Liquid crystal composition, liquid crystal layer, optical laminate, image display device, method for manufacturing optical laminate, compound

Abstract

This invention provides a liquid crystal composition capable of suppressing wind spots and exhibiting excellent liquid crystal alignment and topcoatability after being formed into a layer. The liquid crystal composition of this invention comprises: a leveling agent having a site that is cleaved by at least one action selected from the group consisting of acid, light, and heat; a photoalignment compound; and a liquid crystal compound.

Description

Technical Field

[0001] This invention relates to a liquid crystal composition, a liquid crystal layer, an optical laminate, an image display device, a method for manufacturing an optical laminate, and a compound. Background Technology

[0002] From the perspective of eliminating image color distortion and magnifying viewing angle, optical films such as optical compensation sheets and phase difference films are used in various image display devices. As an optical film, stretched birefringent films have been used, but in recent years, it has been proposed to use optical anisotropic layers formed by liquid crystal compounds to replace stretched birefringent films.

[0003] In forming such an optically anisotropic layer, a liquid crystal layer (photoalignment film) obtained by performing a photoalignment process is sometimes used to orient the liquid crystal compound. In the manufacture of the liquid crystal layer, a method has been proposed to improve the surface properties of the liquid crystal layer obtained using perfluoroalkyl compounds (so-called PFAS) (see Patent Document 1). Previous technical documents Patent documents

[0004] Patent Document 1: International Publication No. 2018 / 216812 Summary of the Invention The technical problem to be solved by the invention

[0005] However, PFAS are difficult to decompose, thus posing a risk of accumulation in the environment or organisms, and therefore, the development of alternatives to PFAS is desired. The inventors, in their research on liquid crystal layers obtained using silicon compounds as an alternative to PFAS, discovered that film thickness inhomogeneities (hereinafter also referred to as "wind spots") in the liquid crystal layer caused by the drying wind during drying occur depending on the solvent used. Furthermore, the obtained liquid crystal layer also requires the orientation of the optical anisotropic layer formed on the liquid crystal layer (hereinafter also referred to as "liquid crystal orientation") and the coatability of the composition for the optical anisotropic layer disposed on the liquid crystal layer (hereinafter also referred to as "top layer coatability").

[0006] Therefore, the objective of this invention is to provide a liquid crystal composition, liquid crystal layer, optical laminate, image display device, method for manufacturing optical laminate, and compound that can suppress wind spots and have excellent liquid crystal orientation and upper layer coating properties after being formed into a layer. means for solving technical problems

[0007] As a result of in-depth research conducted by the inventors to achieve the above-mentioned problems, they discovered that the above-mentioned problems can be achieved through the following structure.

[0008] [1] A liquid crystal composition comprising: A leveling agent having a site that is broken down by at least one action selected from the group consisting of acid, light, and heat; Photooriented compounds; and Liquid crystal compounds. [2] According to the liquid crystal composition described in [1], wherein, The leveling agent described above has a repeating unit A represented by the formula (a1) and a repeating unit B represented by any one of the formulas (b1) to (b3). [3] According to the liquid crystal composition described in [1] or [2], wherein, The content of the leveling agent is 0.01 to 5 parts by mass relative to 100 parts by mass of the liquid crystal compound. [4] According to the liquid crystal composition described in [2], wherein, L 1 It is a group represented by any one of the following formulas (L1) to (L3). [5] The liquid crystal composition according to any one of [1] to [4], wherein, The leveling agent described above has a group represented by the formula (1) described later. [6] According to the liquid crystal composition described in [2] or [4], wherein, The content of the aforementioned repeating unit A is 40% by mass or more and less than 100% by mass relative to the total mass of all repeating units of the aforementioned leveling agent. [7] The liquid crystal composition according to any one of [1] to [6], wherein, The weight-average molecular weight of the above leveling agents is 5,000 to 100,000. [8] The liquid crystal composition according to any one of [1] to [7], wherein, The content of the aforementioned photo-alignment compound is 0.1 to 10 parts by mass relative to 100 parts by mass of the aforementioned liquid crystal compound. [9] The liquid crystal composition according to any one of [1] to [8], wherein, The aforementioned photo-orientation compound has a repeating unit X containing a photo-orientation group and a repeating unit C containing a crosslinking group. The total content of the repeating unit X and the repeating unit C is 99 to 100% by mass relative to the total mass of all repeating units of the photo-alignment compound, and the content of the repeating unit X is 40% by mass or more relative to the total mass of all repeating units of the photo-alignment compound.

[10] The liquid crystal composition according to any one of [1] to [8], wherein, The aforementioned photo-orientation compound has a repeating unit A represented by formula (a1) described later, a repeating unit X having a photo-orientation group, and a repeating unit C having a crosslinking group. The total content of repeating unit A, repeating unit X, and repeating unit C is 99-100% by mass relative to the total mass of all repeating units of the photoalignment compound.

[11] According to the liquid crystal composition described in

[10] , wherein, The content of repeating unit A represented by formula (a1) is 10 to 60% of the total mass of all repeating units of the photo-orientation compound.

[12] A liquid crystal layer formed using any one of [1] to

[11] , and having orientation control capability.

[13] An optical laminate having a liquid crystal layer as described in

[12] and an optical anisotropy layer disposed on the liquid crystal layer.

[14] An image display device having the optical laminate described in

[13] .

[15] A method for manufacturing an optical laminate, comprising: The process of performing photoalignment treatment on a coating obtained using any one of [1] to

[11] to form a liquid crystal layer with orientation control capability; and The process of forming an optically anisotropic layer by coating a polymeric liquid crystal composition containing a polymeric liquid crystal compound onto the aforementioned liquid crystal layer.

[16] A compound having a repeating unit A represented by formula (a1) as described below and a repeating unit B represented by any one of formulas (b1) to (b3) as described below.

[17] According to the compound described in

[16] , wherein, The aforementioned repeating unit A is any one of the repeating units represented by equations (a2) to (a4) described later. Invention Effects

[0009] According to the present invention, a liquid crystal composition, a liquid crystal layer, an optical laminate, an image display device, a method for manufacturing an optical laminate, and a compound are provided that can suppress wind spots and have excellent liquid crystal orientation and upper layer coating properties after being formed into a layer. Detailed Implementation

[0010] The present invention will now be described in detail. The following description of the constituent elements is sometimes made according to representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits. Furthermore, in this specification, for numerical ranges recorded in stages, the upper or lower limit value recorded in a certain numerical range can be replaced with the upper or lower limit value of other numerical ranges recorded in stages. Also, within the numerical ranges recorded in this specification, the upper or lower limit value recorded in a certain numerical range can be replaced with the values ​​shown in the embodiments.

[0012] In this specification, each component may be used alone with one corresponding substance, or with two or more substances used together. Here, regarding each component, when two or more substances are used together, the content of that component, unless otherwise specified, refers to the total content of the substances used together.

[0013] In this specification, the bonding direction of the divalent groups (e.g., -O-CO-) described is not particularly limited; for example, in "L 1z -L 2z -L 3z In the bonding of "L" 2z In the case of -O-CO-, if the bond to L 1z The side position is set as 1 and will be bonded to L 3z The side position is set as 2, then L 2z It can be 1-O-CO- 2, or it could be 1-CO-O- 2.

[0014] [Liquid Crystal Composition] The liquid crystal composition of the present invention comprises: a leveling agent (hereinafter also referred to as "specific compound") having a site that is cleaved by at least one action selected from the group consisting of acid, light, and heat; a photoalignment compound; and a liquid crystal compound.

[0015] In this invention, as described above, if the liquid crystal composition of this invention is used, wind spots can be suppressed, and a liquid crystal layer with excellent liquid crystal orientation and upper layer coating properties after being formed into a layer can be obtained. The exact reasons are unclear, but the inventor speculates as follows. That is, it is speculated that a particular compound has leveling properties (in particular, has repeating unit A represented by formula (a1)) and has a site that is broken down by a specified action, thereby suppressing wind spots while also having excellent upper coating properties and liquid crystal orientation. The following provides a detailed description of the various components that may be included in a liquid crystal composition.

[0016] [Specific compound] The liquid crystal composition of the present invention contains a specific compound. The specific compound preferably has a cleavage site by at least one action selected from the group consisting of acid, light and heat, and has a cleavage site by at least one action selected from the group consisting of acid and light. Furthermore, the specific compound preferably does not have a photo-orientation group, and more preferably does not have either a photo-orientation group or a fluorine atom. Also, the specific compound is preferably a compound other than the photo-orientation compound and the liquid crystal compound described later.

[0017] The site that is cleaved by at least one action selected from the group consisting of acid, light and heat is not particularly limited as long as it is cleaved by the above actions, but a cleavage group that decomposes and generates a polar group by at least one action selected from the group consisting of acid, light and heat is preferred. The number of the aforementioned cleavage sites in a particular compound may be one or more, preferably one to five. Examples of such polar groups include hydroxyl, carbonyl, carboxyl, amino, nitro, ammonium, and cyano groups, with hydroxyl or carboxyl being preferred. "A cleavage group that generates a polar group" refers to a group that generates the aforementioned polar group through cleavage. In this invention, it also includes groups that generate polar groups by reacting with oxygen molecules after free radical cleavage. For example, cleavage groups represented by any one of formulas (rk-1) to (rk-13) can be cited as cleavage groups that generate polar groups.

[0018] [Chemical Formula 1]

[0019] In equations (rk-1) to (rk-13), 1 and 2 indicates the bonding position. R can independently represent a hydrogen atom or a monovalent organic group.

[0020] As a monovalent organic group represented by R, examples include chain or cyclic alkyl groups having 1 to 20 carbon atoms and aryl groups having 6 to 20 carbon atoms that may have substituents.

[0021] The cleavage group represented by formula (rk-10) or formula (rk-11) may have anions. The anions have little effect on cleavage and are therefore not particularly limited, and can be any of inorganic or organic anions. Examples of inorganic anions include, for example, halide ions such as chloride ions and bromide ions; and sulfonate anions. Examples of organic anions include carboxylate anions such as acetate anion; and organic sulfonate anions such as methanesulfonate anion and p-toluenesulfonate anion.

[0022] In this invention, when optical cleavage is used, the cleavage group represented by the above formula (rk-1) is preferred for the sake of improving quantum efficiency. When acid cleavage is used, the cleavage group represented by the above formula (rk-9) is preferred for the sake of improving cleavage speed. Furthermore, as a part that utilizes heat for pyrolysis, the Megafac DS21 (manufactured by DICCorporation) can be cited as an example.

[0023] Certain compounds preferably have biased groups. A biased group refers to a group that, when a compound with a biased group is used to form a film on a substrate, is biased towards the air interface side of the film (a group that enables the compound to be biased towards the air interface side). In other words, it refers to a group that functions to have a greater content of the compound with a biased group on the air interface side of the film than the content of the compound with a biased group on the substrate side of the film. For example, examples of biased groups include groups that have high hydrophobicity and function to make the surface energy of the film surface on the air interface side lower than the surface energy of the film surface on the substrate interface side. Examples of biased groups include groups having fluorine atoms and groups having silicon atoms, preferably groups having two or more silicon atoms, and more preferably groups having two or more groups represented by the formula (S) described later.

[0024] <Repeating Unit A> A particular compound preferably has one or more repeating units A represented by formula (a1).

[0025] [Chemical Formula 2]

[0026] In formula (a1), R 1 and R 2 Each can be used independently to represent a hydrogen atom or an alkyl group. R 3 Represents a hydrogen atom or a substituent. X represents an m+1 valence linkage group. L 1 It indicates an n+1 valent linker group having a site that can be cleaved by at least one action selected from the group consisting of acids, light, and heat. n represents an integer from 1 to 4. m represents an integer from 1 to 5. Rh represents a substituent having two or more groups represented by formula (S) (hereinafter also referred to as "substituent SI"). Among them, in L 1 In the case of multiple occurrences, L 1 They can be the same or different. When there are multiple Rh values, Rh can be the same or different. When there are multiple n values, n can be the same or different.

[0027] As R 1 and R 2 Alkyl groups represented in a certain manner may include, for example, straight-chain alkyl groups with 1 to 18 carbon atoms, branched alkyl groups with 3 to 18 carbon atoms, and cyclic alkyl groups. Specifically, examples include methyl, ethyl, propyl, isopropyl, butyl (e.g., n-butyl, sec-butyl, isobutyl, and tert-butyl) and cyclohexyl. As R 1 and R 2 Hydrogen atoms are preferred.

[0028] As R 3 Substituents can be represented in one manner, for example, hydroxyl, alkyl, alkenyl and aryl. Furthermore, as R 3 The substituent can be represented in one way, for example, -L. R -hydroxyl group, -L R -alkyl, -L R -Alkenyl and -L R -Aryl. L R This indicates a divalent linker. As an L... R The divalent linkages represented include, for example, -O-, -S-, -CO-, and -NR. N -, -CH=CH-, -C≡C-, divalent cyclic groups, alkylene groups, and divalent groups formed by combining them, preferably -CH2-COO-alkylene-hydroxyl.N It represents an alkyl group having 1 to 12 hydrogen atoms or carbon atoms. As R 3 The alkyl group represented by the method is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl or ethyl. As R 3 Preferably, it contains hydrogen atoms or methyl groups.

[0029] The m+1 valence linking group represented by X is not particularly limited. For example, -CO-, -O-, -COO- and -CONH- can be given as divalent (i.e., m=1). If it is a trivalent to hexavalent (i.e., m=2 to 5 integers), it can be a residue obtained by removing m+1 hydrogen atoms bonded to the carbon or nitrogen atoms of the ring that constitutes the aromatic ring (e.g., benzene-1,2,3-trimethyl, etc.). Furthermore, the m+1 valence linker preferably does not have a site that can be cleaved by at least one action selected from the group consisting of acid, light, and heat.

[0030] As L 1 The n+1 valence linking group represented by the action of at least one of the group consisting of acid, light and heat is preferably a hydrocarbon group with an n+1 valence having a site that can be cleaved by at least one of the group consisting of acid, light and heat and may have a substituent, and a portion of the carbon atom constituting the hydrocarbon group may be replaced by a heteroatom. More preferably, it is an aliphatic hydrocarbon group with an n+1 valence having a site that can be cleaved by at least one of the group consisting of acid, light and heat and may have an oxygen atom or a nitrogen atom with an n+1 valence having a carbon atom number of 1 to 10.

[0031] In this invention, considering the reasons for improved topcoatability and liquid crystal alignment, as L 1 Preferably, it is a group represented by any one of formulas (L1) to (L3).

[0032] [Chemical Formula 3]

[0033] In equations (L1) to (L3), 1 indicates the bond position with X. 2 indicates the bonding position with Rh. L x1 L x2 and L x3 Each can independently represent an alkylene group having 1 to 20 carbon atoms with -O-, an aryl group having 6 to 18 carbon atoms with -O-, or a group or single bond formed by combining them. R L1 and R L2 Each can be used independently to represent a hydrogen atom or a substituent. L L1 L L2 and L L3 Each can be used independently to represent a divalent linker. m L1 and m L2 Each can be represented independently as 1 or 2. Among them, when L 1 When the group is represented by formula (L1), n ​​in formula (a1) represents m. L1 +m L2 When L 1 When the group is represented by formula (L2), n in formula (a1) represents 1. When L 1 When the group is represented by formula (L3), n in formula (a1) represents 2. Furthermore, R L2 They can be the same or different. L L1 They can be the same or different. L L3 They can be the same or different.

[0034] As L x1 L x2 and L x3 The alkylene group represented in one manner is preferably an alkylene group having 1 to 20 carbon atoms with -O-, more preferably a linear alkylene group having 1 to 18 carbon atoms with -O-, a branched alkylene group having 3 to 18 carbon atoms with -O-, or a cyclic alkylene group having 3 to 20 carbon atoms with -O-, even more preferably a linear alkylene group having 1 to 18 carbon atoms with -O-, and particularly preferably a linear alkylene group having 1 to 8 carbon atoms with -O-. As L x1 L x2 and L x3 The aryl group represented by the method is preferably an aryl group with 6 to 12 carbon atoms. As L x1 L x2 and L x3 The group formed by the combination represented in one manner is preferably an alkylene aryl group, more preferably an alkylene aryl group with 7 to 30 carbon atoms.

[0035] As R L1 and R L2 Substituents can be represented in one manner, for example, hydroxyl, alkyl, alkenyl and aryl. As R L1 and R L2The alkyl group represented by the method is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl or ethyl. As R L1 and R L2 Preferably, it contains hydrogen atoms or alkyl groups.

[0036] As L L1 L L2 and L L3 The divalent linking group can be, for example, a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, more preferably a straight-chain alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 3 to 18 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, and even more preferably a straight-chain alkylene group having 1 to 8 carbon atoms.

[0037] As m L1 and m L2 Preferably, the same number. Furthermore, m L1 and m L2 The total is preferably an integer from 2 to 4, more preferably 2 or 4.

[0038] The substituent SI represented by Rh is not particularly restricted as long as it has two or more substituents represented by the following formula (S).

[0039] [Chemical Formula 4]

[0040] In formula (S), Indicates the bonding location, R 4 R 5 and R 6 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. Among the substituents represented by Rh, R 4 They can be the same or different. R 5 They can be the same or different. R 6 They can be the same or different.

[0041] As R 4 R 5 and R 6 Alkyl groups represented in a certain way can be, for example, straight-chain alkyl groups with 1 to 18 carbon atoms, branched alkyl groups with 3 to 18 carbon atoms, and cyclic alkyl groups. As R 4 R 5 and R 6The alkenyl group can be represented in one way, for example, alkenyl groups with 2 to 12 carbon atoms. As R 4 R 5 and R 6 The aryl group can be represented in one way, for example, by aryl groups having 6 to 12 carbon atoms. Specifically, examples include phenyl, α-methylphenyl, and naphthyl groups. As R 4 R 5 and R 6 The alkylene aryl group can be represented in one way, for example, alkylene aryl groups with 7 to 30 carbon atoms.

[0042] Considering the reasons for the reduced surface tension of the liquid crystal composition and the ability to further suppress wind spots during the formation of the liquid crystal layer, R in formula (S) 4 R 5 and R 6 Preferably, it is an alkyl group, more preferably a straight-chain alkyl group having 1 to 18 carbon atoms.

[0043] The number of substituent SI represented by formula (S) is two or more. Considering the reasons that the surface tension of the liquid crystal composition is reduced and that wind spots can be further suppressed when forming the liquid crystal layer, it is preferably three to eight, more preferably three to six, and even more preferably three to five.

[0044] The substituent SI is preferably a group represented by formula (S1).

[0045] [Chemical Formula 5]

[0046] In formula (S1), R 4 R 5 and R 6 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. R S Indicates alkyl group, s represents 2 or 3. Among them, R 4 They can be the same or different. R 5 They can be the same or different. R 6 They can be the same or different.

[0047] R in equation (S1) 4 R 5 and R 6 Respectively with R in equation (S) 4 R 5 and R 6 The meanings are the same, and the preferred selection methods are also the same.

[0048] As R S The alkyl group represented is preferably an alkyl group having 1 to 18 carbon atoms, more preferably a straight-chain alkyl group having 1 to 4 carbon atoms, and even more preferably methyl or ethyl.

[0049] As the repeating unit A, it is preferably a repeating unit represented by any one of equations (a2) to (a4).

[0050] [Chemical Formula 6]

[0051] In equations (a2) to (a4), R 1 and R 2 Each can be used independently to represent a hydrogen atom or an alkyl group. R 3 Represents a hydrogen atom or a substituent. X a This indicates -COO- or -CONH-. L x1 L x2 and L x3 Each can independently represent an alkylene group having 1 to 20 carbon atoms with -O-, an aryl group having 6 to 18 carbon atoms with -O-, or a group or single bond formed by combining them. R L1 and R L2 Each can be used independently to represent a hydrogen atom or a substituent. L L1 L L2 and L L3 Each can be used independently to represent a divalent linker. Rh a This refers to the group represented by formula (S1) mentioned above. m L1 and m L2 Each can be represented independently as 1 or 2. Among them, R L2 They can be the same or different. L L1 They can be the same or different. L L3 They can be the same or different. Rh a They can be the same or different.

[0052] R in equations (a2) to (a4) 1 and R 2 respectively with R in equation (a1) 1 and R 2 The meanings are the same, and the preferred selection methods are also the same. R in equations (a2) to (a4)3 R in equation (a1) 3 The meanings are the same, and the preferred selection methods are also the same.

[0053] L in equations (a2) to (a4) x1 L x2 and L x3 The L in equations (L1) to (L3) are respectively x1 L x2 and L x3 The meanings are the same, and the preferred selection methods are also the same.

[0054] R in equations (a2) to (a4) L1 and R L2 R in equations (L1) to (L3) respectively L1 and R L2 The meanings are the same, and the preferred selection methods are also the same.

[0055] L in equations (a2) to (a4) L1 L L2 and L L3 The L in equations (L1) to (L3) are respectively L1 L L2 and L L3 The meanings are the same, and the preferred selection methods are also the same.

[0056] Rh a The group represented by formula (S1) has the same meaning as the group represented by formula (S1) in Rh, and the preferred method is also the same.

[0057] m in equations (a2) to (a4) L1 and m L2 respectively with m in equations (L1) to (L3) L1 and m L2 The meanings are the same, and the preferred selection methods are also the same.

[0058] Repeating unit A can be used alone or in two or more ways. The content of repeating unit A relative to the total mass of all repeating units of a particular compound is preferably 1 to 100% by mass, more preferably 30 to 100% by mass, and even more preferably 40% by mass or more and less than 100% by mass, considering that the weathering pattern is better.

[0059] <Repeating Unit B> Considering the reasons that it can further suppress aggregation within the obtained liquid crystal layer or improve the compatibility with the liquid crystal compound, a particular compound preferably has repeating unit B. A specific compound may have multiple repeating units among the repeating units represented by formula (b1), formula (b2), and formula (b3) as repeating unit B.

[0060] [Chemical Formula 7]

[0061] In equations (b1) to (b3), R b1 R b2 R b3 and R b4 Each can be used independently to represent a hydrogen atom or an alkyl group. L b1 -O- or -NR can be represented independently. Zb -,R Zb Represents a hydrogen atom or a substituent. L b2 Indicates a single bond or a divalent linkage group. A represents an alkylene group. p represents a number greater than 2. SP b1 Each represents a spacer group independently. M b1 Indicates a mesocrystalline group. T b1 Each terminal base is represented independently. Among them, A can be the same or different from each other.

[0062] R in equations (b1) to (b3) b1 and R b2 respectively with R in equation (a1) 1 and R 2 The meanings are the same, and the preferred selection methods are also the same. R in equations (b1) to (b3) b3 R in equation (a1) 3 The meanings are the same, and the preferred selection methods are also the same.

[0063] As R b4 The alkyl group represented in one manner may include, for example, straight-chain alkyl groups with 1 to 18 carbon atoms, branched alkyl groups with 3 to 18 carbon atoms, and cyclic alkyl groups, preferably straight-chain alkyl groups with 1 to 4 carbon atoms, and more preferably methyl or ethyl.

[0064] Regarding L b1 -NR is represented in one way Zb -, as R Zb The substituent represented in one manner is preferably an alkyl group, more preferably a straight-chain alkyl group having 1 to 4 carbon atoms, and even more preferably methyl or ethyl. As L b1 Preferably -O- or -NH-, more preferably -O-.

[0065] As L b2 The divalent linking group represented in one manner can be, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, and more preferably a straight-chain, branched, or cyclic alkylene group having 1 to 18 carbon atoms, a branched, or cyclic alkylene group having 3 to 20 carbon atoms. As L b2 Preferably, it is a single bond or a straight-chain alkylene group having 1 to 18 carbon atoms, more preferably a single bond.

[0066] The alkylene group represented by A preferably has 1 to 4 carbon atoms, more preferably 2 or 3. For example, when A is an alkylene group with 1 carbon atom, -AO- in formula (b1) represents oxymethylene (-CH2O-), and when A is an alkylene group with 2 carbon atom, -AO- in formula (b1) represents oxyethylene (-CH2CH2O-). The aforementioned alkylene groups can be either straight-chain or branched. -(AO) p - It can be an alkylene group formed by the linkage of an oxymethylene group and an oxypropylene group. Furthermore, the bonding sequence of each repeating unit can be either random or block.

[0067] The number represented by p is 2 or more, preferably a number between 2 and 1000, and more preferably a number between 2 and 25.

[0068] SP b1 There are no particular limitations on the spacer group, as long as it is a divalent linker without a ring structure. As SP b1 The spacer group can be, for example, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. As a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkylene group having 1 to 15 carbon atoms is preferred, and an alkylene group having 1 to 8 carbon atoms is more preferred. Specifically, examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, methylhexylene, and heptylene. Furthermore, regarding the spacer groups, one or more non-adjacent -CH2- groups constituting part of a divalent aliphatic hydrocarbon group can be independently substituted by -O-, -CO-, -S-, -NH-, -CH(Q)-, -C(Q)2-, or -N(Q)-. Q independently represents a substituent. The substituent represented by Q is preferably a hydroxyl or alkyl group. The alkyl group is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl.

[0069] M b1 The mesocrystalline groups referred to are the groups that represent the main framework of liquid crystal molecules that contribute 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. Regarding mesocrystalline groups, one can refer, for example, to "Flussige Kristalle in Tabellen II" (VEBDeutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), especially pages 7-16, and to the Liquid Crystal Handbook Editorial Committee, Liquid Crystal Handbook (Maruzen, 2000), especially Chapter 3. As a mesocrystalline group, it is preferred to have a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups, more preferably a group having aromatic hydrocarbon groups (preferably 1 to 5) or a group having alicyclic groups (preferably 1 to 5), and even more preferably a group having 2 to 4 aromatic hydrocarbon groups. From the viewpoint of improving the orientation degree of the liquid crystal cured layer, the substituent group can be present as a mesocrystalline group. As the above-mentioned substituent, alkyl, alkoxy, alkyl ester or acetyl are preferred, and methyl, tert-butyl, methoxy or methyl ester are more preferred.

[0070] As M b1 From the viewpoint that shrinkage craters are further suppressed when forming the liquid crystal curing layer, mesocrystalline groups represented by formula (M1-A) are preferred.

[0071] [Chemical Formula 8]

[0072] In formula (M1-A), Indicates the bonding location, Ph 11 and Ph 12 Each can be independently represented as a divalent aromatic ring group that may have substituents. L m1 It indicates a single bond or a divalent linkage group. n m Represents an integer greater than or equal to 0 or 1. Among them, in Ph 11 In the case of multiple occurrences, Ph 11 They can be the same or different. In L m1 In the case of multiple occurrences, L m1 They can be the same or different.

[0073] As Ph 11 and Ph12 The divalent aromatic ring group represented can be, for example, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring and a group obtained by removing two hydrogen atoms from an aromatic heterocycle. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings. Examples of aromatic heterocycles include furan rings, pyrrole rings, thiophene rings, pyridine rings, thiazole rings, and benzothiazole rings. As Ph 11 and Ph 12 The divalent aromatic ring group represented is preferably a group obtained by removing two hydrogen atoms from a benzene ring (e.g., 1,4-phenyl). Furthermore, as a substituent that may be present in the divalent aromatic ring group, alkyl ester group, alkyl or acetyl group is preferred, methyl ester group or straight-chain alkyl group with 1 to 4 carbon atoms is more preferred, and methyl or ethyl group is even more preferred.

[0074] As L m1 The divalent linkage group represented in one manner can be exemplified by, for example, -CO-, -O-, -S-, -C(=S)-, -C(R)-. m1 (R) m2 -, -C(R) m3 ) = C(R) m4 )-、-N(R m5 R - and the groups that combine them. m1 ~R m5 Each can be an alkyl group, representing a hydrogen atom, a fluorine atom, or a carbon atom numbering 1 to 12, respectively.

[0075] n m Preferably, n is an integer from 1 to 10. m It is also preferred to use integers from 0 to 10.

[0076] As T b1 Examples of terminal groups include, for instance, hydrogen atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms, acyloxy groups with 1 to 10 carbon atoms, amide groups with 1 to 10 carbon atoms, alkoxycarbonylamino groups with 1 to 10 carbon atoms, sulfonamide 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, (meth)acryloyloxy groups, and polymerizable groups formed by combining these groups. As T b1 Preferably, it is a hydrogen atom or a polymeric group, more preferably a hydrogen atom or (meth)acryloyloxy group.

[0077] Repeating unit B can be used alone or in more than two types. The total content of repeating unit A and repeating unit B is preferably 90 to 100% by mass relative to the total mass of all repeating units of a particular compound, more preferably 99 to 100% by mass, and even more preferably 99.9 to 100% by mass. Furthermore, a particular compound preferably has only repeating unit A and repeating unit B as repeating units.

[0078] <Other repeating units> A particular compound may have other repeating units besides repeating unit A and repeating unit B mentioned above. Other repeating units, for example, can be derived from compounds such as maleimide compounds, maleic anhydride, styrene compounds, liquid crystal compounds, and vinyl compounds. Other repeating units can be used individually or in two or more ways.

[0079] A particular compound preferably has a group represented by formula (1).

[0080] [Chemical Formula 9]

[0081] In equation (1), Indicates the bonding location, R 7 R 8 and R 12 Each can be used independently to represent a hydrogen atom or a substituent. R 9 R 10 R 11 R 13 R 14 and R 15 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. x and y independently represent integers from 1 to 3. v and w independently represent integers from 1 to 4. When v represents 1, L 2 L represents a single bond or a divalent linkage group. When v represents an integer from 2 to 4, L 2 This indicates a v+1 valence linkage group. When w represents 1, L 3 L represents a single bond or a divalent linkage group. When w represents an integer from 2 to 4, L 3 This indicates a w+1 valence linkage group. Among them, in R 8In the case of multiple cases, R 8 They can be the same or different. In R 12 In the case of multiple cases, R 12 They can be the same or different. In R 9 In the case of multiple cases, R 9 They can be the same or different. In R 10 In the case of multiple cases, R 10 They can be the same or different. In R 11 In the case of multiple cases, R 11 They can be the same or different. In R 13 In the case of multiple cases, R 13 They can be the same or different. In R 14 In the case of multiple cases, R 14 They can be the same or different. In R 15 In the case of multiple cases, R 15 They can be the same or different.

[0082] As R 7 R 8 and R 12 Substituents can be represented in one manner, for example, hydroxyl, alkyl, alkenyl and aryl. As R 7 R 8 and R 12 The alkyl group represented by the method is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl or ethyl. As R 7 Preferably, it is a hydrogen atom or an alkyl group, more preferably a hydrogen atom. As R 8 and R 12 Preferably, it is a hydrogen atom or an alkyl group, more preferably an alkyl group, and even more preferably a methyl or ethyl group. As R 8 and R 12 It is also preferable that R in formula (S1) S The alkyl group is represented.

[0083] As L 2 and L 3 The divalent linking group represented in one manner can be, for example, a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, more preferably a straight-chain alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 3 to 18 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, and even more preferably a straight-chain alkylene group having 1 to 8 carbon atoms. As L 2 The v+1 valence linkage group and L represented in one way3 The w+1 valence linking group, as indicated by the method, can be, for example, any linking group with a valence of 3 to 5 (i.e., v or w = an integer from 2 to 4). Examples include residues obtained by removing v+1 or w+1 hydrogen atoms from the hydrogen atoms bonded to the carbon or nitrogen atoms of the ring constituting the aromatic ring (e.g., benzene-1,2,3-triyl, etc.) and residues obtained by removing v+1 or w+1 hydrogen atoms from an aliphatic hydrocarbon. Preferably, the aliphatic hydrocarbon has 1 to 20 carbon atoms, and more preferably, it has 1 to 10 carbon atoms.

[0084] R 9 R 10 R 11 R 13 R 14 and R 15 Respectively with R in equation (S) 4 R 5 and R 6 The meanings are the same, and the preferred selection methods are also the same.

[0085] For x and y, 2 or 3 are preferred. As for v and w, 1 or 2 is preferred.

[0086] The following shows specific examples of repeating unit A that a particular compound may have. In the following formula, Me represents a methyl group.

[0087] [Chemical Formula 10]

[0088] The following are specific examples of repeating unit B that a particular compound may have. In the following formula, p represents a number greater than 2, which has the same meaning as p in the above formula (b1).

[0089] [Chemical Formula 11]

[0090] The following are specific examples of other repeating units that a particular compound may have.

[0091] [Chemical Formula 12]

[0092] The weight-average molecular weight of the specific compound is preferably 2,000 to 1,000,000, and more preferably 5,000 to 100,000, considering that the freckles are better. The weight-average molecular weights mentioned above are values ​​determined by gel permeation chromatography (GPC). • Solvent (eluent): Tetrahydrofuran (THF) • Device Name: EcoSEC HLC-8320GPC (Manufactured by TOSOH CORPORATION) • Column: Connect the three tubes: TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (all manufactured by TOSOH CORPORATION). • Column temperature: 40℃ • Sample concentration: 0.1% by mass • Flow rate: 0.35 mL / min • Calibration curves: Calibration curves using six samples of TSK standard polystyrene manufactured based on TOSOH, with Mw=706,000~1013 (Mw / Mn=1.03~1.06).

[0093] A specific compound can be used alone or in more than two forms. The content of the specific compound is preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the liquid crystal compound, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, considering that the whey pattern is better.

[0094] [Photo-oriented compounds] The liquid crystal composition of the present invention contains a photoalignment compound. Photooriented compounds are compounds that have photooriented groups. Furthermore, the photo-orientation compound preferably does not contain fluorine atoms. A photoorientation group refers to a group that has the function of inducing recombination or anisotropic chemical reaction by irradiation with anisotropic light (e.g., plane-polarized light). From the viewpoint of excellent orientation uniformity and good thermal and chemical stability, a photoorientation group that produces at least one of dimerization and isomerization by the action of light is preferred.

[0095] As a photo-oriented group that dimers through the action of light, examples include groups having a skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, and benzophenone derivatives. As a photo-oriented group that isomerizes through the action of light, examples include groups having the skeleton of at least one compound selected from the group consisting of azobenzene compounds, stilbene compounds, spiropyran compounds, cinnamic acid compounds, and hydrazine-β-keto ester compounds.

[0096] As a photo-orientation group, it is preferably a group having a skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives and maleimide derivatives, or a group having a skeleton of at least one compound selected from the group consisting of azobenzene compounds, stilbene compounds and spiropyran compounds, and more preferably a group having a cinnamic acid derivative skeleton or a coumarin derivative skeleton.

[0097] For example, a known structure can be cited as the main chain structure of repeating unit A with photooriented groups. The main chain structure of the repeating unit X having photo-oriented groups is preferably a skeleton selected from the group consisting of (meth)acrylic acids, styrene compounds, siloxanes, cycloolefins, methylpentenes, amides, and aromatic esters, more preferably a skeleton selected from the group consisting of (meth)acrylic acids, siloxanes, and cycloolefins, and even more preferably a (meth)acrylic acid skeleton.

[0098] <Repeating Unit X> The photo-oriented compound preferably has a repeating unit X having a photo-oriented group as described above, more preferably has a repeating unit represented by formula (X1), and even more preferably has a repeating unit represented by formula (X2).

[0099] [Chemical Formula 13]

[0100] In equation (X1), R X1 and R X2 Each can be used independently to represent a hydrogen atom or an alkyl group. R X3 Represents a hydrogen atom or a substituent. L X1 It indicates a single bond or a divalent linkage group. T X Indicates a photooriented group.

[0101] R X1 and R X2 respectively with R in equation (a1) 1 and R 2 The meanings are the same, and the preferred selection methods are also the same. R X3 R in equation (a1) 3 The meanings are the same, and the preferred selection methods are also the same.

[0102] As L X1 The divalent linkage group represented in one manner can be exemplified by, for example, -O-, -S-, -CO-, -NR-. NX-, -CH=CH-, -C≡C-, arylene, alkylene, and divalent groups formed by combining them. R NX This represents a hydrogen atom or a substituent. Alkyl groups are preferred as substituents. As L X1 The alkylene group represented by the embodiment is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 3 to 18 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, even more preferably a cyclic alkylene group having 3 to 20 carbon atoms, and particularly preferably a cyclic alkylene group having 3 to 10 carbon atoms and being a 5- or 6-membered ring alkylene group (a 5- or 6-membered ring cyclic alkylene group having 3 to 10 carbon atoms). As L X1 Preferably -COO- or -CONR NX -, -O-, alkylene groups, or combinations thereof.

[0103] As T X1 The light-orientation groups represented have the same meaning as the light-orientation groups in the aforementioned light-orientation compounds, and the preferred methods are also the same.

[0104] [Chemical Formula 14]

[0105] In equation (X2), R X4 It represents a hydrogen atom or an alkyl group. L X2 It indicates -COO- or -CONH-. L X3 This refers to cyclic alkylene groups, -O-, -S-, -NQ-, -CO-, or combinations thereof. R X5 R X6 R X7 R X8 and R X9 Each can be used independently to represent a hydrogen atom or a substituent.

[0106] As R X4 The alkyl group represented by the method is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl or ethyl. As R X4 Preferably, hydrogen atoms or methyl groups are used.

[0107] As L X2 Preferably, -CONH-.

[0108] As L X3The cyclic alkylene group represented in one manner is preferably a cyclic alkylene group having 3 to 20 carbon atoms, and more preferably a cyclic alkylene group having 5 to 10 carbon atoms. The aforementioned cyclic alkylene groups can be either monocyclic or polycyclic, preferably monocyclic. The number of ring members in the above-mentioned cyclic alkylene group is preferably 3 to 12, more preferably 5 or 6. The preferred cyclic alkylene groups are cyclopentylene or cyclohexylene. As L X3 Preferably, it is a cyclic alkylene group, a cyclic alkylene group-O-, or a cyclic alkylene group-NH-.

[0109] As R X5 R X6 R X7 R X8 and R X9 The substituent represented in one manner is preferably a halogen atom, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a cyano group, an amino group, or an -O-CO- hydrocarbon group (preferably an alkyl group having 1 to 20 carbon atoms).

[0110] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0111] The alkyl group is a straight-chain alkyl group having 1 to 20 carbon atoms, preferably having 1 to 6 carbon atoms, for example, methyl, ethyl and n-propyl. The alkyl group is a branched alkyl group with 3 to 20 carbon atoms, preferably an alkyl group with 3 to 6 carbon atoms, for example, isopropyl and tert-butyl. As a cyclic alkyl group, it is preferably an alkyl group having 3 to 6 carbon atoms, for example, cyclopropyl, cyclopentyl and cyclohexyl.

[0112] Examples of straight-chain haloalkyl groups with 1 to 20 carbon atoms include fluoroalkyl groups with 1 to 4 carbon atoms.

[0113] The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 3 to 18 carbon atoms, and even more preferably an alkoxy group having 6 to 18 carbon atoms. Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-butoxy, methoxyethoxy, n-hexoxy, n-octoxy, n-decoxy, n-dodecoxy, and n-tetradecoxy.

[0114] The aryl group having 6 to 20 carbon atoms is preferred, with 6 to 12 carbon atoms being an example, such as phenyl, α-methylphenyl and naphthyl.

[0115] The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, for example, phenoxy and 2-naphthoxy.

[0116] Examples of amino groups include primary amino groups (-NH2); secondary amino groups such as methylamino groups; and tertiary amino groups such as dimethylamino, diethylamino, dibenzylamino, and groups in which the nitrogen atom of a nitrogen-containing heterocyclic compound (e.g., pyrrolidine, piperidine, and piperazine) is used as a linking bond.

[0117] Considering the reason that photo-alignment compounds readily interact with liquid crystal compounds and that liquid crystal alignment becomes better, R X5 R X6 R X7 R X8 and R X9 In the middle, at least R is preferred X7 The above-mentioned substituents (preferably alkoxy groups with 1 to 20 carbon atoms) further enhance the linearity of the obtained photo-oriented polymer, making it easier to interact with liquid crystal compounds and resulting in better liquid crystal orientation. R is more preferred. X5 R X6 R X8 and R X9 Both represent hydrogen atoms.

[0118] The repeating unit X can be used alone or in more than two types. The content of repeating unit X is preferably 10 to 90% by mass relative to the total mass of all repeating units of the photo-orientation compound, more preferably 20 to 80% by mass, and even more preferably 40 to 80% by mass.

[0119] <Repeating Unit C> The photooriented compound preferably has a repeating unit C, which has a crosslinking group.

[0120] Considering the reason that improving the alignment of liquid crystals by enhancing solvent resistance to suppress alignment relaxation, the photoalignment compound preferably has a repeating unit C, which has a crosslinking group. There is no particular limitation on the type of crosslinking group; known crosslinking groups can be cited. Considering the reason that it improves the adhesion to the upper layer disposed on the liquid crystal layer, cationic polymeric groups or free radical polymeric groups are preferred.

[0121] Examples of cationic polymerizable groups include epoxy, epoxycyclohexyl, and oxocyclobutyl.

[0122] Examples of free radical polymerizable groups include acryloyl, methacryloyl, vinyl, styryl, and allyl.

[0123] As a repeating unit C having crosslinking groups, the repeating unit represented by the following formula (C) is preferred for the reason that the liquid crystal orientation becomes better.

[0124] [Chemical Formula 15]

[0125] In formula (C), R C1 Represents a hydrogen atom or a substituent. L C1 Indicates a single bond or a divalent linkage group. L C2 m C +1 valence linkage group. Z represents a crosslinking group. m C Represents an integer greater than or equal to 1. Among them, multiple Z can be the same or different.

[0126] R C1 R in equation (a1) 3 The meanings of the substituents represented by the different methods are the same, and the preferred methods are also the same.

[0127] As L C1 The divalent linker represented in one manner, for example, can be exemplified by L X1 The divalent linking group represented in one manner, from the perspective of improving liquid crystal orientation, is preferably selected from linear alkylene groups with 1 to 10 carbon atoms that may have substituents, branched or cyclic alkylene groups with 3 to 10 carbon atoms, aryl groups with 6 to 12 carbon atoms that may have substituents, -O-, -CO-, and -N(Q) groups. C A divalent linker consisting of at least two (preferably two to eight) groups from the group consisting of -CO-O-. C Represents a hydrogen atom or a substituent.

[0128] As L C2 The m represented C For the sake of better liquid crystal orientation, the +1 valent linker group is preferably an m group with 1 to 24 carbon atoms that can have substituents. CA hydrocarbon group with a +1 valence and in which a portion of the carbon atom constituting the hydrocarbon group can be replaced by a heteroatom, more preferably an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may contain oxygen or nitrogen atoms, and even more preferably an aliphatic hydrocarbon group with 1 to 5 carbon atoms.

[0129] m C The number of carbon atoms contained in the +1 valence linker is not particularly limited, but from the perspective of improving liquid crystal orientation, it is preferably 1 to 24, more preferably 1 to 10, and even more preferably 1 to 5.

[0130] Considering the reason that liquid crystal alignment has become better, m C Preferably, it is an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1.

[0131] The crosslinking group represented by Z has the same meaning as the crosslinking group in the repeating unit C mentioned above, and the preferred method is also the same.

[0132] As a specific example of the repeating unit C, a repeating unit represented by any one of the following equations C-1 to C-10 can be given.

[0133] [Chemical Formula 16]

[0134] The repeating unit C can be used alone or in more than two types. Considering the reason that the liquid crystal alignment is improved, the content of repeating unit C is preferably 10 to 90% by mass relative to all repeating units of the photoalignment compound, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0135] <Repeating Unit A> The photooriented compound also preferably has the above-mentioned repeating unit A. That is, it is also preferable to have a repeating unit having a site that is cleaved by at least one action selected from the group consisting of acid, light and heat. Repeating unit A can be listed as a repeating unit A that a specific compound can have.

[0136] Repeating unit A can be used alone or in two or more ways. The content of repeating unit A is preferably 10 to 90% by mass relative to the total mass of all repeating units in the photo-alignment compound, more preferably 10 to 60% by mass. Furthermore, the content of repeating unit A is preferably 40% by mass or more relative to the total mass of all repeating units in the photo-alignment compound. The upper limit is preferably 60% by mass or less.

[0137] The total content of repeating unit X and repeating unit C is preferably 99 to 100% by mass relative to the total mass of all repeating units of the photo-orientation compound, more preferably 99.9 to 100% by mass. The total content of repeating unit A, repeating unit X and repeating unit C is preferably 99 to 100% by mass relative to the total mass of all repeating units of the photo-orientation compound, more preferably 99.9 to 100% by mass.

[0138] The photo-alignment compound preferably comprises: a repeating unit X having a photo-alignment group; and a repeating unit C having a crosslinking group, wherein the total content of repeating unit X and repeating unit C is 99-100% by mass relative to the total mass of all repeating units of the photo-alignment compound, and the content of repeating unit X is 40% by mass or more relative to the total mass of all repeating units of the photo-alignment compound. In the above case, the photo-alignment compound preferably comprises only repeating unit X and repeating unit C as repeating units. Furthermore, the photo-orientation compound preferably has repeating unit A represented by formula (a1), repeating unit X having a photo-orientation group, and repeating unit C having a crosslinking group. The total content of repeating unit A, repeating unit X, and repeating unit C is 99 to 100% by mass relative to the total mass of all repeating units of the photo-orientation compound. More preferably, the content of repeating unit A is 10 to 60% by mass relative to the total mass of all repeating units of the photo-orientation compound. In the above case, the photo-orientation compound preferably has only repeating units A, repeating unit X, and repeating unit C as repeating units.

[0139] A single photo-orientation compound can be used alone, or two or more compounds can be used. The content of the photo-alignment compound is preferably 0.01 to 10.0 parts by mass relative to 100 parts by mass of the liquid crystal compound, more preferably 0.1 to 10.0 parts by mass, and even more preferably 0.5 to 5.0 parts by mass from the perspective of improving liquid crystal alignment.

[0140] [Liquid Crystal Compounds] The liquid crystal composition of the present invention contains a liquid crystal compound. The types of liquid crystal compounds are not particularly limited. Generally, liquid crystal compounds can be classified into rod-shaped and disc-shaped types according to their shape. Moreover, each type can be further divided into low-molecular-weight and high-molecular-weight types. High-molecular-weight types usually refer to those with a degree of polymerization of 100 or higher (Polymer Physics and Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).

[0141] As the liquid crystal compound, rod-shaped liquid crystal compounds or disc-shaped liquid crystal compounds (disc-shaped liquid crystal compounds) are preferred. The liquid crystal compound may be two or more rod-shaped liquid crystal compounds, two or more disc-shaped liquid crystal compounds, or a mixture of rod-shaped liquid crystal compounds and disc-shaped liquid crystal compounds.

[0142] As a liquid crystal compound, a polymeric liquid crystal compound having polymeric groups is preferred. As a polymerizable liquid crystal compound, at least one polymerizable liquid crystal compound selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable disk-shaped liquid crystal compounds is preferred. Examples of polymerizable groups include (meth)acryloyl, epoxy, and vinyl groups. By polymerizing a liquid crystal compound having the above-mentioned polymerizable groups, the orientation of the liquid crystal compound can be fixed. Furthermore, the liquid crystal compound does not need to exhibit liquid crystal properties after being fixed by polymerization.

[0143] As a rod-shaped liquid crystal compound, the preferred option is the compound described in paragraphs

[0026] to

[0098] of Japanese Patent Application Publication No. 11-513019 or Japanese Patent Application Publication No. 2005-289980. As a disc-shaped liquid crystal compound, the compounds described in paragraphs

[0020] to

[0067] of Japanese Patent Application Publication No. 2007-108732 or paragraphs

[0013] to

[0108] of Japanese Patent Application Publication No. 2010-244038 are preferred. Furthermore, liquid crystal compounds with reverse wavelength dispersion can also be used as liquid crystal compounds.

[0144] Liquid crystal compounds can be used alone or in combination with two or more compounds. The content of the liquid crystal compound relative to the total solid content (100% by mass) of the liquid crystal composition is preferably 10 to 99% by mass, more preferably 50 to 95% by mass.

[0145] [Solvent] From the viewpoint of operability, the liquid crystal composition of the present invention preferably contains a solvent. As a solvent, it can be any of the single solvent or mixed solvents. As a solvent, it is preferable to have solvent A with a boiling point of 100°C or less, and the content of solvent A is 35% by mass or more relative to the total mass of the solvent. The content of solvent A relative to the total mass of the solvent is preferably 45% by mass or more. The upper limit can be 100% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less. Furthermore, in this specification, "boiling point" refers to the standard boiling point. When conventional liquid crystal compositions contain a specified amount of solvent A as described above, the problem of whey spots becomes more pronounced in conventional liquid crystal compositions. On the other hand, the liquid crystal composition of the present invention can suppress whey spots even as described above.

[0146] Examples of solvents include, for example, ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate, and cyclopentylmethyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated hydrocarbons (e.g., dichloromethane, chloroform, dichloroethane, dichlorobenzene, and chlorotoluene), and esters (…). Organic solvents such as methyl acetate, ethyl acetate, ethyl propionate, butyl acetate and diethyl carbonate, alcohols (e.g. methanol, ethanol, isopropanol, butanol and cyclohexanol), cellosols (e.g. methyl cellosol, ethyl cellosol and 1,2-dimethoxyethane), cellosol acetates, sulfoxides (e.g. dimethyl sulfoxide), amides (e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and 1,3-dimethyl-2-imidazolium ketone), and heterocyclic compounds (e.g. pyridine, etc.) as well as water. Solvents can be used alone or in combination with two or more solvents.

[0147] From the viewpoint that the orientation of the liquid crystal cured layer formed using the liquid crystal composition becomes better and the heat resistance is further improved, organic solvents are preferred as solvents, and ketones and / or esters are more preferred.

[0148] [Photo-acid generator] The liquid crystal composition of the present invention may contain a photoacid generator. Regarding photoacid-generating agents, there are no particular limitations, but compounds that generate acid by sensing active light with a wavelength of 300 nm or higher (preferably 300–450 nm) are preferred. Furthermore, for photoacid-generating agents that do not directly sense active light with a wavelength of 300 nm or higher, as long as they are compounds that sense active light with a wavelength of 300 nm or higher and generate acid by being used in combination with a sensitizer, they can preferably be used in combination with the sensitizer.

[0149] Examples of photoacid generators include, for example, onium salt compounds, trichloromethyltriazine compounds, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Onium salt compounds, imide sulfonate compounds, or oxime sulfonate compounds are preferred, and onium salt compounds or oxime sulfonate compounds are more preferred. One photoacid generator can be used alone or in combination of two or more.

[0150] [Polymerization initiator] The liquid crystal composition of the present invention may contain a polymerization initiator. As a polymerization initiator, a photosensitive compound (i.e., a photopolymerization initiator) is preferred. Examples of photopolymerization initiators include α-carbonyl compounds, azo ethers, α-hydrocarbon-substituted aromatic azo compounds, polynuclear quinone compounds, combinations of triarylimidazolium dimers and p-aminophenyl ketones, acridine, phenazine compounds, oxadiazole compounds, o-acyl oxime compounds, phosphine oxido compounds, and oxime-type polymerization initiators. Commercially available photopolymerization initiators, for example, include IRGACURE-184, IRGACURE-907, IRGACURE-369, IRGACURE-651, IRGACURE (Ominirad)-819, IRGACURE-OXE-01 and IRGACURE-OXE-02 manufactured by BASF.

[0151] Polymerization initiators can be used alone or in combination with two or more. When the liquid crystal composition contains a polymerization initiator, the content of the polymerization initiator relative to the total solid content (100% by mass) of the liquid crystal composition is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass.

[0152] The liquid crystal composition may contain other components besides those mentioned above. Other components include, for example, multifunctional monomers, orientation aids such as horizontal and vertical orientation agents, adhesion modifiers, and plasticizers.

[0153] -Liquid Crystal Layer- There are no particular limitations as long as the liquid crystal layer of the present invention is formed using the liquid crystal composition of the present invention described above. The liquid crystal layer is formed by curing the liquid crystal composition. Furthermore, the liquid crystal layer is preferably a layer whose surface has orientation control capability. Having orientation control capability means having the function of orienting the liquid crystal compound disposed on the liquid crystal layer in a predetermined direction. As a method for forming a liquid crystal layer with orientation control capability, for example, it is preferable to have the following step (step 1): after the photoacid generator in the coating obtained by using the above-mentioned liquid crystal composition generates acid, the coating is subjected to photoorientation treatment to form a liquid crystal layer with orientation control capability. When the liquid crystal composition contains a polymerizable liquid crystal compound, in step 1 above, it is preferable to perform a curing treatment on the coating obtained using the liquid crystal composition, and then perform a treatment to generate acid from the photoacid generator in the coating (hereinafter also simply referred to as "acid generation treatment"). After that, a photoalignment treatment is performed to form a liquid crystal layer. The following is a detailed explanation of the method for performing the above-mentioned curing treatment.

[0154] The method for forming the coating of the liquid crystal composition is not particularly limited. For example, a method can be described by coating the liquid crystal composition onto a support and then performing a drying process as needed. The support will be described in detail later. Furthermore, an orientation layer can be disposed on the support. The method of coating the liquid crystal composition is not particularly limited. Examples of coating methods include spin coating, air knife coating, curtain coating, roller coating, wire rod coating, gravure coating, and mold coating.

[0155] Next, the coating of the liquid crystal composition is subjected to curing and acid generation treatment. As a curing process, examples include light irradiation or heat treatment. Furthermore, the curing conditions are not particularly limited, but ultraviolet light is preferred for polymerization caused by light irradiation. The preferred irradiation dose is 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further optimization of 30mJ / cm 2 ~3J / cm 2 Especially preferred is 50–1000 mJ / cm 2 Furthermore, to promote the polymerization reaction, it can be carried out under heating conditions. The heating temperature is preferably 50–200°C, more preferably 60–150°C. The heating time is preferably 0.5–20 minutes, more preferably 1–5 minutes. Heat treatment and light irradiation treatment can be performed multiple times. For example, they can be performed in the order of heat treatment, light irradiation treatment, and heat treatment again.

[0156] The treatment to generate acid from a photoacid-generating agent in the coating film involves irradiating the liquid crystal composition with light sensitive to the photoacid-generating agent to generate acid. By performing this treatment, if a specific compound has an acid cleavage site, the cleavage site is cleaved. If a photoalignment compound has an acid cleavage site, the cleavage site of the photoalignment compound is also cleaved. The light irradiation treatment described above can be any treatment that sensitizes the photoacid-producing agent; for example, irradiation with ultraviolet light can be used. As the light source, lamps that emit ultraviolet light, such as high-pressure mercury lamps and metal halide lamps, can be used. Furthermore, the irradiation dose is preferably 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further optimization of 30mJ / cm 2 ~3J / cm 2 The preferred strength is 50–1000 mJ / cm³. 2 .

[0157] The aforementioned curing and acid-generating treatments can be performed after the curing treatment or simultaneously. In particular, from a productivity point of view, it is preferable to perform the simultaneous execution of the photoacid-generating agent and the polymerization initiator in the liquid crystal composition when they are exposed to light of the same wavelength.

[0158] The method for performing photoalignment processing on the coating film of the liquid crystal composition formed above (including the cured film of the liquid crystal composition that has undergone curing treatment) is not particularly limited, and known methods can be cited. As a light orientation process, for example, methods can be described such as irradiating a coating of a liquid crystal composition (including a cured film of a liquid crystal composition that has undergone a curing process) with polarized light or irradiating the surface of the coating with unpolarized light from an oblique direction.

[0159] In the optical orientation process, there is no particular limitation on the polarized light irradiated; for example, linearly polarized light, circularly polarized light, and elliptically polarized light can be cited, with linearly polarized light being preferred. Furthermore, the "tilt direction" of irradiating unpolarized light is not particularly limited as long as it is tilted at a polar angle θ (0 < θ < 90°) relative to the normal direction of the coating surface, and can be appropriately selected according to the purpose. θ is preferably 20 to 80°.

[0160] As for the wavelength of polarized or unpolarized light, it is not particularly limited as long as it is light that is photosensitive to photooriented groups. Examples include ultraviolet light, near-ultraviolet light and visible light, with near-ultraviolet light of 250 to 450 nm being preferred. Furthermore, examples of light sources for irradiating polarized or unpolarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps. For ultraviolet or visible light obtained from such light sources, the wavelength range of the irradiation can be limited by using interference filters or color filters. Moreover, by using polarizing filters or polarizing prisms on the light from these light sources, linearly polarized light can be obtained.

[0161] Furthermore, the above describes a method of performing curing and acid generation treatments before performing photo-alignment treatments, but the present invention is not limited to this method, and curing and acid generation treatments may also be performed simultaneously during photo-alignment treatments.

[0162] The above describes in detail a method for forming a liquid crystal layer having a specific compound containing an acid pyrolysis site. However, when forming a liquid crystal layer having a specific compound containing a photopyrolysis site or a thermal pyrolysis site, the above-mentioned acid generation process can be omitted. When photolysis is performed on areas with photolysis sites, the irradiation dose is preferably set to 50–1000 mJ / cm during the aforementioned photoorientation treatment. 2 Within the range. In cases where the thermal decomposition portion is thermally decomposed, the heating temperature is preferably set to 60–150°C during the above-described heating treatment.

[0163] The thickness of the liquid crystal layer is not particularly limited, but considering the reason that the liquid crystal alignment is better, it is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[0164] [Optical laminate] The optical laminate of the present invention has a liquid crystal layer of the present invention and an optical anisotropy layer disposed on the liquid crystal layer. Alternatively, as described above, the surface of the liquid crystal layer preferably has orientation control capability. As one of the preferred embodiments of the optical laminate of the present invention, an optical anisotropic layer disposed on the liquid crystal layer is formed using a polymeric liquid crystal composition containing a polymeric liquid crystal compound, and the liquid crystal layer and the optical anisotropic layer are stacked adjacent to each other. Furthermore, the optical laminate of the present invention preferably has a support for supporting the liquid crystal layer. The preferred embodiments of the optical laminate of the present invention will now be described in detail.

[0165] [Support body] Examples of supports include glass substrates and polymer films. Examples of polymer film materials include cellulose polymers; acrylic polymers containing acrylate polymers such as polymethyl methacrylate and polymers containing lactone rings; thermoplastic norbornene polymers; polycarbonate polymers; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile-styrene copolymers; polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamides; imide polymers; sulfone polymers; polyethersulfone polymers; polyetheretherketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; aromatic ester polymers; polyoxymethylene polymers; epoxy polymers; or polymers composed of mixtures of these polymers.

[0166] The thickness of the support is not particularly limited, but is preferably 5–200 μm, more preferably 10–100 μm, and even more preferably 20–90 μm. The support is preferably a peelable support.

[0167] [Liquid Crystal Layer] The liquid crystal layer is the liquid crystal layer of the present invention described above.

[0168] [Optical Anisotropy Layer] The optical anisotropic layer is preferably formed using a polymeric liquid crystal composition containing a polymeric liquid crystal compound. Among them, as a polymeric liquid crystal composition for forming an optical anisotropic layer, a composition prepared by means of a polymeric liquid crystal compound, a polymerization initiator and a solvent, which are listed as arbitrary components in the liquid crystal composition of the present invention, can be cited as an example.

[0169] The thickness of the optical anisotropic layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[0170] [Manufacturing method of optical laminates] The method for manufacturing the optical laminate of the present invention is a preferred method for manufacturing the optical laminate of the present invention described above, and preferably includes the following steps: after generating acid from a photoacid generator in a coating obtained using the above-described liquid crystal composition, performing a photoorientation treatment on the coating to form a liquid crystal layer with orientation control capability (step 1); and coating a polymeric liquid crystal composition containing a polymeric liquid crystal compound onto the liquid crystal layer to form an optically anisotropic layer (step 2).

[0171] [Process 1] Step 1 is a process of generating acid from a photoacid generator in a coating obtained using the above-mentioned liquid crystal composition, and then performing a photoalignment treatment on the coating to form a liquid crystal layer with orientation control capability. The steps of process 1 are as described above.

[0172] [Process 2] Step 2 is a step of forming an optically anisotropic layer by coating a polymeric liquid crystal composition containing a polymeric liquid crystal compound onto a liquid crystal layer. The method of coating the polymerizable liquid crystal composition is not particularly limited, and the coating method illustrated in step 1 can be cited as an example.

[0173] One method for forming an optically anisotropic layer is to heat-treat a coating of a polymeric liquid crystal composition and then cure it. This heat treatment can orient the polymeric liquid crystal compound. In the above, heat treatment and curing treatment were performed respectively, but curing treatment can also be performed under heating conditions. Furthermore, if orientation is performed without heat treatment depending on the type of polymerizable liquid crystal compound, heat treatment may be omitted. After the coating is heated and before the curing process described later, the coating may be cooled as needed.

[0174] The heat treatment conditions are not particularly limited, as long as they are at the temperature required for the orientation of the polymerizable liquid crystal compound. The heating temperature is typically preferred to be 50–200°C. The heating time is preferably 0.5–20 minutes, more preferably 1–5 minutes.

[0175] The curing method is not particularly limited, and examples include light irradiation and heat treatment, with light irradiation being preferred. Ultraviolet light is preferred as the light used in the light irradiation process. The conditions for light irradiation are not particularly limited; the preferred irradiation dose is 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further preferred is 30 mJ / cm 2 ~3J / cm 2 . Furthermore, the polymerization reaction can be carried out under heating conditions to promote it. Heat treatment and curing treatment can be performed multiple times.

[0176] [Image display device] The image display device of the present invention is an image display device having the optical laminate of the present invention. 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. Preferably, a liquid crystal cell or an organic EL display panel 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 or an organic EL display device that uses an organic EL display panel as a display element is preferred.

[0177] [Compound] The compounds of the present invention are not particularly limited as long as they are the specific compounds described above, and are preferably compounds having repeating unit A represented by formula (a1) and repeating unit B represented by any one of formulas (b1) to (b3). The meanings of repeating unit A and repeating unit B are the same as those of repeating unit A and repeating unit B that the specific compound may have, and the preferred methods are also the same. Furthermore, for other preferred methods besides those described above, the methods of the specific compounds mentioned above can also be referred to. Example

[0178] The following examples and comparative examples further illustrate the features of the present invention. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not to be limited by the specific examples shown below.

[0179] [Example 1] [Fabrication of liquid crystal layer A] A polymeric liquid crystal composition A with the following composition was prepared.

[0180] ―――――――――――――――――――――――――――――――― Polymerizable liquid crystal composition A ―――――――――――――――――――――――――――――――― · 100 parts by weight of mixture A of the following liquid crystal compounds • Acrylate monomer (A-400, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.) 4.2 parts by weight • Polymer A below 2.0 parts by weight • 0.8 parts by weight of the following photo-orientation compound 2-1 • 1-1 0.5 parts by weight of the following specific compounds · 1.9 parts by weight of compound A below • 5.1 parts by weight of the following photopolymerization initiator A • 4.5 parts by weight of the following photoacid-generating agent A 0.2 parts by weight of N,N-diisopropylethylamine · Methyl isobutyl ketone (boiling point 116℃) 238 parts by weight Ethyl propionate (boiling point 99℃) 214 parts by weight · Methyl ethyl ketone (boiling point 80℃) 24 parts by weight ――――――――――――――――――――――――――――――――

[0181] Mixture A of liquid crystal compounds (containing in the following mass percentages: 84%, 14%, and 2% by mass, respectively) [Chemical Formula 17]

[0182] Polymer A (The values ​​in the following formula represent the content (mass%) of each repeating unit relative to all repeating units in the polymer. Weight-average molecular weight: 60,000) [Chemical Formula 18]

[0183] Photo-oriented compound 2-1 (The values ​​in the following formulas represent the content (mass%) of each repeating unit relative to all repeating units in the polymer. Hereinafter, Me represents methyl. Weight-average molecular weight: 95,000) Furthermore, the synthesis method of photoorientation compound 2-1 will be described later. [Chemical Formula 19]

[0184] Specific compound 1-1 (The values ​​in the following formulas represent the content (mass%) of each repeating unit relative to all repeating units in the polymer. Weight-average molecular weight: 35,000) Furthermore, the synthetic method for a specific compound 1-1 will be described later. [Chemical Formula 20]

[0185] Compound A [Chemical Formula 21]

[0186] Photopolymerization initiator A [Chemical Formula 22]

[0187] Photo-acid generator A [Chemical Formula 23]

[0188] Using a #3.0 wire rod, the prepared polymeric liquid crystal composition A was coated onto a cellulose polymer film (TG40, manufactured by FUJIFILM Corporation) as a substrate. The mixture was heated at 80°C for 1 minute and irradiated with 150 mJ / cm² under conditions where the oxygen concentration was less than 100 ppm by volume. 2 The ultraviolet light was then applied. The sample was then annealed at 115°C for 1 minute and irradiated at room temperature with 7.9 mJ / cm². 2 UV light (ultraviolet light) (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passing through a wire grid polarizer (wavelength: 313nm) imparts orientation control capabilities, forming a 0.7μm thick liquid crystal layer A. Furthermore, liquid crystal layer A is a positive C-plate. The thickness retardation Rth (550) of liquid crystal layer A is -70nm.

[0189] <Synthetic method of specific compound 1-1> According to the following scheme, the monomer mB-57, represented by the formula mB-57, was synthesized. In the above scheme, TMS represents trimethylsilyl.

[0190] [Chemical Formula 24]

[0191] <By composition> In a 2000 mL flask equipped with a cooling tube, thermometer, and stirrer, 100 g of 4-chlorobutanal dimethyl acetal (represented by formula a in the above scheme), 118.1 g of 3-buten-1-ol, 1.52 g of (+)-10-camphorsulfonic acid, and 197 mL of hexane were weighed. The mixture was stirred for 30 minutes at 75°C under a nitrogen atmosphere using an external apparatus. The external apparatus was then heated to 78°C, a Dean-Stark apparatus was installed, and 1075 mL of hexane was added dropwise over 3–4.5 hours using a drop pump. Next, 70.9 g of 3-buten-1-ol was added, and the mixture was stirred for 30 minutes. Then, 1075 mL of hexane was added dropwise over 3–4.5 hours using a drop pump. Afterward, the mixture was stirred for 1 hour, the internal temperature was lowered to 50°C, and 2 mL of diisopropylethylamine was added. The organic layer was separated and washed using hexane, acetonitrile, water, and triethylamine, and then concentrated to obtain 260.0 g of compound b (represented by formula b in the above scheme) as a colorless and transparent liquid.

[0192] <Composition of c> In a 2000 mL flask equipped with a cooling tube, thermometer, and stirrer, 130 g of compound b, 1300 μL of Karl Fischer catalyst, and 1300 mL of toluene were weighed and stirred for 30 minutes under a nitrogen atmosphere. The temperature was raised to 45 °C, and 237.3 g of heptamethyltrisiloxane was added dropwise over 2 hours using a drop pump. The mixture was cooled to 25 °C and filtered using a suction filter lined with activated carbon / diatomaceous earth. By concentrating the filtrate, 350.0 g of compound c (represented by formula c in the above scheme) was obtained as a brown liquid.

[0193] Next, in a 3000 mL flask equipped with a cooling tube, thermometer, and stirrer, 330 g of compound c, 63.1 g of sodium methacrylate, 165 mg of BHT, 121.2 g of potassium iodide (KI), and 1650 mL of N,N-dimethylacetamide (DMAc) were weighed and stirred at 85 °C for 7 hours. The mixture was then separated and washed with heptane, ethyl acetate, and water, and the resulting organic phase was concentrated to obtain 350.0 g of monomer mB-57 as a colorless, transparent liquid.

[0194] <Polymerization Reaction> Cyclopentanone (30 parts by mass) as a solvent, each monomer having the repeating unit and content of the specific compound 1-1 shown below, and 2,2'-azobis(isobutyronitrile) (0.1 parts by mass) as a polymerization initiator were added to a flask equipped with a cooling tube, a thermometer and a stirrer. Nitrogen gas was circulated in the flask at 15 mL / min while stirring was carried out by heating in a water bath and maintaining a reflux state for 7 hours. After the reaction was completed, the solution was naturally cooled to room temperature. The obtained solution was then added to a large amount of excess methanol to precipitate the specific compound 1-1. The recovered precipitate was filtered out, washed with a large amount of methanol, and then dried under vacuum at 40°C for 6 hours to obtain the specific compound 1-1.

[0195] <Synthetic method of photoorientation compound 2-1> In a flask equipped with a cooling tube, thermometer, and stirrer, 284.6 parts by mass of 1-methoxy-2-propanol (as solvent), 28.0 parts by mass of the following monomers mA-16, mB-57, and mC-4Cl (41.0 parts by mass) were weighed. While nitrogen gas was flowing into the flask at a rate of 15 mL / min, the flask was heated in a water bath at 70°C. A mixture of 1.74 parts by mass of the polymerization initiator 2,2′-azobis(isobutyrate) dimethyl ester and 16.2 parts by mass of 1-methoxy-2-propanol was added dropwise over 20 minutes. The mixture was stirred under reflux for 9 hours.

[0196] [Chemical Formula 25]

[0197] After the reaction was completed, the mixture was naturally cooled to room temperature. The obtained solution was then added to a large amount of excess methanol / water mixture to precipitate the photo-orientation compound 2-1. The recovered precipitate was filtered out, washed with a large amount of methanol / water, and then vacuum dried at 40°C for 12 hours to obtain the following photo-orientation compound 2-1c having the above-mentioned repeating unit A-16, repeating unit B-57 and repeating unit C-4Cl.

[0198] [Chemical Formula 26]

[0199] Next, 90.0 parts by mass of photoorientation compound 2-1c, 0.18 parts by mass of 4-methoxyphenol, 65.9 parts by mass of triethylamine, 110 parts by mass of acetone, and 110 parts by mass of dimethylacetamide were added to a flask equipped with a cooling tube, thermometer, and stirrer. The mixture was heated in a water bath at 60°C and stirred for 2 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The resulting reaction solution was then added to a large amount of excess methanol / water (1 / 3) to precipitate the polymer. The recovered precipitate was filtered off, washed with a large amount of methanol / water (1 / 3), and dried in a forced-air environment at 40°C for 12 hours, thereby obtaining the photoorientation compound 2-1.

[0200] [Formation of optical laminates] A polymeric liquid crystal composition B with the following composition was prepared.

[0201] ―――――――――――――――――――――――――――――――― Polymerizable liquid crystal composition B ―――――――――――――――――――――――――――――――― • 45.36 parts by weight of the following liquid crystal compound B • 21.84 parts by mass of the following liquid crystal compound C • 20.00 parts by weight of the following liquid crystal compound D • 5.00 parts by weight of the following liquid crystal compound E 7.80 parts by weight of the above-mentioned liquid crystal compound mixture A • 0.50 parts by weight of the above photopolymerization initiator A • 0.09 parts by weight of the following leveling agent B · Cyclopentanone 180.73 parts by weight 53.98 parts by weight of methyl ethyl ketone ――――――――――――――――――――――――――――――――

[0202] Liquid crystal compound B (tBu represents tert-butyl) [Chemical Formula 27]

[0203] Liquid crystal compound C [Chemical Formula 28]

[0204] Liquid crystal compound D [Chemical Formula 29]

[0205] Liquid crystal compound E (Me represents methyl) [Chemical Formula 30]

[0206] Leveling agent B [In the following formula, the values ​​listed in each repeating unit represent the content (mass%) of each repeating unit relative to all repeating units, from left to right: 50% by mass, 38% by mass, 12% by mass. Weight-average molecular weight: 20,000] [Chemical Formula 31]

[0207] Polymerizable liquid crystal composition B was coated onto the previously formed liquid crystal layer A using a wire rod coater #7, forming a composition layer. The formed composition layer was temporarily heated to 120°C on a hot plate, then cooled to 60°C to stabilize its orientation. Then, the film temperature was maintained at 60°C using an ultra-high pressure mercury lamp in a nitrogen atmosphere (oxygen concentration less than 100 ppm by volume) and subjected to a first ultraviolet irradiation (100 mJ / cm²). 2 After that, the film temperature was maintained at 90℃ and subjected to a second ultraviolet irradiation (200mJ / cm). 2 This process fixes the orientation, forming an optically anisotropic layer B with a thickness of 2.8 μm, thus creating an optical laminate. Furthermore, the optically anisotropic layer B is the positive A plate. The in-plane retardation Re(550) of the optically anisotropic layer B at a wavelength of 550 nm is 141 nm, and the angle of the in-plane slow axis relative to the film width direction is 45°. This angle is the angle, with the film width direction as the reference (0°), and expressed as positive counterclockwise when viewing the optically anisotropic layer B disposed on the liquid crystal layer A from the side of the optically anisotropic layer B.

[0208] [Examples 2-15, Comparative Examples 1-2] Regarding the content or type of the evaluation compound (specific compound or comparative compound) or photoalignment compound in the polymeric liquid crystal composition A, the contents are changed as shown in Table 1 below. Otherwise, the polymeric liquid crystal composition A was prepared using the same method as in Example 1, and each optical laminate was obtained. Furthermore, the evaluation compound other than specific compound 1-1 was synthesized following the synthesis steps of specific compound 1-1. The photoalignment compound other than photoalignment compound 2-1 was synthesized following the synthesis steps of photoalignment compound 2-1. The chemical structures of the evaluation compounds or photo-oriented compounds used in the examples and comparative examples are shown below. Furthermore, evaluation compounds 1-1, 1-3 to 1-10 are specific compounds having a site that cleaves through acid action, evaluation compound 1-2 is a specific compound having a site that cleaves through light action, and evaluation compound 1-11 is a comparative compound.

[0209] [Evaluate the compound] [Chemical Formula 32]

[0210] [Chemical Formula 33]

[0211] [Chemical Formula 34]

[0212] [Photo-oriented compounds] [Chemical Formula 35]

[0213] [evaluate] [Evaluation of Wind Spots] Two polarizers were set in orthogonal Nicol configuration, and the fabricated liquid crystal layer A was placed between them to observe whether there were any stripe-like inhomogeneities. The wind spot suppression was evaluated according to the following criteria. A: Unevenness cannot be visually identified. B: Unevenness is almost impossible to visually detect. C: Able to visually identify unevenness.

[0214] [Evaluation of the coating properties of the upper layer] The surface area of ​​the fabricated optical laminate was inspected to an A4 size, and defects that appeared to be circular or elliptical were identified as shrinkage cavities for evaluation of the topcoatability. A: 0 to 1 shrinkage cavities were observed. B: Two to four shrinkage cavities were observed. C: More than 5 shrinkage cavities were observed.

[0215] [Evaluation of liquid crystal orientation] Two polarizers were placed on orthogonal Nicol plates, and the resulting optical laminate was placed between the two polarizers. The degree of light leakage and the surface morphology under a polarizing microscope were observed. A: There is no light leakage, no disorder of liquid crystal pointing vector, and the surface morphology is stable. B: There is no light leakage, the liquid crystal pointing vector disorder is minimal, and the surface morphology is stable. C: Light leakage was observed, the liquid crystal pointing vector was disordered and the surface morphology was unstable.

[0216] Furthermore, in each embodiment, the results of the liquid crystal layer A produced in the above-described [production of liquid crystal layer A] were observed with the naked eye (the size of the observed liquid crystal layer A is A4 size). Agglomerates (e.g., agglomerates derived from a specific compound) were observed in the liquid crystal layer A of embodiment 7, while no agglomerates were observed in the liquid crystal layer A of embodiments other than embodiment 7.

[0217] The evaluation results are shown in the table below. "Weight-average molecular weight" refers to the weight-average molecular weight of each evaluated compound or each photo-oriented compound, and the method for determining its weight-average molecular weight is as described above. The “content” in “evaluation compound” or “photo-orientation compound” indicates the content (parts by mass) of the liquid crystal compound relative to 100 parts by mass in polymeric liquid crystal composition A.

[0218] [Table 1]

[0219] As shown in Table 1 above, in the case of liquid crystal compositions not containing specific compounds, at least one of the following—wind spots, liquid crystal alignment after layer formation, and upper layer coating properties—is poor (Comparative Examples 1-2). On the other hand, it can be seen that in the case of the liquid crystal compound of the present invention, the wind spots, liquid crystal alignment after layer formation, and upper layer coating properties are all excellent (Examples 1-15). It is known that when the content of repeating unit A is 40% by mass or more and less than 100% by mass relative to the total mass of all repeating units of the specific compound, it is possible to further suppress wind spots or agglomeration (agglomeration of the specific compound) (comparison of Examples 1 to 6 with Examples 7 and 9, etc.). It is known that when a specific compound has a group represented by the above formula (1), it can further suppress freckles (comparison of Examples 1-7 with Example 8, etc.). It is known that when the weight-average molecular weight of a specific compound is 5,000 to 100,000, it can further suppress freckles (comparison of Examples 1 to 7 with Example 10, etc.). It is known that when the content of a specific compound is 0.01 to 5 parts by mass relative to 100 parts by mass of the liquid crystal compound, wind spots can be further suppressed (comparison of Examples 1 to 7 with Example 11, etc.). It is known that when the photo-alignment compound has a repeating unit X containing a photo-alignment group and a repeating unit C containing a crosslinking group, the total content of repeating unit X and repeating unit C is 99 to 100% by mass relative to the total mass of all repeating units of the photo-alignment compound, and the content of repeating unit X is 40% by mass or more relative to the total mass of all repeating units of the photo-alignment compound, the liquid crystal alignment is superior (comparison of Examples 1 and 12 with Example 13, etc.). It is known that when the photo-alignment compound has repeating unit A represented by formula (a1), repeating unit X with photo-alignment group, and repeating unit C with crosslinking group, and the total content of repeating unit A, repeating unit X, and repeating unit C is 99 to 100% by mass relative to the total mass of all repeating units of the photo-alignment compound, and the content of repeating unit A represented by formula (a1) is 10 to 60% by mass relative to the total mass of all repeating units of the photo-alignment compound, the liquid crystal alignment is superior (comparison of Examples 1 and 12 with Example 14, etc.). It can be seen that when the content of the photo-alignment compound is 0.1 to 10 parts by mass relative to 100 parts by mass of the liquid crystal compound, the liquid crystal alignment is better (comparison of Examples 1 and 12 with Example 15, etc.).

Claims

1. A liquid crystal composition comprising: A leveling agent having a site that is broken down by at least one action selected from the group consisting of acid, light, and heat; Photooriented compounds; and Liquid crystal compounds.

2. The liquid crystal composition according to claim 1, wherein, The leveling agent has a repeating unit A represented by formula (a1) and a repeating unit B represented by any one of formulas (b1) to (b3). [Chemical Formula 1] In formula (a1), R 1 and R 2 Each can be used independently to represent a hydrogen atom or an alkyl group. R 3 Represents a hydrogen atom or a substituent. X represents an m+1 valence linkage group. L 1 It indicates an n+1 valent linker group having a site that can be cleaved by at least one action selected from the group consisting of acids, light, and heat. n represents an integer from 1 to 4. m represents an integer from 1 to 5. Rh represents a substituent having two or more groups represented by formula (S). [Chemical Formula 2] In formula (S), Indicates the bonding location, R 4 R 5 and R 6 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. [Chemical Formula 3] In equations (b1) to (b3), R b1 R b2 R b3 and R b4 Each can be used independently to represent a hydrogen atom or an alkyl group. L b1 -O- or -NR can be represented independently. Zb -,R Zb Represents a hydrogen atom or a substituent. L b2 Indicates a single bond or a divalent linkage group. A represents an alkylene group. p represents a number greater than 2. SP b1 Each represents a spacer group independently. M b1 Indicates a mesocrystalline group. T b1 Each terminal base is represented independently.

3. The liquid crystal composition according to claim 1, wherein, The leveling agent content is 0.01 to 5 parts by mass relative to 100 parts by mass of the liquid crystal compound.

4. The liquid crystal composition according to claim 2, wherein, L 1 For any of the groups represented by formulas (L1) to (L3), [Chemical Formula 4] In equations (L1) to (L3), 1 indicates the bond position with X. 2 indicates the bonding position with Rh. L x1 L x2 and L x3 Each can independently represent an alkylene group having 1 to 20 carbon atoms with -O-, an aryl group having 6 to 18 carbon atoms with -O-, or a group formed by combining them, or a single bond. R L1 and R L2 Each can be used independently to represent a hydrogen atom or a substituent. L L1 L L2 and L L3 Each can be used independently to represent a divalent linker. m L1 and m L2 Each can be represented independently as 1 or 2. Among them, when L 1 When the group is represented by the formula (L1), n ​​in the formula (a1) represents m. L1 +m L2 When L 1 When the group is represented by the formula (L2), n in the formula (a1) represents 1, and when L 1 When the group is represented by the formula (L3), n in the formula (a1) represents 2.

5. The liquid crystal composition according to claim 1, wherein, The leveling agent has a group represented by formula (1), [Chemical Formula 5] In equation (1), Indicates the bonding location, R 7 R 8 and R 12 Each can be used independently to represent a hydrogen atom or a substituent. R 9 R 10 R 11 R 13 R 14 and R 15 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. x and y represent integers from 1 to 3 independently. v and w independently represent integers from 1 to 4. When v represents 1, L 2 L represents a single bond or a divalent linkage group. When v represents an integer from 2 to 4, L 2 This indicates a v+1 valence linkage group. When w represents 1, L 3 L represents a single bond or a divalent linkage group. When w represents an integer from 2 to 4, L 3 This indicates a w+1 valence linkage group.

6. The liquid crystal composition according to claim 2, wherein, The content of repeating unit A is more than 40% by mass and less than 100% by mass relative to the total mass of all repeating units of the leveling agent.

7. The liquid crystal composition according to claim 1, wherein, The leveling agent has a weight-average molecular weight of 5,000 to 100,000.

8. The liquid crystal composition according to claim 1, wherein, The content of the photo-alignment compound is 0.1 to 10 parts by mass relative to 100 parts by mass of the liquid crystal compound.

9. The liquid crystal composition according to claim 1, wherein, The photo-orientation compound has repeating units X containing photo-orientation groups and repeating units C containing crosslinking groups. The total content of repeating unit X and repeating unit C is 99 to 100% by mass relative to the total mass of all repeating units of the photo-orientation compound, and the content of repeating unit X is 40% by mass or more relative to the total mass of all repeating units of the photo-orientation compound.

10. The liquid crystal composition according to claim 1, wherein, The photo-orientation compound has a repeating unit A represented by formula (a1), a repeating unit X having a photo-orientation group, and a repeating unit C having a crosslinking group. The total content of repeating unit A, repeating unit X, and repeating unit C is 99-100% by mass relative to the total mass of all repeating units of the photo-orientation compound. [Chemical Formula 6] In formula (a1), R 1 and R 2 Each can be used independently to represent a hydrogen atom or an alkyl group. R 3 Represents a hydrogen atom or a substituent. X represents an m+1 valence linkage group. L 1 It indicates an n+1 valent linker group having a site that can be cleaved by at least one action selected from the group consisting of acids, light, and heat. n represents an integer from 1 to 4. m represents an integer from 1 to 5. Rh represents a substituent having two or more groups represented by formula (S). [Chemical Formula 7] In formula (S), Indicates the bonding location, R 4 R 5 and R 6 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl.

11. The liquid crystal composition according to claim 10, wherein, The content of repeating unit A, represented by formula (a1), is 10 to 60% of the total mass of all repeating units of the photo-orientation compound.

12. A liquid crystal layer formed using the liquid crystal composition according to any one of claims 1 to 11, and having orientation control capability.

13. An optical laminate having a liquid crystal layer as described in claim 12 and an optical anisotropy layer disposed on the liquid crystal layer.

14. An image display device having the optical laminate of claim 13.

15. A method for manufacturing an optical laminate, comprising: A process of performing photoalignment treatment on a coating obtained using any one of claims 1 to 11 to form a liquid crystal layer with orientation control capability; and The process of forming an optically anisotropic layer by coating a polymeric liquid crystal composition containing a polymeric liquid crystal compound onto the liquid crystal layer.

16. A compound having: The repeating unit A represented by equation (a1); and The repeating unit B is represented by any one of equations (b1) to (b3). [Chemical Formula 8] In formula (a1), R 1 and R 2 Each can be used independently to represent a hydrogen atom or an alkyl group. R 3 Represents a hydrogen atom or a substituent. X represents an m+1 valence linkage group. L 1 It indicates an n+1 valent linker group having a site that can be cleaved by at least one action selected from the group consisting of acids, light, and heat. n represents an integer from 1 to 4. m represents an integer from 1 to 5. Rh represents a substituent having two or more groups represented by formula (S). [Chemical Formula 9] In formula (S), Indicates the bonding location, R 4 R 5 and R 6 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. [Chemical Formula 10] In equations (b1) to (b3), R b1 R b2 R b3 and R b4 Each can be used independently to represent a hydrogen atom or an alkyl group. L b1 -O- or -NR can be represented independently. Zb -,R Zb Represents a hydrogen atom or a substituent. L b2 Indicates a single bond or a divalent linkage group. A represents an alkylene group. p represents a number greater than 2. SP b1 Each represents a spacer group independently. M b1 Indicates a mesocrystalline group. T b1 Each terminal base is represented independently.

17. The compound according to claim 16, wherein, The repeating unit A is any one of the repeating units represented by equations (a2) to (a4). [Chemical Formula 11] In equations (a2) to (a4), R 1 and R 2 Each can be used independently to represent a hydrogen atom or an alkyl group. R 3 Represents a hydrogen atom or a substituent. X a This indicates -COO- or -CONH-. L x1 L x2 and L x3 Each can independently represent an alkylene group having 1 to 20 carbon atoms with -O-, an aryl group having 6 to 18 carbon atoms with -O-, or a group formed by combining them, or a single bond. R L1 and R L2 Each can be used independently to represent a hydrogen atom or a substituent. L L1 L L2 and L L3 Each can be used independently to represent a divalent linker. Rh a This represents the group represented by formula (S1). m L1 and m L2 Each can be represented independently as 1 or 2. [Chemical Formula 12] In formula (S1), R 4 R 5 and R 6 Each can be independently represented as alkyl, alkenyl, aryl, or alkylene aryl. R S Indicates alkyl group, s represents 2 or 3.

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