TW202112738A - Compound, composition, film, laminate, and display device - Google Patents

Abstract

A compound represented by formula (1). In the formula, Ar1, Ar2, and Ar3 represent a 1,4-phenylene group or an optionally substituted divalent sulfur-containing aromatic heterocyclic group, and at least one of Ar1 and Ar2 has a fluorine atom as a substituent. n represents 1 or 2. R1 represents a single bond or a group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -CH=N-, and -N=CH-. R2 represents an alkylamino group or an alkoxy group. R3 represents a group selected from the group consisting of alkanediyl groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, and alkanediylcarbonyloxy groups. R4 represents a polymerizable group or a hydrogen atom. R4-R3-Ar1-(-R1-Ar2-)n-N=N-Ar3-R2 (1).

Description

Compound, composition, film, laminate and display device

The present invention relates to a compound, composition, film, laminate and display device.

There is a demand for continued thinning of displays such as image display panels, and further thinning is also required for polarizing plates and polarizing elements, which are one of its constituent elements. In response to this requirement, for example, a thin host-guest type polarizing element is proposed, which includes a polarizing film containing a polymerizable liquid crystal compound and a dichroic dye compound (for example, refer to Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2007-510946 [Patent Document 2] Japanese Patent Laid-Open No. 2013-37353

[The problem to be solved by the invention]

However, if ultraviolet (UV) exposure is used in the step of manufacturing the polarizing film provided in the polarizing element, the pigment compound may be modified in some cases, so the processing process may be restricted.

The object of the present invention is to provide a pigment compound with high ultraviolet (UV) durability. [Technical means to solve the problem]

The present invention provides the following [1] to [9]. [1] A compound represented by the following formula (1). R ⁴ -R ³ -Ar ¹ -(-R ¹ -Ar ² -) _n -N=N-Ar ³ -R ² (1) [In formula (1), Ar ¹ , Ar ² and Ar ³ are each independently Represents a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic heterocyclic group which may have a substituent ^{, at least one of Ar 1} and Ar ² has a fluorine atom as a substituent; n represents 1 or 2 R ¹ represents a single bond, or is selected from -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -CH=N- and -N= At least one group in the group consisting of CH-; R ² represents an alkylamino group that may have a polymerizable group or an alkoxy group that may have a polymerizable group; R ³ represents an alkyl group selected from 4 to 20 carbon atoms At least one group in the group consisting of a diyl group, alkanediyloxy group with 2 to 20 carbons, alkanediyloxycarbonyl group with 2 to 20 carbons, and alkanediylcarbonyloxy group with 2 to 20 carbons ; R ⁴ represents a polymerizable group or a hydrogen atom; when n is 2, two R ¹ may be the same or different, and two Ar ² may be the same or different]. [2] The compound as described in [1], wherein in the above formula (1), ^{any one of Ar 1} and Ar ² has one or two fluorine atoms as a substituent. [3] The compound as described in [1] or [2], wherein in the above formula (1), R ¹ is a single bond. [4] The compound as described in any one of [1] to [3], wherein in the above formula (1), n is an integer of 1. [5] The compound as described in any one of [1] to [4], wherein the polymerizable group is a radical polymerizable group. [6] A composition comprising the compound as described in any one of [1] to [5]. [7] A film using the compound as described in any one of [1] to [5] as a forming material. [8] A laminate comprising the film as described in [7]. [9] A display device including the film described in [7]. [Effects of Invention]

According to the present invention, it is possible to provide a pigment compound with high ultraviolet durability.

In this specification, the term "step" not only includes an independent step, but even when it cannot be clearly distinguished from other steps, as long as the intended purpose of the step can be achieved, it is also included in this term. In addition, regarding the content of each component in the composition, when there are multiple substances belonging to each component in the composition, unless otherwise specified, it means the total amount of the multiple substances present in the composition. Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described here, and various changes can be made without detracting from the gist of the present invention.

<Compound> The compound of the present embodiment is a compound that can be used as a dye, and has a structure represented by the following formula (1). R ⁴ -R ³ -Ar ¹ -(-R ¹ -Ar ² -) _n -N=N-Ar ³ -R ² (1)

In formula (1), it is preferable that n represents an integer of 1 or 2, and n is 1. The geometric isomerism of the azo group in the formula (1) may be either cis or trans, preferably trans.

^{Ar 1} , Ar ² and Ar ³ in the formula (1) independently represent a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic heterocyclic group which may have a substituent.

Examples of the substituents in Ar ¹ , Ar ² and Ar ³ include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and butyl; and carbon numbers 1 such as methoxy, ethoxy, and butoxy. Alkoxy group to 10; fluorinated alkyl group with carbon number 1 to 10 such as trifluoromethyl group; cyano group; nitro group; halogen atom such as chlorine atom and fluorine atom; amino group, diethylamino group and pyrrolidinyl group Etc. substituted or unsubstituted amine groups. Here, a substituted amino group means an amino group having one or two alkyl groups having 1 to 10 carbon atoms on the nitrogen atom, or two alkyl groups on the nitrogen atom are bonded to each other to form a carbon number 2 to 8 The amine group of the alkanediyl group. In addition, the unsubstituted amino group is -NH ₂ . Furthermore, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a hexyl group, and the like. Examples of alkanediyl groups having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

^{At least one of Ar 1} and Ar ² of the compound of this embodiment has a fluorine atom as a substituent. The total number of fluorine atoms possessed by Ar ¹ and Ar ² is preferably 1 or more and 4 or less, more preferably 1 or 2, and still more preferably 1. It is preferable ^{that any one of Ar 1} and Ar ² has a fluorine atom as a substituent. It is preferable ^{that any one of Ar 1} and Ar ² has 1 to 4 fluorine atoms, more preferably 1 or 2 fluorine atoms, and still more preferably 1 fluorine atom.

The compound represented by the formula (1) has a fluorine atom as a substituent at least one of ^{Ar 1} and Ar ^{2 and can exhibit excellent ultraviolet durability.} Thereby, in the manufacturing step of the polarizing plate provided with the film composed of the compound represented by the formula (1) as the forming material, even if the ultraviolet exposure is used, the characteristics of the manufactured polarizing plate can be suppressed from degrading, and the manufacturing process can be expanded的options. Here, the ultraviolet durability of the dye compound can be evaluated based on the retention of absorbance before and after ultraviolet irradiation of the film formed of the dye compound, for example. For example, the retention ^{rate of the absorbance of the pigment compound before and after UV irradiation at 3000 mJ/cm 2} is 80% or more, 85% or more, or 90% or more.

The substituent other than the fluorine atom possessed by Ar ¹ , Ar ² and Ar ³ is preferably a methyl group or a methoxy group. Thereby, the compound represented by formula (1) is easier to be included in a high-order liquid crystal structure such as smectic liquid crystal. In addition, the number of substituents other than the fluorine atom possessed by ^{Ar 1} , Ar ² and Ar ^{3 is preferably one or two.} Thereby, the compound represented by formula (1) is easier to be included in a high-order liquid crystal structure such as smectic liquid crystal.

In addition, when n is 1, it is preferable that at least two ^{of Ar 1} , Ar ² and Ar ³ are 1,4-stretched in terms of the simplicity of molecular synthesis and high performance. Phenyl.

Examples ^{of the divalent sulfur-containing aromatic heterocyclic group in Ar 1} , Ar ² and Ar ³ include: selected from thiophene, benzothiophene, dibenzothiophene, benzodithiophene, thienofuran, thienothiophene, The sulfur-containing aromatic heterocyclic compound of the group consisting of furanothiazole, thienothiazole, and benzothiazole is a group formed by removing two hydrogen atoms.

When the compound of the present embodiment includes a structure in which a divalent sulfur-containing aromatic heterocyclic group and 1,4-phenylene are directly bonded, the two-color ratio of the film including the compound is improved. Furthermore, the film containing the compound has a higher maintenance rate of the dichroic ratio when compared before and after UV exposure.

R ¹ represents a single bond, or is selected from -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -CH=N- and -NH=C- At least one linking group in the group consisting of. When there are a plurality of R ¹ , they may be the same or different. R is preferably a single bond, -OC(=O)-, or -C(=O)O-, more preferably a single bond.

R ² represents an alkylamino group which may have a polymerizable group, or an alkoxy group which may have a polymerizable group. The polymerizable group in R ² is preferably a radical polymerizable group, for example, a (meth)acrylate group ((meth)acryloyloxy group), a styryl group (vinylphenyl), etc. are free Among them, the polymerizable group is preferably a (meth)acrylate group. When R ² has a polymerizable group, the number is, for example, one or two, preferably one.

Examples of the alkylamino group of R ² include: an amino group having one or two alkyl groups with a carbon number of 1 to 10 on the nitrogen atom, or two alkyl groups on the nitrogen atom are bonded to each other to form a carbon A cyclic amine group of an alkanediyl group of 2 to 8. Specific examples of the alkylamino group of R ² include: methylamino, ethylamino, dimethylamino, diethylamino, dipropylamino, methylethylamino, methyl Hexylamino, pyrrolidinyl, piperidinyl, linolinyl and the like. The alkylamino group of R ² is preferably at least 1 selected from the group consisting of dimethylamino, diethylamino, dipropylamino, methylethylamino, and methylhexylamino Kind.

Examples of the alkoxy group of R ² include alkoxy groups having 1 to 10 carbon atoms. Specific examples of the alkoxy group of R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, and the like. The alkoxy group of R ² is preferably at least one selected from the group consisting of ethoxy and propoxy.

^{R 3} in formula (1) represents selected from the group consisting of alkanediyl groups having 4 to 20 carbon atoms, alkanediyloxy groups having 2 to 20 carbon atoms, alkanediyloxycarbonyl groups having 2 to 20 carbon atoms, and alkanediyloxycarbonyl groups having 2 to 20 carbon atoms. At least one divalent group in the group consisting of 20 alkanediylcarbonyloxy groups.

Examples of alkanediyl groups having 4 to 20 carbon atoms include n-butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, An alkanediyl group formed by removing one hydrogen atom from an unsubstituted (unsubstituted) straight-chain or branched-chain alkyl group with 4 to 20 carbon atoms, such as n-nonyl and n-decyl. The carbon number of the alkanediyl group is preferably 4-16, more preferably 4-12.

One or more hydrogen atoms constituting the aforementioned alkyl group having 4 to 20 carbon atoms may be substituted with a halogen atom (for example, a fluorine atom), a hydroxyl group, an amino group, or a substituted amino group. Here, as the substituted amino group, for example, N-methylamino group, N-ethylamino group, N,N-dimethylamino group, N,N-diethylamino group, etc. can be exemplified by 1 or 2 Amino groups substituted by an alkyl group with 1 to 20 carbon atoms, etc. Examples of alkyl groups in which one or more hydrogen atoms are substituted with halogen atoms, hydroxyl groups, amino groups, etc. include: fluorobutyl, octafluorobutyl, and other C4-20 haloalkyl groups; hydroxybutyl, hydroxypentyl, Hydroxyalkyl groups with 4 to 20 carbons such as hydroxyhexyl; aminobutyl and 2-(N,N-dimethylamino)butyl groups with unsubstituted or substituted amino groups with 4 to 20 carbons Alkyl and so on.

^{-O- or -NR*} - may be inserted between the carbon atoms constituting the above-mentioned alkyl group. Here, R ^* represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, butyl, and hexyl. Wait. Examples of the alkyl group with -O- or -NR ^* -inserted between carbon atoms include 2-ethoxyethyl, 2-(2-ethoxyethoxy)ethyl, 2-[2- (Ethylamino) ethyl) amino] ethyl and the like.

Examples of alkanediyloxy groups having 2 to 20 carbon atoms include ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and n-pentoxy. , Isopentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy and other unsubstituted linear or branched carbon numbers 2 Alkyloxy group formed by removing 1 hydrogen atom from alkoxy group to 20. The carbon number of the alkanediyloxy group is preferably 2-16, more preferably 2-12.

One or more hydrogen atoms constituting the alkoxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (for example, a fluorine atom), a hydroxyl group, an amino group, or a substituent amino group. The substituent amino group is the same as described above. Examples of alkoxy groups in which one or more hydrogen atoms are substituted by halogen atoms, hydroxyl groups, amino groups, etc. include: tetrafluoroethoxy, octafluorobutoxy and other halogenated alkoxy groups having 2 to 20 carbon atoms; 2-hydroxyethyl Hydroxy alkoxy with 2 to 20 carbons such as oxy; amino ethoxy, 2-(N,N-dimethylamino)ethoxy, etc. have unsubstituted amino or substituted amino groups with carbon number Alkoxy from 2 to 20.

^{-O- or -NR*} - may be inserted between the carbon atoms constituting the above-mentioned alkoxy group. Examples of the alkoxy group with -O- or -NR ^* -inserted between carbon atoms include: methoxymethoxy, 2-ethoxyethoxy, and 2-(2-ethoxyethoxy ) Base and so on. Furthermore, R ^{* is} as described above.

Examples of the alkanediyloxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and isobutoxycarbonyl. , Tertiary butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, n-hexoxycarbonyl, n-heptoxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n- An alkanediyloxycarbonyl group formed by removing one hydrogen atom from an unsubstituted alkoxycarbonyl group with 2 to 20 carbon atoms such as decyloxycarbonyl group. The carbon number of the alkanediyl part of the alkanediyloxycarbonyl group is preferably 1-16, more preferably 1-12.

One or more hydrogen atoms constituting the alkoxycarbonyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (for example, a fluorine atom), a hydroxyl group, an amino group, or an amino group having a substituent. The amino group having a substituent is the same as above. Examples of alkoxycarbonyl groups in which one or more hydrogen atoms are substituted by halogen atoms, hydroxyl groups, amino groups, etc. include fluoroethoxycarbonyl, trifluoroethoxycarbonyl, tetrafluoroethoxycarbonyl, and octafluorobutoxy Carbon 2-20 halogenated alkoxycarbonyl groups such as carbonyl groups.

Examples of the alkanediylcarbonyloxy group having 2 to 20 carbon atoms include acetoxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, and isopropylcarbonyloxy. Butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, isopentylcarbonyloxy, neopentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octyl An alkanediylcarbonyloxy group formed by removing one hydrogen atom from an unsubstituted alkoxy group having 2 to 20 carbon atoms such as n-nonylcarbonyloxy group, n-nonylcarbonyloxy group, and n-decylcarbonyloxy group. The carbon number of the alkanediyl moiety of the alkanediylcarbonyloxy group is preferably 1-16, more preferably 1-12.

One or more hydrogen atoms constituting the alkoxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (for example, a fluorine atom), a hydroxyl group, an amino group, or an amino group having a substituent. The amino group having a substituent is the same as above. Examples of the alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom, a hydroxyl group, etc. include halogenated acyloxy groups having 2 to 20 carbon atoms such as tetrafluoroethylcarbonyloxy and octafluorobutylcarbonyloxy.

^{R 4} in the formula (1) represents a polymerizable group or a hydrogen atom. The polymerizable group in R ⁴ is preferably a radical polymerizable group, for example, a (meth)acrylate group, a styryl group, etc., and among them, a (meth)acrylate group is preferred.

The compound represented by formula (1) is preferably a dichroic dye. Dichroic pigments refer to pigments with properties that the absorbance in the direction of the long axis of the molecule is different from the absorbance in the direction of the short axis of the molecule. The dichroic pigment preferably has the characteristic of absorbing visible light, more preferably has a maximum absorption wavelength (λ _MAX ) in the range from 380 nm to 680 nm, and more preferably has a maximum absorption in the range from 420 nm to 520 nm Wavelength (λ _MAX ).

As specific examples of the compound represented by formula (1), the following compounds represented by formula (2-2) to formula (2-102) can be cited, but the present invention is not limited to these.

[化1]

[化2]

[化3]

[化4]

[化5]

[化6]

[化7]

[化8]

[化9]

[化10]

[化11]

[化12]

[化13]

[化14]

[化15]

[化16]

[化17]

The compound represented by formula (1) is preferably selected from formula (2-2) to formula (2-102) from formula (2-2) to formula (2-7), formula (2-9) to formula ( 2-30), formula (2-34) to formula (2-42), and formula (2-47) to formula (2-102) represented by any one of the group consisting of at least one compound , Among them, more preferably selected from formula (2-3) to formula (2-7), formula (2-9) to formula (2-30), formula (2-34) to formula (2-42), And at least one of the group consisting of a compound represented by any one of formula (2-47) to formula (2-102), particularly preferably selected from formula (2-4) to formula (2-7) , Formula (2-9) to Formula (2-30), Formula (2-37) to Formula (2-41), and Formula (2-47) to Formula (2-102) At least one compound from the group consisting of compounds, more preferably selected from formula (2-4) to formula (2-7), formula (2-9) to formula (2-30), formula (2-37) ) To the group of compounds represented by any one of formula (2-41), formula (2-47) to formula (2-65), and formula (2-75) to formula (2-102) At least one of them, especially more preferably selected from formula (2-4) to formula (2-7), formula (2-9) to formula (2-30), formula (2-47) to formula (2- 65), and at least one of the group consisting of compounds represented by any one of formula (2-75) to formula (2-102).

(Production method) The method for producing the compound represented by formula (1) (hereinafter also referred to as compound (1)) will be described. Compound (1) can use, for example, a compound represented by formula (1X) [hereinafter, also referred to as compound (1X)] and a compound represented by formula (1Y) [hereinafter, also referred to as compound (1Y)], by It is produced by the steps shown in the following reaction formula.

[化18]

In the above reaction formula, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ and R ⁴ have the same meanings as those in formula (1). Re ¹ and Re ² are a combination of groups capable of forming a linking group or a single bond represented by ^{R 1 by mutual reaction.} Examples of the combination of Re ¹ and Re ^{2 include the following.} When R ¹ is a single bond, a combination of a dihydroxyboronyl group or a dialkoxyboronyl group and a halogen atom, etc. may be mentioned. When R ¹ is -C(=O)O- or -OC(=O)-, examples include the combination of a carboxyl group and a hydroxyl group, a combination of a carbonyl halide group and a hydroxyl group, and a combination of a carbonyloxyalkyl group and a hydroxyl group. Wait. When R ¹ is -C≡C-, for example, a combination of a halogen atom and an ethynyl group (-C≡CH) and the like can be mentioned. When R ¹ is -CH=CH-, for example, a combination of a halogen atom and a vinyl group (-CH=CH _{2) and the like can be mentioned.} When R ¹ is -CH=N- or -N=CH-, for example, a combination of a formyl group and an amino group can be cited.

In the above reaction formula, the production method using the compound (1X) ^{having R 4} -R ^{3 -and the compound (1Y) having R 2} -is described, but compound (1) can also be produced by the following method: A compound obtained by protecting R ⁴ -R ³ -with an appropriate protecting group ^{and a compound obtained by protecting R 2} -with an appropriate protecting group are reacted with each other, and then an appropriate deprotection reaction is performed.

The reaction conditions when the compound (1X) is reacted with the compound (1Y) can be appropriately selected according to the types of the compound (1X) and the compound (1Y) to be used, and the best known conditions are appropriately selected.

For example, when R ¹ is a single bond, Re ¹ is a dihydroxyoxyboron group or a dialkoxyoxyboron group, and Re ² is a halogen group, for example, refer to Netherton, MR; Fu, GC Org. Lett. 2001 , 3 (26), 4295-4298. etc., using the reaction conditions of Suzuki coupling. Compound (1) can be obtained _{by adding a Pd catalyst such as PdCl 2} dppf and heating in the presence of potassium acetate using a mixed solvent of diethylene glycol dimethyl ether and water as a solvent. The reaction temperature can be selected depending on the type of compound (1X) and compound (1Y), for example, a range of room temperature to 160°C, preferably a range of 60°C to 150°C. As a reaction time, the range of 15 minutes to 48 hours is mentioned, for example. In addition, when Re ¹ is a halogen atom, and Re ² is a dihydroxy oxyboron group or a dialkoxy oxyboron group, the same can be implemented.

Furthermore, ^{the compound (1X) in which Re 1} is a dihydroxyboronyl group or a dialkoxyboronyl group can be obtained by, for example, lithiuming the bromide group in ^{Ar 1 with n-butyl lithium and then making trialkoxyboron} The alkane functions by introducing a dihydroxyboronyl group or a dialkoxyboronyl group and is obtained. In addition, ^{the compound (1Y) in which Re 2} is a dihydroxyboronyl group or a dialkoxyboronyl group can be obtained by, for example, lithiuming ^{the bromide group in Ar 2} with n-butyllithium and then making a trialkoxyborane group. The compound functions by introducing a dihydroxyboronyl group or a dialkoxyboronyl group and is obtained.

The azo structure in the compound (1Y) can be referred to, for example, the description of the production examples in paragraphs [0220] to [0268] of International Publication WO2016/136561, etc. The aromatic amine having a primary amino group is obtained by using sodium nitrite or the like. The compound is converted into a diazonium salt, and it is constructed by coupling it with an aromatic compound.

For example ^{, for the reaction conditions when R 1} is -C(=O)O-, Re ¹ is a carboxyl group, and Re ² is a hydroxyl group, refer to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y .; Ma, DJ Org. Chem. 2009, 74 (3), 4542-4546. etc. use dehydration condensation reaction. For example, the conditions for condensation in a solvent in the presence of an esterification condensing agent can be cited. As the solvent, a solvent capable of dissolving the compound (1X) and the compound (1Y) at the same time, such as chloroform, can be mentioned. As the esterification condensing agent, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC·HCl), diisopropylcarbodiimide (IPC )Wait. In this case, it is preferable to further use a base such as N,N-dimethylaminopyridine (DMAP) in combination. The reaction temperature can be selected depending on the type of compound (1X) and compound (1Y), for example, a range of -15°C to 70°C, preferably a range of 0°C to 40°C. As a reaction time, the range of 15 minutes to 48 hours is mentioned, for example. In addition, when R ¹ is -OC(=O)-, Re ¹ is a hydroxyl group, and Re ² is a carboxyl group, the same can be implemented.

For example, when R ¹ is -C≡C-, Re ¹ is an ethynyl group (-C≡CH), and Re ² is a halogen atom, the compound (1) can be synthesized by using Pd and Cu as a catalyst. . In addition, when Re ¹ is a halogen atom and Re ² is an ethynyl group (-C≡CH), the same can be implemented.

For example, when R ¹ is -C=C-, Re ¹ is vinyl (-CH=CH ₂ ), and Re ² is a halogen group, the Heck reaction using Pd catalyst and phosphorus ligand can be used to synthesize the compound (1). In addition, when Re ¹ is a halogen atom and Re ² is a vinyl group (-CH=CH ₂ ), the same can be implemented.

For example, when R ¹ is -CH=N-, Re ¹ is a formyl group, and Re ² is an amine group, compound (1) can be synthesized by applying a general dehydration condensation reaction. In addition, when R ¹ is -N=CH-, Re ¹ is an amino group, and Re ² is a methyl group, the same can be implemented.

When the compound R (1) in the case of ³ carbon atoms alkoxy group having 2 to 20 bis carbonyl group to the obtained sum, the transesterification may be of generally by reacting other alkoxy R ³ changes of 2 to 20 carbon atoms of Diyloxycarbonyl. In the transesterification reaction, for example, Chen, C.-T.; Kuo, J.-H.; Ku, C.-H.; Weng, S.-S.; Liu, C.-YJ Org. Chem. 2005, 70 (4), 1328-1339. For reference, TiO(acac) ₂ (name: bis(2,4-pentanedionyl) titanium(IV) oxide) can be used as a Lewis acid catalyst A method of heating with alcohol compounds in a solvent. As the solvent, a hydrocarbon-based aromatic compound such as xylene and toluene can be used. In addition, other alkanediyloxycarbonyl groups having 2 to 20 carbon atoms include those with different alkanediyl moieties, which may have different carbon numbers, and may also have different substituents.

The reaction time of the production method of compound (1) can also appropriately sample the reaction mixture in the reaction process, and confirm the compound (1X) and compound ( It is determined by the degree of disappearance of 1Y) and the degree of production of compound (1).

The compound (1) can be extracted from the reaction mixture after the reaction by well-known methods such as recrystallization, reprecipitation, extraction, and various chromatographic methods, or by appropriately combining these operations.

<Composition> The composition containing the compound represented by formula (1) will be described. The composition of this embodiment is comprised including the compound represented by Formula (1), for example as a pigment compound, and other components, such as a liquid medium, if necessary. Regarding the content of the compound represented by formula (1) in the composition, relative to 100 parts by mass of the solid content of the composition, it is preferably 50 parts by mass or less, and more preferably in the range of 0.1 parts by mass to 10 parts by mass, More preferably, it is the range of 0.1 mass part or more and 5 mass parts or less. If it is in the above range, the compound represented by formula (1) can be sufficiently dispersed. Thereby, it is possible to efficiently obtain a film in which the occurrence of defects in the compound represented by the formula (1) as a forming material is sufficiently suppressed. In addition, in this specification, the solid content refers to the total amount of the components from the composition in which volatile components such as solvents are removed.

[Other ingredients] (Other pigment compounds) The composition may further include at least one other coloring compound other than the compound represented by formula (1), for example, dichroic coloring. As other pigment compounds, for example, azo pigments such as monoazo pigments, bisazo pigments, trisazo pigments, tetrazo pigments, stilbene azo pigments, etc., are preferably selected from the group consisting of these At least one. The composition may contain one kind of other coloring compound alone, or two or more kinds in combination. For example, when used as a coating-type polarizing plate material, the other pigment compound contained in the composition preferably has a maximum absorption wavelength in a wavelength range different from the compound represented by formula (1). When used as a coating type polarizing plate material, the composition preferably contains the compound represented by formula (1) and contains three or more dichroic dyes in combination, and more preferably contains three or more azo dyes in combination. When the composition includes three or more pigment compounds with different absorption wavelengths, for example, the film formed by the composition can absorb the entire visible light.

When the composition contains other pigment compounds, the content is preferably 50 parts by mass or less relative to 100 parts by mass of the solid content of the composition, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably The range is from 0.1 part by mass to 5 parts by mass. If it is in the above-mentioned range, other dye compounds can be sufficiently dispersed.

(Polymerizable liquid crystal compound) The composition may contain at least one type of polymerizable liquid crystal compound in addition to the compound represented by formula (1). The polymerizable liquid crystal compound is a compound that has a polymerizable group in the molecule and can assume a liquid crystal phase by alignment. The polymerizable liquid crystal compound is preferably a compound capable of exhibiting a liquid crystal phase by individual alignment. The composition may include one single polymerizable liquid crystal compound, or two or more polymerizable liquid crystal compounds.

The polymerizable group means a group that participates in a polymerization reaction, and a photopolymerizable group is preferred. Here, the polymerizable group refers to a group capable of participating in the polymerization reaction by living radicals, acids, etc. generated from the polymerization initiator described below. Examples of polymerizable groups include vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, acryloxy groups, methacryloxy groups, and oxirane groups. , And oxetanyl. Among them, the polymerizable group is preferably at least one selected from the group consisting of acryloxy group, methacryloxy group, vinyloxy group, oxirane group, and oxetanyl group, and more Preferably it is propylene oxy group.

The polymerizable liquid crystal compound may be one that can constitute a thermotropic liquid crystal type polymer, or one that can constitute a lyotropic liquid crystal type polymer.

The polymerizable liquid crystal compound may be a compound in a nematic liquid crystal phase, a compound in a smectic liquid crystal phase, or a compound in both a nematic liquid crystal phase and a smectic liquid crystal phase. It is preferably a compound exhibiting a smectic liquid crystal phase, and more preferably a compound exhibiting a higher order smectic liquid crystal phase. The composition containing the polymerizable liquid crystal compound in the smectic liquid crystal phase can provide a polarizing film with more excellent polarization performance.

Even in a state where the compound represented by formula (1) is dispersed in dense molecular chains formed by a polymerizable liquid crystal compound in a smectic liquid crystal phase, it can exhibit high dichroism. Therefore, a composition containing the compound represented by the formula (1) and a polymerizable liquid crystal compound, particularly a polymerizable liquid crystal compound in a smectic liquid crystal phase, can provide a polarizing film with a high two-color ratio.

Examples of the higher order smectic liquid crystal phase include: smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J Phase, smectic K phase, and smectic L phase. Among them, the smectic B phase, the smectic F phase, and the smectic I phase are preferable, and the smectic B phase is more preferable. If the smectic liquid crystal phase exhibited by the polymerizable liquid crystal compound is these higher order smectic phases, a polarizing film with a higher degree of alignment order can be obtained. A polarizing film obtained from a composition containing a polymerizable liquid crystal compound exhibiting a high-order smectic liquid crystal phase with a high degree of alignment appears to be derived from a hexagonal phase or a crystal-like high-order structure in the X-ray diffraction measurement. Rouge crest. The Buhrer wave peak is derived from the wave peak of the surface periodic structure of molecular alignment. The period interval (order period) of the polarizing film obtained from the composition is preferably 0.30 nm or more and 0.60 nm or less.

The type of liquid crystal phase exhibited by the polymerizable liquid crystal compound can be confirmed by the method shown below, for example. That is, a suitable substrate is prepared, a solution containing a polymerizable liquid crystal compound and a solvent is applied to the substrate to form a coating film, and then heat treatment or reduced pressure treatment is performed to thereby the coating film contains The solvent is removed. Then, the coating film formed on the substrate is heated to the temperature of the isotropic phase, and then slowly cooled, and the liquid crystal phase presented thereby is measured by texture observation using a polarizing microscope and X-ray diffraction measurement Or differential scanning calorimetry to check. In this inspection, for example, it can be confirmed that the liquid crystal phase becomes a nematic liquid crystal phase by being cooled to the first temperature, and then a smectic liquid crystal phase is formed by cooling slowly to the second temperature.

The polymerizable liquid crystal compound is preferably a compound represented by formula (4) (hereinafter, sometimes referred to as "compound (4)").

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (4) In the formula, X ¹ , X ² and X ³ are independent respectively, which means The 1,4-phenylene group which may have a substituent, or the cyclohexane-1,4-diyl group which may have a substituent; wherein ^{at least one of X 1} , X ² and X ³ is a group which may have a substituent _{In addition, at least 1 of -CH 2} -constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or -NR-; here , R represents an alkyl group or a phenyl group with carbon numbers 1 to 6; Y ¹ and Y ² are independent of each other and represent a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -(C=O)O-,- O (C = O) O - , - N = N -, - CR a = CR b -, - C≡C-, or -CR ^a = N-; R ^a and R ^b each independently represents a hydrogen atom or a C An alkyl group having a number of 1 to 4; U ¹ represents a hydrogen atom or a polymerizable group; U ² represents a polymerizable group; W ¹ and W ² are independent of each other and represent a single bond, -O-, -S-, -(C=O )O-, or -O(C=O)O-; V ¹ and V ² are independent of each other and represent an alkanediyl group with a carbon number of 1 to 20 that may have a substituent, and -CH ₂ -constituting the alkanediyl group is also Can be substituted with -O-, -S- or -NH-)

The 1,4-phenylene group which may have a substituent is preferably the 1,4-phenylene group which has no substituent. The cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent. The trans-cyclohexane-1,4-diyl group which may have a substituent is preferably the trans-cyclohexane-1,4-diyl group which has no substituent.

As the 1,4-phenylene group which may have a substituent, or the cyclohexane-1,4-diyl group which may have a substituent, the optional substituents include methyl, ethyl, n-butyl and other carbon number 1 Up to 4 alkyl groups, cyano groups, and halogen atoms, etc.

Y ^{1 is} preferably a single bond, -CH ₂ CH ₂ -, or -(C=O)O-, and Y ^{2 is} preferably -CH ₂ H ₂ -or -CH ₂ O-.

U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. U ² is a polymerizable group. U ¹ and U ^{2 are} preferably both a polymerizable group, and more preferably are both a photopolymerizable group. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under lower temperature conditions.

The polymerizable groups represented by U ¹ and U ² may be different from each other, but are preferably the same. Examples of polymerizable groups include vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, acryloxy groups, methacryloxy groups, and oxirane groups. , And oxetanyl. Among them, ^{the polymerizable groups represented by U 1} and U ² are preferably selected from vinyloxy, acryloxy, methacryloxy, oxiranyl, and oxetanyl groups. At least one of the group, more preferably acryloxy group.

Examples of the alkanediyl group represented by V ¹ and V ² include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4- Diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10- Diyl, tetradecane-1,1-diyl, and eicosan-1,20-diyl. V ¹ and V ^{2 are} preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.

Examples of the substituent optionally possessed by the alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group and a halogen atom. The alkanediyl group is preferably an alkanediyl group having no substituents, and more preferably a straight-chain alkanediyl group having no substituents.

W ¹ and W ^{2 are} preferably independent of each other and are a single bond or -O-.

Specific examples of the compound (4) include compounds represented by the following formula (4-1) to (4-43). When the compound (4) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans type.

[化19]

[化20]

[化21]

[化22]

[化23]

[化24]

[化25]

[化26]

[化27]

Among them, compound (4) is preferably selected from formula (4-5), formula (4-6), formula (4-7), formula (4-8), formula (4-9), formula (4- 10), formula (4-11), formula (4-12), formula (4-13), formula (4-14), formula (4-15), formula (4-22), formula (4-24) ), formula (4-25), formula (4-26), formula (4-27), formula (4-28), and formula (4-29) At least one of the compounds represented.

Compound (4) can be produced, for example, by a method described in publicly known documents such as Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156.

The composition may also contain two or more polymerizable liquid crystal compounds. When combining two or more types of polymerizable liquid crystal compounds, it is preferable that at least one of them is the compound (4), and it is more preferable that two or more of them are the compound (4). By combining two or more types of polymerizable liquid crystal compounds, there are cases where the liquid crystal phase can be temporarily maintained even at a temperature below the liquid crystal-crystal phase transition temperature. Regarding the content of the compound (4) contained in the composition, relative to the total mass of all polymerizable liquid crystal compounds in the composition, the total is preferably 40% by mass or more, more preferably 60% by mass or more, and all can be polymerized. The sexual liquid crystal compound is compound (4). If the content of the compound (4) is within the above range, the polymerizable liquid crystal compound is easily aligned with a higher degree of alignment order, and the compound represented by the formula (1) is aligned along it, thereby obtaining excellent polarized light Performance polarizing film.

Regarding the content ratio of the polymerizable liquid crystal compound in the composition, from the viewpoint of improving the orientation of the polymerizable liquid crystal compound, relative to 100 parts by mass of the solid content of the composition, it is preferably 70 parts by mass or more and 99.5 parts by mass or less , More preferably 80 parts by mass or more and 99 parts by mass or less, and still more preferably 80 parts by mass or more and 94 parts by mass or less.

(Polymer compound) The composition may further include a polymer compound in addition to the compound represented by formula (1). When the composition contains a polymer compound, it is possible to constitute a composition in which the compound represented by formula (1) is dispersed in the polymer compound.

The polymer compound that can be included in the composition is not particularly limited as long as the compound represented by formula (1) can be dispersed. Examples include polyolefins such as polyethylene and polypropylene; and cyclic olefins such as norene polymers. Resin; polyalkylene ether, polyvinyl alcohol; polymethacrylate; polyacrylate, etc. These high molecular compounds have liquid crystal organic groups. Among them, polymethacrylate and polyacrylate are preferred from the viewpoint that it is easy to uniformly disperse the compound represented by formula (1). The polymer compound contained in the composition may be one type or two or more types.

The polymer compound that can be contained in the composition may also be a liquid crystal polymer compound, and examples thereof include polymers of the above-mentioned polymerizable liquid crystal compound. The polymerizable liquid crystal compound as a constituent monomer of the polymer of the polymerizable liquid crystal compound may be one type or two or more types. The composition may also include the above-mentioned polymerizable liquid crystal compound and a polymer thereof.

The weight average molecular weight of the polymer compound in terms of polystyrene is, for example, 10,000 or more and 200,000 or less, preferably 20,000 or more and 150,000 or less.

When the composition contains a polymer compound, its content can be appropriately selected depending on the purpose and the like. The content of the polymer compound relative to 100 parts by mass of the solid content of the composition is preferably 70 parts by mass or more and 99.5 parts by mass or less, more preferably in the range of 80 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more The range of 94 parts by mass or less.

When the composition contains the compound (1) and the polymerizable liquid crystal compound, the content of the compound (1) in the composition relative to 100 parts by mass of the polymerizable liquid crystal compound is usually 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and still more preferably 0.1 parts by mass or more and 5 parts by mass or less. If the content of the compound (1) is 50 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound, there will be less confusion in the alignment of the polymerizable liquid crystal compound and the compound (1), and a higher degree of alignment order can be obtained. The tendency of the membrane.

When the composition contains the compound (1) and the polymer compound, the content of the compound (1) in the composition relative to 100 parts by mass of the polymer compound is usually 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.1 parts by mass Part or more and 20 parts by mass or less, more preferably 0.1 part by mass or more and 10 parts by mass or less, and still more preferably 0.1 part by mass or more and 5 parts by mass or less. When the above-mentioned polymer compound is a liquid crystal polymer compound, if the content of the compound (1) is 50 parts by mass or less relative to 100 parts by mass of the liquid crystal polymer compound, the liquid crystal polymer compound and the compound (1) There is less confusion in the alignment, and there is a tendency to obtain a film with a higher degree of alignment order.

The composition preferably further includes a liquid medium such as a solvent and a polymerization initiator, and may further include a photosensitizer, a polymerization inhibitor, a leveling agent, and the like as needed.

(Solvent) The solvent is preferably a solvent that can completely dissolve the compound (1), the polymerizable liquid crystal compound, and the polymer compound. In addition, it is preferably a solvent that is inert in the polymerization reaction of the polymerizable liquid crystal compound.

Examples of solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, and ethylene diethyl ether. Alcohol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl Ketone solvents such as isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; and Chlorine-containing solvents such as chloroform and chlorobenzene. These solvents may be used alone or in combination of two or more kinds.

When the composition contains a solvent, the content ratio of the solvent is preferably 50% by mass or more and 98% by mass or less with respect to the total amount of the composition. In other words, the solid content in the composition is preferably 2% by mass or more and 50% by mass or less. If the solid content is 50% by mass or less, the viscosity of the composition becomes low, the thickness of the film obtained from the composition becomes substantially uniform, and there is a tendency that unevenness is not easily generated on the film. The content ratio of the solid component can be determined in consideration of the thickness of the film to be manufactured.

(Polymerization initiator) The polymerization initiator is a compound capable of starting the polymerization reaction of the polymerizable liquid crystal compound. The polymerization initiator is preferably a photopolymerization initiator in terms of being able to start the polymerization reaction under lower temperature conditions. Specifically, photopolymerization initiators capable of generating active radicals or acids by the action of light can be cited. Among them, photopolymerization initiators that generate free radicals by the action of light are preferred.

As the polymerization initiator, a benzoin compound, a benzophenone compound, a benzophenone compound, an oxyphosphine oxide compound, a tris compound, an iodonium salt, a sulfonium salt, etc. can be mentioned. The polymerization initiator may be appropriately selected from known polymerization initiators depending on the purpose and the like. Moreover, a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned.

Examples of the benzophenone compound include benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzophenone-4'-methyl diphenyl sulfide, 3,3,4,4-Tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, etc.

Examples of the phenanone compound include diethoxyacetophenone, 2-methyl-2-𠰌line-1-(4-methylthiophenyl)propan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-𠰌linephenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl Base-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1- Hydroxycyclohexyl phenyl ketone and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

As the phosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, and the like can be mentioned.

Examples of the tris compound include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris, 2,4-bis(trichloromethyl) Yl)-6-(4-methoxynaphthyl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1 ,3,5-tris𠯤、2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tris𠯤、2 ,4-Bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tris, 2,4-bis(trichloromethyl)-6- [2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-tris and 2,4-bis(trichloromethyl)-6-[2-( 3,4-Dimethoxyphenyl)vinyl]-1,3,5-tri 𠯤 and the like.

Examples of the sulphur salt and sulphur salt include salts represented by the following formulae.

[化28]

As the polymerization initiator, a commercially available product may also be used. Commercially available polymerization initiators include: Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369 (manufactured by BASF JAPAN Co., Ltd.); Seikuol (registered trademark) BZ, Z, and BEE ( Seiko Chemical Co., Ltd.); kayacure (registered trademark) BP100, and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); Adeka Optomer SP-152, and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A, And TAZ-PP (manufactured by Nihon SiberHegner Co., Ltd.); and TAZ-104 (manufactured by SANWA CHEMICAL Co., Ltd.), etc.

When the composition contains a polymerization initiator, its content may be appropriately determined depending on the type and amount of the polymerizable liquid crystal compound contained in the composition. The content of the polymerization initiator relative to 100 parts by mass of the polymerizable liquid crystal compound is, for example, 0.001 part by mass or more, 0.01 part by mass or more, or 0.1 part by mass or more, for example, 30% by mass or less, 10% by mass or less, or 8% by mass or less. In addition, the content of the polymerization initiator relative to 100 parts by mass of the polymerizable liquid crystal compound is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and still more preferably 0.1 parts by mass or more. Parts by mass or less. If the content of the polymerizable initiator is within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the alignment of the polymerizable liquid crystal compound.

等𠮿酮化合物(例如2,4-二乙基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

)；蒽及含烷氧基之蒽(例如二丁氧基蒽)等蒽化合物；啡噻𠯤及紅螢烯等。光敏劑可單獨使用1種或將2種以上組合使用。(Photosensitizer) When the composition contains a photopolymerization initiator, the composition preferably contains at least one type of photosensitizer. Since the composition contains a photopolymerization initiator and a photosensitizer, there is a tendency that the polymerization reaction of the polymerizable liquid crystal compound can be further promoted. Examples of the photosensitizer include: ketone and 9-oxysulfur

And other ketone compounds (such as 2,4-diethyl 9-oxysulfur)

, 2-isopropyl 9-oxysulfur 𠮿

); anthracene compounds such as anthracene and alkoxy-containing anthracene (such as dibutoxyanthracene); phenanthrene and fluorene. The photosensitizer can be used alone or in combination of two or more.

When the composition contains a photosensitizer, the content of the photosensitizer in the composition may be appropriately determined depending on the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound. The content of the photosensitizer in the composition relative to 100 parts by mass of the polymerizable liquid crystal compound is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass or less, and still more preferably 0.5 part by mass or more. Parts by mass or less.

(Polymerization inhibitor) The composition may also contain at least one type of polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butylcatechol), pyrogallol, 2, Radical scavengers such as 2,6,6-tetramethyl-1-piperidinyloxy free radicals; thiophenols; β-naphthylamines and β-naphthols, etc.

By including the polymerization inhibitor in the composition, the progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.

When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition relative to 100 parts by mass of the polymerizable liquid crystal compound is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass Parts or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less.

(Leveling agent) The composition may also include at least one leveling agent. The leveling agent has the function of adjusting the fluidity of the composition and making the coating film obtained by applying the composition flatter. Specifically, a surfactant can be mentioned. The leveling agent is preferably at least one selected from the group consisting of a leveling agent having a polyacrylate compound as a main component and a leveling agent having a fluorine atom-containing compound as a main component. The leveling agent can be used individually by 1 type or in combination of 2 or more types.

As a leveling agent with polyacrylate compound as the main component, for example, "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK -358N", "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" (BYK Chemie), etc.

As a leveling agent mainly composed of a compound containing a fluorine atom, for example, "MEGAFAC (registered trademark) R-08", "MEGAFAC (registered trademark) R-30", "MEGAFAC (registered trademark) R-90" ", "MEGAFAC (registered trademark) F-410", "MEGAFAC (registered trademark) F-411", "MEGAFAC (registered trademark) F-443", "MEGAFAC (registered trademark) F-445", "MEGAFAC (registered trademark) Trademark) F-470", "MEGAFAC (registered trademark) F-471", "MEGAFAC (registered trademark) F-477", "MEGAFAC (registered trademark) F-479", "MEGAFAC (registered trademark) F-482" And "MEGAFAC (registered trademark) F-483" (DIC (shares)); "Surflon (registered trademark) S-381", "Surflon (registered trademark) S-382", "Surflon (registered trademark) S-383" , "Surflon (registered trademark) S-393", "Surflon (registered trademark) SC-101", "Surflon (registered trademark) SC-105", "KH-40" and "SA-100" (AGC SEIMI CHEMICAL ( Stock)); "E1830", "E5844" (Daikin Fine Chemical Laboratory (stock)); "Eftop EF301", "Eftop EF303", "Eftop EF351" and "Eftop EF352" (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) Wait.

When the composition contains a leveling agent, the content of the leveling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the polymer compound. The above 3 parts by mass or less. If the content of the leveling agent is within the above range, it is easy to align the polymerizable liquid crystal compound horizontally, and unevenness is unlikely to occur, and there is a tendency to obtain a smoother film such as a polarizing film.

If the content of the leveling agent is within the above range, it is easy to horizontally align liquid crystal polymer compounds such as polymerizable liquid crystal compounds or polymers of polymerizable liquid crystal compounds, and the obtained film tends to be smoother. If the content of the leveling agent exceeds the above range with respect to the polymerizable liquid crystal compound, unevenness may occur in the obtained film.

The composition may contain other additives in addition to the above. Examples of other additives include coloring agents such as mold release agents, stabilizers, antioxidants, and bluing agents, flame retardants, lubricants, and the like. When the composition contains other additives, the content of the other additives relative to the solid content of the composition is preferably more than 0% and 20% by mass or less, more preferably more than 0% and 10% by mass or less.

＜Membrane＞ The film of this embodiment is obtained by using the compound represented by formula (1) as a forming material, and can constitute a polarizing film, for example. That is, the film may be a film containing a compound represented by formula (1), a film containing a composition containing a compound represented by formula (1), or a composition containing a compound represented by formula (1) Hardened object. The film containing the compound represented by the formula (1) can be formed by applying the compound represented by the formula (1) to a substrate and forming a film. In addition, a film including a composition containing the compound represented by formula (1) can be formed by applying the composition to a substrate and forming a film. In addition, when the composition containing the compound represented by the formula (1) contains a polymerizable liquid crystal compound, a film containing a cured product obtained by polymerizing the polymerizable liquid crystal compound can be provided by applying the composition to a substrate After film formation, the polymerizable liquid crystal compound is polymerized and cured to form it.

＜Laminated body＞ The laminate of the present embodiment includes a film using the compound represented by formula (1) as a forming material. The layered product may include a substrate and a film formed on the substrate and the compound represented by formula (1) as a forming material. The laminate may constitute a polarizing plate, for example. The laminate can be produced by applying a composition containing the compound represented by formula (1) to a substrate, and forming a film of the applied composition.

The layered body of this embodiment can be manufactured by a manufacturing method including the following steps A and B, and optionally a step C. When the composition contains a liquid crystal polymer compound in addition to the compound represented by formula (1), it is preferable to further align the liquid crystal polymer compound in step B. When the composition includes a polymerizable liquid crystal compound in addition to the compound represented by formula (1), it is preferable to include steps A, B, and C.

The laminated body can be manufactured by a manufacturing method including the following steps: Step A: coating a composition containing at least compound (1) on the surface of the substrate to form a coating film; Step B: heating to remove the solvent and align at least one of the liquid crystal polymer compound and the polymerizable liquid crystal compound contained in the formed coating film with the compound (1); Step C: Polymerize the polymerizable liquid crystal compound by irradiating the aligned polymerizable liquid crystal compound with active energy rays.

(Step A) The substrate may be any of a glass substrate, a resin substrate, etc., but a resin substrate is preferred. By using a film substrate containing resin, a thinner laminate can be obtained.

The resin substrate is preferably a transparent resin substrate. Transparent resin substrate refers to a transparent substrate that can transmit light, especially visible light. Transparency refers to the visual sensitivity of light that spans the wavelength range from 380 nm to 780 nm, and the transmittance becomes More than 80% characteristics.

Examples of the resin constituting the substrate include: polyolefins such as polyethylene, polypropylene, norene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid Esters; polyacrylates; cellulose esters such as triacetyl cellulose, diethyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polyether; polyether; polyether Ketones; polyphenylene sulfide; polyphenylene ether, etc. Preferably, it is at least one selected from the group consisting of cellulose ester, cyclic olefin resin, polycarbonate, polyether agglomerate, polyethylene terephthalate, or polymethacrylate.

As long as the thickness of the base material is such that it can be operated practically, it is preferably thinner, but if it is too thin, the strength may decrease and the workability may be poor. The thickness of the substrate is usually 5 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less.

(Step B) In the case where the above-mentioned composition contains a solvent, the solvent is usually removed from the formed coating film. Examples of the solvent removal method include natural drying method, ventilation drying method, heat drying and reduced pressure drying method.

When the formed coating film contains a liquid crystal polymer compound and a polymerizable liquid crystal compound, the liquid crystal phase can usually be formed by aligning in the following way: heating to a temperature above the temperature at which it turns into a solution state, and then cooling to liquid crystal The temperature of the alignment.

When the formed coating film contains a liquid crystal polymer compound and a polymerizable liquid crystal compound, the temperature at which the liquid crystal polymer compound and the polymerizable liquid crystal compound are aligned should be preliminarily used to include the liquid crystal polymer compound and The composition of the polymerizable liquid crystal compound may be obtained by observing the texture and the like. In addition, solvent removal and liquid crystal alignment can also be performed at the same time. The temperature at this time also depends on the type of solvent or polymerizable liquid crystal compound to be removed, but it is preferably 50°C or more and 200°C or less, and when the substrate is a resin substrate, it is more preferably 80°C or more The range below 130°C.

(Step C) When a polymerizable liquid crystal compound is included in the formed coating film, the polymerizable liquid crystal compound is polymerized by irradiating the aligned polymerizable liquid crystal compound with active energy rays.

By polymerizing the aligned polymerizable liquid crystal compound, a polarizing film including the polymerizable liquid crystal compound polymerized in an aligned state and the compound (1) aligned together with the polymerizable liquid crystal compound can be obtained.

A polarizing film containing a polymerizable liquid crystal compound polymerized while maintaining a smectic liquid crystal phase and the previous host-guest polarizing film, which is obtained by polymerizing a polymerizable liquid crystal compound while maintaining a nematic liquid crystal phase. Compared with the polarizing film, the polarizing performance is higher, and compared with the polarizing film formed by coating only the dichroic dye or the lyotropic liquid crystal compound, the polarizing performance and strength are superior.

As a radiation source of active energy rays, any radiation source that generates ultraviolet rays, electron beams, X-rays, etc. may be sufficient. It is preferably a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp and other light sources with a luminous distribution below 400 nm.

＜Display device＞ The display device is a device having a display element, and is a device including a light-emitting element or a light-emitting device as a light-emitting source. As a display device having the film of this embodiment, preferably a polarizing film, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device ( For example, field emission display devices (FED), surface conduction electron emission display devices (SED), electronic paper (display devices using electronic ink, electrophoretic elements, etc.), plasma display devices, projection display devices (e.g., grid-shaped Light valve (GLV) display device, digital micro-mirror device (DMD) display device), and piezoelectric ceramic display, etc. The liquid crystal display device includes any one of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. The display devices can be display devices that display two-dimensional images, or stereoscopic display devices that display three-dimensional images.

The film (preferably a polarizing film) of this embodiment can be effectively used in liquid crystal display devices, organic electroluminescence (EL) display devices, and inorganic electroluminescence (EL) display devices, in particular. The above-mentioned organic EL display device is preferably configured to include at least the film of the present embodiment, a polarizing film and an organic EL element. The organic EL device can use a device having a well-known structure.

As the film of this embodiment, it is preferable to use a circularly polarizing plate of a laminate of a polarizing film and a quarter-wavelength plate, and it is particularly effective for organic electroluminescence (EL) display devices and inorganic electroluminescence (EL) displays. Device. The above-mentioned organic EL display device includes at least the layered body of the present embodiment, and is preferably constituted by a circularly polarizing plate and an organic EL element.

When the film of this embodiment is preferably a polarizing film used in a liquid crystal display device, the film may be provided outside the liquid crystal cell, or may be provided inside the liquid crystal cell. The liquid crystal cell is preferably composed of at least the film of the present embodiment, which is a polarizing film, a liquid crystal layer, and a substrate. [Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited by these examples.

Example 1: Synthesis of compound (2-2) In order to synthesize compound (2-2), compound (2-2-a) is synthesized first. Then, the compound (2-2-a) and the compound (2-1-c) are subjected to Suzuki coupling to obtain the compound (2-2). In addition, compound (2-1-c) is synthesized via compound (2-1-b).

Synthesis of compound (2-2-a) The abbreviation for EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride; 1.21 g, 6.00 mmol) and DMAP (N,N-dimethylaminopropyl) Abbreviation for pyridine; 0.074 g, 0.60 mmol) in dichloromethane (60 mL) was added n-hexanol (1.20 mL, 9.6 mmol) and 4-bromo-2,3,5,6-tetrafluorobenzoic acid in sequence (1.64 g, 6.00 mmol). After stirring at room temperature for 5 hours, the reaction solution was washed with water, then with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator to obtain compound (2-2-a) (1.69 g) , Yield 79%).

[化29]

Synthesis of compound (2-1-b) Mix 4-bromoaniline (13.2 g, 77.6 mmol), 35% hydrochloric acid (22.0 mL, 249 mmol), and water (200 mL) and cool to 0°C to 5°C. A solution of sodium nitrite (13.0 g, 189 mmol) in water (26 mL) was added dropwise. Then, it stirred for 30 minutes while maintaining 0 degreeC to 5 degreeC, and further added amidosulfuric acid (11.0 g, 113 mmol), and prepared the diazonium liquid. On the other hand, N,N-dimethylaniline (14.0 mL, 111 mmol), sodium acetate (24.8 g, 302 mmol), methanol (200 mL), and water (100 mL) were mixed and cooled to 0°C To 5°C, add dropwise the total amount of diazonium solution just prepared. After the dropwise addition, the temperature was raised to normal temperature, and the precipitated solid was separated by filtration to obtain compound (2-1-b) (21.0 g, yield 90%).

[化30]

Synthesis of compound (2-1-c) The compound (2-1-b) (18.3 g, 60.0 mmol) in THF (450 mL) solution was cooled to -78°C, and 1.57 M n-butyllithium hexane solution (38.0 mL, 59.7 mmol) was added dropwise to it . Thereafter, while maintaining -78°C and stirring for 30 minutes, iPrOBpin (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Abbreviation for alkane; 11.0 mL, 64.8 mmol). After the addition, the temperature was raised to normal temperature and stirred for 30 minutes. A solution of ammonium chloride (60 g) in water (400 mL) was added to stop the reaction, the organic layer was separated, washed with saturated brine, then dried with magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by reprecipitation with chloroform/hexane to obtain compound (2-1-c) (16.7 g, yield 79%).

[化31]

Synthesis of compound (2-2) Pd was added to a solution of compound (2-2-a) (396 mg, 1.11 mmol) and compound (2-1-c) (351 mg, 1.00 mmol) in THF (10 mL) ₂ dba ₃ (22.9 mg, 0.025 mmol), and P(t-Bu) ₃ ·HBF ₄ (14.4 mg, 0.050 mmol) and stir. Furthermore, 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was added, and it stirred under reflux for 9 hours. Add THF to the reaction solution, pass through a short silica gel column, and concentrate with an evaporator. The obtained solid was purified by silica gel column chromatography (chloroform/toluene=20/80). Furthermore, it was purified by fractionation GPC (gel permeation chromatograph) to obtain compound (2-2) (88 mg, yield 18%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.97-7.89 (m, 4H), 7.60-7.57 (m, 2H), 6.79-6.76 (m, 2H), 4.42 (t, 2H) , 3.11 (s, 6H), 1.78 (tt, 2H), 1.49-1.42 (m, 2H), 1.38-1.33 (m, 4H), 0.91 (t, 3H).

[化32]

Example 2: Synthesis of Compound (2-3) In order to synthesize compound (2-3), compound (2-3-a) is synthesized first. Then, the compound (2-3-a) and the above-mentioned compound (2-1-c) are subjected to Suzuki coupling to obtain the compound (2-3).

Synthesis of compound (2-3-a) To the chloroform (80 mL) solution of EDC·HCl (1.61 g, 8.41 mmol) and DMAP (0.098 g, 0.80 mmol), add ethanol (1.85 g, 40.1 mmol), and 4-bromo-2,6-di in order. Fluorobenzoic acid (1.90 g, 8.01 mmol). After stirring at room temperature for 4 hours, the reaction solution was washed with water, and then washed with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator. It was dissolved in a mixed solvent of chloroform/hexane=1/1, passed through a short silica gel column, and concentrated with an evaporator to obtain compound (2-3-a) (1.32 g, yield 62%).

[化33]

Synthesis of compound (2-3) Pd was added to a solution of compound (2-3-a) (292 mg, 1.10 mmol) and compound (2-1-c) (351 mg, 1.00 mmol) in THF (10 mL) ₂ (dba) ₃ (22.7 mg, 0.0248 mmol), and P(t-Bu) ₃ ·HBF ₄ (15.2 mg, 0.0524 mmol) and stir. Furthermore, 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was added, and it heated and stirred at 60 degreeC for 4.5 hours. Methanol (20 mL) was added to the reaction solution, the precipitated solid was filtered out, and purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (2-3) (161 mg, yield 39%) ).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.95-7.89 (m, 4H), 7.69-7.66 (m, 2H), 7.26-7.22 (m, 2H), 6.79-6.75 (m, 2H), 4.45 (q, 2H), 3.11 (s, 6H), 1.42 (t, 3H).

[化34]

Example 3: Synthesis of Compound (2-4) In order to synthesize compound (2-4), compound (2-4-a) is synthesized first. Then, the compound (2-4-a) and the above-mentioned compound (2-1-c) are subjected to Suzuki coupling to obtain the compound (2-4).

Synthesis of compound (2-4-a) Add ethanol (1.84 g, 40.0 mmol) and 4-bromo-2-fluorobenzoic acid to a solution of EDC・HCl (1.61 g, 8.41 mmol) and DMAP (0.098 g, 0.80 mmol) in chloroform (80 mL). (1.75 g, 8.00 mmol). After stirring at room temperature for 3.5 hours, the reaction solution was washed with water, and then washed with saturated brine. It dried with magnesium sulfate and concentrated with an evaporator to obtain compound (2-4-a) (1.60 g, yield 81%).

[化35]

Synthesis of compound (2-4) Pd was added to a solution of compound (2-4-a) (552 mg, 2.23 mmol) and compound (2-1-c) (704 mg, 2.01 mmol) in THF (10 mL) ₂ (dba) ₃ (46.1 mg, 0.0503 mmol), and P(t-Bu) ₃ ·HBF ₄ (29.0 mg, 0.100 mmol) and stir. Furthermore, 3 M potassium phosphate aqueous solution (2.0 mL, 6.0 mmol) was added, and it heated and stirred at 60 degreeC for 3.5 hours. Water (20 mL) was added to the reaction solution, the precipitated solid was filtered out, and purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (2-4) (480 mg, yield 61%) ).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.02 (dd, 1H), 7.95-7.89 (m, 4H), 7.74-7.70 (m, 2H), 7.50 (dd, 1H), 7.43 (dd, 1H), 6.80-6.76 (m, 2H), 4.43 (q, 2H), 3.11 (s, 6H), 1.43 (t, 3H).

[化36]

Example 4: Synthesis of compound (2-5) To synthesize compound (2-5), firstly, compound (2-5-b) is synthesized via compound (2-5-a). Then, the compound (2-5-b) and ethyl 4-bromobenzoate were subjected to Suzuki coupling to obtain the compound (2-5).

Synthesis of compound (2-5-a) 4-Bromo-2-fluoroaniline (14.3 g, 75.0 mmol), 35% hydrochloric acid (22.0 mL, 249 mmol), and water (200 mL) were mixed and cooled to 0°C to 5°C, and sub- A solution of sodium nitrate (7.76 g, 112 mmol) in water (26 mL). Thereafter, while maintaining 0°C to 5°C, stirring for 30 minutes, and further adding amidosulfuric acid (4.36 g, 45.0 mmol) to prepare a diazonium liquid. On the other hand, dimethylaniline (13.6 g, 113 mmol), sodium acetate (24.6 g, 300 mmol), methanol (200 mL), and water (100 mL) were mixed and cooled to 0°C to 5°C, Add dropwise the total amount of diazonium liquid just prepared. After the dropwise addition, the temperature was raised to normal temperature, and the precipitated solid was separated by filtration to obtain compound (2-5-a) (15.8 g, yield 66%).

[化37]

The synthesis of compound (2-5-b) is based on compound (2-5-a) (3.23 g, 10.0 mmol), B ₂ pin ₂ (bis(pinacol ester) diborane; 2.79 g, 11.0 mmol) and _{PdCl 2} dppf (249 mg, 0.305 mmol) was added to a solution of potassium acetate (2.99 g, 30.4 mmol) in 1,4-dioxane (60 mL), and the mixture was heated and stirred at 80° C. for 7 hours. The reaction solution was separated with toluene/water, the organic layer was washed with water, and then washed with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by reprecipitation with chloroform/hexane to obtain compound (2-5-b) (2.53 g, yield 69%).

[化38]

_{Synthesis of compound (2-5) Pd 2} was added to a solution of ethyl 4-bromobenzoate (0.763 g, 3.33 mmol) and compound (2-5-b) (1.11 g, 3.00 mmol) in THF (30 mL) (dba) ₃ (69.8 mg, 0.0762 mmol), and P(t-Bu) ₃ ·HBF ₄ (45.0 mg, 0.155 mmol) and stir. Furthermore, 3 M potassium phosphate aqueous solution (4.0 mL, 12.0 mmol) was added, and it heated and stirred at 60 degreeC for 4 hours. Methanol (20 mL) was added to the reaction solution, the precipitated solid was filtered out, and purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (2-5) (904 mg, yield 77%) ).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.15-8.12 (m, 2H), 7.95-7.91 (m, 2H), 7.84 (d, 1H), 7.72-7.68 (m, 2H) , 7.52-7.45 (m, 2H), 6.79-6.75 (m, 2H), 4.42 (q, 2H), 3.12 (s, 6H), 1.43 (t, 3H).

[化39]

Example 5: Synthesis of Compound (2-7) In order to synthesize the compound (2-7), first, the compound (2-6-a) is synthesized via the above-mentioned compound (2-5-a). Then, the compound (2-6-a) and 4-n-octyloxybenzoic acid are dehydrated and condensed to obtain the compound (2-7).

The synthesis of compound (2-6-a) is based on compound (2-5-a) (1.61 g, 5.00 mmol) and potassium hydroxide (0.83 g, 15 mmol) in 1,4-dioxane (7.5 mL), _{Pd 2} (dba) ₃ (91.6 mg, 0.100 mmol) and t-BuXPhos (170 mg, 0.401 mmol) were added to the mixed solution of water (7.5 mL) and heated at 100° C. and stirred for 1.5 hours. Acetic acid (1 mL) was added to the reaction solution to stop the reaction, and the solution was separated with ethyl acetate/water. The organic layer was washed with water, and then washed with saturated brine, and then dried with magnesium sulfate. The evaporator performs concentration. The obtained solid was purified by silica gel column chromatography (ethyl acetate/chloroform=10/90) to obtain compound (2-6-a). (1.02 g, yield 79%).

[化40]

Synthesis of compound (2-7) To the chloroform (10 mL) solution of EDC·HCl (207 mg, 1.05 mmol) and DMAP (13.4 mg, 0.10 mmol), compound (2-6-a) (0.260 g, 1.00 mmol), and 4- N-octyloxybenzoic acid (0.251 g, 1.00 mmol). After stirring at room temperature for 6 hours, the reaction solution was washed with water, and then washed with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by recrystallization (chloroform/methanol) to obtain compound (2-7) (379 mg, yield 77%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.15-8.11 (m, 2H), 7.92-7.88 (m, 2H), 7.81 (dd, 1H), 7.16 (dd, 2H), 7.07 -7.04 (m, 2H), 6.99-6.95 (m, 2H), 6.76-6.72 (m, 2H), 4.04 (t, 2H), 3.09 (s, 6H), 1.82 (tt, 2H), 1.51-1.43 (m, 2H), 1.40-1.24 (m, 8H), 0.89 (t, 3H).

[化41]

Example 6: Synthesis of Compound (2-101) In order to synthesize compound (2-101), compound (2-101-a) is synthesized first. Then, the compound (2-101-a) and the above-mentioned compound (2-5-b) are subjected to Suzuki coupling to obtain the compound (2-101-b). Then, the compound (2-101) is obtained by the transesterification reaction.

Synthesis of compound (2-101-a) To a solution of copper(II) bromide (6.48 g, 29.0 mmol) in acetonitrile (200 mL), add isobutyl nitrite (4.40 mL, 37 mmol) and 2-aminobenzothiazole-6-carboxyl in order Ethyl ester (5.56 g, 25.0 mmol). After stirring at 65°C for 1.5 hours, the reaction solution was cooled to room temperature, and then 0.4 M hydrochloric acid (200 mL) was injected to stop the reaction. After separation with chloroform/water, the organic layer was washed with water, and then washed with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator to obtain compound (2-101-a) (6.56 g) , Yield 92%).

[化42]

The synthesis of compound (2-101-b) was in the solution of compound (2-101-a) (0.631 g, 2.21 mmol) and compound (2-5-b) (0.739 g, 2.00 mmol) in THF (20 mL) Pd ₂ (dba) ₃ (0.0464 g, 0.0507 mmol), and P(t-Bu) ₃ ·HBF ₄ (0.0290 g, 0.100 mmol) were added and stirred. Furthermore, 3 M potassium phosphate aqueous solution (2.0 mL, 6.0 mmol) was added, and it heated and stirred at 60 degreeC for 12 hours. Methanol was added to the reaction solution, and the precipitated solid was filtered out to obtain compound (2-101-b) (0.782 g, yield 87%).

[化43]

The synthesis of compound (2-101) makes compound (2-101-b) (0.450 g, 1.00 mmol), TiO(acac) ₂ (abbreviation for bis(2,4-pentanedionyl) titanium(IV) oxide) A solution of 0.132 g, 0.504 mmol) and n-hexanol (0.512 g, 5.01 mmol) in p-xylene (15 mL) was heated to reflux for 4 hours. Methanol was added to the reaction solution, the precipitated solid was filtered out, and purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (2-101) (0.366 g, yield 72%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.65 (d, 1H), 8.19 (dd, 1H), 8.11 (d, 1H), 8.02 (dd, 1H), 7.97-7.91 (m , 3H), 7.88 (dd, 1H), 6.79-6.75 (m, 2H), 4.38 (t, 2H), 3.13 (s, 6H), 1.82 (tt, 2H), 1.52-1.45 (m, 2H), 1.40-1.34 (m, 4H), 0.92 (t, 3H).

[化44]

Example 7: Synthesis of Compound (2-76) Suzuki coupling of 2-bromo-5-n-butylthienothiazole and the above-mentioned compound (2-5-b) gave compound (2-76).

Compound (2-76) was synthesized in 2-bromo-5-n-butylthienothiazole (0.304 g, 1.10 mmol) and compound (2-5-b) (0.369 g, 1.00 mmol) in THF (10 mL) Pd ₂ (dba) ₃ (0.0367 mg, 0.0400 mmol), and P(t-Bu) ₃ ·HBF ₄ (0.0232 mg, 0.0800 mmol) were added to the solution and stirred. Furthermore, 3 M potassium phosphate aqueous solution (2.0 mL, 6.0 mmol) was added, and it heat-stirred for 16 hours. Methanol was added to the reaction solution, the precipitated solid was filtered out, and purified by silica gel column chromatography (chloroform/toluene = 10/90) to obtain compound (2-76) (0.127 g, yield 29%) .

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 9.95-7.91 (m, 2H), 7.87-7.81 (m, 2H), 7.77 (dd, 1H), 6.95 (s, 1H), 6.78 -6.74 (m, 2H), 3.12 (s, 6H), 2.92 (t, 2H), 1.74 (tt, 2H), 1.44 (tq, 2H), 0.97 (t, 3H).

[化45]

Example 8: Synthesis of Compound (2-102) In order to synthesize the compound (2-102), first, the compound (2-102-b) is synthesized via the above-mentioned compound (2-101-a) and the compound (2-102-a). Next, compound (2-102-d) was synthesized via compound (2-102-c). Compound (2-102-b) and compound (2-102-d) are subjected to Suzuki coupling to obtain compound (2-102).

Synthesis of compound (2-102-a) Compound (2-101-a) (10.3 g, 36.0 mmol), lithium hydroxide monohydrate (7.55 g, 180 mmol), and THF (360 mL) were mixed and cooled to 0°C to 5°C, and added Add water (120 mL) and increase the temperature to room temperature. After stirring at room temperature for 3 days, 1 M hydrochloric acid (200 mL) was injected to stop the reaction. After separation with ethyl acetate/water, the organic layer was washed with water, and then washed with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator to obtain compound (2-102-a) ( 9.02 g, yield 97%).

[化46]

Synthesis of compound (2-102-b) Add n-hexanol (1.61 g, 15.7 mmol) and compound (2-102-a) to the chloroform (150 mL) solution of EDC·HCl (3.02 g, 15.8 mmol) and DMAP (184 mg, 1.50 mmol) in sequence (3.87 g, 15.0 mmol). After stirring at room temperature for 7.5 hours, the reaction solution was washed with water, followed by washing with saturated brine, drying with magnesium sulfate and passing through a short silica gel column, and then concentrating with an evaporator to obtain compound (2- 102-b) (4.44 g, yield 87%).

[化47]

Synthesis of compound (2-102-c) 4-Bromo-3-fluoroaniline (1.90 g, 10.0 mmol), 35% hydrochloric acid (3.0 mL, 34 mmol), and water (25 mL) were mixed and cooled to 0°C to 5°C, and added dropwise to it. A solution of sodium nitrate (0.69 mg, 10.0 mmol) in water (2.5 mL) was used to prepare a diazonium solution. On the other hand, dimethylaniline (1.33 g, 11.0 mmol), sodium acetate (3.28 g, 40.0 mmol), methanol (25.0 mL), and water (12.5 mL) were mixed and cooled to 0°C to 5°C, Add dropwise the total amount of diazonium liquid just prepared. After the dropping, the temperature was raised to normal temperature, and the precipitated solid was separated by filtration to obtain compound (2-102-c) (2.59 g, yield 80%).

[化48]

The synthesis of compound (2-102-d) is in compound (2-102-c) (2.26 g, 7.00 mmol), B ₂ pin ₂ (official name is bis(pinacol ester) diborane; 1.96 g, 7.70) _{PdCl 2} dppf (0.286 g, 0.351 mmol) was added to a 1,4-dioxane (35 mL) solution of potassium acetate (2.06 g, 21.0 mmol) and potassium acetate (2.06 g, 21.0 mmol), followed by heating and stirring at 80°C for 15 hours. The reaction solution was separated with toluene/water, the organic layer was washed with water, and then washed with saturated brine, dried with magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by reprecipitation with chloroform/hexane to obtain compound (2-102-d) (1.74 g, yield 67%).

[化49]

Compound (2-102) was synthesized in compound (2-102-b) (0.378 g, 1.10 mmol) and compound (2-102-d) (0.369 g, 1.00 mmol) in 1,4-dioxane (10 (mL) Pd ₂ (dba) ₃ (0.0231 g, 0.0252 mmol) and P(t-Bu) ₃ ·HBF ₄ (0.0145 g, 0.0500 mmol) were added to the solution and stirred. Furthermore, 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was added, and it heat-stirred at 100 degreeC for 3 hours. Methanol was added to the reaction solution, the precipitated solid was filtered out, purified by silica gel column chromatography using chloroform as the developing solvent, and then purified by reprecipitation with chloroform/methanol to obtain compound (2-102 ) (0.356 g, yield 71%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.68 (d, 1H), 8.57 (dd, 1H), 8.20 (dd, 1H), 8.14 (d, 1H), 7.95-7.91 (m , 2H), 7.83 (dd, 1H), 7.72 (dd, 1H), 6.80-6.76 (m, 2H), 4.38 (t, 2H), 3.14 (s, 6H), 1.82 (tt, 2H), 1.52- 1.45 (m, 2H), 1.40-1.34 (m, 4H), 0.92 (t, 3H).

[化50]

Example 9: Synthesis of Compound (2-77) Suzuki coupling of 2-bromo-5-n-butylthienothiazole and the above-mentioned compound (2-102-d) gave compound (2-77).

Compound (2-77) was synthesized in 1,4-bis 2-bromo-5-n-butylthienothiazole (0.307 g, 1.11 mmol) and compound (2-102-d) (0.370 g, 1.00 mmol) _{Pd 2} (dba) ₃ (0.023 g, 0.0251 mmol), and P(t-Bu) ₃ ·HBF ₄ (0.015 g, 0.0517 mmol) were added to the ethane (10 mL) solution and stirred. Furthermore, 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was added, and it heated and stirred for 4 hours. Methanol was added to the reaction solution, the precipitated solid was filtered out, purified by silica gel column chromatography using chloroform as the developing solvent, and then purified by reprecipitation with chloroform/methanol to obtain compound (2-77 ) (0.317 g, yield 72%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.42 (dd, 1H), 7.92-7.89 (m, 2H), 7.78 (dd, 1H), 7.68 (dd, 1H), 6.97 (s , 1H), 6.79-6.75 (m, 2H), 3.12 (s, 6H), 2.93 (t, 2H), 1.75 (tt, 2H), 1.45 (tq, 2H), 0.97 (t, 3H).

[化51]

Comparative Example 1: Synthesis of Compound (2-1) In order to synthesize compound (2-1), compound (2-1-a) is synthesized first. Then, the compound (2-1-a) and the above-mentioned compound (2-1-c) are subjected to Suzuki coupling to obtain the compound (2-1).

Synthesis of compound (2-1-a) To a solution of EDC·HCl (1.36 g, 7.10 mmol) and DMAP (0.083 g, 0.68 mmol) in dichloromethane (60 mL) was added n-hexanol (0.90 mL, 7.2 mmol), and 4-bromobenzoic acid ( 1.36 g, 6.76 mmol). After stirring at room temperature for 6 hours, the reaction solution was washed with water, followed by washing with saturated brine, drying with magnesium sulfate, and concentrating with an evaporator to obtain compound (2-1-a) (1.70 g) , Yield 88%).

[化52]

Compound (2-1) was synthesized in compound (2-1-a) (285 mg, 1.00 mmol), compound (2-1-c) (457 mg, 1.30 mmol), and potassium acetate (650 mg, 6.63 mmol) _{PdCl 2} dppf (41.0 mg, 0.0502 mmol) was added to the mixed solution of diethylene glycol dimethyl ether (13 mL) and water (2 mL), and heated and stirred at 140°C for 4 hours. After adding THF to the reaction solution and passing it through a short silica gel column, it is concentrated with an evaporator. After washing the obtained solid with methanol/water, it was purified by silica gel column chromatography (chloroform/toluene=20/80) to obtain compound (2-1) (238 mg, yield 55%) .

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.14-8.11 (m, 2H), 7.95-7.89 (m, 4H), 7.76-7.71 (m, 4H), 6.80-6.76 (m, 2H), 4.35 (t, 2H), 3.11 (s, 6H), 1.79 (tt, 2H), 1.51-1.44 (m, 2H), 1.37-1.33 (m, 4H), 0.92 (t, 3H).

[化53]

＜Evaluation＞ Preparation of the composition 1 g of poly(methyl methacrylate) (PMMA, manufactured by Aldrich, Mw=about 120,000) 10% by mass toluene aqueous solution, 4 mg of the compound (2-2) obtained in Example 1, and photo-radical start (Irgacure 369) 6 mg was mixed and heated at 80°C for 30 minutes to prepare composition E1.

Use compound (2-3) to (2-5), compound (2-7), compound (2-101), compound (2-76), compound (2-102), compound (2-77) or compound (2-1) Except for replacing the compound (2-2), compositions E2 to E9 and composition C1 were obtained in the same manner as described above.

Film formation Use a glass substrate as a transparent substrate. The composition E1 was spin-coated on a glass substrate using a spin coater (MS-A100, rotation speed of 1000 rpm, 20 seconds) to form a thin film, and a laminate for evaluation was obtained.

Except for using the composition E2 to E9 or the composition C1 instead of the composition E1, a thin film was formed in the same manner as above, and a laminate for evaluation was obtained, respectively.

Absorbance measurement For the laminate for evaluation obtained in the above, the UV-vis spectrum was measured using a spectrophotometer (manufactured by Varian, CARYUV-vis-NIR Spectrophotometer 5E) at room temperature (25°C) to obtain the maximum absorption wavelength (λ) _max1 ) and absorbance (abs ₁ ) at the maximum absorption wavelength (λ _max1 ). After that, an exposure machine (manufactured by Dainippon Scientific Research, MA-1300A) was used to irradiate the evaluation laminate with 3000 mJ/cm ² of UV light at 25°C, and then the UV-vis spectrum was measured again to obtain the UV irradiation The maximum absorption wavelength (λ _max2 ) and the absorbance (abs ₂ ) at the maximum absorption wavelength (λ _max2 ). Divide the absorbance after UV irradiation (abs ₂ ) by the absorbance before UV irradiation (abs ₁ ) to calculate the absorbance maintenance rate (%). The results are shown in Table 1. When the retention rate of the absorbance of the laminate exceeds 80%, it is regarded as good as a polarizing plate.

[Table 1] Compound Before UV irradiation After UV irradiation Absorbance maintenance rate (%) Absorbance (abs ₁ ) λ _max1 (nm) First suction (abs ₂ ) λmax2 (nm) Example 1 2-2 0.184 439 0.157 439 85.3 Example 2 2-3 0.204 443 0.181 443 88.7 Example 3 2-4 0.172 442 0.164 442 95.4 Example 4 2-5 0.192 460 0.179 460 93.2 Example 5 2-7 0.16 432 0.135 432 84.4 Example 6 2-101 0.458 485 0.409 484 89.3 Example 7 2-76 0.398 480 0.324 478 81.4 Example 8 2-102 0.75 481 0.888 482 91.7 Example 9 2-77 0.718 476 0.659 476 92 Comparative example 1 2-1 0.204 436 0.16 436 78.4

According to Table 1, it can be seen that the ultraviolet (UV) durability of the compound represented by formula (1) is relatively high.

Claims (9)

A compound represented by the following formula (1); R ⁴ -R ³ -Ar ¹ -(-R ¹ -Ar ² -) _n -N=N-Ar ³ -R ² (1) [in formula (1) , Ar ¹ , Ar ² and Ar ³ each independently represent a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic heterocyclic group which may have a substituent, and at least one of ^{Ar 1} and Ar ² Has a fluorine atom as a substituent; n represents an integer of 1 or 2; R ¹ represents a single bond, or is selected from -OC(=O)-, -C(=O)O-, -C≡C-, -CH= At least one group in the group consisting of CH-, -CH=N- and -N=CH-; R ² represents an alkylamino group that may have a polymerizable group, or an alkoxy group that may have a polymerizable group; R ³ represents selected from the group consisting of alkanediyl groups having 4 to 20 carbon atoms, alkanediyloxy groups having 2 to 20 carbon atoms, alkanediyloxycarbonyl groups having 2 to 20 carbon atoms, and alkanediylcarbonyl groups having 2 to 20 carbon atoms At least one group in the group consisting of oxy; R ⁴ represents a polymerizable group or a hydrogen atom; when n is 2, two R ¹ may be the same or different, and two Ar ² may be the same or different ]. The compound of claim 1, wherein in the above formula (1), ^{any one of Ar 1} and Ar ² has 1 or 2 fluorine atoms as a substituent. The compound of claim 1 or 2, wherein in the above formula (1), R ¹ is a single bond. The compound according to any one of claims 1 to 3, wherein in the above formula (1), n is an integer of 1. The compound according to any one of claims 1 to 4, wherein the polymerizable group is a radical polymerizable group. A composition comprising the compound according to any one of claims 1 to 5. A film using the compound of any one of claims 1 to 5 as a forming material. A laminate comprising the film as claimed in claim 7. A display device provided with a film as claimed in claim 7.