Composition, compound, film, laminate, and display device

Abstract

To provide a composition capable of forming a polarization film excellent in light fastness, and dichroic ratio.SOLUTION: A composition contains a compound represented by the formula (1), and a mesomorphism compound including at least one of a polymerizable liquid crystal compound and a mesomorphism polymer compound. n is 1 or 2. Ar1, Ar2 and Ar3 are each independently a 1,4-phenylene group or a bivalent sulfur-containing aromatic heterocyclic group. R1 is an alkoxy group or an alkylamino group. R2 is a -OC(=O)-, -C(=O)- or -N=N-. R3 is a bivalent group constituted by at least one selected from the group consisting of -CH2-, -N(R5)-, -C(=O)-, -O- and -S-. R5 is a hydrogen atom or an aliphatic group. However, a case of bonding tow selected from the group consisting of -N(R5)-, -O- and -S- is excluded. R4 is a hydrogen atom, a polymerizable group or a trialkylsilyloxy group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition, a compound, a film, a laminate, and a display device.

Background Art

[0002] There has been a continuous demand for thinning of displays such as image display panels, and further thinning is required for polarizing plates, polarizers, etc., which are one of the components thereof. In response to such demands, for example, a thin host-guest type polarizer provided with a polarizing film containing a polymerizable liquid crystal compound and a dye compound exhibiting dichroism has been proposed (see, for example, Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In host-guest type polarizers, further performance improvement is required. An object of the present invention is to provide a compound having high light resistance and polarization performance, a composition containing the compound, a film formed from the composition, a laminate including the film, and a light-emitting device including the laminate.

Means for Solving the Problems

[0005] The present invention provides the following [1] to [9]. [1] A composition containing a compound represented by the following formula (1) and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound.

Chemical Formula

Chemical Formula

Chemical formula

Advantages of the Invention

[0006] According to the present invention, it is possible to provide a compound having high light resistance and polarization performance, a composition containing the compound, a film formed from the composition, a laminate including the film, and a display device including the laminate.

Embodiments for Carrying Out the Invention

[0007] In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved. In addition, the content of each component in the composition means the total amount of the plurality of substances corresponding to each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. Furthermore, the upper and lower limits of the numerical ranges described in this specification can be arbitrarily selected and combined with the numerical values exemplified as the numerical ranges. Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0008] <Composition> The composition according to the present embodiment includes a compound represented by the following formula (1) and a liquid crystal compound. The liquid crystal compound includes at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound. The composition is used, for example, as a forming material for a polarizing film. That is, the composition may be a composition for forming a polarizing film. A polarizing plate including a polarizing film obtained using the composition as a forming material can improve, for example, light resistance against visible light and suppress a decrease in absorbance at the maximum absorption wavelength of the compound represented by formula (1). In addition, a polarizing plate including a polarizing film obtained using the composition as a forming material can achieve an excellent dichroic ratio.

[0009] The compound represented by the following formula (1), where Ar 1 has a thioether group at a specific position, can exhibit high light resistance and an excellent dichroic ratio. This can be considered as follows, for example. Generally, the photo-degradation of a compound that is a dichroic dye is considered to start from the excited state of the molecule. When a sulfur (S) atom is introduced at a specific position of the compound, it can quickly return from the excited state to the ground state due to, for example, the heavy atom effect, and it is considered that the light resistance is improved. Also, generally, compounds containing an S atom are used as antioxidants, and it is also speculated that by introducing an S atom at a specific position of the compound, it functions like an antioxidant and the light resistance is improved.

[0010] The dichroic ratio exhibited by the dichroic dye is affected by the orientation with the host liquid crystal. Generally, when a larger S atom than an oxygen (O) atom or the like is introduced into a compound that is a dichroic dye, it is expected that the orientation with the host liquid crystal is inhibited and the dichroic ratio decreases. However, in the present invention where an S atom is introduced at a specific position, an excellent dichroic ratio is achieved. This can be considered, for example, because the orbital overlap between the S atoms and Ar 1 is relatively small, so the interaction between the compound and the host liquid crystal becomes large.

[0011]

Chemical formula

[0012] In formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent a 1,4-phenylene group or a divalent sulfur-containing heterocyclic group which may have a substituent, and preferably represent a 1,4-phenylene group which may have a substituent. Examples of the divalent sulfur-containing heterocyclic group include a benzothiazole diyl group, a thienothiazole diyl group and a thiazole diyl group, and preferably a benzothiazole diyl group.

[0013] Ar 1 , Ar2 and Ar 3 The substituents in may be at least one selected from the group consisting of a halogen atom, a hydroxy group, a methyl group, and a methoxy group, preferably a fluorine atom, a chlorine atom, a hydroxy group, a methyl group, or a methoxy group, more preferably a fluorine atom or a hydroxy group. Ar 1 , Ar 2 and Ar 3 The number of substituents in each of, and is independently, for example, 0, 1, or 2, preferably 0 or 1.

[0014] R 1 represents an alkoxy group which may have a polymerizable group or an alkylamino group which may have a polymerizable group, preferably represents an alkylamino group which may have a polymerizable group. The alkylamino group may be a monoalkylamino group or a dialkylamino group, preferably a dialkylamino group. R 1 is more preferably a dimethylamino group, a diethylamino group, an ethylmethylamino group, a pyrrolidyl group, a piperidyl group, a morpholinyl group, an oxazolidinyl group, a methoxy group, or an ethoxy group.

[0015] R 1 At least one of the hydrogen atoms of the group represented by may be substituted with a polymerizable group. Here, examples of the polymerizable group include a (meth)acrylate group ((meth)acryloyloxy group), a vinylphenyl group, a vinyl group, an epoxy group, etc. The polymerizable group is preferably a radical polymerizable group, and among them, a (meth)acrylate group is preferable. When R 1 has a polymerizable group, the number thereof is, for example, 1 or 2, preferably 1.

[0016] R 2 represents at least one group selected from the group consisting of -OC(=O)-, -C(=O)O-, and -N=N-, preferably -OC(=O)-, -C(=O)O-, or -N=N-, more preferably -OC(=O)- or -N=N-.

[0017] R 3 represents a divalent group composed of at least one selected from the group consisting of -CH 2 -, -N(R 5 ), -C(=O)-, -O- and -S-, provided that the case where two selected from the group consisting of -N(R 5 ), -O- and -S- are bonded is excluded. R 5 represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. When R 5 is an aliphatic group, preferably the number of carbon atoms of R 5 may be 1 to 3. Specific examples of the aliphatic group represented by R 5 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and the like.

[0018] R 3 The divalent group represented by may be composed of, for example, only 1 to 20 methylene groups (-CH 2 -), or may be composed of 1 to 20 methylene groups (-CH 2 -) and a divalent group containing at least one selected from the group consisting of -N(R 5 ), -C(=O)-, -O- and -S-. Examples of the divalent group containing at least one selected from the group consisting of -N(R 5 ), -C(=O)-, -O- and -S- include, for example, -N(R 5 ), -O-, -S-, -C(=O)-, -OC(=O)-, -C(=O)O-, -N(R 5 )C(=O)-, -C(=O)N(R 5 )- and the like.

[0019] R 3The divalent group represented by may be represented by a partial structure of any of the following formulas (1a) to (1h). p and q may each independently be a number from 1 to 20 in each formula, preferably a number from 1 to 12, more preferably a number from 1 to 8. The sum of p and q may be, for example, from 1 to 40, preferably from 1 to 20. Note that both ends of the following partial structures are each bonded to R 4 and S in formula (1).

[0020] [Chemical formula]

[0021] R 3 At least one of the hydrogen atoms of the methylene groups constituting the divalent group represented by may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group or a substituted amino group. Here, examples of the substituted amino group include an amino group substituted with one or two alkyl groups having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N,N-dimethylamino group, an N,N-diethylamino group, etc. Also, at least one of the hydrogen atoms of the methylene groups constituting the divalent group represented by R 3 may be substituted with an alkyl group. The number of carbon atoms of the alkyl group for substitution may be, for example, from 1 to 10, preferably from 1 to 6.

[0022] R 3 The divalent group represented by is preferably an alkanediyl group composed only of methylene groups (-CH 2 -), more preferably an alkanediyl group having 1 to 12 carbon atoms.

[0023] R 4represents a hydrogen atom, a polymerizable group, or a trialkylsilyloxy group. Examples of the polymerizable group include a (meth)acrylate group ((meth)acryloyloxy group), a vinylphenyl group, a vinyl group, an epoxy group, etc. The polymerizable group is preferably a radically polymerizable group, and among them, a (meth)acrylate group is preferred. The alkyl group in the trialkylsilyloxy group may have 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms. The alkyl group may be linear or branched. The three alkyl groups in the trialkylsilyloxy group may be the same or different. R 4 is preferably a hydrogen atom.

[0024] n represents an integer of 1 or 2, and preferably represents 1. When n is 2, the two Rs 2 may be the same as or different from each other, and the two Ars 2 may be the same as or different from each other.

[0025] The compound represented by the formula (1) may have a maximum absorption wavelength (λmax) of, for example, 350 nm or more and 700 nm or less, and preferably 380 nm or more and 650 nm or less. The maximum absorption wavelength is measured at room temperature (for example, 25 °C) for a chloroform solution of the compound represented by the formula (1). The maximum absorption wavelength of the compound represented by the formula (1) can be adjusted to a desired wavelength by appropriately selecting, for example, the skeletal structures of Ar 1 , Ar 2 and Ar 3 , the substituents in Ar 1 , Ar 2 and Ar 3 , n, R 1 and the like.

[0026] Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-55), but the present invention is not limited thereto.

[0027]

Chemical formula

[0028] [Chemical formula]

[0029] [Chemical formula]

[0030] From the viewpoints of light resistance and dichroic ratio, the compound represented by formula (1) is preferably at least one selected from the group consisting of compounds represented by any of formulas (1-1) to (1-32), and more preferably at least one selected from the group consisting of compounds represented by any of formulas (1-1) to (1-17).

[0031] Method for producing the compound represented by formula (1) The compound represented by formula (1) can be produced by appropriately applying a conventionally known synthesis method. Specifically, for the azo structure (-N=N-) in the compound represented by formula (1), for example, referring to the description of the production examples in paragraphs

[0220] to

[0268] of International Publication WO2016 / 136561, an aromatic amine compound having a primary amino group can be converted into a diazonium salt with sodium nitrite or the like, and then constructed by diazo coupling with an aromatic compound. In addition, the azo structure containing a thiazole structure can be constructed, for example, referring to the description in J. Mol. Struct., 2011, 987, 158.

[0032] R 3 The compound represented by the divalent group represented by formula (1a), (1c) to (1h) can be produced as a compound having a desired alkanediyl sulfide group by applying an SN2 substitution reaction to a precursor having a sulfanyl group. The SN2 substitution reaction may appropriately apply conventionally known reaction conditions, or may refer to the description in, for example, J. Am. Chem. Soc., 2008, 130, 13079.

[0033] R 3 The compound represented by the divalent group represented by the formula (1b) can be synthesized, for example, by applying a dehydration condensation reaction using a precursor having a carboxy group and a precursor having a sulfanyl group with reference to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74 (3), 4542-4546. Specifically, for example, the conditions for condensation in the presence of an esterification condensing agent in a solvent can be mentioned.

[0034] When the compound represented by the formula (1) contains -OC(=O)- or C(=O)O-, it can be synthesized, for example, by applying a dehydration condensation reaction using a precursor having a carboxy group and a precursor having a hydroxy group with reference to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74 (3), 4542-4546. Specifically, for example, the conditions for condensation in the presence of an esterification condensing agent in a solvent can be mentioned.

[0035] When the compound represented by the formula (1) contains -NHC(=O)- or C(=O)NH-, it can be synthesized by applying a dehydration condensation reaction using a precursor having a carboxy group and a precursor having an amino group. Specifically, for example, the conditions for condensation in the presence of an amidation condensing agent in a solvent can be mentioned.

[0036] When the compound represented by the formula (1) has a trialkylsilyloxy group, it can be synthesized by using a precursor having a hydroxy group and trialkylsilyl halide and applying the conditions of a general silylation reaction in the presence of a base. The conditions for the SN2 substitution reaction can refer to, for example, J. Am. Chem. Soc., 1972, 94, 6190, etc.

[0037] In the production of the compound represented by formula (1), when the hydroxyl group in the synthetic intermediate inhibits the target reaction, the hydroxyl group can be appropriately protected, and the target reaction can be carried out by removing the protecting group after the reaction. As the protecting group, common ones such as an acetyl group, a silyl group, and a methyl group can be used. Known reaction conditions for protection and deprotection can be used.

[0038] In the production method of the compound represented by formula (1), the reaction time can also be determined by appropriately sampling the reaction mixture during the reaction and confirming the degree of disappearance of the starting compound, the degree of formation of the compound represented by formula (1), etc. by known analytical means such as liquid chromatography and gas chromatography.

[0039] From the reaction mixture after the reaction, the compound represented by formula (1) can be taken out by known methods such as recrystallization, reprecipitation, extraction, and various chromatographies, or by appropriately combining these operations.

[0040] The composition may further contain at least one other dye compound other than the compound represented by formula (1), for example, a dichroic dye. Examples of other dye compounds include azo dyes such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and at least one selected from the group consisting of these is preferred. The composition may contain one other dye compound alone or in combination of two or more. For example, when used as a coating type polarizing plate material, the other dye compound contained in the composition preferably has a maximum absorption wavelength in a wavelength range different from that of the compound represented by formula (1). For example, when used as a coating type polarizing plate material, the composition preferably contains a combination of three or more dichroic dyes including the compound represented by formula (1), and more preferably contains a combination of three or more azo dyes. By containing a combination of three or more dye compounds having different maximum absorption wavelengths in the composition, for example, absorption can be obtained over the entire visible light range by the film formed from the composition.

[0041] When the composition contains other dye compounds, the content thereof is preferably 50 parts by mass or less, more preferably in the range of 0.1 part by mass or more and 10 parts by mass or less, and still more preferably in the range of 0.1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the solid content of the composition. Within the above range, the other dye compounds can be sufficiently dispersed.

[0042] Liquid crystalline compound In addition to the compound represented by the formula (1), the composition contains a liquid crystalline compound containing at least one of a polymerizable liquid crystalline compound and a liquid crystalline polymer compound. The composition may contain only one of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound, or may contain both. Further, the polymerizable liquid crystalline compound and the liquid crystalline polymer compound contained in the composition may each be two or more kinds. By the composition containing at least one of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound, a composition in which the compound represented by the formula (1) is dispersed in the liquid crystalline compound can be formed.

[0043] The liquid crystalline polymer compound may constitute a thermotropic liquid crystal type polymer or a lyotropic liquid crystal type polymer. The liquid crystalline polymer compound is preferably a constituent of a thermotropic liquid crystal type polymer in terms of enabling precise film thickness control.

[0044] As the classification of liquid crystals, depending on the structure of the molecular arrangement in the liquid crystal state, they are classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals. Among them, smectic liquid crystals are preferably used in the application of polarizing films. Therefore, the polymerizable liquid crystalline compound is preferably a polymerizable smectic liquid crystalline compound, and the liquid crystalline polymer compound is preferably a smectic liquid crystalline polymer compound.

[0045] By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity and a polymer compound exhibiting smectic liquid crystallinity, a polarizing film with a high degree of orientation order can be formed. The liquid crystal state exhibited by the polymerizable liquid crystal compound and the liquid crystalline polymer compound is preferably a smectic phase (smectic liquid crystal state), and from the viewpoint of achieving a higher degree of orientation order, a higher-order smectic phase (higher-order smectic liquid crystal state) is more preferable. Here, the higher-order smectic phase means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase. Among these, the smectic B phase, the smectic F phase, and the smectic I phase are more preferable. A polarizing film with a high degree of orientation order gives Bragg peaks derived from higher-order structures such as a hexatic phase and a crystal phase in X-ray diffraction measurement. The Bragg peak means a peak derived from the surface periodic structure of molecular orientation. The periodic interval (order period) of the polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less. The polymerizable liquid crystal compound or the liquid crystalline polymer compound may be a polymerizable smectic liquid crystal compound or a smectic liquid crystalline polymer compound that shows Bragg peaks derived from higher-order structures in X-ray diffraction measurement.

[0046] Polymerizable liquid crystal compound A polymerizable liquid crystal compound is a compound having at least one polymerizable group in the molecule and capable of exhibiting a liquid crystal phase by orientation. The polymerizable liquid crystal compound is preferably a compound capable of exhibiting a liquid crystal phase by orientation alone. The polymerizable group means a functional group that can participate in a polymerization reaction, and is preferably a radical polymerizable group.

[0047] The polymerizable liquid crystal compound is not particularly limited as long as it has at least one polymerizable group and preferably exhibits smectic liquid crystallinity, and known polymerizable liquid crystal compounds can be used. Specifically, for example, a compound represented by the following formula (A) (hereinafter, also referred to as "polymerizable liquid crystal compound (A)") is preferably mentioned as the polymerizable liquid crystal compound.

[0048] [Chemical formula]

[0049] In formula (A), m is an integer from 1 to 3. X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, the plurality of X 1 may be the same as or different from each other. At least three selected from the group consisting of X 1 , X 2 and X 3 represent a divalent hydrocarbon 6-membered ring group. Y 1 , Y 2 , W 1 and W 2 each independently represent a single bond or a divalent linking group. When m is 2 or 3, Y 1 may be the same as or different from each other. V 1 and V 2 each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. At least one of -CH 2 - constituting the alkanediyl group may be substituted with -O-, -CO-, -S- or -NH-. U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.

[0050] Examples of the divalent aromatic group in X 1 , X 2 and X 3 include a 1,4-phenylene group, a 1,4-naphthylene group (naphthalene-1,4-diyl group), etc. Examples of the divalent alicyclic hydrocarbon group include a cyclohexane-1,4-diyl group, etc. X 1 , X 2 and X 3At least one of the divalent aromatic group and the divalent alicyclic hydrocarbon group in [the compound] may have a substituent. Examples of the substituent include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, and n-butyl group, cyano group, halogen atom, and the like. At least one of the -CH 2 - constituting the divalent alicyclic hydrocarbon group may be substituted with -O-, -S- or -NR-. Here, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

[0051] X 1 、X 2 およびX 3 Examples of the divalent hydrocarbon 6-membered ring group in [the compound] include a 1,4-phenylene group which may have a substituent, a cyclohexane-1,4-diyl group which may have a substituent, and the like.

[0052] X 1 、X 2 およびX 3 The divalent aromatic group in [the compound] is preferably a 1,4-phenylene group which may have a substituent, more preferably an unsubstituted 1,4-phenylene group. The divalent alicyclic hydrocarbon group is preferably a cyclohexane-1,4-diyl group which may have a substituent, more preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and even more preferably an unsubstituted trans-cyclohexane-1,4-diyl group.

[0053] Y 1 およびY 2 each independently represents a single bond or a divalent linking group. The divalent linking group is, for example, at least one selected from the group consisting of -CH 2 CH 2 -, -CH 2 O-, -(C=O)O-, -O(C=O)O-, -N=N-, -CR a =CR b -, -C≡C- and -CR a =N-. Here, R a およびR b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y1 is preferably -CH 2 CH 2 -, -(C=O)O- or a single bond. Y 2 is preferably -CH 2 CH 2 - or -CH 2 O-.

[0054] W 1 and W 2 each independently represent a single bond or a divalent linking group. The divalent linking group is, for example, at least one selected from the group consisting of -O-, -S-, -(C=O)O- and -O(C=O)O-. W 1 and W 2 each independently are preferably a single bond or -O-.

[0055] V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms. At least one of the -CH 2 - constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or -NH-.

[0056] V 1 and V 2 Examples of the alkanediyl group represented by include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,1-diyl group and an icosane-1,20-diyl group. V 1 and V 2 are preferably an alkanediyl group having 2 to 12 carbon atoms, more preferably an alkanediyl group having 6 to 12 carbon atoms.

[0057] Examples of the substituent that an optionally substituted C1-C20 alkanediyl group may have include a cyano group and a halogen atom. The alkanediyl group is preferably an alkanediyl group having no substituent, more preferably a linear alkanediyl group having no substituent.

[0058] U 1 and U 2 each independently represents a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group. U 1 and U 2 are preferably polymerizable groups. U 1 and U 2 are preferably both polymerizable groups, and more preferably both radical polymerizable groups. U 1 The polymerizable group represented by U 2 and the polymerizable group represented by U 1 and U 2 may be different from each other, but are preferably the same type of group. U 1 and U 2 Examples of the polymerizable group in U

[0059] Specific examples of the polymerizable liquid crystal compound (A) include compounds represented by the following formulas (A-1) to (A-17). When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably in the trans form.

[0060]

Chemical formula

[0061]

Chemical formula

[0062] [Chemical formula]

[0063] Among them, the polymerizable liquid crystal compound (A) is preferably at least one selected from the group consisting of compounds represented by any of formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17). The polymerizable liquid crystal compound (A) may be used alone or in combination of two or more.

[0064] The polymerizable liquid crystal compound (A) can be produced, for example, by the methods described in known literatures such as Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156.

[0065] Liquid crystalline polymer compound The liquid crystalline polymer compound may be a compound obtained by polymerizing the polymerizable liquid crystal compound (hereinafter also referred to as a polymer of the polymerizable liquid crystal compound), or may be other liquid crystalline polymer compounds, and preferably is a polymer of the polymerizable liquid crystal compound.

[0066] Polymers of the polymerizable liquid crystal compounds may use two or more of the polymerizable liquid crystal compounds as raw material monomers. Further, the polymers of the polymerizable liquid crystal compounds may contain other monomers other than the polymerizable liquid crystal compounds as raw material monomers.

[0067] The content ratio of the polymerizable liquid crystal compound in the polymer of the polymerizable liquid crystal compound is usually 1 mol% or more and 100 mol% or less with respect to the total amount of the structural units derived from the polymerizable liquid crystal compound constituting the polymer of the polymerizable liquid crystal compound. From the viewpoint of enhancing the orientation of the polymer of the polymerizable liquid crystal compound, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0068] Examples of the other liquid crystalline polymer compounds include polymer compounds having a liquid crystalline group. For example, as the polymer compound serving as the main skeleton, there are polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers, polyvinyl alcohol; polymethacrylic acid esters; polyacrylic acid esters; etc. These polymer compounds have a liquid crystalline group. Among them, polymethacrylic acid esters and polyacrylic acid esters having a liquid crystalline group are preferred.

[0069] The other liquid crystalline polymer compounds may contain two or more types of liquid crystalline groups. The liquid crystalline group may be contained in the main chain of the polymer compound serving as the main skeleton, may be contained in the side chain of the polymer compound serving as the main skeleton, or may be contained in both the main chain and the side chain of the polymer compound serving as the main skeleton. Examples of the liquid crystalline group include a group formed by removing one hydrogen atom from a compound having at least two hydrocarbon six-membered ring structures, or a group formed by removing two hydrogen atoms from the compound.

[0070] The content ratio of the liquid crystalline group in the other liquid crystalline polymer compounds is usually 1 mol% or more and 100 mol% or less with respect to the total amount of the structural units constituting the polymer compound serving as the main skeleton of the other liquid crystalline polymer compounds. From the viewpoint of enhancing the orientation of the other liquid crystalline polymer compounds, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0071] In a composition, when combining two or more types of polymerizable liquid crystal compounds, it is preferable that at least one of them is a polymerizable liquid crystal compound (A), and more preferably two or more of them are polymerizable liquid crystal compounds (A). By combining two or more types of polymerizable liquid crystal compounds, it may be possible to temporarily maintain a liquid crystal phase even at a temperature below the liquid crystal-crystalline phase transition temperature. The total content of the polymerizable liquid crystal compound (A) contained in the composition is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total mass of all the polymerizable liquid crystal compounds in the composition, and all the polymerizable liquid crystal compounds may be polymerizable liquid crystal compound (A). When the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compounds are likely to be arranged with a high degree of orientation order, and by aligning the compound represented by the formula (1) along with them, a polarizing film having excellent polarization performance can be obtained.

[0072] From the viewpoint of enhancing the orientation of the polymerizable liquid crystal compound and the liquid crystalline polymer compound, the total content ratio of the polymerizable liquid crystal compound and the liquid crystalline polymer compound in the composition is, for example, 50 parts by mass or more, preferably 70 parts by mass or more and 99.9 parts by mass or less, more preferably 70 parts by mass or more and 99.5 parts by mass or less, still more preferably 80 parts by mass or more and 99 parts by mass or less, particularly preferably 80 parts by mass or more and 94 parts by mass or less, and even more preferably 80 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the solid content of the composition.

[0073] The total content of the compound represented by the formula (1) in the composition is usually 0.1 part by mass or more and 50 parts by mass or less, preferably 0.1 part by mass 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, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. When the total content of the compound represented by the formula (1) with respect to the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound is 50 parts by mass or less, there is a tendency that the orientation disorder of the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the compound represented by the formula (1) is small, and a polarizing film having a high degree of orientation order can be obtained.

[0074] Polymer compound In addition to the compound represented by the formula (1) and the polymerizable liquid crystal compound, the composition may further contain a polymer compound. When the composition contains a polymer compound, the compound represented by the formula (1) may be more easily dispersed in the composition. The polymer compound that the composition can contain is not particularly limited as long as it can disperse the compound represented by the formula (1). From the viewpoint of easily uniformly dispersing the compound represented by the formula (1), acrylic polymers such as polymethyl methacrylate (PMMA) are preferred. Also, the polymer compound may be a polymer compound obtained by polymerizing the above-mentioned polymerizable liquid crystal compound. 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.

[0075] When the composition contains a polymer compound, its content can be appropriately selected according to the purpose and the like. The content of the polymer compound is preferably 10 parts by mass or less, more preferably in the range of 5.0 parts by mass or less, and still more preferably in the range of 3.0 parts by mass or less, based on 100 parts by mass of the solid content of the composition.

[0076] The composition preferably further contains a liquid medium such as a solvent and a polymerization initiator, and may further contain a photosensitizer, a polymerization inhibitor, a leveling agent, etc. as required.

[0077] Solvent The solvent is preferably a solvent that can completely dissolve the compound represented by formula (1), the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the polymer compound. Further, it is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.

[0078] Examples of the solvent include alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, chlorine-containing solvents, etc. These solvents may be used alone or in combination of two or more.

[0079] 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 based on the total amount of the composition. In other words, the content ratio of the solid content in the composition is preferably 2% by mass or more and 50% by mass or less. When the solid content is 50% by mass or less, the viscosity of the composition becomes low, and the film obtained from the composition, for example, the thickness of the film becomes substantially uniform, and the film is less likely to have unevenness. The content ratio of such a solid content can be determined in consideration of the thickness of the film to be produced.

[0080] Polymerization initiator The polymerization initiator is a compound that can initiate the polymerization reaction of the polymerizable liquid crystal compound. The polymerization initiator is preferably a photoinitiator in that it can initiate the polymerization reaction under lower temperature conditions. Specifically, photoinitiators that can generate active radicals or acids by the action of light are included, and among them, photoinitiators that generate radicals by the action of light are preferred.

[0081] Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts. The polymerization initiator can be appropriately selected from known polymerization initiators according to the purpose and the like. Further, the polymerization initiator can be used alone or in combination of two or more.

[0082] When the composition contains a polymerization initiator, its content may be appropriately determined according to the type and amount of the polymerizable liquid crystal compound contained in the composition. The content of the polymerization initiator is, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more, and for example, 30% by mass or less, 10% by mass or less, or 8% by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound. Also, the content of the polymerization initiator 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 even more preferably 0.1 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound. When the content of the polymerizable initiator is within the above range, polymerization can be carried out without disturbing the alignment of the polymerizable liquid crystal compound.

[0083] Photosensitizer When the composition contains a photoinitiator, the composition may preferably contain at least one kind of photosensitizer. When the composition contains a photoinitiator and a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound tends to be more promoted. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone; anthracene compounds such as anthracene and alkoxy group-substituted anthracene; phenothiazine and rubrene; and the like. The photosensitizer can be used alone or in combination of two or more.

[0084] When the composition contains a photosensitizer, the content of the photosensitizer in the composition may be appropriately determined according to the type and amount of the photoinitiator and the polymerizable liquid crystal compound. The content of the photosensitizer in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound.

[0085] Polymerization inhibitor The composition may contain at least one polymerization inhibitor. Examples of the polymerization inhibitor include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (e.g., butylcatechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols; and the like. By including a polymerization inhibitor in the composition, the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.

[0086] When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition 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 and 8 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound.

[0087] Leveling agent The composition may contain at least one leveling agent. The leveling agent has a function of adjusting the fluidity of the composition and making the coating film obtained by applying the composition flatter. Specifically, surfactants can be mentioned as the leveling agent. As the leveling agent, at least one selected from the group consisting of a leveling agent mainly composed of a polyacrylate compound and a leveling agent mainly composed of a fluorine atom-containing compound is preferable. The leveling agent can be used alone or in combination of two or more.

[0088] When the composition contains a leveling agent, the content of the leveling agent is preferably 0.05 part by mass or more and 5 parts by mass or less, more preferably 0.05 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal compound and the liquid crystalline polymer compound, and unevenness is less likely to occur, and a smoother film, for example, a polarizing film, tends to be obtained.

[0089] Antioxidant The composition may contain an antioxidant. The antioxidant is not particularly limited as long as the composition can exhibit the effects of the present invention, and known antioxidants can be used. From the viewpoint of having a high inhibitory effect on the photo-degradation of the compound represented by the formula (1), a so-called primary antioxidant having an action of capturing radicals and preventing auto-oxidation is preferable. Therefore, it is more preferable that the antioxidant contained in the composition is at least one selected from the group consisting of phenolic compounds, alicyclic alcohol compounds, and amine compounds. The antioxidant may be used alone or in combination of two or more kinds.

[0090] The content of the antioxidant in the composition is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the composition. When the content of the antioxidant is at least the above lower limit value, the photo-degradation of the compound represented by the formula (1) can be more effectively suppressed. Further, when the content of the antioxidant is at most the above upper limit value, it is difficult to more disorder the alignment of the polymerizable liquid crystal compound, and a higher inhibitory effect on the photo-degradation of the compound represented by the formula (1) can be expected.

[0091] The composition may contain other additives other than the above. Examples of other additives include mold release agents, stabilizers, colorants such as bluing agents, flame retardants, lubricants, and the like. When the composition contains other additives, the content of the other additives is preferably more than 0% and 20% by mass or less, more preferably more than 0% and 10% by mass or less based on the solid content of the composition.

[0092] The composition can be produced by a conventionally known method for preparing a composition. For example, it can be prepared by mixing and stirring the compound represented by the formula (1), a liquid crystal compound, and, if necessary, additives such as an antioxidant and a leveling agent.

[0093] <Compound> The compound according to this embodiment is represented by the following formula (2).

[0094] [Chemical formula]

[0095] In formula (2), Ar 11 , Ar 12 and Ar 13 each independently represent a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group which may have at least one selected from the group consisting of a halogen atom, a hydroxy group, a methyl group and a methoxy group as a substituent. The details of Ar 11 , Ar 12 and Ar 13 are the same as those of Ar 1 , Ar 2 and Ar 3 in formula (1), respectively, and the preferred embodiments are also the same.

[0096] R 11 represents an alkoxy group which may have a polymerizable group or an alkylamino group which may have a polymerizable group. R 12 represents -OC(=O)- or -C(=O)O-. R 13 represents a divalent group composed of at least one selected from the group consisting of -CH 2 -, -N(R 15 )-, -C(=O)-, -O- and -S-. R 15 represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. However, the case where two selected from the group consisting of -N(R 15 )-, -O- and -S- are bonded is excluded. R 14 represents a hydrogen atom, a polymerizable group or a trialkylsilyloxy group. The details of R 11 , R 13 and R 14 are the same as those of R 1 , R 3 and R 4 in formula (1), respectively, and the preferred embodiments are also the same.

[0097] Moreover, the compound according to this embodiment may be represented by the following formula (3).

[0098] [ka]

[0099] In formula (3), Ar 21 , Ar 22 and Ar 23 each independently represents a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group. 21 , Ar 22 and Ar 23 At least one of Ar has 1 to 3 substituents selected from the group consisting of halogen atoms, hydroxy groups, methyl groups, and methoxy groups. 21 , Ar 22 and Ar 23 For details, see Ar 21 , Ar 22 and Ar 23 In formula (1), except that at least one of Ar 1 , Ar 2 and Ar 3 The same applies to each of the above, and preferred embodiments are also the same.

[0100] R 21 R represents an alkoxy group which may have a polymerizable group, or an alkylamino group which may have a polymerizable group. 23 -CH 2 -, -N(R 25 R represents a divalent group consisting of at least one selected from the group consisting of -C(=O)-, -O-, and -S-. 25 represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. 25 )-, -O-, and -S- are not included. 24 R represents a hydrogen atom, a polymerizable group, or a trialkylsilyloxy group. 21 , R 23 and R 24The details of R in formula (1) 1 and R 3 and R 4 are the same as each of them, and the preferred embodiments are also the same.

[0101] <Film> The film according to this embodiment may be a film containing the compound represented by formula (1) as a forming material, or may be a film obtained from a composition containing the compound represented by formula (1) and a liquid crystalline compound as a forming material. The film made of the composition may be formed by applying the composition to a substrate and forming a film. Further, when the composition contains a polymerizable liquid crystalline compound, the film containing a cured product obtained by polymerizing the polymerizable liquid crystalline compound may be formed by applying the composition to a substrate, forming a film, and then polymerizing and curing the polymerizable liquid crystalline compound.

[0102] The composition can form a film excellent in light resistance and having a high absorbance retention rate, for example, a polarizing film. Therefore, the film according to this embodiment includes a polarizing film formed from a composition containing the compound represented by formula (1) and a liquid crystalline compound, and having an excellent absorbance retention rate. Further, the composition can form a film having a high degree of orientation order, for example, a polarizing film. Therefore, the film according to this embodiment includes a polarizing film formed from a composition containing the compound represented by formula (1) and a liquid crystalline compound, and having a high degree of orientation order. A film having a high degree of orientation order can exhibit, for example, an excellent dichroic ratio.

[0103] Here, in a polarizing film having a high degree of orientation order, Bragg peaks derived from higher-order structures such as a hexatic phase and a crystal phase are obtained in X-ray diffraction measurement. Therefore, in the polarizing film formed from the composition, it is preferable that the polymerizable liquid crystalline compound or the liquid crystalline polymer compound is oriented so as to show a Bragg peak in X-ray diffraction measurement, and it is more preferable that it is a "horizontal orientation" in which the molecules of the polymerizable liquid crystalline compound or the liquid crystalline polymer compound are oriented in the direction of absorbing light. The high degree of orientation order showing a Bragg peak can be realized by controlling the type of the polymerizable liquid crystalline compound or the liquid crystalline polymer compound used, the amount of the compound represented by formula (1), and the like.

[0104] Regarding the compound represented by formula (1) and the liquid crystalline compound that constitute the composition used for forming the film, they are as described above.

[0105] The film can be produced, for example, by a method including the following steps. Step A: Forming a coating film of a composition containing the compound represented by formula (1), a liquid crystalline compound, and a solvent. Step B: Removing at least a part of the solvent from the coating film. Step C: After raising the temperature to a temperature equal to or higher than the temperature at which the liquid crystalline compound undergoes a phase transition to the liquid phase, lowering the temperature to cause the liquid crystalline compound to undergo a phase transition to the smectic phase (smectic liquid crystal state), and Step D: Optionally, polymerizing the polymerizable liquid crystalline compound while maintaining the smectic phase (smectic liquid crystal state).

[0106] The formation of the coating film of the composition can be carried out, for example, by applying the composition onto a substrate, an alignment film described later, etc. Also, the composition may be directly applied onto a retardation film constituting a polarizing plate or other layers.

[0107] The substrate is usually a transparent substrate. When the substrate is not installed on the display surface of the display element, for example, when a laminate obtained by removing the substrate from the film is installed on the display surface of the display element, the substrate does not have to be transparent. The transparent substrate means a substrate having transparency that can transmit light, particularly visible light, and the transparency refers to a property in which the transmittance for light rays in the wavelength range of 380 nm or more and 780 nm or less is 80% or more. Specific examples of the transparent substrate include a light-transmissive resin substrate.

[0108] Examples of the resin constituting the light-transmitting resin substrate include polyolefin; cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose ester; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketone; polyphenylene sulfide; and polyphenylene oxide. From the viewpoints of easy availability and transparency, polyethylene terephthalate, polymethacrylate, cellulose ester, cyclic olefin resin, or polycarbonate is preferred.

[0109] The properties required for the substrate vary depending on the film configuration, but usually, a substrate with as small a retardation as possible is preferred. Examples of substrates with as small a retardation as possible include cellulose ester films having no retardation such as Zero Tack (Konica Minolta Opto Inc.) and Z Tack (Fuji Film Co., Ltd.). Also, an unstretched cyclic olefin resin substrate is preferred. Hard coat treatment, antireflection treatment, antistatic treatment, etc. may be performed on the surface of the substrate without the film laminated.

[0110] 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, more preferably 20 μm or more and 100 μm or less. If it is above the lower limit value, a decrease in strength is suppressed, and the processability tends to be good.

[0111] Examples of the method for applying the composition to the substrate or the like include known methods such as coating methods such as spin coating method, extrusion method, gravure coating method, die coating method, bar coating method, applicator method, and printing methods such as flexo method.

[0112] Next, a dry coating film is formed by removing at least a part of the solvent contained in the coating film obtained from the composition by drying or the like. Further, when the polymerizable liquid crystal compound is contained in the coating film, the dry coating film is formed by performing drying under the condition that the polymerizable liquid crystal compound does not polymerize. Examples of the drying method of the coating film include natural drying method, ventilation drying method, heat drying, vacuum drying method, and the like.

[0113] Furthermore, in order to cause the liquid crystal compound to undergo a phase transition to the liquid phase, after raising the temperature to a temperature equal to or higher than the temperature at which the liquid crystal compound undergoes a phase transition to the liquid phase, the temperature is lowered to cause the liquid crystal compound to undergo a phase transition to the smectic phase (smectic liquid crystal state). Such a phase transition may be carried out after removing the solvent in the coating film, or may be carried out simultaneously with the removal of the solvent.

[0114] When the composition contains a polymerizable liquid crystal compound, a film containing a cured product of the polymerizable liquid crystal compound is formed by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound. As the polymerization method, a photopolymerization method is preferable. In photopolymerization, the light irradiated on the dry coating film is appropriately selected according to the type of the photoinitiator contained in the dry coating film, the type of the polymerizable liquid crystal compound (particularly, the type of the polymerizable group possessed by the polymerizable liquid crystal compound), and the amount thereof. Specific examples thereof include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and active electron beams. Among them, ultraviolet light is preferable in terms of easy control of the progress of the polymerization reaction and the availability of widely used photopolymerization apparatuses in the art. It is preferable to select the types of the polymerizable liquid crystal compound and the photoinitiator contained in the composition so that photopolymerization is possible by ultraviolet light. Further, during polymerization, the polymerization temperature can also be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. By adopting such a cooling means, if the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature, even if a substrate with relatively low heat resistance is used, a film can be appropriately formed. During photopolymerization, a patterned film can also be obtained by performing masking, development, or the like.

[0115] Examples of the light source for the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources that emit light in a wavelength range of 380 nm or more and 440 nm or less, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

[0116] The ultraviolet irradiation intensity is usually 10 mW / cm 2 or more and 3,000 mW / cm 2 or less. The ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is usually 0.1 second or more and 10 minutes or less, preferably 0.1 second or more and 5 minutes or less, more preferably 0.1 second or more and 3 minutes or less, and even more preferably 0.1 second or more and 1 minute or less. When irradiated once or a plurality of times with such an ultraviolet irradiation intensity, the integrated light amount is 10 mJ / cm 2 or more and 3,000 mJ / cm 2 or less, which is preferable.

[0117] By performing photopolymerization, the polymerizable liquid crystal compound polymerizes while maintaining a liquid crystal state of a smectic phase, preferably a higher-order smectic phase, and a film is formed. The film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase has an advantage of high polarization performance as compared with a conventional host-guest type polarizing film, that is, a film composed of a nematic liquid crystal state. Further, it also has an advantage of excellent strength as compared with a film coated with only a dichroic dye or a lyotropic liquid crystal.

[0118] The thickness of the film can be appropriately selected according to the display device or the like to be applied, preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and even more preferably 1 μm or more and 3 μm or less.

[0119] When the film is used as a polarizing film, it is preferably formed on an alignment film. The alignment film has an alignment regulating force for aligning a polymerizable liquid crystal compound and a liquid crystalline polymer compound in a desired direction. As the alignment film, a composition containing a liquid crystalline compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound is preferably used, which has solvent resistance that does not dissolve by coating or the like, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound. Examples of such alignment films include alignment films containing an alignment polymer, photo-alignment films, and groove alignment films having an uneven pattern or a plurality of grooves on the surface. From the viewpoint of the accuracy of the alignment angle and the quality, a photo-alignment film is preferred.

[0120] <Laminate> The laminate according to this embodiment may include a film containing the compound represented by formula (1) as a forming material, or may include a film formed from a composition containing the compound represented by formula (1) and a liquid crystalline compound as a forming material. The laminate may include a substrate and a film containing the compound represented by formula (1) disposed on the substrate as a forming material, or may include a substrate, an alignment film disposed on the substrate, and a film formed from the compound represented by formula (1) disposed on the alignment film as a forming material. The film containing the compound represented by formula (1) as a forming material may constitute a polarizing film. Further, the substrate may be a retardation film. The laminate can constitute, for example, a polarizing plate. The laminate can be manufactured, for example, by forming a film on a substrate according to the above-described film manufacturing method.

[0121] From the viewpoints of the flexibility and visibility of the display device, the thickness of the laminate is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and still more preferably 25 μm or more and 100 μm or less.

[0122] When the laminate includes a retardation film as a substrate, the thickness of the retardation film can be appropriately selected according to the applicable display device.

[0123] <Display device> The display device of this embodiment includes the laminate, and the laminate may be a polarizing plate. The display device can be obtained, for example, by bonding a laminate as a polarizing plate to the surface of the display device via an adhesive layer. A display device is a device having a display element and includes a light-emitting element or a light-emitting device as a light source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (e.g., a field emission display device (FED), a surface field emission display device (SED)), an electronic paper (a display device using an electrophoretic element, etc.), a plasma display device, a projection display device (e.g., a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD)), and a piezoelectric ceramic display, etc. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device, etc. These display devices may be display devices for displaying two-dimensional images or may be stereoscopic display devices for displaying three-dimensional images. In particular, as the display device, an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.

Example

[0124] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. Note that "normal temperature" and "RT" are 23°C.

[0125] Example 1: Synthesis of Compound 1-1 Compound 1-1 was synthesized according to the following scheme.

[0126]

Chemical formula

[0127] Synthesis of Compound (1-1-a) 4-Aminobenzenethiol (3.96 g, 31.6 mmol), sodium hydroxide (1.56 g, 3.91 mmol), 1-bromopentane (4.1 mL, 31.6 mL), and acetone (300 mL) were mixed and heated under reflux for 7 hours. After allowing to cool to room temperature, water was added, and the organic layer was extracted with chloroform. The obtained organic layer was dried over magnesium sulfate and concentrated. The crude reaction product was purified by silica gel column chromatography using chloroform and hexane as the developing solvents to obtain compound (1-1-a) (4.94 g, yield 80%).

[0128]

Chemical formula

[0129] Synthesis of aniline protecting group Sodium bisulfite (78.0 g, 750 mmol) and water (150 mL) were mixed, heated to 70 °C, and an aqueous solution of 37% formaldehyde (44.3 mL, 600 mmol) was added dropwise. After complete addition of the total amount, it was cooled to 40 °C, and aniline (45.7 mL, 500 mmol) was added dropwise over 1 hour and stirred for 9 hours. It was cooled to 0 °C, and the precipitated solid was filtered off to obtain the aniline protecting group (96.0 g, yield 100%).

[0130]

Chemical formula

[0131] Synthesis of compound (1-1-b) Compound (1-1-a) (0.78 g, 4.0 mmol), 35% hydrochloric acid (1.25 g), acetic acid (4.8 mL), and water (7.2 mL) were mixed and cooled from 0 °C to 5 °C. A solution of sodium nitrite (0.28 mg, 4.0 mmol) in water (0.5 mL) was added dropwise thereto, and the diazo solution was prepared by stirring for 30 minutes. Aniline protecting group (1.26 g, 4.0 mmol), sodium acetate (1.31 g, 16.0 mmol), methanol (8.0 mL), and water (4.0 mL) were mixed and cooled from 0 °C to 5 °C, and the entire amount of the diazo solution prepared earlier was added dropwise. After the addition was complete, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound (1-1-b) (0.97 g, yield 58%)

[0132]

Chemical formula

[0133] Synthesis of compound (1-1-c) Compound (1-1-b) (0.95 g, 2.3 mmol) and sodium hydroxide (2.50 g, 0.63 mmol) were dissolved in water (50 mL) and stirred at 70 °C for 4 hours. The obtained solid was filtered off to obtain compound (1-1-c). It was used directly in the next reaction without further purification.

[0134]

Chemical formula

[0135] Synthesis of compound (1-1) The compound (1-1-c) (0.78 g, 2.6 mmol) obtained above, 35% hydrochloric acid (0.83 g, 7.8 mmol), acetic acid (9.4 mL), and water (4.7 mL) were mixed and cooled from 0 °C to 5 °C, and a solution of sodium nitrite (0.36 g, 5.2 mmol) in water (0.7 mL) was added dropwise thereto, and the mixture was stirred for 30 minutes to prepare a diazo solution. N,N-dimethylaniline (0.48 g, 3.9 mmol), sodium acetate (0.86 g, 10.4 mmol), methanol (5.2 mL), and water (2.6 mL) were mixed and cooled from 0 °C to 5 °C, and the entire amount of the diazo solution prepared earlier was added dropwise. After the addition was complete, the temperature was raised to room temperature, and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (1-1) (0.067 g, yield 7%).

[0136] [Chemical formula]

[0137] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 8.01 (d, 2H), 7.97 (d, 2H), 7.92 (d, 2H), 7.87 (d, 2H), 7.39 (d, 2H), 6.77 (d, 2H), 3.11 (s, 6H), 3.02 (t, 2H), 1.73 (quin, 2H), 1.50 - 1.42 (m, 2H), 1.42 - 1.34 (m, 2H), 0.92 (t, 3H)

[0138] Example 2: Synthesis of Compound (1 - 2) Compound (1 - 2) was synthesized according to the following scheme.

[0139] [Chemical formula]

[0140] Synthesis of Compound (1 - 2 - a) 3,4 - Difluoronitrobenzene (6.36 g, 40.0 mmol), 1 - butanethiol (3.30 g, 36.6 mmol), and potassium carbonate (11.06 g, 80.0 mmol) were dissolved in DMF (100 mL) and stirred at 90 °C for 3 hours. After returning to room temperature, water was added and the organic layer was extracted with chloroform. The obtained organic layer was dried over sodium sulfate and then concentrated to obtain Compound (1 - 2 - a) (7.18 g, yield 86%).

[0141] [Chemical formula]

[0142] Synthesis of Compound (1 - 2 - b) Compound (1-2-a) (1.16 g, 5.05 mmol) and sodium disulfide nonahydrate (1.96 g, 8.0 mmol) were dissolved in a mixed solvent of water (10 mL) and ethanol (10 mL), and stirred at 90 °C for 5 hours. After returning to room temperature, water (100 mL) was added to precipitate a solid, which was filtered off to obtain compound (1-2-b) (0.65 g, yield 65%).

[0143]

Chemical formula

[0144] Synthesis of Compound (1-2-c) Compound (1-2-b) (0.194 g, 1.0 mmol), 35% hydrochloric acid (0.3 mL, 3.0 mmol), and water (2 mL) were mixed and cooled from 0 °C to 5 °C, and a solution of sodium nitrite (0.075 g, 1.1 mmol) in water (0.2 mL) was added dropwise thereto. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 0 °C to 5 °C to prepare a diazo solution. The aniline protecting group (0.32 g, 1.5 mmol), sodium acetate (0.33 g, 4.0 mmol), and water (4.0 mL) were mixed and cooled from 0 °C to 5 °C, and the entire amount of the diazo solution prepared above was added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 4 hours, then raised to 50 °C and stirred for 1 hour. After returning to room temperature, sodium hydroxide (1.0 g, 25.0 mmol) was added, the temperature was raised to 90 °C and stirred for 2 hours. After cooling to room temperature, the precipitated solid was filtered off and further washed with water to obtain compound (1-2-c) (0.26 g, yield 88%).

[0145]

Chemical formula

[0146] Synthesis of Compound (1-2) Compound (1-2-c) (0.26 g, 0.86 mmol), 35% hydrochloric acid (0.25 mL), acetic acid (3.0 mL) and water (3.0 mL) were mixed and cooled from 0 °C to 5 °C. A solution of sodium nitrite (0.074 g, 1.1 mmol) in water (0.2 mL) was added dropwise thereto, and the mixture was stirred for 30 minutes to prepare a diazo solution. N,N-Dimethylaniline (0.18 g, 1.5 mmol), sodium acetate (0.33 g, 4.0 mmol), methanol (4.0 mL), and water (2.0 mL) were mixed and cooled from 0 °C to 5 °C. The entire amount of the diazo solution prepared above was added dropwise. After completion of the addition, the temperature was raised to room temperature, and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain Compound (1-2) (0.039 g, yield 10%).

[0147]

Chemical formula

[0148] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 8.01 (t, 2H), 7.99 (t, 2H), 7.92 (d, 2H), 7.75 (dd, 1H), 7.63 (dd, 1H), 7.43 (t, 1H), 6.77 (d, 2H), 3.12 (s, 6H), 3.02 (t, 2H), 1.70 (quin, 2H), 1.55 - 1.46 (m, 2H), 0.96 (t, 3H)

[0149] Example 3: Synthesis of Compound (1-9) 4-Dimethylaminoazobenzene-4'-carboxylic acid (0.27 g, 1.0 mmol), 4-(methylthio)phenol (0.17 g, 1.2 mmol), 4-dimethylaminopyridine (0.012 g, 0.10 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.29 g, 1.50 mmol) were dissolved in tetrahydrofuran (10 mL) and stirred at room temperature for 10 hours. Water (20 mL) was added, and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (1-9) (0.31 g, yield 65%).

[0150]

Chemical formula

[0151] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 8.29 (d, 2H), 7.92 (d, 4H), 7.34 (d, 2H), 7.18 (d, 2H), 6.77 (d, 2H), 3.12 (s, 6H), 2.51 (s, 3H)

[0152] Example 4: Synthesis of Compound (1-10) Compound 1-10 was synthesized according to the following scheme.

[0153]

Chemical formula

[0154] Synthesis of Compound (1-10-a) 4-Amino-2-fluorobenzoic acid (7.76 g, 50.0 mmol), 35% hydrochloric acid (13.2 mL), and water (10.0 mL) were mixed and cooled from 0 °C to 5 °C, and a solution of sodium nitrite (3.55 g, 51.5 mmol) in water (6.5 mL) was added dropwise thereto, followed by stirring for 30 minutes to prepare a diazo solution. N,N-Dimethylaniline (9.09 g, 75.0 mmol), sodium acetate (16.42 g, 200 mmol), methanol (67.0 mL), and water (33.0 mL) were mixed and cooled to 0 °C to 5 °C, and the entire amount of the diazo solution prepared previously was added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 2 hours. The precipitated solid was filtered off. The obtained solid was washed with water (200 m) to obtain compound (1-10-a) (13.98 g, yield 97%).

[0155]

Chemical formula

[0156] Synthesis of compound (1-10) Compound (1-10-a) (0.29 g, 1.0 mmol), 4-(methylthio)phenol (0.17 g, 1.2 mmol), 4-dimethylaminopyridine (0.012 g, 0.10 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.29 g, 1.50 mmol) were dissolved in tetrahydrofuran (10 mL) and stirred at room temperature for 2 hours. Water (20 mL) was added, and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (1-10) (0.28 g, yield 56%)

[0157]

Chemical formula

[0158] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 8.19 (t, 1H), 7.92 (d, 2H), 7.73 (dd, 1H), 7.62 (dd, 1H), 7.33 (d, 2H), 7.19 (d, 2H), 6.76 (d, 2H), 3.14 (s, 6H), 2.51 (s, 3H)

[0159] Comparative Example 1: Synthesis of compound (2-1) Compound (2-1-a) was synthesized by a known diazo coupling method. Compound (2-1-a) (0.52 g, 1.5 mmol), potassium carbonate (0.62 g, 4.5 mmol), and iodobutane (0.55 g, 3.0 mmol) were reacted in dimethylacetamide (7.5 mL) at 100 °C for two hours. After cooling to room temperature, methanol (25 mL) was added, and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain Compound (2-1) (0.24 g, yield 40%)

[0160]

Chemical formula

[0161] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 7.96 (d, 4H), 7.92 (dt, 4H), 7.00 (d, 2H), 6.76 (d, 2H), 4.05 (t, 2H), 3.10 (s, 6H), 1.81 (quin, 2H), 1.56 - 1.44 (m, 2H), 0.99 (t, 3H)

[0162] Comparative Example 2: Synthesis of Compound (2-2) Compound (2-2) was synthesized according to the following scheme.

[0163]

Chemical formula

[0164] Synthesis of Compound (2-2-a) 4-Amino-4’-dimethylaminoazobenzene (2.40 g, 10.0 mmol), 35% hydrochloric acid (2.6 mL), acetic acid (30.0 mL), and water (30.0 mL) were mixed and cooled from 0 °C to 5 °C. Aqueous solution of sodium nitrite (1.03 g, 15.0 mmol) in water (2.0 mL) was added dropwise thereto, and the mixture was stirred for 30 minutes to prepare a diazo solution. 2-Fluorophenol (1.69 g, 15.0 mmol), sodium acetate (4.92 g, 60.0 mmol), methanol (40.0 mL), and water (20.0 mL) were mixed and cooled to 0 °C to 5 °C, and the entire amount of the diazo solution prepared previously was added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the precipitated solid was filtered off. The obtained solid was washed with water to obtain Compound (2-2-a) (0.52 g, yield 19%).

[0165]

Chemical formula

[0166] Synthesis of Compound (2-2) Compound (2-2-a) (0.54 g, 1.5 mmol), potassium carbonate (0.62 g, 4.5 mmol), and iodobutane (0.55 g, 3.0 mmol) were reacted in dimethylacetamide (7.5 mL) at 100 °C for two hours. After cooling to room temperature, methanol (20 mL) was added, and the precipitated solid was filtered off. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain Compound (2-1) (0.17 g, yield 27%)

[0167]

Chemical formula

[0168] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 7.97 (d, 4H), 7.90 (d, 2H), 7.76 (d, 1H), 7.71 (dd, 1H), 7.07 (t, 1H), 6.76 (d, 2H), 4.13 (t, 2H), 3.10 (s, 6H), 1.85 (quin, 2H), 1.58 - 1.48 (m, 2H), 1.00 (t, 3H)

[0169] Comparative Example 3: Synthesis of Compound (2-3) For Compound (2-3), it was synthesized according to the production method described in Paragraph 0171 of JP-A-2013-209367.

[0170]

Chem.

[0171] Example 11: Preparation of Composition E1 Containing Compound 1-1 The following components were mixed and stirred at 80 °C for 1 hour to obtain Composition E1. · 75 parts by mass of polymerizable liquid crystal compound (A-6) · 25 parts by mass of polymerizable liquid crystal compound (A-7) · 4.0 parts by mass of compound (1-1) · Photoinitiator: 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan Ltd.) 6 parts by mass · Levelling agent: Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts by mass · Solvent: o-xylene 250 parts by mass

[0172] The structures of the polymerizable liquid crystal compound (A-6) and the polymerizable liquid crystal compound (A-7) are shown below.

[0173]

Chem.

[0174] The polymerizable liquid crystal compound (A-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). Also, the polymerizable liquid crystal compound (A-7) was produced according to this method.

[0175] Examples 12, 13 and 14: Preparation of Compositions E2, E3 and E4 Compositions E2, E3 and E4 as examples were obtained in the same manner as in Example 1, except that compound (1-2), compound (1-9) and compound (1-10) were used instead of compound (1-1), respectively.

[0176] Comparative Examples 11, 12, and 13: Preparation of Compositions C1, C2, and C3 Compositions C1, C2, and C3, which are comparative examples, were obtained in the same manner as in Example 1, except that compound (2-1), compound (2-2), and compound (2-3) whose synthesis methods were described above were used instead of compound (1-1), respectively.

[0177] Manufacture of Polarizing Plate 1. Formation of Alignment Film A glass substrate was used as the transparent substrate. A 2 mass% aqueous solution of polyvinyl alcohol (fully saponified polyvinyl alcohol 1000, manufactured by Wako Pure Chemical Industries, Ltd.) (composition for forming an alignment layer) was applied onto the glass substrate by spin coating, and after drying, a film with a thickness of 100 nm was formed. Subsequently, the surface of the obtained film was subjected to rubbing treatment to form an alignment film, and a substrate with an alignment film formed thereon was obtained on the glass substrate.

[0178] 2. Formation of Polarizing Film The composition obtained above was applied onto the alignment film of the substrate obtained above by spin coating, heated and dried on a hot plate at 120 °C for 3 minutes, and then quickly cooled to 70 °C or lower (the temperature at which a smectic liquid crystal phase is exhibited during temperature reduction) to obtain a laminate in which a dry film was formed on the alignment film.

[0179] Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO INC.), ultraviolet rays were irradiated onto the dry film at an exposure amount of 2400 mJ / cm 2 (based on 365 nm) to polymerize the polymerizable liquid crystal compound contained in the dry film while maintaining the liquid crystal state of the composition, and a polarizing film was formed from the dry film to obtain a polarizing plate.

[0180] Evaluation For the polarizing plate obtained above, the dichroic ratio was measured as follows. The absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction at the maximum absorption wavelength (λmax) of the polarizing film of the polarizing plate were measured by the double beam method using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with an apparatus in which a folder equipped with the laminate (2) was set. A mesh for cutting the light amount by 50% was installed on the reference side of the folder. From the measured values of the absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction, the ratio (A2 / A1) was calculated and taken as the dichroic ratio (DR).

[0181] Also, the absorbance retention rate under the following light resistance conditions was calculated as follows. The absorbance retention rate (A3 / A4; %) was obtained by dividing the absorbance (A3) after the light resistance test in the absorption axis direction at the maximum absorption wavelength of the polarizing film of the polarizing plate by the absorbance (A4) before the light resistance test and converting it to a percentage. The results of the dichroic ratio (DR) and the absorbance retention rate are shown in Tables 1, 2 and 3.

[0182] The light irradiation conditions in the light resistance test are as follows. Equipment used: Ci4000 manufactured by ATLAS Light source used: Xenon arc lamp Exposure conditions: 120 W / m 2 (300 nm - 400 nm) Test time: 20 hours Exposure dose: 8640 KJ / m 2 Temperature: 65 °C

[0183]

Table 1

[0184]

Table 2

[0185]

Table 3

[0186] It can be seen that a polarizing plate having a film formed of a composition containing the compound represented by the formula (1) from Table 1 as a forming material has improved light resistance and dichroic ratio.

Claims

1. A composition comprising a compound represented by the following formula (1) and a liquid crystalline compound containing at least one of a polymerizable smectic liquid crystal compound and a smectic liquid crystalline polymer compound. 【Chemical 1】 [In formula (1), n represents an integer of 1 or 2. Ar １ 、 Ar ２ and Ar ３ each independently represents a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group which may have at least one selected from the group consisting of a halogen atom, a hydroxy group, a methyl group and a methoxy group as a substituent. R １ represents an alkoxy group which may have a polymerizable group or an alkylamino group which may have a polymerizable group. R ２ represents at least one group selected from the group consisting of -OC(=O)-, -C(=O)O- and -N=N-. R ３ represents a divalent group composed of at least one selected from the group consisting of -CH ２ -, -N(R ５ ), -C(=O)-, -O- and -S-. R ５ represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. However, it excludes the case where two selected from the group consisting of -N(R ５ ), -O- and -S- are bonded to each other. R ４ represents a hydrogen atom, a polymerizable group or a trialkylsilyloxy group. When n is 2, the two Rs ２ may be the same as or different from each other, and the two Ars ２ may be the same as or different from each other.]

2. The composition according to claim 1, wherein the polymerizable smectic liquid crystal compound is a compound represented by the following formula (A). 【Chemical 2】 [In formula (A), m is an integer from 1 to 3. X １ , X ２ and X ３ each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, a plurality of X １ may be the same as or different from each other. X １ , X ２ and X ３ at least three selected from the group consisting of represent a divalent hydrocarbon 6-membered ring group. Y １ 、 Y ２ 、 W １ and W ２ each independently represents a single bond or a divalent linking group. When m is 2 or 3, the plurality of Y １ may be the same as or different from each other. V １ and V ２ each independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. At least one of the —CH ２ — may be replaced by —O—, —CO—, —S— or —NH—. U １ and U ２ each independently represents a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.

3. The composition according to claim 1 or 2, wherein in the compound represented by the above formula (1), n is 1.

4. A film using the composition according to any one of claims 1 to 3 as a forming material.

5. A film using, as a forming material, a composition comprising a compound represented by the following formula (1) and a liquid crystalline compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound, and showing a Bragg peak in X-ray diffraction measurement. 【Chemical Formula 3】 [In formula (1), n represents an integer of 1 or 2. Ar1, Ar2 and Ar3 each independently represent a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group which may have at least one selected from the group consisting of a halogen atom, a hydroxy group, a methyl group and a methoxy group as a substituent. R1 represents an alkoxy group which may have a polymerizable group or an alkylamino group which may have a polymerizable group. R2 represents at least one group selected from the group consisting of -OC(=O)-, -C(=O)O- and -N=N-. R3 represents a divalent group composed of at least one selected from the group consisting of -CH2-, -N(R5)-, -C(=O)-, -O- and -S-. R5 represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. However, the case where two selected from the group consisting of -N(R5)-, -O- and -S- are bonded is excluded. R4 represents a hydrogen atom, a polymerizable group or a trialkylsilyloxy group. When n is 2, the two R2s may be the same or different from each other, and the two Ar2s may be the same or different from each other. ]

6. A laminate comprising the film according to claim 4 or 5.

7. A display device comprising the laminate according to claim 6.

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