizer has an arrangement structure formed by a first dichroic material and an arrangement structure formed by a second dichroic material.

[0018] [2] According to the polarizer described in [1], in the arrangement structure formed by the first dichroic material, the first dichroic material forms an association compound, and in the arrangement structure formed by the second dichroic material, the second dichroic material forms an association compound.

[0019] [3] The polarizer according to [1] or [2] satisfies the following equations (I) and (II).

[0020] |λM-λ1|≤5nm……(I)

[0021] |λ1-λ1'|≥5nm……(II)

[0022] In equations (I) and (II) above,

[0023] λM refers to the maximum absorption wavelength in the difference spectrum between the absorption spectrum of a film formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound, and the absorption spectrum of a film formed from a composition containing a second dichroic substance and a liquid crystal compound but not the first dichroic substance.

[0024] λ1 refers to the maximum absorption wavelength in the absorption spectrum of a film formed from a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance.

[0025] λ1' refers to the maximum absorption wavelength in the absorption spectrum of a solution containing a substance with the first dichroism.

[0026] [4] The polarizer according to any one of [1] to [3] satisfies the following formulas (III) and (IV).

[0027] |λC-λ2|≤5nm……(III)

[0028] |λ²-λ²'|≥5nm……(IV)

[0029] In equations (III) and (IV) above,

[0030] λC refers to the maximum absorption wavelength in the difference spectrum between the absorption spectrum of a film formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound, and the absorption spectrum of a film formed from a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance.

[0031] λ2 refers to the maximum absorption wavelength in the absorption spectrum of a film formed from a composition containing a second dichroic substance and a liquid crystal compound but not a first dichroic substance.

[0032] λ2' refers to the maximum absorption wavelength in the absorption spectrum of a solution containing a second dichroic substance.

[0033] [5] The polarizer according to any one of [1] to [4], wherein, in the arrangement structure formed by the first dichroic material, the first dichroic material forms a crystal structure, and in the arrangement structure formed by the second dichroic material, the second dichroic material forms a crystal structure.

[0034] [6] The polarizer according to any one of [1] to [5] satisfies the following formula (V).

[0035] 0.9 ≤ MO / M ≤ 1.1……(V)

[0036] In the above formula (V),

[0037] MO refers to the intensity of the peaks originating from the periodic structure of the first dichroic substance in the X-ray diffraction spectrum of a film formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound.

[0038] M refers to the intensity of the peaks originating from the periodic structure of the first dichroic substance in the X-ray diffraction spectrum of a film formed from a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance.

[0039] [7] The polarizer according to any one of [1] to [6] satisfies the following formula (VI).

[0040] 0.9≤≤CO / C≤≤1.1……(VI)

[0041] In the above formula (VI),

[0042] CO refers to the intensity of the peak originating from the periodic structure of the second dichroic substance in the X-ray diffraction spectrum of a film formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound.

[0043] C refers to the intensity of the peaks originating from the periodic structure of the second dichroic substance in the X-ray diffraction spectrum of a film formed from a composition containing a second dichroic substance and a liquid crystal compound but not a first dichroic substance.

[0044] [8] The polarizer according to any one of [1] to [7], wherein the first dichroic material is a dichroic material having a maximum absorption wavelength in the range of 455 nm or more and less than 560 nm.

[0045] The second dichroic substance is a dichroic substance that has the maximum absorption wavelength in the range of 560 nm to 700 nm.

[0046] [9] According to the polarizer of [8], the polarizer forming composition further contains a third dichroic material having a maximum absorption wavelength in the range of 380 nm or more and less than 455 nm.

[0047]

[10] The polarizer according to any one of [1] to [9], wherein the absolute value of the difference between the logP value of the side chain of the first dichroic material and the logP value of the side chain of the second dichroic material is 1.1 or more.

[0048]

[11] An image display device having a polarizer as described in any one of [1] to

[10] .

[0049] Invention Effects

[0050] As shown below, according to the present invention, it is possible to provide a polarizer with high orientation and an image display device having the above-described polarizer. Attached Figure Description

[0051] Figure 1 This is a conceptual diagram representing an example of a state having an arrangement structure formed by a first dichroic substance and an arrangement structure formed by a second dichroic substance.

[0052] Figure 2 It is a conceptual diagram representing a way of arranging structures.

[0053] Figure 3 This is a graph showing the XRD (X-ray diffraction) spectrum corresponding to the polarizer 1 (film 1) of Example 1.

[0054] Figure 4This is a graph showing the XRD spectrum corresponding to polarizer 1-1 (film 1-1).

[0055] Figure 5 This is a graph showing the XRD spectrum corresponding to polarizer 1-3 (film 1-3). Detailed Implementation

[0056] The present invention will now be described in detail.

[0057] The description of the constituent elements described below is sometimes made according to representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0058] In addition, in this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit.

[0059] Furthermore, each component may be used alone as a single equivalent substance, or it may be used in combination with two or more substances. Here, regarding each component, unless otherwise specified, when using two or more substances together, the content of that component refers to the total content of the combined substances.

[0060] Furthermore, "(meth)acrylate" is a term that means "acrylate" or "methacrylate", "(meth)acrylic acid" is a term that means "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" is a term that means "acryloyl" or "methacryloyl".

[0061] [Polarizer]

[0062] The polarizer of the present invention is a polarizer formed by a polarizer forming composition containing a liquid crystal compound, a first dichroic substance and a second dichroic substance.

[0063] Furthermore, the polarizer of the present invention has an arrangement structure formed of a first dichroic material (hereinafter also simply referred to as the "first arrangement structure") and an arrangement structure formed of a second dichroic material (hereinafter also simply referred to as the "second arrangement structure"). That is, the polarizer of the present invention is a polarizer having both the first arrangement structure and the second arrangement structure.

[0064] In this invention, the first arrangement structure refers to the state in which two or more molecules of a first dichroic substance aggregate to form an aggregate in a polarizer, wherein the molecules of the first dichroic substance are arranged periodically in the aggregate. Similarly, the second arrangement structure refers to the state in which two or more molecules of a second dichroic substance aggregate to form an aggregate in a polarizer, wherein the molecules of the second dichroic substance are arranged periodically in the aggregate.

[0065] Figure 1This is a conceptual diagram representing an example of a state having an arrangement structure formed by a first dichroic substance and an arrangement structure formed by a second dichroic substance.

[0066] Figure 1 The polarizer P shown has molecules M of a first dichroic substance, molecules C of a second dichroic substance, and molecules L of a liquid crystal compound.

[0067] And, as Figure 1 As shown, aggregates G consisting of molecules M comprising two or more molecules and aggregates G consisting of molecules C comprising two or more molecules are formed. In these aggregates G, the long axis directions of molecules M or molecules C are aligned in the same direction, and molecules M or molecules C are arranged in a manner that is periodically offset from each other by a width w.

[0068] Furthermore, the first and second permutation structures are not limited to... Figure 1 The arrangement structure, for example, such as Figure 2 As shown, molecule M (molecule C in the second arrangement) can be configured with a periodic offset of angle a.

[0069] Furthermore, in a polarizer, the first dichroic material can polymerize. Similarly, in a polarizer, the second dichroic material can polymerize.

[0070] [Composition for polarizer formation]

[0071] The polarizer forming composition (hereinafter also referred to as "the composition") used in the formation of the polarizer of the present invention contains a liquid crystal compound, a first dichroic substance, and a second dichroic substance. Depending on the need, the composition may also contain a third dichroic substance, a solvent, a polymerization initiator, an interface modifier, or other components.

[0072] The following is a description of each component.

[0073] <Liquid Crystal Compounds>

[0074] This composition contains a liquid crystal compound. By containing a liquid crystal compound, the precipitation of dichroic substances can be suppressed while enabling the dichroic substances to be oriented with a high degree of orientation.

[0075] Liquid crystal compounds are liquid crystal compounds that do not exhibit dichroism.

[0076] As such a liquid crystal compound, either a low-molecular-weight liquid crystal compound or a high-molecular-weight liquid crystal compound can be used. Here, "low-molecular-weight liquid crystal compound" refers to a liquid crystal compound that does not have repeating units in its chemical structure. And, "high-molecular-weight liquid crystal compound" refers to a liquid crystal compound that has repeating units in its chemical structure.

[0077] Examples of low-molecular-weight liquid crystal compounds include those described in Japanese Patent Application Publication No. 2013-228706.

[0078] Examples of polymeric liquid crystal compounds include the thermotropic liquid crystal polymer disclosed in Japanese Patent Application Publication No. 2011-237513. Furthermore, the polymeric liquid crystal compound may have crosslinking groups (e.g., acryloyl and methacryloyl groups) at its ends.

[0079] Liquid crystal compounds can be used alone or in combination with two or more.

[0080] The content of the liquid crystal compound is preferably 25 to 2500 parts by mass relative to the content of the dichroic substance in the composition (100 parts by mass), more preferably 33 to 2000 parts by mass, and even more preferably 50 to 1000 parts by mass. Because the content of the liquid crystal compound is within the above range, the orientation degree of the polarizer is further improved.

[0081] In addition, "the content of dichroic substances in the composition" refers to the total amount of the first dichroic substance and the second dichroic substance. If the composition contains a third dichroic substance, the content of the third dichroic substance is also included in the total amount.

[0082] Considering the reason for further improving the orientation degree of the obtained polarizer, the liquid crystal compound is preferably a polymeric liquid crystal compound containing a repeating unit (hereinafter also referred to as "repeating unit (1)") represented by the following formula (1). In addition, in the following description, "further improving the orientation degree of the obtained polarizer" is also referred to as "the effect of the present invention is even better".

[0083] [Chemical Formula 1]

[0084]

[0085] In the above formula (1), P1 represents the main chain of the repeating unit, L1 represents the single bond or divalent linking group, SP1 represents the spacer group, M1 represents the mesocrystalline group, and T1 represents the terminal group.

[0086] As the main chain of the repeating unit represented by P1, specifically, for example, groups represented by the following formulas (P1-A) to (P1-D) can be cited, wherein, from the viewpoint of the diversity of monomers as raw materials and ease of operation, groups represented by the following formula (P1-A) are preferred.

[0087] [Chemical Formula 2]

[0088]

[0089] In the above formulas (P1-A) to (P1-D), "*" indicates the bonding position with L1 in the above formula (1).

[0090] In the above equations (P1-A) to (P1-D), R 1 R 2 R 3 and R 4 Each of the above-mentioned alkyl groups independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group can be a straight-chain or branched alkyl group, or an alkyl group having a cyclic structure (cycloalkyl). Furthermore, the number of carbon atoms in the alkyl group is preferably 1 to 5.

[0091] The group represented by the above formula (P1-A) is preferably a unit of a portion of the structure of a poly(meth)acrylate obtained by polymerization of (meth)acrylate.

[0092] The group represented by the above formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of a compound having an epoxy group.

[0093] The group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetane compound having an oxetane.

[0094] The group represented by the above formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one of alkoxysilyl and silanol groups. Here, as a compound having at least one of alkoxysilyl and silanol groups, an example can be a compound having the formula SiR 14 (OR 15 Compounds containing a group represented by )2. Where R... 14 R in (P1-D) 14 Multiple Rs with the same meaning 15 Each can be independently represented as either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0095] In the above formula (1), L1 is a single bond or a divalent linking group.

[0096] Examples of divalent linking groups represented by L1 include -C(O)O-, -OC(O)-, -O-, -S-, and -C(O)NR. 3 -、-NR 3 C(O)-, -SO2- and -NR 3 R 4 - etc. In the formula, R 3 and R 4 Each of the following can be independently represented: a hydrogen atom and an alkyl group having 1 to 6 carbon atoms that may have substituents.

[0097] In the case where P1 is a group represented by formula (P1-A), from the perspective of the superior effect of the present invention, L1 is preferably a group represented by -C(O)O-.

[0098] When P1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond for the sake of better performance of the present invention.

[0099] In the above formula (1), considering reasons such as easy liquid crystal properties and availability of raw materials, the spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of ethylene oxide structure, propylene oxide structure, polysiloxane structure and fluorinated alkylene structure.

[0100] Here, SP 1 preferably represents an ethylene oxide structure consisting of *-(CH2-CH2O). n1 -* indicates a group. In the formula, n1 represents an integer from 1 to 20, and * indicates the bonding position with L1 or M1 in the above formula (1). For the sake of better effects of the present invention, n1 is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, and most preferably 3.

[0101] Furthermore, considering the superior effects of the present invention, the propylene oxide structure represented by SP1 is preferably composed of *-(CH(CH3)-CH2O). n2 -* indicates a group. In the formula, n2 represents an integer from 1 to 3, and * indicates the bonding position with L1 or M1.

[0102] Furthermore, considering the superior effects of the present invention, the polysiloxane structure represented by SP1 is preferably composed of *-(Si(CH3)2-O). n3 -* indicates a group. In the formula, n3 represents an integer from 6 to 10, and * indicates the bonding position with L1 or M1.

[0103] Furthermore, considering the superior effects of the present invention, the fluorinated alkylene structure represented by SP1 is preferably composed of *-(CF2-CF2). nn4- * indicates a group. In the formula, n4 represents an integer from 6 to 10, and * indicates the bonding position with L1 or M1.

[0104] In the above formula (1), M1 represents the mesocrystalline group, which is the group that represents the main framework of the liquid crystal molecules that contributes to the formation of liquid crystals. Liquid crystal molecules exhibit liquid crystal properties in an intermediate state (intermediate phase) between the crystalline state and the isotropic liquid state. There are no particular limitations on the mesocrystalline group; for example, one can refer to "Fluussige Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), especially the records on pages 7 to 16, as well as the records in the Liquid Crystal Handbook (Maruzen, 2000), edited by the Liquid Crystal Handbook Editorial Committee, especially Chapter 3.

[0105] As a mesocrystalline group, it is preferred, for example, a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups.

[0106] From the perspective of the superior effect of the present invention, the mesocrystalline group preferably has aromatic hydrocarbon groups, more preferably 2 to 4 aromatic hydrocarbon groups, and even more preferably 3 aromatic hydrocarbon groups.

[0107] From the viewpoints of liquid crystal properties, liquid crystal phase transition temperature adjustment, raw material availability and synthetic applicability, and from the viewpoint of superior effects of the present invention, groups represented by the following formula (M1-A) or the following formula (M1-B) are preferred as mesocrystalline groups, and groups represented by formula (M1-B) are more preferred.

[0108] [Chemical Formula 3]

[0109]

[0110] In formula (M1-A), A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. These groups can be substituted with alkyl, fluoroalkyl, alkoxy, or substituents.

[0111] The divalent group represented by A1 is preferably a 4- to 6-membered ring. Furthermore, the divalent group represented by A1 can be a monocyclic ring or a fused ring.

[0112] * indicates the bonding position with SP1 or T1.

[0113] Examples of divalent aromatic hydrocarbon groups represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetraphenyl-diyl. From the perspective of the diversity of mesocrystalline framework design or the availability of raw materials, phenylene or naphthylene is preferred, and phenylene is more preferred.

[0114] The divalent heterocyclic group represented by A1 can be either aromatic or non-aromatic, and from the viewpoint of further improving the degree of orientation, a divalent aromatic heterocyclic group is preferred.

[0115] Examples of atoms other than carbon that constitute a divalent aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. When an aromatic heterocyclic group has multiple atoms forming rings other than carbon, these atoms may be the same or different.

[0116] Specific examples of divalent aromatic heterocyclic groups include pyridinyl (pyridin-diyl), pyridazinyl (pyridinyl), imidazole-diyl, thiophene (thiophene-diyl), quinolineyl (quinoline-diyl), isoquinolineyl (isoquinoline-diyl), oxazole-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thienothiazole-diyl, thiazonothiazole-diyl, thienothiphene-diyl, and thienooxazole-diyl, etc.

[0117] Specific examples of divalent alicyclic groups represented by A1 include cyclopentylene and cyclohexylene.

[0118] In formula (M1-A), a1 represents an integer from 1 to 10. When a1 is 2 or higher, multiple A1 values ​​can be the same or different.

[0119] In formula (M1-B), A2 and A3 are independently divalent groups selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as A1 in formula (M1-A), therefore their descriptions are omitted.

[0120] In formula (M1-B), a2 represents an integer from 1 to 10. When a2 is 2 or more, multiple A2s can be the same or different, multiple A3s can be the same or different, and multiple LA1s can be the same or different. For the sake of superior performance of the present invention, a2 is preferably an integer of 2 or more, and more preferably 2.

[0121] In formula (M1-B), when a2 is 1, LA1 is a divalent linking group. When a2 is 2 or more, each of the plurality of LA1s is independently a single bond or a divalent linking group, and at least one of the plurality of LA1s is a divalent linking group. When a2 is 2, for the sake of better effects of the present invention, it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond.

[0122] In formula (M1-B), examples of divalent linking groups represented by LA1 include -O- and -(CH2). g -、-(CF2)g -、-Si(CH3)2-、-(Si(CH3)2O) g -、-(OSi(CH3)2) g -(g represents an integer from 1 to 10.), -N(Z)-, -C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)2-C(Z')2-, -C(O) -, -OC(O)-, -C(O)O-, -OC(O)O-, -N(Z)C(O)-, -C(O)N(Z)-, -C(Z)=C(Z')-C(O)O-, -OC(O) -C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z')-C(O)N(Z”)-, -N(Z”)-C(O)-C(Z)=C(Z ')-, -C(Z)=C(Z')-C(O)-S-, -SC(O)-C(Z)=C(Z')-, -C(Z)=NN=C(Z')-(Z, Z', Z" independently represent hydrogen, C 1-C4 alkyl, cycloalkyl, aryl, cyano, or halogen atoms. -C≈C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O-), and -C(O)S-, etc. Among these, -C(O)O- is preferred for reasons of superior performance of the present invention. LA1 may also be a combination of two or more of these groups.

[0123] As a specific example of M1, the following structure can be given. Additionally, in the following specific example, "A..." c " " indicates acetyl group.

[0124] [Chemical Formula 4]

[0125]

[0126] [Chemical Formula 5]

[0127]

[0128] [Chemical Formula 6]

[0129]

[0130] [Chemical Formula 7]

[0131]

[0132] [Chemical Formula 8]

[0133]

[0134] [Chemical Formula 9]

[0135]

[0136] [Chemical Formula 10]

[0137]

[0138] In the above formula (1), examples of terminal groups represented by T1 include hydrogen atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, alkoxycarbonyloxy groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms (ROC(O)-: R is alkyl), acyloxy groups with 1 to 10 carbon atoms, acylamino groups with 1 to 10 carbon atoms, alkoxycarbonylamino groups with 1 to 10 carbon atoms, sulfonylamino groups with 1 to 10 carbon atoms, aminosulfonyl groups with 1 to 10 carbon atoms, carbamoyl groups with 1 to 10 carbon atoms, thionyl groups with 1 to 10 carbon atoms, urea groups with 1 to 10 carbon atoms, and groups containing (meth)acryloyloxy groups. Examples of groups containing (meth)acryloyloxy groups include those represented by -LA (L represents a single bond or a linking group. Specific examples of linking groups are the same as L1 and SP1 described above. A can be a group represented by (meth)acryloyloxy).

[0139] For the sake of superior effects of the present invention, T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group. These terminal groups can be further replaced by these groups or polymerizable groups described in Japanese Patent Application Publication No. 2010-244038.

[0140] For the sake of superior performance of the present invention, the number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, and particularly preferably 1 to 7. When the number of atoms in the main chain of T1 is 20 or less, the orientation degree of the polarizer is further improved. Here, "main chain" in T1 refers to the longest molecular chain bonded to M1, and hydrogen atoms are not included in the number of atoms in the main chain of T1. For example, when T1 is n-butyl, the number of atoms in the main chain is 4; when T1 is sec-butyl, the number of atoms in the main chain is 3.

[0141] From the perspective of the superior effect of the present invention, the content of repeating unit (1) is preferably 20 to 100% by mass relative to 100% by mass of all repeating units in the polymeric liquid crystal compound.

[0142] In this invention, the content of each repeating unit contained in the polymeric liquid crystal compound is calculated based on the loading amount (mass) of each monomer used to obtain each repeating unit.

[0143] The repeating unit (1) in the polymeric liquid crystal compound may be a single unit or may contain two or more units. For the sake of better performance of the present invention, it is preferable to include two repeating units (1) in the polymeric liquid crystal compound.

[0144] In the case where the polymeric liquid crystal compound contains two repeating units (1), from the perspective of the superior effect of the present invention, it is preferable that the terminal group represented by T1 in one (repeating unit A) is alkoxy, and the terminal group represented by T1 in the other (repeating unit B) is a group other than alkoxy.

[0145] For the sake of superior effects of the present invention, the terminal group represented by T1 in the repeating unit B above is preferably alkoxycarbonyl, cyano or a group containing (meth)acryloyloxy, more preferably alkoxycarbonyl or cyano.

[0146] From the perspective of the superior effect of the present invention, the ratio (A / B) of the content of the repeating unit A in the polymeric liquid crystal compound to the content of the repeating unit B in the polymeric liquid crystal compound is 50 / 50 to 95 / 5, more preferably 60 / 40 to 93 / 7, and even more preferably 70 / 30 to 90 / 10.

[0147] (weight average molecular weight)

[0148] For the sake of superior performance of the present invention, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. If the Mw of the polymeric liquid crystal compound is within the above range, the polymeric liquid crystal compound is easier to process.

[0149] In particular, from the viewpoint of suppressing cracks during coating, the weight average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 10,000 or more, and more preferably 10,000 to 300,000.

[0150] Furthermore, from the viewpoint of the temperature range of orientation, the weight average molecular weight (Mw) of the polymeric liquid crystal compound is preferably less than 10,000, and preferably more than 2,000 and less than 10,000.

[0151] Here, the weight-average molecular weight and number-average molecular weight in this invention are values ​​determined by gel permeation chromatography (GPC).

[0152] • Solvent (eluent): N-methylpyrrolidone

[0153] • Device Name: TOSOH HLC-8220GPC

[0154] • String: Connects 3 TOSOH TSKgel SuperAWM-H tubes (6mm x 15cm) for use

[0155] • Column temperature: 25℃

[0156] • Sample concentration: 0.1% by mass

[0157] • Flow rate: 0.35 ml / min

[0158] Calibration curves: Calibration curves for seven samples of TOSOH-prepared TSK standard polystyrene up to Mw = 2,800,000–1,050 (Mw / Mn = 1.03–1.06).

[0159] (logP value)

[0160] In this invention, considering the ease of adjusting the compatibility with the first and second dichroic substances described later, the logP value of the liquid crystal compound is preferably 4.0 to 10, more preferably 4.3 to 9.5, and even more preferably 4.3 to 5.5.

[0161] Here, the logP value is an indicator of the hydrophilicity and hydrophobicity of a chemical structure, sometimes referred to as the hydrophilicity / hydrophobicity parameter. The logP value can be calculated using software such as ChemBioDrawUltra or HSPiP (Ver. 4.1.07). It can also be experimentally determined using methods such as those described in OECD Guidelines for the Testing of Chemicals, Section 1, Test No. 117. In this invention, unless otherwise stated, the logP value is the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07).

[0162] <First dichroic substance>

[0163] The first dichroic substance contained in the composition is not particularly limited as long as it is a compound different from the second dichroic substance described later. Examples include previously known dichroic substances such as visible light absorbing substances (dichroic pigments), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet light absorbing substances, infrared light absorbing substances, nonlinear optical substances, carbon nanoparticles, and inorganic substances (such as quantum rods).

[0164] Preferably, the compound has a core of dichroic material, i.e., a chromophore, and a side chain bonded to the end of the chromophore.

[0165] Specific examples of chromogenic groups include aromatic cyclic groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups, etc., preferably having both aromatic hydrocarbon groups and azo groups, and more preferably having diazo or triazo structures having aromatic hydrocarbon groups and two or three azo groups.

[0166] As a side chain, it is not particularly restricted; for example, R from equation (2) discussed later can be cited. 1 R 2 and R 3 The group indicated.

[0167] As the first dichroic substance, a dichroic pigment compound having a structure represented by the following formula (2) is preferably cited.

[0168] [Chemical Formula 11]

[0169]

[0170] In equation (2), m represents 1 or 2.

[0171] In equation (2), Ar 1 Ar 2 and Ar 3 Each can be independently represented as a phenylene group that may have substituents, a naphthylene group that may have substituents, or a heterocyclic group that may have substituents.

[0172] As a heterocyclic group, it can be either aromatic or non-aromatic.

[0173] Examples of atoms other than carbon that constitute aromatic heterocyclic groups include nitrogen, sulfur, and oxygen atoms. When an aromatic heterocyclic group has multiple atoms forming rings other than carbon, these atoms may be the same or different.

[0174] Specific examples of aromatic heterocyclic groups include pyridinyl (pyridine-diyl), pyridazine-diyl, imidazole-diyl, thiophene (thiophene-diyl), quinolineyl (quinoline-diyl), isoquinolineyl (isoquinoline-diyl), oxazolyl-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thiazothiazole-diyl, and thienzothiaphene-diyl, etc.

[0175] In equation (2), R 1The alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkyl carbonate, alkylamino, acylamino, alkylcarbonylamino, alkoxycarbonylamino, alkylsulfonylamino, alkylaminosulfonyl, alkylcarbamoyl, alkylsulfinyl, alkylurea, alkylphosphamide, alkylimino, and alkylsilyl groups are straight-chain or branched groups that represent hydrogen atoms and may have substituents having 1 to 20 carbon atoms.

[0176] The carbon atoms of the above alkyl groups can be substituted with -O-, -CO-, -C(O)-O-, -O-C(O)-, -Si(CH3)2-O-Si(CH3)2-, -N(R1')-, -N(R1')-CO-, -CO-N(R1')-, -N(R1')-C(O)-O-, -OC(O)-N(R1')-, -N(R1')-C(O)-N(R1')-, -CH=CH-, -C≡C-, -N=N-, -C(R1')=CH-C(O)- or -OC(O)-O-.

[0177] In R 1 In the case of groups other than hydrogen atoms, the hydrogen atoms of each group can be replaced by halogen atoms, nitro, cyano, -N(R1')2, amino, -C(R1')=C(R1')-NO2, -C(R1')=C(R1')-CN or -C(R1')=C(CN)2.

[0178] R1' represents a straight-chain or branched alkyl group with 1 to 6 hydrogen atoms or carbon atoms. When multiple R1's exist in a group, they can be the same or different.

[0179] In equation (2), R 2 and R 3 Each of the following groups can independently represent a hydrogen atom and may have substituents of alkyl, alkenyl, alkoxy, acyl, alkoxycarbonyl, alkylamide, alkylsulfonyl, aryl, arylcarbonyl, arylsulfonyl, aryloxycarbonyl, or arylamide groups that are straight-chain or branched and may have 1 to 20 carbon atoms.

[0180] The carbon atoms of the above alkyl groups can be substituted by -O-, -S-, -C(O)-, -C(O)-O-, -OC(O)-, -C(O)-S-, -SC(O)-, -Si(CH3)2-O-Si(CH3)2-, -NR2'-, -NR2'-CO-, -CO-NR2'-, -NR2'-C(O)-O-, -OC(O)-NR2'-, -NR2'-C(O)-NR2'-, -CH=CH-, -C≡C-, -N=N-, -C(R2')=CH-C(O)- or -OC(O)-O-.

[0181] In R 2 and R 3 In the case of groups other than hydrogen atoms, the hydrogen atoms of each group can be replaced by halogen atoms, nitro groups, cyano groups, -OH groups, -N(R2')2, amino groups, -C(R2')=C(R2')-NO2, -C(R2')=C(R2')-CN, and -C(R2')=C(CN)2.

[0182] R2' represents a straight-chain or branched alkyl group with 1 to 6 hydrogen atoms or carbon atoms. When multiple R2's exist in various groups, they can be the same or different.

[0183] R 2 and R 3 They can bond together to form a ring, R 2 Or R 3 It can also be used with Ar 3 They bond together to form a ring.

[0184] From the perspective of lightfastness, R 1 Preferably, it has an electron-withdrawing group, R 2 and R 3 Preferably, the group has low electron-donating ability.

[0185] As a specific example of such a group, as R 1 Examples of R groups include alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkylsulfonylamino, alkylaminosulfonyl, alkylsulfinyl, and alkylurea. 2 and R 3 Examples of such groups include those with the following structures. Furthermore, in formula (2) above, the groups with the following structures include R. 2 and R 3 It is represented by the form of the bonded nitrogen atoms.

[0186] [Chemical Formula 12]

[0187]

[0188] Hereinafter, specific examples of dichroic pigment compounds having the structure represented by the above formula (2) are shown, but the present invention is not limited thereto.

[0189] [Chemical Formula 13]

[0190]

[0191] [Chemical Formula 14]

[0192]

[0193] In this invention, from the viewpoint of adjusting the hue of the polarizer, the first dichroic material is preferably a dichroic material having a maximum absorption wavelength in the range of 455 nm or more and less than 560 nm, more preferably a dichroic material having a maximum absorption wavelength in the range of 455 to 555 nm, and even more preferably a dichroic material having a maximum absorption wavelength in the range of 455 to 550 nm.

[0194] In particular, as the first dichroic material with the maximum absorption wavelength in the range of 455 nm to less than 560 nm and the second dichroic material described later, if the second dichroic material with the maximum absorption wavelength in the range of 560 nm to less than 700 nm is used, it is easier to adjust the hue of the polarizer.

[0195] Here, the maximum absorption wavelength (nm) of the dichroic substance is determined by using a solution in a good solvent and measuring the ultraviolet-visible spectrum in the wavelength range of 380–800 nm using a spectrophotometer.

[0196] Furthermore, in this invention, considering the ease of forming the first arrangement structure, the difference between the logP value of the liquid crystal compound and the logP value of the first dichroic substance is preferably 3.4 or more, and more preferably 4.6 or more.

[0197] For the same reason, the logP value of the first dichroic substance is preferably 8 to 15 or less, and more preferably 9.2 to 13 or less.

[0198] <Second dichroic substance>

[0199] The second dichroic substance contained in the composition is not particularly limited as long as it is a compound different from the first dichroic substance mentioned above. Examples include visible light absorbing substances (dichroic pigments), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet light absorbing substances, infrared light absorbing substances, nonlinear optical substances, carbon nanoparticles, inorganic substances (such as quantum rods), and other conventionally known dichroic substances.

[0200] Preferably, the compound has a core of dichroic material, i.e., a chromophore, and a side chain bonded to the end of the chromophore.

[0201] Specific examples of chromogenic groups include aromatic cyclic groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups, etc., preferably having both aromatic cyclic groups and azo groups, more preferably having a bisazo structure having an aromatic heterocyclic group (preferably thienothiazolyl) and two azo groups.

[0202] As a side chain, it is not particularly restricted, and can be cited as an example of R from equation (3) discussed later. 4 R 5Or R 6 The group indicated.

[0203] As a second dichroic substance, a dichroic pigment compound having a structure represented by the following formula (3) is preferably cited.

[0204] [Chemical Formula 15]

[0205]

[0206] In equation (3), R 4 and R 5 R represents a substituent. 6 and R 7 Each can be used to represent a hydrogen atom or a substituent independently.

[0207] In equation (3), Ar 4 and Ar 5 Each can be independently represented as a divalent aromatic group that may have substituents.

[0208] In equation (3), E represents a single bond or any one of nitrogen, oxygen and sulfur atoms.

[0209] In equation (3), Q represents an oxygen atom or a sulfur atom.

[0210] In formula (3), L represents a single bond, -N=N-, -CR=N-, -CR=CR'-, or -C(=O)-NR-. R and R' independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an alkyl group with 1 to 6 carbon atoms.

[0211] In equation (3), n represents 0 or 1. Specifically, n is 0 when E is a single bond, an oxygen atom, or a sulfur atom, and n is 1 when E is a nitrogen atom.

[0212] In equation (3) above, for R 4 and R 5 The term "substituent" will be explained.

[0213] Examples of substituents include groups with electron-donating or electron-withdrawing properties introduced to adjust the hue of a pigment, or groups with cross-linking (polymerizing) properties introduced to fix orientation.

[0214] As R 4 The substituents represented, for example, can be those corresponding to R in equation (2) above. 1 Same group.

[0215] As R 5 The substituents are indicated, for example, alkyl groups that can be substituted.

[0216] Alkyl groups are preferably alkyl groups having 1 to 20 carbon atoms.

[0217] Here, the carbon atoms constituting the above-mentioned alkyl groups can be substituted with -O-, -CO-, -C(O)-O-, -OC(O)-, -Si(CH3)2-O-Si(CH3)2-, -N(R)-, -N(R)-CO-, -CO-N(R)-, -N(R)-C(O)-O-, -OC(O)-N(R)-, -N(R)-C(O)-N(R')-, -CH=CH-, -C≡C-, -N=N-, -C(R)=N-, -C(R)=CH-C(O)-, or -OC(O)-O-. R and R' represent alkyl groups, preferably alkyl groups having 1 to 10 carbon atoms.

[0218] The hydrogen atom bonded to the carbon atom of the alkyl group can be replaced by a halogen atom, a nitro group, a cyano group, -N(R)(R')-, an amino group, -C(R)=C(R')-NO2, -C(R)=C(R')-CN, or -C(R)=C(CN)2. R and R' represent alkyl groups, preferably alkyl groups having 1 to 10 carbon atoms.

[0219] In equation (3) above, for R 6 and R 7 The term "hydrogen atom or substituent" is explained.

[0220] Here, as R 6 and R 7 The "substituent" represented in one way can be exemplified by R in equation (3). 5 The "substituent" indicates the same group. Additionally, in R... 6 In the case of substituents, it can interact with R. 5 They connect to form a ring structure.

[0221] In equation (3), for Ar 4 and Ar 5 The term "can have a divalent aromatic group with substituents" is used for explanation.

[0222] Examples of substituents mentioned above include substituent group G described in paragraphs

[0237] to

[0240] of Japanese Patent Application Publication No. 2011-237513. Among them, halogen atoms, alkyl groups, alkoxy groups, alkoxy carbonyl groups (e.g., methoxy carbonyl, ethoxy carbonyl, etc.), aryloxy carbonyl groups (e.g., phenoxy carbonyl, 4-methylphenoxy carbonyl, 4-methoxyphenyl carbonyl, etc.), alkyl groups are more preferred, and alkyl groups having 1 to 5 carbon atoms are even more preferred.

[0223] On the other hand, examples of divalent aromatic groups include divalent aromatic hydrocarbon groups and divalent aromatic heterocyclic groups.

[0224] Examples of divalent aromatic hydrocarbon groups include arylene groups with 6 to 12 carbon atoms, specifically phenylene, cumene, mesitylene, methylphenylene, and xylene. Among these, phenylene is preferred.

[0225] Furthermore, the divalent aromatic heterocyclic group described above is preferably derived from a monocyclic or bicyclic heterocyclic group. Examples of atoms other than carbon constituting the aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. When the aromatic heterocyclic group has multiple atoms constituting rings other than carbon, these atoms may be the same or different. Specifically, examples of aromatic heterocyclic groups include pyridyl (pyridin-diyl), quinoline (quinoline-diyl), isoquinoline (isoquinoline-diyl), benzothiadiazole-diyl, phthalimide-diyl, and thiophenthiazol-diyl (hereinafter simply referred to as "thiophenthiazolyl").

[0226] Among the aforementioned divalent aromatic groups, divalent aromatic hydrocarbon groups are preferred.

[0227] In formula (3), as mentioned above, E represents a single bond or any one of nitrogen, oxygen and sulfur atoms, preferably a single bond or nitrogen atom.

[0228] In formula (3), as described above, Q represents an oxygen atom or a sulfur atom, preferably a sulfur atom.

[0229] In formula (3), as described above, L represents a single bond, -N=N-, -CR=N-, -CR=CR'-, or -C(=O)-NR-, and R and R' independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an alkyl group having 1 to 6 carbon atoms. Preferably, it is -N=N-, or -C(=O)-NH-.

[0230] The following are specific examples of dichroic azo dyes having a structure represented by formula (3), but the present invention is not limited thereto.

[0231] [Chemical Formula 16]

[0232]

[0233] [Chemical Formula 17]

[0234]

[0235] [Chemical Formula 18]

[0236]

[0237] [Chemical Formula 19]

[0238]

[0239] In this invention, from the viewpoint of adjusting the hue of the polarizer, the second dichroic material is preferably a dichroic material having a maximum absorption wavelength in the range of 560 nm to 700 nm, more preferably a dichroic material having a maximum absorption wavelength in the range of 560 to 650 nm, and even more preferably a dichroic material having a maximum absorption wavelength in the range of 560 to 640 nm.

[0240] Furthermore, in this invention, considering the ease of forming the second arrangement structure, the difference between the logP value of the liquid crystal compound and the logP value of the second dichroic substance is preferably 4.3 or more, and more preferably 5.4 or more.

[0241] For the same reason, the logP value of the second dichroic substance is preferably 8 or more, and more preferably 10 or more.

[0242] (Difference in logP values)

[0243] Furthermore, in this invention, considering the ease of forming the first and second arrangement structures, the difference between the logP value of the side chain of the first dichroic substance and the logP value of the side chain of the second dichroic substance (hereinafter also simply referred to as "side chain logP difference") is preferably 1.1 or more, and more preferably 1.3 or more.

[0244] Furthermore, in the presence of multiple side chains of the first dichroic substance or the second dichroic substance, the logP difference of at least one side chain preferably satisfies the above value.

[0245] Here, the side chains of the first dichroic substance and the second dichroic pigment refer to the groups bonded to the ends of the chromophores. For example, in the case where the first dichroic substance is a compound represented by formula (2), R in formula (2) refers to the group that is attached to the end of the chromophore. 1 R 2 and R 3 If it is a side chain, in the case that the second dichroic substance is a compound represented by the above formula (3), R in the above formula (3) 4 R 5 and R 6 It is a side chain. In particular, when the first dichroic substance is a compound represented by formula (2) above, and the second dichroic substance is a compound represented by formula (3) above, in R... 1 With R 4 The difference in logP values, R 1 With R 5 The difference in logP values, R 2 With R 4 The difference in logP values ​​and R3 With R 4 Among the differences in logP values, at least one logP difference preferably satisfies the above value.

[0246] <Third dichroic substance>

[0247] The composition preferably contains a third dichroic substance, which is different from the first and second dichroic substances described above.

[0248] In this invention, from the viewpoint of adjusting the hue of the polarizer, the third dichroic material is preferably a dichroic material having a maximum absorption wavelength in the range of 380 nm or more and less than 455 nm, and more preferably a dichroic material having a maximum absorption wavelength in the range of 385 nm or more and less than 454 nm.

[0249] As a specific example of the third dichroic substance, among the compounds represented by formula (1) disclosed in International Publication No. 2017 / 195833, compounds other than the first dichroic substance and the second dichroic substance described above can be cited.

[0250] (Content of dichroic substances)

[0251] The content of the dichroic substance in the composition is preferably 0.1 to 99 parts by mass relative to the total amount of the dichroic substance and the liquid crystal compound (100 parts by mass), more preferably 1 to 60 parts by mass, and particularly preferably 1.5 to 30 parts by mass.

[0252] The content of the first dichroic substance is preferably 6 to 50 parts by mass relative to 100 parts by mass of the dichroic substance in the composition, and more preferably 8 to 45 parts by mass.

[0253] The content of the second dichroic substance is preferably 40 to 90 parts by mass relative to 100 parts by mass of the dichroic substance in the composition, and more preferably 55 to 85 parts by mass.

[0254] When the composition contains a third dichroic substance, the content of the third dichroic substance is preferably 3 to 40 parts by mass relative to 100 parts by mass of the dichroic substance in the composition, and more preferably 5 to 35 parts by mass.

[0255] Solvent

[0256] From an operability point of view, the composition preferably contains a solvent.

[0257] Examples of solvents include ketones (such as acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (such as dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrotitol, and cyclopentylmethyl ether), aliphatic hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (such as benzene, toluene, xylene, and trimethylbenzene), halogenated carbons (such as dichloromethane, chloroform, dichloroethane, dichlorobenzene, and chlorotoluene), and esters (such as ethyl acetate). Organic solvents such as methyl esters, ethyl acetate, butyl acetate, diethyl carbonate, etc., alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexyl), cellosols (e.g., methyl cellosol, ethyl cellosol, and 1,2-dimethoxyethane), cellosol acetates, sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide and dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolinone), and heterocyclic compounds (e.g., pyridine) and water are used. These solvents can be used alone or in combination of two or more.

[0258] For the sake of superior performance of the present invention, organic solvents are preferred among these solvents, and halogenated carbons or ketones are more preferred.

[0259] When the composition contains a solvent, for the sake of better effects of the present invention, the solvent content relative to the total mass of the composition is preferably 70 to 99.5% by mass, more preferably 80 to 99% by mass, and even more preferably 85 to 98% by mass.

[0260] Interface Modifiers

[0261] The composition preferably contains an interface modifier. By including an interface modifier, the smoothness and orientation of the coated surface are improved, or depressions and unevenness are controlled, thereby improving in-plane uniformity.

[0262] As an interface modifier, an interface modifier that horizontally aligns the polymer liquid crystal compound is preferred, and compounds (horizontal alignment agents) described in paragraphs

[0253] to

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

[0018] to

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

[0263] When the composition contains an interface modifier, for the sake of better performance of the present invention, the content of the interface modifier is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to the total 100 parts by mass of the liquid crystal compound and the dichroic substance in the composition.

[0264] <Polymerization initiator>

[0265] For the sake of superior effects of the present invention, the composition of the present invention preferably contains a polymerization initiator.

[0266] There are no particular limitations on the use of a polymerization initiator, but it is preferred to use a photosensitive compound, i.e., a photopolymerization initiator.

[0267] As photopolymerization initiators, a wide variety of compounds can be used without particular restrictions. Examples of photopolymerization initiators include α-carbonyl compounds (as described in U.S. Patent Nos. 2,367,661 and 2,367,670), azobin ethers (as described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic azobin compounds (as described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (as described in U.S. Patent Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazolium dimers and p-aminophenyl ketones (as described in U.S. Patent Nos. 2,367,661 and 2,367,670). Japanese Patent No. 3549367, acridine and phenazine compounds (Japanese Patent Application Publication No. 60-105667 and US Patent No. 4239850), oxadiazole compounds (US Patent No. 4212970), and acylphosphine oxide compounds (Japanese Patent Application Publication No. 63-040799, Japanese Patent Application Publication No. 5-029234, Japanese Patent Application Publication No. 10-095788, and Japanese Patent Application Publication No. 10-029997), etc.

[0268] Commercially available products can also be used as photopolymerization initiators, such as Irgacure184, Irgacure907, Irgacure369, Irgacure651, Irgacure819 and IrgacureOXE-01 manufactured by BASF.

[0269] When the composition contains a polymerization initiator, for the sake of better performance of the present invention, the content of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to the total 100 parts by mass of the liquid crystal compound and the dichroic substance in the composition, more preferably 0.1 to 15 parts by mass. If the content of the polymerization initiator is 0.01 parts by mass or more, the polarizer has good durability; since it is 30 parts by mass or less, the polarizer orientation becomes better.

[0270] <Substituent>

[0271] The substituents in this specification will be explained.

[0272] Examples of substituents include alkyl groups (preferably alkyl groups with 1 to 20 carbon atoms, more preferably alkyl groups with 1 to 12 carbon atoms, and especially preferably alkyl groups with 1 to 8 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl), alkenyl groups (preferably alkenyl groups with 2 to 20 carbon atoms, more preferably alkenyl groups with 2 to 12 carbon atoms, and especially preferably alkenyl groups with 2 to 8 carbon atoms, such as vinyl, aryl, 2-butenyl, and 3-pentenyl), alkynyl groups (preferably alkenyl groups with 2 to 20 carbon atoms, more preferably alkenyl groups with 2 to 12 carbon atoms, and especially preferably alynyl groups with 2 to 8 carbon atoms, such as propynyl and 3-pentynyl), and aryl groups (…). The preferred carbon groups are aryl groups with 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl, 2,6-diethylphenyl, 3,5-ditrifluoromethylphenyl, styryl, naphthyl, and biphenyl, etc.; substituted or unsubstituted amino groups (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, such as unsubstituted amino, methylamino, dimethylamino, diethylamino, and aniline, etc.); alkoxy groups (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as methoxy, ethoxy, and butoxy, etc.); and oxycarbonyl groups (preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms). The number of carbon atoms is 2 to 15, especially preferably 2 to 10, for example, methoxycarbonyl, ethoxycarbonyl and phenoxycarbonyl, etc.); acyloxy (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, acetoxy, benzoyloxy, acryloyl and methacryloyl, etc.); amide (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, acetoxy and benzoylamide, etc.); alkoxycarbonylamino (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino, etc.); aryloxycarbonylamino ( Preferably, the number of carbon atoms is 7 to 20, more preferably 7 to 16, and especially preferably 7 to 12 (examples include phenoxycarbonylamino, etc.); sulfonylamino (preferably 1 to 20 carbon atoms, more preferably 1 to 10, and especially preferably 1 to 6, examples include methanesulfonylamino and benzenesulfonylamino, etc.); aminosulfonyl (preferably 0 to 20 carbon atoms, more preferably 0 to 10, and especially preferably 0 to 6, examples include aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, and phenylaminosulfonyl, etc.); carbamoyl (preferably 1 to 20 carbon atoms, more preferably 1 to 10, and especially preferably 1 to 6 carbon atoms).Examples of substituted carbamoyl groups include unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl, etc.; alkylthio groups (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, and especially preferably with 1 to 6 carbon atoms, such as methylthio and ethylthio, etc.); arylthio groups (preferably with 6 to 20 carbon atoms, more preferably with 6 to 16 carbon atoms, and especially preferably with 6 to 12 carbon atoms, such as phenylthio, etc.); and sulfonyl groups (preferably with 1 to 2 carbon atoms). 0. More preferably, the number of carbon atoms is 1 to 10, and particularly preferably, the number of carbon atoms is 1 to 6, for example, methanesulfonyl and toluenesulfonyl, etc.); sulfinyl (preferably, the number of carbon atoms is 1 to 20, more preferably, the number of carbon atoms is 1 to 10, and particularly preferably, the number of carbon atoms is 1 to 6, for example, methanesulfinyl and benzenesulfinyl, etc.); urea (preferably, the number of carbon atoms is 1 to 20, more preferably, the number of carbon atoms is 1 to 10, and particularly preferably, the number of carbon atoms is 1 to 6, for example, unsubstituted urea, methylurea and benzene, etc.). The following groups are preferred: hydroxyl, mercapto, halogen (e.g., fluorine, chlorine, bromine, and iodine), cyano, nitro, hydroxamic acid, sulfinyl, hydrazine, imino, azo, heterocyclic (preferably with 1 to 30 carbon atoms, more preferably with 1 to 12 carbon atoms, such as those with a nitrogen atom). Heterocyclic groups containing heteroatoms such as oxygen and sulfur atoms, including, for example, epoxy, oxacyclobutyl, imidazolyl, pyridinyl, quinolinyl, furanyl, piperidinyl, morpholino, maleimide, benzoxazole, benzimidazolyl, and benzothiazole, etc.; silyl groups (preferably with 3 to 40 carbon atoms, more preferably with 3 to 30 carbon atoms, and especially preferably with 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl, etc.); carboxyl, sulfonic acid, and phosphate groups, etc.

[0273] [Associations in polarizers]

[0274] In this invention, considering the reasons for further improving the orientation degree and light resistance of the polarizer and making it easier to adjust the hue of the polarizer, in the arrangement structure formed by the first dichroic material (first arrangement structure), the first dichroic material preferably forms an associative compound, and in the arrangement structure formed by the second dichroic material (second arrangement structure), the second dichroic material preferably forms an associative compound.

[0275] Here, as a verification method for the formation of an association of the first dichroic substance in the first arrangement structure, a method based on measuring the maximum absorption wavelength using a film formed as follows can be cited.

[0276] In addition, when manufacturing each film (polarizer), in addition to changing the type of dichroic substance contained in each film, the type of the underlying layer (e.g., substrate), the concentration of the composition, and the coating conditions are also considered, and care should be taken to ensure that the area and thickness of the film are equal.

[0277] Specifically, a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound is cast onto a substrate (e.g., blue glass). The composition is heated on a hot plate until it becomes a liquid crystal, and then cooled to room temperature to form film 1 (corresponding to the polarizer of the present invention). Then, the absorption spectrum of film 1 is measured in the wavelength range of 380 to 800 nm at 1 nm intervals.

[0278] Furthermore, except for using a composition containing a second dichroic substance and a liquid crystal compound but not a first dichroic substance, films 1-2 were formed using the same method. Then, the absorption spectra of films 1-2 were measured at 1 nm intervals in the wavelength range of 380 to 800 nm.

[0279] Next, the difference spectrum is obtained by subtracting the absorption spectrum of membrane 1-2 from the absorption spectrum of membrane 1, and then the maximum absorption wavelength λM of the obtained difference spectrum is determined.

[0280] Furthermore, except for using a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance, film 1-1 was formed using the same method. Then, the absorption spectrum of film 1-1 was measured in the wavelength range of 380 to 800 nm at 1 nm intervals, and the maximum absorption wavelength λ1 was measured.

[0281] Furthermore, determine the maximum absorption wavelength λ1' in the absorption spectrum of the solution containing the first dichroic substance.

[0282] Next, by satisfying the following equations (I) and (II) with the maximum absorption wavelengths λM, λ1, and λ1', it can be confirmed that the first dichroic substance forms an associative compound based on the reasons shown below.

[0283] |λM-λ1 |≤5nm.…..(I)

[0284] |λ1-λ1'|≥5nm.…..(II)

[0285] That is, the difference in composition between membrane 1 and membrane 1-2 is the presence or absence of the first dichroic substance. Therefore, it can be predicted that the difference spectrum between the absorption spectra of membrane 1 and the absorption spectra of membrane 1-2 is roughly consistent with the absorption spectrum originating from the first dichroic substance.

[0286] Therefore, when the maximum absorption wavelength λM of the difference spectrum and the maximum absorption wavelength λ1 of the absorption spectrum of film 1-1 satisfy the above equation (I), it can be said that the first dichroic substance exists in film 1 (polarizer) without being absorbed by the second dichroic substance.

[0287] On the other hand, the absorption spectrum of the solution containing the first dichroic substance can be understood as the absorption spectrum of one molecule of the first dichroic substance. Therefore, when the maximum absorption wavelength λ1' of the absorption spectrum and the maximum absorption wavelength λ1 of the absorption spectrum of membrane 1-1 satisfy the above formula (II), the first dichroic substances associate with each other in membrane 1-1, and thus it can be said that the maximum absorption wavelength shifts.

[0288] Therefore, by satisfying the above equations (I) and (II), it can be said that the first dichroic substance does not interact with the second dichroic substance, while the first dichroic substances form an association with each other.

[0289] On the other hand, as a verification method for the formation of an association of the second dichroic substance in the second arrangement structure, a method based on measuring the maximum absorption wavelength using a film formed as follows can be cited.

[0290] In addition, when manufacturing each film (polarizer), in addition to changing the type of dichroic substance contained in each film, the type of the underlying layer (e.g., substrate), the concentration of the composition, and the coating conditions are also considered, and care should be taken to ensure that the area and thickness of the film are equal.

[0291] Specifically, a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound is cast onto a substrate (e.g., blue glass). The composition is heated on a hot plate until it becomes a liquid crystal, and then cooled to room temperature to form film 1 (corresponding to the polarizer of the present invention). Then, the absorption spectrum of film 1 is measured in the wavelength range of 380 to 800 nm at 1 nm intervals.

[0292] Furthermore, except for using a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance, film 1-1 was formed using the same method. Then, the absorption spectrum of film 1-1 was measured at 1 nm intervals in the wavelength range of 380 to 800 nm.

[0293] Next, the difference spectrum is obtained by subtracting the absorption spectrum of membrane 1-1 from the absorption spectrum of membrane 1, and the maximum absorption wavelength λC of the obtained difference spectrum is then determined.

[0294] Furthermore, except for using a composition containing a second dichroic substance and a liquid crystal compound but not a first dichroic substance, films 1-2 were formed using the same method. Then, the absorption spectrum of films 1-2 was measured at 1 nm intervals in the wavelength range of 380 to 800 nm, and the maximum absorption wavelength λ2 was measured.

[0295] Furthermore, determine the maximum absorption wavelength λ2' in the absorption spectrum of the solution containing the second dichroic substance.

[0296] Next, by satisfying the following equations (III) and (IV) with the above maximum absorption wavelengths λC, λ2, and λ2', it can be confirmed that the second dichroic substance forms an associative compound based on the reasons shown below.

[0297] |λC-λ2|≤5nm......(III)

[0298] |λ²-λ²'|≥5nm.…..(IV)

[0299] That is, the difference in composition between membrane 1 and membrane 1-1 is the presence or absence of the second dichroic substance. Therefore, it can be predicted that the difference spectrum between the absorption spectra of membrane 1 and membrane 1-1 is roughly consistent with the absorption spectrum originating from the second dichroic substance.

[0300] Therefore, when the maximum absorption wavelength λC of the difference spectrum and the maximum absorption wavelength λ2 of the absorption spectrum of film 1-2 satisfy the above equation (III), it can be said that the second dichroic substance exists in film 1 (polarizer) without being absorbed by the first dichroic substance.

[0301] On the other hand, the absorption spectrum of the solution containing the second dichroic substance can be understood as the absorption spectrum of one molecule of the second dichroic substance. Therefore, when the maximum absorption wavelength λ2' of the absorption spectrum and the maximum absorption wavelength λ2 of the absorption spectrum of membrane 1-2 satisfy the above equation (IV), the second dichroic substances associate with each other in membrane 1-2, and thus it can be said that the maximum absorption wavelength shifts.

[0302] Therefore, by satisfying equations (III) and (IV) above, it can be said that the second dichroic substance does not interact with the first dichroic substance, and the second dichroic substances form an association with each other.

[0303] [Crystal Structure in Polarizers]

[0304] In this invention, considering the reasons that the orientation degree and light resistance of the polarizer are further improved and the hue of the polarizer can be easily adjusted, in the arrangement structure formed by the first dichroic material (first arrangement structure), it is preferable that the first dichroic material forms a crystal structure, and in the arrangement structure formed by the second dichroic material (second arrangement structure), the second dichroic material forms a crystal structure.

[0305] Here, the formation of a crystal structure by the first dichroic material in the first arrangement structure and the formation of a crystal structure by the second dichroic material in the second arrangement structure can be confirmed by comparing the X-ray diffraction (XRD) spectra of the following polarizers (films).

[0306] • Polarizer 1 (film 1): A film formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound.

[0307] • Polarizer 1-1 (film 1-1): A film formed from a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance.

[0308] • Polarizer 1-2 (film 1-2): A film formed of a composition containing a second dichroic substance and a liquid crystal compound but not a first dichroic substance.

[0309] • Polarizer 1-3 (film 1-3): A film formed of a composition containing a liquid crystal compound but not containing a first dichroic substance and a second dichroic substance.

[0310] <Polarizer Construction>

[0311] The polarizers described above are fabricated using the same method. For example, care is taken to ensure that the concentration of the coating solution or the coating conditions are consistent, and that the area and thickness of the film are the same.

[0312] The above-mentioned methods for manufacturing polarizers are not particularly restricted as long as they are the same. If polarizer 1 (film 1) contains an interface modifier, other polarizers are set to contain films containing the same amount of interface modifier as polarizer 1.

[0313] (XRD measurement)

[0314] Regarding the aforementioned polarizer, XRD measurements were performed under the same conditions (e.g., ensuring consistent film thickness, measurement area, and measurement conditions).

[0315] For example, XRD measurements are performed as follows.

[0316] For each polarizer, X-ray diffraction analysis was performed using the in-plane method. Hereinafter, X-ray diffraction analysis using the in-plane method will also be referred to as "in-plane XRD". In-plane XRD is performed using a thin-film X-ray diffraction apparatus under the following conditions by irradiating the surface of the polarizer layer with X-rays. Furthermore, the polarizer is configured such that the incident direction of the X-rays is parallel to the orientation direction of the liquid crystal compound and the dichroic material along their long axis, which is defined as the azimuth angle. In-plane XRD was performed in all directions at 15° intervals, and the peaks were analyzed. The direction within the substrate plane where the peak intensity is highest is determined by scanning. The in-plane spectra measured along the obtained direction are then compared with the XRD spectra described later. Regarding peak intensity, values ​​normalized to the film thickness corresponding to the X-ray penetration length at an X-ray incident angle of 0.2° are used.

[0317] (condition)

[0318] · Use a Cu X-ray source (CuKa, output 45 kV, 200 mA)

[0319] · X-ray incident angle: 0.2°

[0320] · Use an optical system: parallel optical system (CBO (Cross Beam Optics), PB (Parallel Beam))

[0321] · Incident side: incident slit 0.2 mm, incident parallel slit plane PSC (Parallel Slit Collimator) 0.5 degree, long side limiting slit 10 mm

[0322] · Receiving side: receiving slit 20 mm, receiving parallel slit plane PSA (Parallel Slit Analyzer) 0.5 degree

[0323] · Detector: HyPix3000 manufactured by Rigaku Corporation (0D mode)

[0324] [[ID=​​​​​​​​​​​​​​​​​​​​​​​​Next, the X-ray peaks at various angles of polarizer 1, polarizer 1-1, and polarizer 1-2 are compared.

[0332] In the case where peak M originating from the first dichroic substance present in polarizer 1-1 and peak C originating from the second dichroic substance present in polarizer 1-2 are observed in polarizer 1, the first dichroic substance forms a crystal structure on its own in polarizer 1, and the second dichroic substance forms a crystal structure on its own in polarizer 1.

[0333] For the sake of ease of forming the first arrangement structure, the polarizer of the present invention preferably satisfies the following formula (V).

[0334] 0.9 ≤ MO / M ≤ 1.1……(V)

[0335] In the above formula (V),

[0336] MO refers to the intensity of the peak originating from the periodic structure of the first dichroic substance in the X-ray diffraction spectrum of a film (film 1) formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound.

[0337] M refers to the intensity of the peaks originating from the periodic structure of the first dichroic substance in the X-ray diffraction spectrum of a film (film 1-1) formed from a composition containing a first dichroic substance and a liquid crystal compound but not a second dichroic substance.

[0338] For the sake of ease of forming a second arrangement structure, the polarizer of the present invention preferably satisfies the following formula (VI).

[0339] 0.9≤≤CO / C≤≤1.1……(VI)

[0340] In the above formula (VI),

[0341] CO refers to the intensity of the peak originating from the periodic structure of the second dichroic substance in the X-ray diffraction spectrum of a film (film 1) formed from a composition containing a first dichroic substance, a second dichroic substance, and a liquid crystal compound.

[0342] C refers to the intensity of the peak originating from the periodic structure of the second dichroic substance in the X-ray diffraction spectrum of a film (film 1-2) formed from a composition that does not contain the first dichroic substance, the second dichroic substance, and the liquid crystal compound.

[0343] [Methods for manufacturing polarizers]

[0344] The method for manufacturing the polarizer of the present invention is not particularly limited, but considering that the polarizer obtained has a higher degree of orientation, it is preferable to have a method comprising the following steps in sequence (hereinafter also referred to as "the manufacturing method"): a step of coating the above-described composition onto an alignment film to form a coating film (hereinafter also referred to as "coating film forming step"); and a step of orienting the dichroic substance contained in the above-described coating film (hereinafter also referred to as "orientation step").

[0345] The following is a description of each process.

[0346] <Coating Formation Process>

[0347] The coating film formation process is a process of forming a coating film by coating the above-described composition onto an alignment film. The liquid crystal compound in the coating film is horizontally aligned through the interaction between the alignment film and (in the case where the composition contains an interface modifier) ​​the interface modifier.

[0348] By using the composition containing the aforementioned solvent, or by heating the composition to make it into a molten liquid or other liquid, the composition can be easily coated onto an alignment film.

[0349] Commonly known methods for coating this composition include roller coating, gravure printing, spin coating, wire rod coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0350] (Orientation film)

[0351] The alignment film can be any film as long as it is a film that horizontally aligns the liquid crystal compound contained in the composition.

[0352] Orientation films can be formed by friction treatment of the film surface with organic compounds (preferably polymers), tilted evaporation of inorganic compounds, formation of layers with microgrooves, or accumulation of organic compounds (e.g., ω)-tricresanoic acid, dioctadecylmethylammonium chloride, methyl stearate) based on the Langmuir-Blodgett method (LB film). Furthermore, orientation films that generate orientation functions by applying an electric field, a magnetic field, or light irradiation are also known. In this invention, from the viewpoint of ease of controlling the pretilt angle of the orientation film, an orientation film formed by friction treatment is preferred; from the viewpoint of orientation uniformity, a photo-oriented orientation film formed by light irradiation is also preferred.

[0353] (1) Friction-treated orientation film

[0354] Polymer materials used for alignment films formed by friction processing are described in numerous documents, and many commercially available products are readily available. In this invention, polyvinyl alcohol or polyimide and its derivatives are preferably used. Regarding the alignment film, refer to the description on page 43, line 24 to page 49, line 8 of International Publication No. 2001 / 88574A1. The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm.

[0355] (2) Photo-aligned film

[0356] Photoalignment materials for alignment films formed by light irradiation have been described in numerous documents. In this invention, preferred examples include: Japanese Patent Application Publication Nos. 2006-285197, 2007-076839, 2007-138138, 2007-094071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, Japanese Patent No. 3883848, and Japanese Patent No. 4151746. Nitrogen compounds; aromatic ester compounds disclosed in Japanese Patent Application Publication No. 2002-229039; maleimides and / or alkenyl-substituted naphthalene diimides having photo-orientation units disclosed in Japanese Patent Application Publication Nos. 2002-265541 and 2002-317013; photocrosslinkable silane derivatives disclosed in Japanese Patent Nos. 4205195 and 4205198; and photocrosslinkable polyimides, polyamides, or esters disclosed in Japanese Patent Publication Nos. 2003-520878, 2004-529220, or 4162850. More preferably, azo compounds, photocrosslinkable polyimides, polyamides, or esters.

[0357] A photo-alignment film is manufactured by irradiating a photo-alignment film formed from the above materials with linearly polarized light or unpolarized light.

[0358] In this specification, "linearly polarized light irradiation" and "unpolarized light irradiation" refer to operations used to induce a photoreaction in a photoalignment material. The wavelength of the light used varies depending on the photoalignment material used, and is not particularly limited as long as it is the wavelength required for the photoreaction. The peak wavelength of the light used in the irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light with a peak wavelength of 400 nm or less.

[0359] Light sources used in illumination can include commonly used light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury-xenon lamps, and carbon arc lamps, as well as various lasers [e.g., semiconductor lasers, helium-neon lasers, argon-ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers], light-emitting diodes, and cathode ray tubes.

[0360] As a method to obtain linearly polarized light, one can use a polarizer (e.g., an iodine polarizer, a dichroic material polarizer, or a wire grating polarizer), a reflective polarizer utilizing a prism element (e.g., a Glan-Thomson prism) or a Brewster angle, or light emitted from a laser source that has polarized light. Furthermore, filters or wavelength conversion elements can be used to selectively illuminate only the desired wavelength.

[0361] When the irradiated light is linearly polarized, a method is employed to irradiate the alignment film surface perpendicularly or obliquely from the top or back surface relative to the alignment film. The incident angle of the light varies depending on the photoalignment material, but is preferably 0–90° (perpendicular), and more preferably 40–90°.

[0362] In the presence of unpolarized light, the alignment film is irradiated with unpolarized light at an angle. The incident angle is preferably 10–80°, more preferably 20–60°, and even more preferably 30–50°.

[0363] The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

[0364] When patterning is required, one can use a method that applies light using a photomask to the pattern as many times as needed during pattern creation, or write the pattern by laser scanning.

[0365] <Orientation Process>

[0366] The alignment process is a process of orienting the dichroic material contained in the coating film. Thus, the polarizer of the present invention can be obtained. It can be understood that in the alignment process, the dichroic material is oriented along the liquid crystal compound oriented through the alignment film.

[0367] The orientation process may include a drying process. This drying process removes components such as solvents from the coating film. The drying process can be performed by placing the coating film at room temperature for a specified time (e.g., natural drying), or by heating and / or air supply.

[0368] Here, the dichroic substance contained in the composition is sometimes oriented through the above-described coating film formation process or drying treatment. For example, in the case where the composition is prepared as a coating liquid containing a solvent, sometimes the coating film is dried to remove the solvent from the coating film, thereby orienting the dichroic substance contained in the coating film, thus obtaining the polarizer of the present invention.

[0369] The orientation process preferably includes a heat treatment. This further aligns the dichroic material contained in the coating, resulting in a higher degree of orientation of the obtained polarizer.

[0370] From the perspective of manufacturing applicability, the heat treatment is preferably 10–250°C, more preferably 25–190°C. Furthermore, the heating time is preferably 1–300 seconds, more preferably 1–60 seconds.

[0371] The alignment process can include a cooling process performed after the heat treatment. The cooling process involves cooling the heated coating to approximately room temperature (20–25°C). This further fixes the orientation of the dichroic substances contained in the coating, resulting in a further improvement in the orientation degree of the obtained polarizer. The cooling method is not particularly limited and can be implemented using known methods.

[0372] Through the above steps, the polarizer of the present invention can be obtained.

[0373] <Other processes>

[0374] The method of the present invention may include a step of curing the polarizer (hereinafter also referred to as the "curing step") after the above-described orientation step.

[0375] The curing process is carried out, for example, by heating and / or light irradiation (exposure). Preferably, the curing process is carried out by light irradiation.

[0376] The light source used for curing can be various light sources such as infrared, visible light, or ultraviolet light, but ultraviolet light is preferred. Furthermore, during curing, ultraviolet light can be irradiated while heating is being performed, or ultraviolet light can be irradiated through a filter that transmits only a specific wavelength.

[0377] Furthermore, exposure can also be performed in a nitrogen environment. In the case of polarizer curing via free radical polymerization, the polymerization hindrance caused by oxygen is reduced, therefore exposure in a nitrogen environment is preferred.

[0378] [Layered Body]

[0379] The laminate of the present invention has a substrate, an alignment film disposed on the substrate, and the polarizer of the present invention disposed on the alignment film.

[0380] Furthermore, the laminate of the present invention may also have a λ / 4 plate on the polarizer of the present invention described above.

[0381] Furthermore, the laminate of the present invention may also have a barrier layer between the polarizer and the λ / 4 plate described above.

[0382] The layers constituting the laminate of the present invention will be described below.

[0383] [Substrate]

[0384] The substrate can be appropriately selected, for example, glass and polymer films. The light transmittance of the substrate is preferably 80% or higher.

[0385] When using a polymer film as a substrate, an optically isotropic polymer film is preferred. Specific examples and preferred embodiments of the polymer are described in paragraph

[0013] of Japanese Patent Application Publication No. 2002-022942. Furthermore, even polymers that readily exhibit birefringence, such as polycarbonate or polysulfone, which are known in the past, can be used, and polymers whose birefringence can be reduced by modifying the molecules described in International Publication No. 2000 / 26705 can also be used.

[0386] [Orientation film]

[0387] Since the orientation film is as described above, its description is omitted.

[0388] [Polarizer]

[0389] Since the polarizer of the present invention is as described above, its description is omitted.

[0390] [λ / 4 board]

[0391] The so-called "λ / 4 plate" is a plate with λ / 4 function. Specifically, it is a plate that has the function of converting linearly polarized light of a certain wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).

[0392] For example, as a single-layer structure, the λ / 4 plate can be a stretched polymer film or a phase difference film with an optical anisotropy layer having λ / 4 function on a support. As a multi-layer structure, the λ / 4 plate can be a broadband λ / 4 plate formed by stacking λ / 4 plates and λ / 2 plates.

[0393] The λ / 4 plate and the polarizer of the present invention can be disposed in contact, or other layers can be disposed between the λ / 4 plate and the polarizer of the present invention. Examples of such layers include adhesive layers or bonding layers and barrier layers for ensuring a tight seal.

[0394] [Blocking layer]

[0395] When the laminate of the present invention includes a barrier layer, the barrier layer is disposed between the polarizer of the present invention and the λ / 4 plate. Alternatively, when the polarizer of the present invention has other layers besides the barrier layer (e.g., an adhesive layer or bonding layer) between it and the λ / 4 plate, the barrier layer can be disposed, for example, between the polarizer of the present invention and other layers.

[0396] The barrier layer, also known as the gas barrier layer (oxygen barrier layer), has the function of protecting the polarizer of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers.

[0397] Regarding the barrier layer, for example, one can refer to paragraphs

[0014] to

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

[0042] to

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

[0045] to

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

[0010] to

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

[0021] to

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

[0398] 〔use〕

[0399] The laminate of the present invention can be used, for example, as a polarizing element (polarizer), such as as a linear polarizer or a circular polarizer.

[0400] In the absence of an optically anisotropic layer such as the λ / 4 plate described above, the laminate of the present invention can be used as a linear polarizer.

[0401] On the other hand, when the laminate of the present invention has the above-mentioned λ / 4 plate, the laminate can be used as a circular polarizer.

[0402] [Image display device]

[0403] The image display device of the present invention has the polarizer or the laminate of the present invention described above.

[0404] The display element used in the image display device of the present invention is not particularly limited, and examples include liquid crystal cells, organic electroluminescent (hereinafter referred to as "EL") display panels and plasma display panels.

[0405] Preferably, a liquid crystal cell or an organic EL display panel is used, and more preferably, a liquid crystal cell is used. That is, as the image display device of the present invention, a liquid crystal display device that uses a liquid crystal cell as a display element, an organic EL display device that uses an organic EL display panel as a display element, and more preferably, a liquid crystal display device is used.

[0406] Liquid crystal display device

[0407] As an example of the image display device of the present invention, a liquid crystal display device is preferably provided that has the polarizer and liquid crystal cell of the present invention described above. More preferably, a liquid crystal display device is provided that has the laminate (but not including the λ / 4 plate) and liquid crystal cell of the present invention described above.

[0408] Furthermore, in this invention, it is preferable to use the laminate of this invention as the front polarizing element among the polarizing elements disposed on both sides of the liquid crystal cell, and more preferably, the laminate of this invention is used as both the front and rear polarizing elements.

[0409] The liquid crystal unit constituting a liquid crystal display device will be described in detail below.

[0410] <Liquid Crystal Unit>

[0411] The liquid crystal cells used in the liquid crystal display device are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode or TN (Twisted Nematic) mode, but are not limited to these.

[0412] In TN mode liquid crystal cells, when no voltage is applied, the rod-shaped liquid crystal molecules are essentially horizontally aligned, and then twisted at 60–120°. TN mode liquid crystal cells are most commonly used in color TFT (Thin Film Transistor) liquid crystal display devices, as documented in numerous publications.

[0413] In a VA mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In addition to (1) a narrow VA mode liquid crystal cell in which the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and substantially horizontally oriented when a voltage is applied (as described in Japanese Patent Application Publication No. 2-176625), there are also: (2) a liquid crystal cell in which the VA mode is multi-domain (MVA mode) in order to expand the field of view (as described in SID97, Digest oftech.Papers 28 (1997) 845); (3) a liquid crystal cell in which the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied (n-ASM mode) (as described in the proceedings of the Japan Liquid Crystal Conference 58-59 (1998)); and (4) a SURVIVA L mode liquid crystal cell (published in LCD International 98). Furthermore, it can be any of the following: PVA (Patterned Vertical Alignment), Optical Alignment, and PSA (Polymer-Sustained Alignment). Detailed information on these modes can be found in Japanese Patent Application Publication Nos. 2006-215326 and 2008-538819.

[0414] In an IPS-mode liquid crystal cell, rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate. By applying an electric field parallel to the substrate surface, the liquid crystal molecules respond in a planar manner. The IPS mode displays black without an applied electric field, and the absorption axes of the upper and lower polarizers are orthogonal. Methods for reducing light leakage and improving the field of view when displaying black in the tilt direction using optical compensation plates are disclosed in Japanese Patent Application Publication Nos. 10-054982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0415] [Organic EL Display Device]

[0416] As an example of the image display device of the present invention, namely an organic EL display device, a preferred embodiment may be a device having, in order from the visual recognition side, the polarizer, the λ / 4 plate, and the organic EL display panel of the present invention described above.

[0417] More preferably, the laminate of the present invention, having a λ / 4 plate, and the organic EL display panel are arranged sequentially from the visual recognition side. In this case, the laminate includes a substrate, an alignment film, a polarizer of the present invention, a barrier layer provided as needed, and a λ / 4 plate, arranged sequentially from the visual recognition side.

[0418] Furthermore, organic EL display panels are display panels made of organic EL elements, which are formed by sandwiching an organic light-emitting layer (organic electroluminescent layer) between electrodes (between the cathode and the anode). The structure of organic EL display panels is not particularly limited and can adopt known structures.

[0419] Example

[0420] The present invention will now be described in more detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing order shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0421] [Synthesis example 1]

[0422] The first dichroic substance M1 was synthesized via the following route.

[0423] [Chemical Formula 20]

[0424]

[0425] 10g of butylaniline, 100mL of water, 40mL of methanol and 20mL of hydrochloric acid were mixed and cooled in an ice bath while 5.1g of sodium nitrite and 10mL of water were added and stirred for 1 hour.

[0426] Next, after adding amide sulfuric acid (0.8 g), the mixture was stirred for another 30 minutes to prepare reaction solution 1.

[0427] Aniline protectant X (19.6 g), sodium acetate (22.0 g), water (200 mL), and methanol (50 mL) were mixed and cooled in an ice bath. The prepared reaction solution 1 was added dropwise while the internal temperature was below 5 °C. The mixture was stirred at 5 °C for 30 minutes and then at 25 °C for 1 hour.

[0428] Then, sodium hydroxide (16.1 g) and water (50 mL) were added, and the mixture was heated and stirred at 80 °C for 1 hour. After cooling, the solid obtained from the neutralization with hydrochloric acid was recovered by vacuum filtration to give compound M1-1 (3.2 g).

[0429] Compound M1-1 (2.0 g), water (4 mL), methanol (20 mL), and hydrochloric acid (2.4 mL) were mixed, cooled in an ice bath, and sodium nitrite (0.6 g) and water (2 mL) were added and stirred for 1 hour. After further adding amide sulfuric acid (0.1 g), the mixture was stirred for another 30 minutes to prepare reaction solution 2.

[0430] 1-Phenylopyridine (1.6 g), sodium acetate (2.6 g), water (40 mL), and methanol (40 mL) were mixed and cooled in an ice bath. Reaction solution 1 was added dropwise while the internal temperature was below 5 °C, and the mixture was stirred at 5 °C for 30 minutes, followed by stirring at 25 °C for 1 hour. After stirring, the solid was recovered by vacuum filtration to obtain 1.6 g of the first dichroic substance M1. The following shows the obtained first dichroic substance M1. 1 H-NMR (Nuclear Magnetic Resonance) data.

[0431] 1 H-NMR (solvent: CDCl3) δ (ppm): 0.96 (t, 3H), 1.40 (m, 2H), 1.68 (m, 2H), 2.07 (m, 4H), 2.70(t, 2H), 3.42(m, 4H), 6.64(d, 2H), 7.34(d, 2H), 7.83-8.03(m, 8H)

[0432] [Synthesis example 2]

[0433] Then, the second dichroic substance C1 was synthesized via the following route.

[0434] [Chemical Formula 21]

[0435]

[0436] 27.8 g of 4-nitrophenol, 44.6 g of 11-bromononanol, and 30.4 g of potassium carbonate were dissolved in 150 ml of N,N-dimethylacetamide (DMAc), and stirred at an external temperature of 105 °C for 2 hours. The mixture was then cooled to room temperature (23 °C) and subjected to separation washing with ethyl acetate and then with a 10% ammonium chloride aqueous solution. After drying the organic layer with magnesium sulfate, concentration was performed to obtain a white solid.

[0437] Next, 150 ml of DMAc was added to the solid, and the mixture was stirred in an ice bath. The temperature of the reaction system was maintained below 15°C, and 18.1 g of acrylate chloride was added dropwise. After the addition, the mixture was stirred at room temperature for 1 hour. Then, the mixture was subjected to separation washing with ethyl acetate and 10% ammonium chloride aqueous solution. After drying with magnesium sulfate, the mixture was concentrated to give a yellow solid, Cl-1.

[0438] In addition, 89.4 g (1.6 mol) of Fe powder, 8.9 g (166 mol) of ammonium chloride, 210 ml of 2-propanol, and 88 ml of water were mixed and refluxed at an external temperature of 105°C. A yellow solid (A) dissolved in 88 ml of 2-propanol upon heating was added dropwise to this refluxed system. After the addition was complete, the mixture was refluxed for 30 minutes. After cooling to room temperature, the iron powder was removed by diatomaceous earth filtration. The filtrate was then subjected to separation washing with ethyl acetate and water, and the organic layer was washed three times in water.

[0439] The organic layer was dried with sodium sulfate and then concentrated. Purification was performed using a column chromatography method to give 8.0 g of compound C1-2.

[0440] 2-Aminothiophene was synthesized from 2-nitrothiophene according to the method described in the literature (Journal of Medicinal Chemistry, 2005, Vol. 48, p. 5794).

[0441] The obtained compound C-2 (5.5 g) was added to a mixture of 15 ml of 12 mol / L hydrochloric acid, 30 ml of water, and 30 ml of THF (tetrahydrofuran). The mixture was cooled to below 5°C. 1.4 g of sodium nitrite was dissolved in 9 ml of water and added dropwise. The mixture was stirred for 1 hour at below 5°C to prepare a diazonium salt solution.

[0442] Next, 2.4 g of 2-aminothiophene hydrochloride was dissolved in 12 ml of water and 6 ml of hydrochloric acid, and the prepared diazonium salt solution was added dropwise at an internal temperature of 0 °C. The reaction solution was then allowed to rise to room temperature and stirred for 2 hours.

[0443] The precipitated solid was filtered off and dried to obtain 6.1 g of red-orange solid C1-3.

[0444] The 5.6 g of red-orange solid C1-3 obtained above was suspended and dissolved in 100 ml of acetic acid, and 1.5 g of sodium thiocyanate was added at room temperature. While water cooling was performed and the internal temperature was maintained below 20 °C, 2.0 g (24.8 mmol) of bromine was added dropwise.

[0445] After stirring at room temperature for 2 hours, 100 ml of water was added, the solid was filtered off and dried to obtain 5.5 g of black solid C1-4.

[0446] Add 4.7g of the black solid C1-4 obtained above to 6ml of hydrochloric acid and 6ml of acetic acid. While keeping the mixture ice-cold, add 5ml of an aqueous solution of 0.72g of sodium nitrite dropwise below 0°C. After stirring for 1 hour, add 0.52mg of amide sulfuric acid to obtain a diazonium salt solution.

[0447] A diazonium salt solution was added dropwise while maintaining a 10 mL methanol solution of 2.3 g of N-ethyl-N-(2-acryloyloxyethyl)aniline below 0 °C. The temperature was raised to room temperature (23 °C), and after stirring for 1 hour, 30 mL of water was added, and the resulting solid was filtered off. Purification by column chromatography yielded 0.51 g of a dark purple solid, representing the second dichroic substance C1. The following shows the obtained second dichroic substance C1... 1 H-NMR data.

[0448] In addition, N-ethyl-N-(2-acryloyloxyethyl)aniline is synthesized from N-ethylaniline using U.S. Patent No. 7601849 and known methods.

[0449] 1 H-NMR (solvent: CDCl3) δ (ppm): 1.20-1.50 (m, 17H), 1.60-1.90 (m, 8H) 3.40 (t, 2H), 3.50 (t, 2H), 4.05 (t, 2H), 4.10 (t, 2H), 4.20 (t, 2 H), 5.80-5.85(d, 2H), 6.10-6.15(dd, 2H), 6.38-6.43(d×2, 2H), 6.70(d, 2H), 7.00(d, 2H), 7.82(s, 1H) 7.88(d, 2H), 7.95(d, 2H)

[0450] [Synthesis example 3]

[0451] Then, the third dichroic substance Y1 was synthesized via the following route.

[0452] [Chemical Formula 22]

[0453]

[0454] First, 10 g of compound y1-1 was synthesized according to the literature (Chem.Eur.J.2004.10.2011).

[0455] Compound y1-1 (10 g) was dissolved in water (300 mL) and hydrochloric acid (17 mL), cooled in an ice bath, and sodium nitrite (3.3 g) was added with stirring for 30 minutes. Following the addition of amide sulfuric acid (0.5 g), m-toluidine (5.1 g) was added, and the mixture was stirred at room temperature (23 °C) for 1 hour. After stirring, the solid obtained from neutralization with hydrochloric acid was recovered by vacuum filtration to give 3.2 g of compound y1-2.

[0456] Compound y1-2 (1.0 g) was dissolved in a THF solution consisting of tetrahydrofuran (30 mL, THF), water (10 mL), and hydrochloric acid (1.6 mL). The solution was cooled in an ice bath, and sodium nitrite (0.3 g) was added and stirred for 30 minutes. Then, amide sulfuric acid (0.5 g) was added. Meanwhile, phenol (0.4 g) was dissolved in potassium carbonate (2.76 g) and water (50 mL). After cooling in an ice bath, the above THF solution was added dropwise, and the mixture was stirred at room temperature (23 °C) for 1 hour.

[0457] After stirring, water (200 mL) was added, and the precipitated solid was filtered off by suction filtration to obtain 1.7 g of compound y1-3.

[0458] Compound y1-3 (0.6 g), compound y1 (0.8 g), and potassium carbonate (0.95 g) were dissolved in DM Ac (30 mL, dimethylacetamide) and stirred at 90 °C for 3.5 hours. After stirring, water (300 mL) was added, and the precipitated solid was removed by suction filtration to obtain 0.3 g of a yellow-orange fixed third dichroic substance Y1. The following shows the obtained third dichroic substance Y1. 1 H-NMR data.

[0459] 1 H-NMR (solvent: CDCl3) δ (ppm): 1.93 (m, 8H), 4.11 (m, 4H), 4.29 (m. 4H), 5.83-5.87 (d, 2H), 6.10-6.18 (dd, 2H), 6.39-6.45 (d, 2H), 7.02 (d, 2H). ,7.77-8.13(m,15H)

[0460] [Synthesis Example 4]

[0461] The liquid crystal compound L1 is prepared in the following order.

[0462] <Synthesis of Compound L1-2>

[0463] [Chemical Formula 23]

[0464]

[0465] 2-Chloroethoxyethoxyethanol (244 g) and potassium carbonate (200 g) were added to a solution of butyl paraben (201 g) in N,N-dimethylformamide (300 mL). After stirring at 95 °C for 9 hours, toluene (262 mL) and water (660 mL) were added, and concentrated hydrochloric acid (147 g) was added dropwise. After stirring for 10 minutes, the mixture was allowed to stand and the reaction solution was washed by separation. A 28 wt% (28% by mass) sodium methoxide methanol solution (500 g) and water (402 mL) were added to the resulting organic layer, and the mixture was stirred at 50 °C for 2 hours. The organic solvent was then distilled off by concentration, and water (402 mL) was added, followed by further concentration at 50 °C until the weight reached 1.13 kg. Water (478 mL) was added to the resulting solution, and concentrated hydrochloric acid (278 g) was added dropwise. Ethyl acetate (1.45 kg) was added, and the mixture was stirred at 30 °C for 10 minutes. The aqueous layer was removed by separation. Next, 20 wt% saline solution (960 mL) was added, and the mixture was stirred at 30 °C for 10 minutes. The aqueous layer was removed by separation. N-methylpyrrolidone (824 g) was added to the resulting organic layer, and the mixture was concentrated at 70 °C for 4 hours to obtain 1.13 kg of N-methylpyrrolidone solution containing compound (L1-1). The next step was carried out using 1085 g of the obtained (L1-1) N-methylpyrrolidone solution. N,N-dimethylaniline (189 g) and 2,2,6,6-tetramethylpiperazine (1.5 g) were added to the obtained (L1-1) N-methylpyrrolidone solution (1085 g). After cooling the internal temperature, chloroacrylate (122 g) was added dropwise to keep the internal temperature below 10 °C. After stirring at an internal temperature of 10°C for 2 hours, methanol (81 g) was added dropwise, and the mixture was stirred for 30 minutes. Ethyl acetate (1.66 kg), 10 wt% saline solution (700 mL), and 1 N hydrochloric acid solution (840 mL) were then added, and the aqueous layer was removed by separation. Next, 10 wt% saline solution (800 mL) was added, and the mixture was stirred at 30°C for 10 minutes, and the aqueous layer was removed by separation. Then, 20 wt% saline solution (800 mL) was added, and the mixture was stirred at 30°C for 10 minutes, and the aqueous layer was removed by separation. A mixed solvent of hexane / isopropanol (1780 mL / 900 mL) was added to the resulting organic layer, and after cooling to 5°C and stirring for 30 minutes, the mixture was filtered to obtain 209 g of a white solid compound (L1-2) (65% yield in step 3).

[0466] 1H-NMR (solvent: CDCl3) δ (ppm): 3.67-3.78 (m, 6H), 3.87-3.92 (m, 2H), 4.18-4.23 (m, 2H), 4.31-4.35 (m, 2H), 5.80-5.85(m, 1H), 6.11-6.19(m, 1H), 6.40-6.46(m, 1H), 6.93-6.98(m, 2H), 8.02-8.07(m, 2H)

[0467] <Synthesis of Compound L1-3>

[0468] [Chemical Formula 24]

[0469]

[0470] A solution of 70 mL of methanesulfonyl chloride (MsCl) in tetrahydrofuran (THF) was added, and the internal temperature was cooled to -5 °C. A solution of compound (L1-2) (66.7 mmol, 21.6 g) and diisopropylethylamine (DIPEA) (75.6 mmol, 13.0 mL) in THF was added dropwise to prevent the internal temperature from rising above 0 °C. After stirring at -5 °C for 30 minutes, N,N-dimethyl-4-aminopyridine (DMAP) (200 mg) was added, followed by dropwise addition of a solution of diisopropylethylamine (75.6 mmol, 13.0 mL), 4-hydroxy-4'-methoxybiphenyl (60.6 mmol, 12.1 g) in tetrahydrofuran (THF), and dimethylacetamide (DMAc) to prevent the internal temperature from rising above 0 °C. The mixture was then stirred at room temperature for 4 hours. After stopping the reaction with the addition of methanol (5 mL), water and ethyl acetate were added. The solvent was removed from the organic layer extracted with ethyl acetate by rotary evaporation, and the mixture was purified by column chromatography using ethyl acetate and hexane to give 18.7 g of compound (L1-3) as a white solid (61% yield). In the structural formula, Me represents methyl.

[0471] 1 H-NMR (solvent: CDCl3) δ (ppm): 3.65-3.82 (m, 6H), 3.85 (s, 3H), 3.85-3.95 (m, 2H), 4.18-4.28 (m, 2H), 4.28-4.40 (m, 2H), 5.82(dd, 1H), 6.15(dd, 1H), 6.43(dd, 1H), 6.90-705(m, 4H), 720-7.30(m, 2H), 7.45-7.65(m, 4H), 8.10-8.20(m, 2H)

[0472] It contains the following compound (L1-b) as an impurity.

[0473] [Chemical Formula 25]

[0474]

[0475] n is an integer other than 3 (L1-b)

[0476] (Synthesis of compound L1-23)

[0477] [Chemical Formula 26]

[0478]

[0479] Methyl 4-(4-hydroxyphenyl)benzoate was synthesized by the method described in Journal of Polymer Science, Part A: Polymer Chemistry, 2012, vol. 50, pp. 3936-3943.

[0480] 2,2,6,6-Tetramethylpiperidine-1-oxy (68 mg) was added to an ethyl acetate solution (44 mL) of methanesulfonyl chloride (MsCl) (54.8 mmol, 6.27 g), and the internal temperature was cooled to -5 °C. A THF solution of the compound (L1-2) synthesized above (52.6 mmol, 17.1 g) and diisopropylethylamine (DIPEA) (57.0 mol, 7.36 g) was added dropwise to prevent the internal temperature from rising above 0 °C. After stirring at -5 °C for 30 min, a DMAc solution of methyl 4-(4-hydroxyphenyl)benzoate (43.8 mmol, 10.0 g), N-methylimidazolium (NMI) (1.8 g) was added, followed by dropwise addition of diisopropylethylamine (75.6 mmol, 13.0 mL) to prevent the internal temperature from rising above 0 °C. The mixture was then stirred at room temperature for 4 h. The reaction was stopped by adding water and ethyl acetate. The organic layer extracted with ethyl acetate was separated and the solvent was removed by rotary evaporation. The organic layer was then purified by column chromatography using ethyl acetate and hexane to give 20.4 g of compound (L1-23) as a white solid (yield 87%).

[0481] 1H-NMR (solvent: CDCl3) δ (ppm): 3.68-3.80 (m, 6H), 3.87-3.95 (m, 2H), 3.95 (s, 3H), 4.20-4.27 (m, 2H), 4.31-4.37 (m, 2H), 5 .83(dd, 1H), 6.16(dd, 1H), 6.43(dd, 1H), 6.97-7.05(m, 2H), 7.28-7.35(m, 2H), 7.64-7.72(m, 4H), 8.08-8.20(m, 4H)

[0482] As an impurity, it contains the following compound (L1-b2).

[0483] [Chemical Formula 27]

[0484]

[0485] n is an integer other than 3 (L1-2b)

[0486] Synthesis of Liquid Crystal Compound L1

[0487] [Chemical Formula 28]

[0488]

[0489] Compounds (L1-3) (84 g), (L1-23) (21 g), and butylated hydroxytoluene (BHT) (158 mg) were dissolved in anisole (337 g). Dimethyl 2,2'-azobis(2-methylpropionic acid) (1660 mg) (trade name "V-601") was added at room temperature and stirred. The resulting anisole solution was added dropwise over 2 hours to anisole (84 g) heated to 80°C under nitrogen. After the addition was complete, the mixture was stirred at 80°C for 4 hours. The resulting reaction solution was added dropwise to methanol (1080 mL), and the precipitate was collected by filtration. The residue was washed with acetonitrile to give 100 g of a white solid, compound (L1) (95% yield). The weight-average molecular weight (Mw) of the obtained polymer was 13300.

[0490] In addition, the molecular weight was calculated in polystyrene by gel permeation chromatography (GPC) using a column connected to three TOSOH TSKgelSuperAWM-H (manufactured by Tosoh Corporation) and N-methylpyrrolidone as the solvent.

[0491] [Example 1]

[0492] [Fabrication of Transparent Support 1]

[0493] On a 40 μm thick TAC substrate (TG40, manufactured by Fujifilm Corporation), an alignment film coating liquid 9 with the following composition was continuously coated using a #8 wire rod. Then, a transparent support 1 with a 0.8 μm thick polyvinyl alcohol (PVA) alignment film formed on the TAC substrate was obtained by drying with warm air at 100°C for 2 minutes.

[0494] In addition, modified polyvinyl alcohol was added to the orientation film coating solution at a solid content concentration of 4 wt%.

[0495]

[0496]

[0497] Modified polyvinyl alcohol

[0498] [Chemical Formula 29]

[0499]

[0500] [Formation of Orientation Film 1]

[0501] To 1 part by mass of photo-alignment material E-1 with the following structure, 41.6 parts by mass of butoxyethanol, 41.6 parts by mass of dipropylene glycol monomethyl and 15.8 parts by mass of pure water were added. The solution obtained by pressure filtration using a membrane filter was 0.45 μm to prepare a coating solution 1 for photo-alignment film.

[0502] Next, the obtained photoalignment film was coated onto the transparent support 1 with coating solution 1 and dried at 60°C for 1 minute. Then, linearly polarized ultraviolet light (illuminance 4.5mW, irradiation dose 500mJ / cm²) was exposed using a polarized ultraviolet light exposure apparatus. 2 The resulting coating is irradiated to produce an orientation film 1.

[0503] [Chemical Formula 30]

[0504]

[0505] [The Construction of Polarizer 1]

[0506] On the obtained alignment film 1, the following polarizer forming composition 1 is continuously coated with a #7 wire bar to form the coating film 1.

[0507] Next, the coating 1 is heated at 140°C for 90 seconds and then cooled to room temperature (23°C).

[0508] Next, heat at 90°C for 60 seconds, then cool again to room temperature.

[0509] Then, a high-pressure mercury lamp was used at an illuminance of 28 mW / cm². 2 The polarizer 1 is fabricated on the alignment film 1 by irradiating it for 60 seconds under the irradiation conditions.

[0510]

[0511] [Chemical Formula 31]

[0512]

[0513] [Construction of Polarizers 1-1 to 1-3]

[0514] On the obtained alignment film 1, the following polarizer forming compositions 1-1 to 1-3 are continuously coated onto the #7 wire bar to form coating films 1-1 to 1-3.

[0515] Next, each coating was heated at 140°C for 90 seconds, and then cooled to room temperature (23°C).

[0516] Next, heat at 90°C for 60 seconds, then cool to room temperature.

[0517] Then, a high-pressure mercury lamp was used at an illuminance of 28 mW / cm². 2 Irradiate for 60 seconds under the irradiation conditions, thereby fabricating polarizer 1-1 (film 1-1), polarizer 1-2 (film 1-2), and polarizer 1-3 (film 1-3) on the alignment film 1.

[0518]

[0519]

[0520]

[0521] Calculation of maximum absorption wavelength

[0522] Regarding the fabricated polarizers 1, 1-1, and 1-2, the absorbance of the anisotropic films in the wavelength region of 380 nm to 780 nm was measured using a multi-channel spectrometer (manufactured by Op toSiriu Corporation, product name "QE65000") with a 1 nm spacing. The absorption spectra of each polarizer were also measured, and the maximum absorption wavelengths were calculated. The results are shown in Table 1 below.

[0523] λ1: The maximum absorption wavelength in the absorption spectrum of polarizer 1-1

[0524] λM: The maximum absorption wavelength in the difference spectrum between the absorption spectra of polarizer 1 and polarizer 1-2.

[0525] λ2: The maximum absorption wavelength in the absorption spectrum of polarizer 1-2

[0526] λC: The maximum absorption wavelength in the difference spectrum between the absorption spectrum of polarizer 1 and the absorption spectrum of polarizer 1-1.

[0527] Furthermore, for the first dichroic substance (dichroic substance M1) and the second dichroic substance (dichroic substance C1), tetrahydrofuran solutions were prepared, and the absorbance in the wavelength region of 380 nm to 780 nm was measured using a UA-3100PC (manufactured by SHIMADZU CORPORATION) at a 1 nm interval. The maximum absorption wavelength (λ1') of the first dichroic substance and the maximum absorption wavelength (λ2') of the second dichroic substance were calculated. The results are shown in Table 1 below.

[0528] <xrd>

[0529] Furthermore, the polarizers 1, 1-1 and 1-3 were cut into 40mm × 40mm sizes, and in-plane XRD was performed by irradiating the polarizer surfaces with X-rays using a thin film evaluation X-ray diffraction apparatus (manufactured by Rigaku Corporation, trade name: "SmartLab") under the following conditions.

[0530] In addition, the polarizer is configured such that the incident direction of the X-rays is parallel to the orientation of the liquid crystal compound and the dichroic material along their long axis, which is set as the azimuth angle. In-plane XRD in all directions in 15° increments. (Scanning), through the observation of peaks The direction within the substrate plane where the peak intensity is highest is determined by scanning. Both measurements were performed using CuKα at an incident angle of 0.20°.

[0531] (condition)

[0532] • Use a Cu-ray source (CuKα, output 45kV, 200mA)

[0533] • X-ray incident angle 0.2°

[0534] • Optical system used: Parallel optical system (CBO(PB))

[0535] • 0.2mm incident slit, 0.5-degree in-plane PSC of the parallel incident slit, and 10mm long-side limiting slit.

[0536] • Light-receiving slit on the receiving side: 20mm; PSA within the parallel light-receiving slit plane: 0.5 degrees.

[0537] • Detector: HyPix3000 (OD mode) manufactured by Rigaku Corporation.

[0538] Scanning conditions: Set the range of 1–40 degrees to 0.008 degrees / step and 2.0 degrees / minute.

[0539] Scanning conditions: Set the range of -120 to 120 degrees to 0.5 degrees / step and 9.6 degrees / minute.

[0540] In polarizers 1-3, peaks were observed at positions with 2θ of 2.8°, 4.9°, and 7.9° in the 90° direction (as determined above). Figure 3 ).

[0541] In contrast, in polarizer 1-1, in addition to 2.8°, 4.9°, and 7.9°, a peak was also observed at 6.4° (reference). Figure 2 ).

[0542] Therefore, it can be concluded that Figure 2 The peak at 6.4° is derived from the first dichroic substance M1. The peak intensity (M) of this peak is 412.

[0543] Similarly, in polarizer 1, peaks were observed at positions of 2.8°, 4.9°, 6.4°, and 7.9°, just as in polarizer 1-1 (reference). Figure 1 The peak intensity (MO) of the 6.4° peak is 400.

[0544] Therefore, it can be inferred that in polarizer 1 and polarizer 1-1, an arrangement structure (specifically a crystal structure) based on the formation of the first dichroic material is formed, thereby the peaks originating from the first dichroic material M1 in polarizer 1 and polarizer 1-1 become of the same intensity.

[0545] In addition, the value of peak intensity (MO) relative to peak intensity (M), i.e., MO / M, can be calculated to be 0.97.

[0546] In polarizers 1-3, no peak was observed in the 30° direction (as determined above) within the range of 2θ from 1 to 15°.

[0547] In contrast, in polarizers 1-2, a peak was observed at a position where 2θ is 3.7°, with a peak intensity (C) of 610.

[0548] Therefore, the peak at 3.7° originates from the second dichroic substance C1.

[0549] Similarly, in polarizer 1, a peak was observed at the same position as in polarizers 1-2, at 3.7°. The peak intensity (CO) of this peak was 600.

[0550] Therefore, it can be inferred that: in polarizer 1 and polarizer 1-2, an arrangement structure (specifically a crystal structure) based on the second dichroic material is formed, thereby the peaks originating from the second dichroic material C1 in polarizer 1 and polarizer 1-2 become of the same intensity.

[0551] In addition, the value of peak intensity (CO) relative to peak intensity (C), i.e., CO / C, can be calculated to be 0.98.

[0552] [Creation of Layer 1]

[0553] <Formation of transparent resin layer (barrier layer) 1>

[0554] On polarizer 1, the following curable composition 1 was continuously coated with a #2 wire bar and dried at 60°C for 5 minutes.

[0555] Then, a high-pressure mercury lamp was used at an illuminance of 28 mW / cm². 2 The curable composition 1 was cured by irradiation for 60 seconds under the specified irradiation conditions, thus producing a laminate with a transparent resin layer (barrier layer) 1 formed on the polarizer 1. This yielded the laminate 1 of Example 1.

[0556] When the transparent resin layer 1 was cut into a cross section using a slicing cutter and the film thickness was measured by observation using a scanning electron microscope (SEM), the film thickness was approximately 1.0 μm.

[0557]

[0558] KAYARAD PET-30

[0559] [Chemical Formula 32]

[0560]

[0561] [Examples 2-9, Comparative Examples 1 and 2]

[0562] Using the polarizer forming composition described in Table 1 below instead of polarizer forming composition 1, the polarizer and the laminate were fabricated in the same order as in Example 1, and the maximum absorption wavelength was calculated in the same manner as in Example 1. The results are shown in Table 1 below.

[0563] Furthermore, regarding the polarizers fabricated in Examples 2 to 9, XRD spectra were compared in the same manner as in Example 1. In polarizer 2, which corresponds to polarizer 1, peak M originating from the first dichroic substance present in polarizer 2-1, which corresponds to polarizer 1-1, and peak C originating from the second dichroic substance present in polarizer 2-2, which corresponds to polarizer 1-2, were observed. In polarizer 2, it was confirmed that the first dichroic substance forms a crystal structure on its own, and the second dichroic substance forms a crystal structure on its own.

[0564] On the other hand, regarding the polarizers fabricated in Comparative Examples 1 and 2, XRD spectra were compared with those in Example 1. As a result, it was not confirmed that the first dichroic material formed a crystal structure on its own, nor that the second dichroic material formed a crystal structure on its own.

[0565] Additionally, the following is a summary of the ingredients used in the examples, including Example 1.

[0566] [Chemical Formula 33]

[0567]

[0568] [Chemical Formula 34]

[0569]

[0570] [Chemical Formula 35]

[0571]

[0572] [Chemical Formula 36]

[0573]

[0574] [evaluate]

[0575] The polarizers and laminates of the embodiments and comparative examples obtained as described above were evaluated as follows.

[0576] [Orientation Degree]

[0577] With the linear polarizer inserted into the light source side of an optical microscope (Nikon Corporation, product name "ECL IPSEE600 POL"), the stacks of the examples and comparative examples were placed on the sample stage. The absorbance of the anisotropic films in the wavelength region of 380 nm to 780 nm was measured using a multi-channel spectrometer (OptoSirius Corporation, product name "QE65000") at 1 nm intervals, and the orientation degree was calculated using the following formula. The results are shown in Table 1 below.

[0578] Orientation degree: S=((Az0 / Ay0)-1) / ((Az0 / Ay0)+2)

[0579] Az0: Absorbance of polarized light along the absorption axis of the pigment film.

[0580] Ay0: Absorbance of polarized light along the polarization axis of the pigment film.

[0581] In the above formula, "Az0" represents the absorbance of polarized light along the absorption axis of the anisotropic absorber film, and "Ay0" represents the absorbance of polarized light along the polarization axis of the anisotropic absorber film.

[0582]

[0583] Based on the measurement results of the maximum absorption wavelength shown in Table 1, it can be inferred that the first dichroic material forms an association compound and the second dichroic material forms an association compound in the polarizers of Examples 1 to 9.

[0584] Furthermore, based on the XRD spectrum measurement results of Examples 1 to 9, it can be inferred that the first dichroic material forms a crystal structure on its own in the polarizer of Example 1, and the second dichroic material forms a crystal structure on its own.

[0585] Therefore, it can be said that the polarizer in the embodiment has an arrangement structure formed by a first dichroic material and an arrangement structure formed by a second dichroic material, respectively.

[0586] Thus, the polarizers according to the embodiments having an arrangement result formed by the first dichroic material and an arrangement structure formed by the second dichroic material respectively, as shown in the evaluation results in Table 1, exhibit a higher degree of orientation compared to the polarizers of the comparative examples.

[0587] Symbol Explanation

[0588] P - polarizer, M - molecule of the first dichroic substance, C - molecule of the second dichroic substance, L - molecule of the liquid crystal compound, G - aggregate, w - width, a - angle.< / xrd>

Claims

1. A polarizer formed from a polarizer-forming composition containing a liquid crystalline compound and a dichroic substance, the dichroic substance containing at least a first dichroic substance having a maximum absorption wavelength in a range of 455 nm or more and less than 560 nm, and a second dichroic substance having a maximum absorption wavelength in a range of 560 nm or more and 700 nm or less, a content of the dichroic substance is 0.1 to 99 parts by mass with respect to 100 parts by mass of a total amount of the liquid crystalline compound and the dichroic substance, a content of the first dichroic substance is 6 to 50 parts by mass with respect to 100 parts by mass of the content of the dichroic substance, a content of the second dichroic substance is 40 to 90 parts by mass with respect to 100 parts by mass of the content of the dichroic substance, the polarizer has an alignment structure formed from the first dichroic substance and an alignment structure formed from the second dichroic substance, the alignment structure formed from the first dichroic substance refers to a state in which two or more molecules of the first dichroic substance aggregate to form an aggregate in the polarizer, and the molecules of the first dichroic substance are periodically aligned in the aggregate, the alignment structure formed from the second dichroic substance refers to a state in which two or more molecules of the second dichroic substance aggregate to form an aggregate in the polarizer, and the molecules of the second dichroic substance are periodically aligned in the aggregate.

2. The polarizer according to claim 1, wherein in the alignment structure formed from the first dichroic substance, the first dichroic substance forms an associate, and in the alignment structure formed from the second dichroic substance, the second dichroic substance forms an associate.

3. The polarizer according to claim 1 or 2, which satisfies the following formulas (I) and (II), |λM-λ1|≤5nm (I) |λ1-λ1'|≥5nm (II) wherein in the formulas (I) and (II), λM is a maximum absorption wavelength in a difference spectrum between an absorption spectrum of a film formed from a composition containing the first dichroic substance, the second dichroic substance, and the liquid crystalline compound, and an absorption spectrum of a film formed from a composition containing the second dichroic substance and the liquid crystalline compound without containing the first dichroic substance, λ1 is a maximum absorption wavelength in an absorption spectrum of a film formed from a composition containing the first dichroic substance and the liquid crystalline compound without containing the second dichroic substance, λ1' is a maximum absorption wavelength in an absorption spectrum of a solution in which the first dichroic substance is dissolved.

4. The polarizer of claim 1 or 2, wherein, the polarizer satisfies the following formulas (III) and (IV), |λC-λ2|≤5nm (III) |λ2-λ2'|≥5nm (IV) in the formulas (III) and (IV), λC is a maximum absorption wavelength in a difference spectrum between an absorption spectrum of a film formed of a composition containing the first dichroic substance, the second dichroic substance, and the liquid crystalline compound and an absorption spectrum of a film formed of a composition containing the first dichroic substance and the liquid crystalline compound without containing the second dichroic substance, λ2 is a maximum absorption wavelength in an absorption spectrum of a film formed of a composition containing the second dichroic substance and the liquid crystalline compound without containing the first dichroic substance, λ2' is a maximum absorption wavelength in an absorption spectrum of a solution in which the second dichroic substance is dissolved.

5. The polarizer according to claim 1 or 2, wherein in the alignment structure formed of the first dichroic substance, the first dichroic substance forms a crystal structure, and in the alignment structure formed of the second dichroic substance, the second dichroic substance forms a crystal structure.

6. The polarizer of claim 1 or 2, wherein, the polarizer satisfies the following formula (V), 0.9 ≤ MO / M ≤ 1.1 (V) in the formula (V), MO is an intensity of a peak derived from a periodic structure of the first dichroic substance in an X-ray diffraction spectrum of a film formed of a composition containing the first dichroic substance, the second dichroic substance, and the liquid crystalline compound, M is an intensity of a peak derived from a periodic structure of the first dichroic substance in an X-ray diffraction spectrum of a film formed of a composition containing the first dichroic substance and the liquid crystalline compound without containing the second dichroic substance.

7. The polarizer of claim 1 or 2, wherein, the polarizer satisfies the following formula (VI), 0.9 ≤ CO / C ≤ 1.1 (VI) in the formula (VI), CO is an intensity of a peak derived from a periodic structure of the second dichroic substance in an X-ray diffraction spectrum of a film formed of a composition containing the first dichroic substance, the second dichroic substance, and the liquid crystalline compound, C is an intensity of a peak derived from a periodic structure of the second dichroic substance in an X-ray diffraction spectrum of a film formed of a composition containing the second dichroic substance and the liquid crystalline compound without containing the first dichroic substance.

8. The polarizer according to claim 1 or 2, wherein the composition for forming the polarizer further contains a third dichroic substance having a maximum absorption wavelength in a range of 380 nm or more and less than 455 nm.

9. The polarizer according to claim 8, wherein the content of the third dichroic substance is 3 to 40 parts by mass with respect to 100 parts by mass of the content of the dichroic substance.

10. The polarizer according to claim 1 or 2, wherein an absolute value of a difference between a log P value of a side chain of the first dichroic substance and a log P value of a side chain of the second dichroic substance is 1.1 or more.

11. An image display device having the polarizer according to any one of claims 1 to 10.

Images