JP2018180219A - Laminate, composition for forming alignment film, and alignment film - Google Patents

Abstract

Provided is a laminate containing an alignment film that can be easily formed at a lower temperature. Moreover, the composition for alignment film formation and an alignment film are provided. A laminated body including a first substrate, a first alignment film containing a triptycene derivative, and a liquid crystal layer. [Selection] Figure 1

Description

  The present invention relates to a laminate, a composition for forming an alignment film, and an alignment film.

2. Description of the Related Art Conventionally, a large number of devices including liquid crystal display devices and liquid crystal cells such as light control devices are known. A liquid crystal cell generally includes a liquid crystal layer and two substrates disposed to face each other with the liquid crystal layer interposed therebetween. An alignment film may be provided between the substrate and the liquid crystal layer in order to align the liquid crystal compound constituting the liquid crystal layer.
Patent Document 1 describes a liquid crystal alignment film formed from a composition for a liquid crystal alignment film containing a predetermined polyimide resin precursor.

JP-A-5-34700

  The present inventors examined a laminate including the liquid crystal alignment film described in Patent Document 1, and a substrate, the liquid crystal alignment film, and a liquid crystal layer. When forming an alignment film, it is necessary to heat under predetermined conditions, the production process becomes complicated, and there is a limitation in selection of the material of the above-mentioned substrate, in other words, using a substrate with lower heat resistance. Found out that there is a problem that

  Then, this invention makes it a subject to provide the laminated body which contains the alignment film which can be formed simply by lower temperature (henceforth "it has an effect of this invention."). Another object is to provide a composition for forming an alignment film, and an alignment film.

  MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be achieved with the following structure, as a result of earnestly examining in order to achieve the said subject.

[1] A laminate comprising a first substrate, a first alignment film containing a triptycene derivative, and a liquid crystal layer in this order.
[2] The laminate according to [1], wherein the triptycene derivative is a compound represented by the general formula (1).
[3] The laminate according to [1] or [2], further comprising a second substrate on the liquid crystal layer, wherein the first substrate and the second substrate face each other via the liquid crystal layer.
[4] The laminate according to [3], further including a second alignment film containing a triptycene derivative between the second substrate and the liquid crystal layer.
[5] A transparent electrode layer is further provided at at least one location selected from the group consisting of: between the first substrate and the first alignment film, and between the second substrate and the second alignment film, The laminated body as described in [4].
[6] The laminate according to any one of [3] to [5], wherein at least one substrate selected from the group consisting of the first substrate and the second substrate is made of a transparent resin.
[7] The liquid crystal layer contains a liquid crystal compound having a negative dielectric anisotropy, or is formed using a liquid crystal compound having a negative dielectric anisotropy, [1] to [6] The laminated body in any one of.
[8] The laminate according to any one of [1] to [7], wherein the liquid crystal layer contains a polymer obtained by polymerizing a polymerizable compound.
[9] The laminate according to [8], wherein the polymerizable compound is a polymerizable rod-like liquid crystal compound.
[10] The laminate according to any one of [1] to [9], wherein the liquid crystal layer further contains a dichroic dye.
[11] A composition for forming an alignment film containing a triptycene derivative.
[12] The composition for forming an alignment film according to [11], wherein the triptycene derivative is a compound represented by the general formula (1).
[13] An alignment film formed using the composition for forming an alignment film according to [11] or [12].

  According to the present invention, it is possible to provide a laminate containing an alignment film which can be easily formed at a lower temperature. In addition, a composition for forming an alignment film and an alignment film can also be provided.

It is a schematic sectional drawing of the laminated body which concerns on 1st embodiment of this invention. It is a schematic sectional drawing of the laminated body which concerns on 2nd embodiment of this invention. It is a schematic sectional drawing of the laminated body which concerns on 3rd embodiment of this invention.

Hereinafter, the present invention will be described in detail.
The description of the configuration requirements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
Moreover, in the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes not only those containing no substituent but also those containing a substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, far ultraviolet, extreme ultraviolet (EUV), X-ray, electron beam and the like. In the present specification, light means actinic rays and radiation. Unless otherwise specified, the "exposure" in the present specification includes not only exposure by far ultraviolet rays, X-rays, EUV and the like but also drawing by particle beams such as electron beams and ion beams.
Also, as used herein, "(meth) acrylate" represents acrylate and methacrylate. Moreover, in this specification, "(meth) acryl" represents an acryl and methacryl. Also, as used herein, “(meth) acryloyl” represents acryloyl and methacryloyl.

[Laminated body (first embodiment)]
The laminate according to the first embodiment of the present invention has a first substrate (hereinafter also referred to as “first substrate”) and a first alignment film containing a triptycene derivative (hereinafter “first alignment film”). And a liquid crystal layer in this order.

A schematic cross-sectional view of the laminate according to the first embodiment of the present invention is shown in FIG. The stacked body 100 includes the first substrate 101, the first alignment film 102, and the liquid crystal layer 103 in this order.
In the laminate 100 of FIG. 1, the first substrate 101, the first alignment film 102, the first alignment film 102, and the liquid crystal layer 103 are in contact with each other, but the laminate 100 of the present embodiment is There is no particular limitation as long as the first substrate 101, the first alignment film 102, and the liquid crystal layer 103 are provided in this order. As will be described later, another layer may be provided between each layer, for example, in a form in which a transparent electrode layer is provided between the first substrate 101 and the first alignment film 102 (this form will be described later), etc. It may be.

[First substrate]
The first substrate 101 is not particularly limited, and a substrate made of a known material can be used. As a material of the first substrate 101, for example, glass or resin may be mentioned.
The glass is not particularly limited, and known glasses can be used. Among them, alkali-free glasses for display applications are preferable.
The resin is not particularly limited, and known plastics can be used. Examples of the plastic include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyether sulfone, polysulfone, polyarylate, cyclic polyolefin, polyimide, and acetyl cellulose-based film.
Among them, when the first substrate is a transparent resin, the laminate has more excellent flexibility, and the amount of light transmitted through the laminate can be controlled more easily. In the present specification, “transparent” means that the average transmittance of wavelengths in the visible light range is 80% or more at the thickness used for the laminate.

  The thickness of the first substrate 101 is not particularly limited, but generally 0.01 to 2.0 μm is preferable. The first substrate 101 may be opaque, colored and transparent, or colorless and transparent, and is preferably colorless and transparent.

[First alignment film]
The first alignment film contains a triptycene derivative and has a function as a vertical alignment film.
The thickness of the first alignment film is not particularly limited, but in general, 0.001 to 1.0 μm is preferable.
Whether the first alignment film has a function as a vertical alignment film can be determined by the following method. First, an alignment film containing a triptycene derivative (hereinafter, also simply referred to as a "triptycene alignment film") is formed on a transparent substrate (for example, a glass substrate), and the triptycene alignment films are disposed to face each other with a spacer interposed therebetween. After that, a composition containing a liquid crystal compound is injected into a space formed by a spacer and two transparent substrates provided with a triptycene alignment film to form a liquid crystal layer (in the present specification, “the liquid crystal cell It is also called "). When the liquid crystal cell is observed with a polarization microscope (crossed Nicol) and it is a dark field, it is judged that the liquid crystal compound is vertically aligned in the liquid crystal layer and the triptycene alignment film has a function as a vertical alignment film it can.

The content of the triptycene derivative in the first alignment film is not particularly limited, but generally, 1 to 100% by mass is preferable with respect to the total mass of the first alignment film. The triptycene derivatives may be used alone or in combination of two or more. When two or more triptycene derivatives are used in combination, the total content is preferably in the above range. The content of the triptycene derivative in the first alignment film being 100% by mass means that the first alignment film is made of the triptycene derivative.
The first alignment film may contain components other than the triptycene derivative described later (for example, solvents and the like can be mentioned), but it is more preferably formed from the triptycene derivative. In the present specification, the triptycene alignment film (including the first alignment film and the second alignment film described later) is formed of the triptycene derivative when the triptycene alignment film is formed only of the triptycene derivative, and This includes both cases where unintended impurities and the like are contained in the triptycene alignment film.

<Triptycene derivative>
As a triptycene derivative, a Janus type triptycene derivative is preferable in that a uniform film is easily formed on the first substrate 101.

  Triptycene consists of two different planes of planes formed by carbon atoms at positions 1, 8 and 13 represented by the above formula, and planes formed by carbon atoms at positions 4, 5, and 16 contains. As used herein, Janus type triptycene derivatives are intended to be triptycene derivatives in which the two different aspects have different characteristics. The different characteristics are not particularly limited, but examples include a form in which a predetermined substituent is contained on one side.

As the triptycene derivative, a compound represented by the following general formula (1) is preferable.

In the general formula (1), R ¹ represents a saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms, and the above-mentioned hydrocarbon group may contain one or more substituents. Also, preferably, one or more carbon atoms in the above hydrocarbon group are an oxygen atom, a sulfur atom, a silicon atom, or -NR ^5- (wherein R ⁵ is a hydrogen atom, 1 carbon atom To 10 alkyl groups or aryl groups having 6 to 30 carbon atoms).

In the general formula (1), the saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms as R ¹ is not particularly limited, and may be linear or branched. It may well contain a cyclic structure.
As a carbon number of R < ¹ >, 2-30 are preferable and 5-30 are more preferable.
As R ¹ , for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group and the like can be mentioned.
The aromatic hydrocarbon (aromatic ring) contained in the arylene group is not particularly limited, and may be monocyclic, polycyclic, or condensed cyclic. Although it does not restrict | limit especially as carbon number of the aromatic hydrocarbon which an arylene group contains, 6-30 are preferable, 6-20 are more preferable, and 6-12 are still more preferable.
The arylene group may contain a plurality of aromatic rings. The arylene group may further contain an alkylene group, an alkenylene group or an alkynylene group between a plurality of aromatic rings or at the end of the aromatic ring.
The carbon-carbon double bond for forming an alkenylene group, the carbon-carbon triple bond for forming an alkynylene group, and the aromatic ring for forming an arylene group are among saturated alkylene groups (terminal And / or unsaturated carbon-carbon bonds may be arranged regularly or irregularly.
Specific examples of the saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms for R ¹ include C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₁ , C ₁₂ , C ₁₃ , and the like. C ₁₄ , C ₁₅ , C ₁₆ or C ₁₇ linear or branched alkylene group (linear is more preferable); 1 to 3 of the above-mentioned alkylene groups (which may be terminal) An alkylene group in which a carbon-carbon double bond is regularly or irregularly arranged; an alkylene group of-(-CH = CH-) _n- (n represents an integer of 3 to 8); Alkylene group in which 1 to 3 carbon-carbon triple bonds are regularly or irregularly arranged inside (which may be terminal);-(-Ph-CH = CH-) _m -Ph- (wherein Ph Is a p-phenylene group, and m is an integer of 1 to 4. An arylene group etc. Can be mentioned.

The substituent which the divalent hydrocarbon group represented by R ^{1 in} the general formula (1) may contain is not particularly limited, but a halogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms An alkyloxy group of 1 to 5 (preferably 1 to 3 is preferred) halogen atoms substituted with an alkyl group of 1 to 5 carbon atoms; 1 to 5 (preferably 1 to 3 preferred) halogen atoms The alkoxy group having 1 to 5 carbon atoms; the amino group; the amino group substituted with one or two alkyl groups having 1 to 5 carbon atoms; and the like. In the present specification, the term "substituent" is as defined above.
As said C1-C5 alkyl group, a linear or branched alkyl group is mentioned. As such an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and the like can be mentioned, for example. . As carbon number, 1-4 are preferable and 1-3 are more preferable. In addition, in this specification, when it says "a C1-C5 alkyl group", it is the same as that of the above.
As said C1-C5 alkoxy group, the group which the oxygen atom couple | bonded with the said C1-C5 alkyl group is mentioned. As such an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, butoxy group, pentyloxy group and the like can be mentioned. In the present specification, the term "C1-C5 alkoxy group" refers to the same as above.

In the general formula (1), one or more carbon atoms in the divalent hydrocarbon group of R ¹ may be substituted with an oxygen atom, a sulfur atom, a silicon atom or -NR ^5- Good.
The form of substitution is not particularly limited, and examples include a form in which one or two or more carbon atoms in the chain of carbon atoms of -C-C-C- are substituted by another atom. As specific examples of the above, —C—O—C—, —C—S—C—, and —C—SiH ₂ —C— (wherein a hydrogen atom bonded to a silicon atom in the formula is a halogen atom, 1 carbon atom -10 alkyl group, or may be substituted by a C1-C10 alkoxy group), -C-NR < ⁵ > -C-, etc. are mentioned. Such substitution with other atoms may be regular or irregular in the order of substitution.
As said C1-C10 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, an isobutyl group, a sec-butyl group, a tert- butyl group, a pentyl group, hexyl is mentioned, for example And octyl groups. As carbon number, 1-8 are preferable and 1-5 are more preferable. In the present specification, the term "C1-C10 alkyl group" is the same as above.
As said C1-C10 alkoxy group, the group which oxygen atom-bonded to said C1-C10 alkyl group is mentioned. As such an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group etc. are mentioned, for example. In the present specification, the term "C1-C10 alkoxy group" refers to the same as above.
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms.
As a C6-C30 aryl group, a monocyclic, polycyclic, or a fused ring aryl group is mentioned. As such an aryl group, a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthryl group etc. are mentioned, for example. As a carbon number, 6-18 are preferable and 6-12 are more preferable. In the present specification, the term "C6-C30 aryl group" refers to the same as above.

In the general formula (1), ^{R 2} is a group ^-R 1 -Z (. - represented by "* ^R 1 -Z", * is representative of a bond position), a hydrogen atom, or a 1 to 4 carbon atoms Represents a saturated or unsaturated hydrocarbon group.
When R ² is a group -R ¹ -Z, Z is a hydrogen atom, a group which can be bonded or adsorbed to the surface of a solid substrate, or a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, a phosphorus atom, a halogen atom And 1 to 15 atoms selected from the group consisting of silicon atoms, as well as end groups consisting of monovalent atomic groups composed of hydrogen atoms.
Here, the group capable of binding or adsorbing to the surface of the solid substrate is, in addition to the first substrate 101 already described, for example, quartz, sapphire, silicon, germanium, silicon oxide, gold, platinum, silver, copper, indium oxide , ITO (Indium Tin Oxide), GaAs, CdS, polyolefin, polyacrylic, polyether sulfone, polyimide, polyethylene terephthalate, collagen, starch, and a group having interaction with a solid substrate (interaction (interaction Sex group).
In the membrane using the above-mentioned triptycene derivative, the triptycene skeleton portion has a membrane forming ability. Furthermore, according to the triptycene derivative containing an interactive group, the position of the formed film on the substrate is more likely to be stabilized.
And a monovalent atom composed of 1 to 15 atoms selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, carbon atom, phosphorus atom, halogen atom, and silicon atom, and hydrogen atom The terminal group consisting of a group is a monovalent group, and the number of atoms constituting the atomic group is preferably 1 to 10, and more preferably 1 to 6.

As Z, for example, an alkyl group having 1 to 10 carbon atoms; a linear or branched alkenyl group having 2 to 15 carbon atoms (preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms); A linear or branched alkynyl group having 2 to 15 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms); 6 to 15 carbon atoms (preferably 6 to 12 carbon atoms) An aryl group having 6 to 15 carbon atoms (preferably having 6 to 12 carbon atoms) containing a monocyclic, polycyclic or fused cyclic aromatic ring having a number of 6 to 10 is more preferable, An alkylene group, an alkenylene group, or an alkynylene group may be contained between the aromatic ring and the aromatic ring or at the terminal)); and 1 to 7 halogen atoms in any position of the alkyl group having 1 to 10 carbon atoms C 1-10 haloalkyl substituted with ; ^{-OR 11 (R} 11 is a hydrogen atom or an alkyl group having 1 to 10 carbon ^{atoms.); - SR 11 (R} 11 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) -SOR ¹¹ (R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms); -SO ₂ R ¹¹ (R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms _{^{.); - N (R 12}} ) 2 (R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); -. CO- R ¹³ (R ¹³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); —OCO—R ¹³ (R ¹³ represents a hydrogen atom having 1 to 10 carbon atoms) Represents an alkyl group or an aryl group having 6 to 12 carbon atoms); ^{O-R 13 (R} 13 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon ^{atoms.); - OCOO-R 14} (R 14 is 1 to 10 carbon atoms Or an aryl group having 6 to 12 carbon atoms); -CON (R ¹³ ) ₂ (R ¹³ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or carbon -NR ¹³ CO-R ¹³ (wherein R ¹³ is each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); the ^{expressed); -. N (R 13} ) CON (R 13) 2 (R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. And -CO-NR ¹³ -N (R ¹³ ) ₂ (R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); -SiR ⁹ R ¹⁰ -O-R ¹³ (R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or R ¹³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); -O-SiR ⁹ R ¹⁰ -O-R ¹³ (R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an alkyl having 1 to 3 carbon atoms represents an amino group which may be substituted with a group, R ¹³ is a hydrogen atom, the number of carbon atoms 10 alkyl group, or an aryl group having 6 to 12 carbon ^{atoms); -. SiR 9 R 10} -N (R 13) 2 (R 9, R 10 are each independently a hydrogen atom, a carbon R ¹³ represents an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or an amino group which may be substituted with an alkyl group of 1 to 3 carbon atoms; R ¹³ represents a hydrogen atom or an alkyl of 1 to 10 carbon atoms Or an aryl group having 6 to 12 carbon atoms); -NH-SiR ⁹ R ¹⁰ -O-R ¹³ (R ⁹ and R ¹⁰ each independently represent a hydrogen atom or 1 to 3 carbon atoms And an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, R ¹³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or , An aryl group having 6 to 12 carbon atoms); -P (OR ¹⁵ ₂ (wherein, R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); -P (= O) (OR) ¹⁵ ) ₂ (wherein, R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms); and the like.

In general formula (1), R ³ represents a group -R ¹ -Z, a hydrogen atom, or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms. The forms of R ¹ and Z are as described above.
In the general formula (1), when one or both of R ² and R ³ are a group -R ¹ -Z, a plurality of R ¹ and Z may be the same or different.

In the general formula (1), three R ^{4 s} may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, a monoalkyl substituted amino group, a dialkyl substitution An amino group, an alkyl group having 1 to 10 carbon atoms which may contain a substituent, an alkenyl group having 2 to 10 carbon atoms which may contain a substituent, 2 to 10 carbon atoms which may contain a substituent And an alkoxy group having 1 to 10 carbon atoms which may contain a substituent, an alkylthio group having 1 to 10 carbon atoms which may contain a substituent, a formyl group (aldehyde group), and a substituent An alkylcarbonyl group having 1 to 10 carbons which may be substituted, an alkoxycarbonyl group having 1 to 10 carbons which may contain a substituent, an alkylcarbonyloxy group having 1 to 10 carbons which may contain a substituent, Substituent And 1 to 5 at least one hetero atom selected from the group consisting of an aryl group having 6 to 30 carbon atoms which may contain, or a nitrogen atom, an oxygen atom, and a sulfur atom, and a carbon atom And an optionally substituted 5- to 8-membered heteroaryl group containing 2 to 10 members.

Examples of the monoalkyl-substituted amino group of R ⁴ include an amino group in which one hydrogen atom of an amino group (—NH ₂ ) is substituted with an alkyl group having 1 to 10 carbon atoms, and more specifically And a methylamino group and an ethylamino group.
Examples of the dialkyl substituted amino group of R ⁴ include an amino group in which two hydrogen atoms of an amino group (—NH ₂ ) are substituted with an alkyl group having 1 to 10 carbon atoms, and more specifically, A dimethylamino group, a diethylamino group, and a methylethylamino group etc. are mentioned. The two alkyl groups may be the same or different.

The alkenyl group having 2 to 10 carbon atoms of R ⁴ is a group having one or more carbon-carbon double bonds, and has 2 to 10 carbon atoms in total (preferably 2 to 8 carbon atoms in total, preferably 2 to 6). And the like) is more preferable.). Examples of such alkenyl groups include vinyl, 1-methyl-vinyl, 2-methyl-vinyl, n-2-propenyl, 1,2-dimethyl-vinyl, 1-methyl-propenyl, Examples include 2-methyl-propenyl group, n-1-butenyl group, n-2-butenyl group, and n-3-butenyl group. In the present specification, the term "alkenyl group having 2 to 10 carbon atoms" is as defined above.

The alkynyl group having 2 to 10 carbon atoms as R ⁴ is a group having one or more carbon-carbon triple bonds, and has 2 to 10 carbon atoms in total (preferably 2 to 8 carbon atoms in total, preferably 2 to 6). And more preferably straight chain or branched chain alkynyl groups. Examples of such alkynyl groups include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, and n-3-butynyl group, etc. Can be mentioned. In the present specification, the term “C 2-10 alkynyl group” means the same as above.

The alkylthio group having 1 to 10 carbon atoms R ^4, include a group the sulfur atom is bonded to an alkyl group having 1 to 10 carbon atoms which has already been described. Examples of such an alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, a butylthio group, and a pentylthio group. The sulfur atom in these alkylthio groups may be sulfinyl (-SO-) or sulfonyl (-SO _2- ). In the present specification, the term "alkylthio group having 1 to 10 carbon atoms" is as defined above.

The alkyl group having 1 to 10 carbon atoms R ^4, include groups carbonyl group to an alkyl group having 1 to 10 carbon atoms which has already been described (-CO- group) is bonded. As such an alkyl carbonyl group, a methyl carbonyl group, an ethyl carbonyl group, n-propyl carbonyl group, isopropyl carbonyl group etc. are mentioned, for example. In the present specification, the term "alkylcarbonyl group having 1 to 10 carbon atoms" is as defined above.

The alkoxycarbonyl group having 1 to 10 carbon atoms R ^4, oxycarbonyl group (-O-CO- group) groups attached to an alkyl group having 1 to 10 carbon atoms which has already been described. As such an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, an isopropoxycarbonyl group etc. are mentioned, for example. In the present specification, the term "C1-C10 alkoxycarbonyl group" is the same as above.

The alkylcarbonyloxy group having 1 to 10 carbon atoms R ^4, include groups carbonyloxy group to an alkyl group having 1 to 10 carbon atoms which has already been described (-CO-O-group) is bonded. As such an alkyl carbonyloxy group, a methyl carbonyloxy group, an ethyl carbonyloxy group, n-propyl carbonyloxy group, an isopropyl carbonyloxy group etc. are mentioned, for example. In the present specification, the term "alkylcarbonyloxy group having 1 to 10 carbon atoms" is as defined above.

Having a substituent containing 1 to 5 at least one hetero atom selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom of R ⁴ and containing 2 to 10 carbon atoms As a favorable 5- to 8-membered heteroaryl group (hereinafter, also referred to as "heterocyclic group"), 1 to 5 (1 to 3 is preferable, 1 to 2 is more preferable) nitrogen atoms Monocyclic, polycyclic, containing a 5- to 8-membered (preferably 5- to 6-membered) ring containing at least one hetero atom selected from the group consisting of an oxygen atom and a sulfur atom, Alternatively, a fused cyclic heteroaryl group can be mentioned. As such a heterocyclic group, 2-furyl group, 2-thienyl group, 2-pyrrolyl group, 2-pyridyl group, 2-indole group, benzoimidazolyl group etc. are mentioned, for example. In the present specification, the term "heterocyclic group" is as defined above.

In the general formula (1), X may be the same or different, and each independently represents 1 to 5 selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, carbon atom, and silicon atom And a linker group (bivalent linking group) consisting of a divalent atom group composed of atoms and hydrogen atoms.
The structure of the linker group is not particularly limited as long as it connects a triptycene skeleton and a divalent hydrocarbon group R ¹ group.
As a suitable form of X, for example, -O-; -S-; -SO-; -SO _2- ; -NR ^6- (R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms _{.); - CH 2 -;} - CH 2 -CH 2 -; - CH = CH -; -; a _{C 4} H 2 S- (hydrogen atom from any position of the thiophene - C 6 _{H 4} - (phenylene _group) total remaining after removing two divalent linking group); - CO -; - OCO -; - COO -; - OCOO -; - CONR 61 - (R 61 is a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms the ^{expressed); -. NR 62 CO- (} R 62 is a hydrogen atom or an alkyl group having 1 or 2 carbon ^{atoms); -. NHCONH -, -} CO-NR 63 -NR 63 - (R 63 is Each independently represents a hydrogen atom or a methyl group); -SiR ⁹ R ¹⁰ -O- ( R ⁹ and R ¹⁰ may be each independently substituted with a hydrogen atom, an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or an alkyl group of 1 to 3 carbon atoms -O-SiR ⁹ R ¹⁰ -O- (R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms Or an amino group which may be substituted with an alkyl group of 1 to 3 carbon atoms); -SiR ⁹ R ¹⁰ -NH- (R ⁹ and R ¹⁰ each independently represent a hydrogen atom or carbon number Represents an amino group which may be substituted with an alkyl group of 1 to 3, an alkoxy group of 1 to 3 carbon atoms, or an alkyl group of 1 to 3 carbon atoms); -NH-SiR ⁹ R ¹⁰ -O- ( R ^{9, R 10} are each independently a hydrogen atom, 1 to 3 carbon atoms alkyl Group, an alkoxy group having 1 to 3 carbon atoms, or, and a.) Or the like representing the amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms.
As preferred X group in the general formula [II], -O-; -S-; -SO-; -SO _2- ; -NR ^6- (wherein, R ⁶ is a hydrogen atom, or 1 to 4 carbon atoms represents an alkyl _{group); -. CH 2 -;} - CH = CH -; - CO -; - OCO -; - CONR 61 - ( ^{wherein, R 61} is a hydrogen atom, or an alkyl of 1 to 3 carbon atoms And -NR ⁶² CO- (wherein R ⁶² represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms), and the like, and particularly preferred X is -O-; -NR ^6- (wherein, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms); -CH _2- ; -CO- and the like.

  The above triptycene derivatives can be synthesized as appropriate, for example, with reference to the methods described in, for example, WO 2014/11980, WO 2014/125527, and WO 2016/010061.

[Liquid crystal layer]
The laminate 100 according to the present embodiment includes the liquid crystal layer 103 on the first alignment film 102. The liquid crystal layer 103 is not particularly limited as long as it is a layer formed using a liquid crystal compound.
The thickness of the liquid crystal layer 103 is not particularly limited, but in general, 0.1 to 100 μm is preferable.

<One form of liquid crystal layer>
As one mode, the liquid crystal layer 103 is a layer containing a compound having liquid crystallinity (hereinafter, also referred to as “liquid crystal compound” in the specification). In this embodiment, the liquid crystal layer 103 may contain a liquid crystal compound, and may contain other components as long as the effects of the present invention are exhibited. Examples of other components include polymers obtained by polymerizing a polymerizable compound, dichroic dyes, and solvents. Below, each component which the liquid crystal layer 103 in this form contains is explained in full detail.

(Liquid crystal compound)
The liquid crystal layer 103 contains a liquid crystal compound. The content of the liquid crystal compound in the liquid crystal layer 103 is not particularly limited, but generally, 1 to 99% by mass is preferable with respect to the total mass of the liquid crystal layer 103, and 10 to 100% by mass is more preferable. The liquid crystal compounds may be used alone or in combination of two or more. When two or more liquid crystal compounds are used in combination, the total content is preferably within the above range.

The liquid crystal compound contained in the liquid crystal layer 103 is not particularly limited, and a known liquid crystal compound can be used. The liquid crystal compound is preferably a liquid crystal compound exhibiting a nematic phase or a smectic phase, more preferably a liquid crystal compound exhibiting a nematic phase.
Examples of liquid crystal compounds include azomethine compounds, cyanobiphenyl compounds, cyanophenyl esters, fluorine-substituted phenyl esters, cyclohexanecarboxylic acid phenyl esters, fluorine-substituted cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, fluorine-substituted phenylcyclohexanes, cyano-substituted phenylpyrimidines Fluorine-substituted phenyl pyrimidine, alkoxy-substituted phenyl pyrimidine, fluorine-substituted alkoxy-substituted phenyl pyrimidine, phenyl dioxane, tolane compounds, fluorine-substituted tolane compounds, alkenyl cyclohexyl benzonitrile, bicyclooctane liquid crystal compounds, cubane liquid crystal compounds, etc. It can be mentioned.
In addition, as the liquid crystal compound, the liquid crystal compounds described on pages 154 to 192 and pages 715 to 722 of “Liquid Crystal Device Handbook” (edited by Committee 142 of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989) are used. It can also be done.
More specifically, liquid crystal compounds of Merck (ZLI-4692, MLC-6267, 6284, 6287, 6288, 6406, 6422, 6423, 6425, 6435, 6437, 7700, 7800, 9000, 9100, 9200, 9300, And 10000 etc.), Chisso's liquid crystal compounds (LIXON 5036xx, 5037xx, 5039xx, 5040xx, and 5041xx etc.), and ADEKA's liquid crystal compounds (HA-11757, and CA-32150 etc.). It is not restricted.

  The dielectric anisotropy of the liquid crystal compound is not particularly limited. By having dielectric anisotropy as the whole liquid crystal composition, a change in alignment state due to application of a voltage can be expressed. The dielectric anisotropy of the liquid crystal compound is preferably negative in that the liquid crystal is changed in the horizontal direction by vertically aligning the liquid crystal and applying a voltage in the vertical direction in the state where no voltage is applied. Here, that the dielectric constant anisotropy of the liquid crystal compound is negative means that the dielectric constant in the direction perpendicular to the long axis of the liquid crystal compound is larger than the dielectric constant in the long axis direction. Whether the liquid crystal compound has negative dielectric anisotropy can be measured by the method described in the Handbook of Liquid Crystal Handbook, Liquid Crystal Handbook, Maruzen Co., Ltd., pp. 209-210.

  As a liquid crystal compound having negative dielectric constant anisotropy, for example, a liquid crystal compound described in paragraphs 0012 to 0064 of JP-A-2009-265317 can be used, and the above contents are incorporated in the present specification.

Polymerizable Liquid Crystal Compound The liquid crystal layer according to the present embodiment may contain a liquid crystal compound (polymerizable liquid crystal compound) containing a polymerizable group as the liquid crystal compound. The polymerizable liquid crystal compound is not particularly limited, and examples thereof include known polymerizable liquid crystal compounds.
As a polymeric group, a radically polymerizable group, a cationically polymerizable group, an anionically polymerizable group etc. are mentioned, for example. Examples of the radically polymerizable group include a (meth) acryloyl group, an acrylamide group, a vinyl group, a styryl group, and an allyl group. As a cationically polymerizable group, a vinyl ether group, oxiranyl group, and oxetanyl group etc. are mentioned. Among these, a (meth) acryloyl group is preferable.
In the present specification, a (meth) acryloyl group intends an acryloyl group and a methacryloyl group.

  The number of polymerizable groups in the polymerizable liquid crystal compound is not particularly limited, but is preferably 1 or more in that the resulting liquid crystal layer has more excellent mechanical properties and less change with time of the properties of the liquid crystal layer. And 2 or more are more preferable. The upper limit of the number of polymerizable groups in the polymerizable liquid crystal composition is not particularly limited, but generally 6 or less is preferable.

  The polymerizable liquid crystal compound is not particularly limited, and known polymerizable liquid crystal compounds can be used. Generally, polymerizable liquid crystal compounds can be classified into rod-like types (rod-like liquid crystal compounds) and disk-like types (discotic liquid crystal compounds, disk-like liquid crystal compounds) according to their shapes, and laminates having more excellent effects of the present invention A polymerizable rod-like liquid crystal compound is preferable in that a body is obtained. Any compound can be used as the polymerizable liquid crystal compound. In addition, two or more kinds of polymerizable liquid crystal compounds may be used in combination.

  The liquid crystal layer 103 may contain a liquid crystal compound, and may contain other components. Hereinafter, other components contained in the liquid crystal layer will be described.

(Polymer in which a polymerizable compound is polymerized)
The liquid crystal layer preferably further contains a polymer obtained by polymerizing a polymerizable compound. The polymerizable compound is intended to be a compound containing at least one polymerizable group in one molecule, and contains a plurality of polymerizable groups in that the orientation state of liquid crystal molecules can be more stably maintained (multifunctional compound (multifunctional compound) ) Polymerizable compounds are preferred.
The form of the polymerizable group is not particularly limited, and the form is as described above as the polymerizable group which the polymerizable liquid crystal composition may contain.
When the liquid crystal layer contains the above-described polymer, the desired alignment state of the liquid crystal compound can be more stably maintained, and the alignment state is less likely to be disturbed by heating and / or time.

It does not restrict | limit especially as a polymeric compound, According to the kind of liquid crystal compound to be used, a well-known polymeric compound can be selected suitably. That is, in the case of using a rod-like liquid crystal compound as the liquid crystal compound, when a rod-like polymerizable compound is used, the alignment state of the rod-like liquid crystal compound is more stabilized and the alignment state is less likely to be disturbed.
The polymerizable compound is not particularly limited, but the compounds described in paragraphs 0012 to 0030 of JP-A 2003-307720, the compounds described in paragraphs 0063 to 0069 of JP-A 2005-181582, JP-A 2009 Compounds described in paragraphs [0030] to [0102] of JP-A-102639; compounds described in paragraphs [0024] to [0051] in JP-A-2009-132718; and [0015] described in JP-A-2010-33093; The above compounds can also be used, and the above contents are incorporated herein.
Moreover, as a polymeric compound, the polymeric liquid crystal compound already demonstrated can also be used. Moreover, as said polymeric compound, the radically polymerizable monomer etc. which are used for a PSA (Polymer Sustained Alignment) system can also be used.
Moreover, as a non-bar-like thing among the said polymeric compounds, the compound described in 0117-0119 stage of Unexamined-Japanese-Patent No. 2015-43073 can also be used, and the said content is integrated in this specification.

  It does not restrict | limit especially as a method to polymerize a polymeric compound and to obtain a polymer, A well-known method can be used. As a method of polymerizing a polymerizable compound, typically, a liquid crystal composition containing a polymerizable compound and a liquid crystal compound is injected between the substrates to align the liquid crystal compound (as a method of aligning the liquid crystal compound, Examples include a method of using an alignment film, a method of applying a voltage, and the like), and a method of forming a polymer by energy application (heat and / or light) to a polymerizable compound. If it is made above, it will be easy to maintain the orientation state of a liquid crystal compound.

(Dichroic dye)
The liquid crystal layer 103 preferably further contains a dichroic dye.
The dichroic dye means a dye having a property in which the absorbance in the major axis direction of the molecule and the absorbance in the minor axis direction are different.

  The content of the dichroic dye in the liquid crystal layer is not particularly limited, but generally, 0.01 to 20% by mass is preferable with respect to the total mass of the liquid crystal layer. The dichroic dyes may be used alone or in combination of two or more. When two or more dichroic dyes are used in combination, the total content is preferably within the above range.

The dichroic dye is not particularly limited, and known dichroic dyes can be used.
The dichroic dye may be a dye or a pigment. Examples of dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes.

<Other Forms of Liquid Crystal Layer>
In another embodiment, the liquid crystal layer 103 is a layer formed by using a liquid crystal compound, in which the liquid crystal phase of the liquid crystal compound is fixed, and which does not exhibit liquid crystallinity.
The layer in which the liquid crystal phase is fixed means a layer in which the alignment of the liquid crystal compound in the desired liquid crystal phase is maintained, and typically, a liquid crystal compound (polymerizable liquid crystal compound) containing a polymerizable group In the desired alignment state, and then polymerize and harden the polymerizable liquid crystal compound by ultraviolet light, heating, etc. to form a layer without fluidity, and simultaneously change the alignment form by external field or external force It is preferable to use a layer which has been changed to a non-generating state.

The form of the liquid crystal compound is the same as that of the liquid crystal compound described above, and the preferable form is also the same as that described above. Moreover, when using a polymeric liquid crystal compound as a liquid crystal compound, as the form, it is the same as that of the polymeric liquid crystal compound already demonstrated, and a preferable form is also the same as the above.
The liquid crystal layer according to the present embodiment is preferably formed using a liquid crystal compound having negative dielectric anisotropy, and is formed using a polymerizable liquid crystal compound having negative dielectric anisotropy. Is more preferred. In this case, the dielectric anisotropy of the compound (typically, a polymer obtained by polymerizing the polymerizable liquid crystal compound) constituting the formed liquid crystal layer may no longer be negative.

[Method of manufacturing laminate]
It does not restrict | limit especially as a manufacturing method of a laminated body, A well-known method can be used. As a method of manufacturing a laminate, a first alignment film is formed on a first substrate using a composition for forming an alignment film containing a triptycene derivative in that the laminate can be manufactured more efficiently. It is preferable to contain a process (alignment film forming process) and a process (liquid crystal layer forming process 1) of forming a liquid crystal layer on the first alignment film using a liquid crystal composition containing a liquid crystal compound in this order. . Below, each said process is demonstrated.

<Alignment film formation process>
The alignment film forming step is a step of forming a first alignment film on the first substrate using the composition for forming an alignment film containing a triptycene derivative.
It does not restrict | limit especially as a method to form a triptycene alignment film on a 1st board | substrate, A coating method, vapor deposition method, etc. can be used.
Examples of the coating method include spin coating method, immersion method, casting method, inkjet method, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, and die coating method.
As a vapor deposition method, PVD (physical vapor deposition), CVD (chemical vapor deposition), etc. are mentioned, for example.

(Composition for forming alignment film)
The composition for forming an alignment film is not particularly limited as long as it contains a triptycene derivative, but it is preferable to contain a solvent in that the triptycene alignment film can be formed more easily. The content of the solvent in the composition for forming an alignment film is not particularly limited, but in general, the solid content of the composition for forming an alignment film is preferably adjusted to be 0.1 to 50% by mass.
The solvent contained in the composition for forming an alignment film is not particularly limited, and the form thereof is as described above as the solvent which the first alignment film may contain.

Further, the alignment film forming step may further include the step of heating the formed first alignment film (annealing step). The heating temperature in the annealing step is not particularly limited, and can be appropriately selected according to the melting point of the triptycene derivative, etc. Among them, the heating temperature is preferably approximately the same as the melting point of the triptycene derivative.
As heating temperature, 60-230 degreeC is generally preferable, and 100 degreeC-230 degreeC is more preferable. The heating time is not particularly limited, but generally 10 to 3000 seconds are preferable. When the method of manufacturing the laminate includes an annealing step, a first alignment film having a more uniform thickness can be obtained.

Furthermore, the alignment film forming step may further include a step of cooling the first alignment film heated in the annealing step (cooling step). When the cooling step is included, the triptycene derivative in the first alignment film is more easily oriented.
The cooling rate is not particularly limited, but in general, 0.5 to 10 ° C./min is preferable.

<Liquid Crystal Layer Forming Step 1>
The liquid crystal layer forming step 1 is a step of forming a liquid crystal layer on the first alignment film using a liquid crystal composition containing a liquid crystal compound. The method of forming the liquid crystal layer on the first alignment film is not particularly limited, and a coating method or the like can be used.
Examples of the coating method include spin coating method, immersion method, casting method, inkjet method, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, and die coating method.

Heating / Exposing Step The liquid crystal layer forming step 1 further includes the step of heating and / or exposing the liquid crystal layer after applying the liquid crystal compound on the first alignment film to obtain the liquid crystal layer May be In particular, when the liquid crystal composition contains a polymerizable compound such as a polymerizable liquid crystal compound, the laminate obtained by the method for producing a laminate containing the above steps has a more stable alignment state of the liquid crystal compound in the liquid crystal layer. It is easy to be maintained.
The light source etc. which have already been explained can be used as the exposure treatment, and there is no particular limitation. For example, the polymerizable composition layer is cured by irradiating light with an irradiation dose of 0.1 to 1000 mJ / cm ^{2 with} an ultraviolet lamp. Form can be mentioned.
Although it does not restrict | limit especially as temperature of heat processing, For example, 30-100 degreeC is preferable, and 50-90 degreeC is more preferable. Moreover, as heating time, 0.1 to 5 minutes are preferable.

Aging Step The liquid crystal layer forming step 1 may further include a aging step before the step of heating and / or exposing the liquid crystal layer.
The ripening step is a step for bringing the liquid crystal compound in the liquid crystal layer into a desired liquid crystal phase.
For example, in a form in which the liquid crystal composition is prepared as a composition containing a solvent, the liquid crystal layer may be dried to remove the solvent, whereby a desired liquid crystal phase may be obtained.
In addition, the liquid crystal layer may be heated to have a transition temperature to a liquid crystal phase. For example, by temporarily heating the liquid crystal layer to the temperature of the isotropic phase and then cooling the liquid crystal layer to the liquid crystal phase transition temperature, a stable liquid crystal phase can be obtained. The aging temperature and the aging time in the aging step can be appropriately selected according to the type of liquid crystal compound contained in the liquid crystal composition.

(Liquid crystal composition)
The liquid crystal composition is not particularly limited as long as it contains the liquid crystal compound described above, but solvents, polymerizable compounds, polymerization initiators, sensitizers, dichroic dyes, alignment control agents, surfactants, etc. May be contained. Below, each component which a liquid crystal composition contains is demonstrated.

Liquid Crystal Compound The liquid crystal composition contains a liquid crystal compound. The content of the liquid crystal compound in the liquid crystal composition is not particularly limited, but generally 10 to 99% by mass is preferable and 10 to 100% by mass is more preferable with respect to the total solid content of the liquid crystal composition. The liquid crystal compounds may be used alone or in combination of two or more. When two or more liquid crystal compounds are used in combination, the total content is preferably within the above range.
The form of the liquid crystal compound contained in the liquid crystal composition is as described above for the liquid crystal compound contained in the liquid crystal layer.

-Solvent The liquid crystal composition may contain a solvent. When the liquid crystal composition contains a solvent, the liquid crystal film can be formed more easily. When the liquid crystal composition contains a solvent, the content of the solvent in the liquid crystal composition is not particularly limited, but generally, the total solid content of the liquid crystal composition is adjusted to be 1 to 100% by mass. preferable. The solvents may be used alone or in combination of two or more. When two or more solvents are used in combination, the total content is preferably within the above range.

It does not restrict | limit especially as a solvent which a liquid-crystal composition contains, A well-known solvent can be used. As the solvent, for example, lactones such as γ-butyrolactone; acetones such as methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone and 2-heptanone; methanol, ethanol, isopropanol etc. Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, and derivatives thereof; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate Glycol esters, etc .; monomethyl ether, monoethyl ether, monopropyl ether of the above polyhydric alcohols or the above esters And monoethers or monoether esters such as monobutyl ether; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate, etc. Esters; Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene, and aromatic systems such as mesitylene Organic solvents; Cyclic ethers such as dioxane and / or tetrahydrofuran (THF); Amides such as dimethylformamide and dimethylacetamide; And the like. These solvents may be used alone or in combination of two or more.
Preferred solvents include dimethylformamide and amides such as dimethylacetamide, cyclic ethers such as dioxane, and sulfur-containing solvents such as dimethylsulfoxide. Particularly preferred solvents include polar solvents such as dimethylformamide and tetrahydrofuran.

Polymerizable Compound The liquid crystal composition preferably contains a polymerizable compound. When the liquid crystal composition contains a polymerizable compound, the alignment state of the liquid crystal compound can be more stably maintained. The content of the polymerizable compound in the liquid crystal composition is not particularly limited, but in general, 0.1 to 10% by mass is preferable with respect to the total solid content of the liquid crystal composition. The polymerizable compounds may be used alone or in combination of two or more. When two or more types of polymerizable compounds are used in combination, the total content is preferably in the above range.
The polymerizable compound is preferably a polymerizable rod-like liquid crystal compound. In addition, as a form of a polymeric compound and a polymeric rod-shaped liquid crystal compound, it is as having already demonstrated.

  When the polymerizable compound is a polymerizable rod-like liquid crystal compound, the preferable range of the content of the polymerizable rod-like liquid crystal compound in the liquid crystal composition follows the description of the preferable range of the content of the liquid crystal compound in the liquid crystal composition. I assume.

Polymerization Initiator The liquid crystal composition preferably contains a polymerization initiator. When the liquid crystal composition contains a polymerization initiator, the alignment state of the liquid crystal compound can be more stably maintained. The content of the polymerization initiator in the liquid crystal composition is not particularly limited, but generally 0.01 to 10% by mass is preferable with respect to the total solid content of the liquid crystal composition. The polymerization initiator may be used alone or in combination of two or more. When two or more types of polymerization initiators are used in combination, the total content is preferably within the above range.

  The polymerization initiator is not particularly limited, and known polymerization initiators can be used. As a polymerization initiator, a thermal polymerization initiator, a photoinitiator, etc. are mentioned. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler's benzoyl benzoates, α-amyloxime esters, phosphine oxides, ketals, anthraquinones, thioxanthones, propiophenones, azo compounds, and the like. Oxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, benzyls, benzoins, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonic acid esters And lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins, and acyl phosphine oxides.

  Specific examples of the photopolymerization initiator, preferred embodiments, commercially available products and the like are described in paragraphs 0133 to 0151 of JP 2009-098658 A, and the above contents are incorporated in the present specification. As a commercial item of a photoinitiator, IRGACURE 819 (Bis (2,4,6- trimethyl benzoyl) -phenyl phosphine oxide, BASF Corporation make) etc. are mentioned, for example.

-Dichroic pigment The liquid crystal composition preferably contains a dichroic pigment. When the liquid crystal composition contains a dichroic dye, the resulting laminate has better polarization absorption performance. In the present specification, polarization absorption performance intends the ability to efficiently absorb linear polarization in a specific direction.
The content of the dichroic dye in the liquid crystal composition is not particularly limited, but generally, 0.01 to 20% by mass is preferable with respect to the total solid content of the liquid crystal composition. The dichroic dyes may be used alone or in combination of two or more. When two or more dichroic dyes are used in combination, the total content is preferably within the above range.
The form of the dichroic dye is as described above as the dichroic dye contained in the liquid crystal layer.

Sensitizer The liquid crystal composition may contain a sensitizer. The content of the sensitizer in the liquid crystal composition is not particularly limited, but generally 0.01 to 10% by mass is preferable with respect to the total solid content of the liquid crystal composition. The sensitizers may be used alone or in combination of two or more. When two or more sensitizers are used in combination, the total content is preferably within the above range.

The sensitizer is not particularly limited, and known sensitizers can be used.
Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and thioxanthone. Examples of commercially available sensitizers include "KAYACURE" series manufactured by Nippon Kayaku Co., Ltd.

Alignment Control Agent The liquid crystal composition may contain an alignment control agent. The content of the alignment control agent in the liquid crystal composition is not particularly limited, but generally 0.01 to 10% by mass is preferable with respect to the total solid content of the liquid crystal composition. The alignment control agent may be used alone or in combination of two or more. When two or more types of alignment control agents are used in combination, the total content is preferably within the above range.

The orientation control agent is not particularly limited, and known orientation control agents can be used.
As an orientation control agent, for example, a low molecular orientation control agent or a high molecular orientation control agent can be used. Examples of low-molecular alignment control agents include, for example, paragraphs 0009 to 0083 of JP-A-2002-20363, paragraphs 0111-0120 of JP-A-2006-106662, and 0021-0029 of JP-A-2012-211306. The description of the paragraph can be referred to, the contents of which are incorporated herein. In addition, as the alignment control agent of a polymer, for example, the description of paragraphs 0021 to 0057 of JP-A 2004-198511 and the paragraphs 0121 to 0167 of JP-A 2006-106661 can be referred to. It is incorporated in the specification.
By using the alignment control agent, for example, the liquid crystal compound can be more easily brought into the homogeneous alignment state in which the liquid crystal compound is aligned in parallel with the surface of the layer.

Surfactant The liquid crystal composition may contain a surfactant. The content of the surfactant in the liquid crystal composition is not particularly limited, but generally 0.01 to 10% by mass is preferable with respect to the total solid content of the liquid crystal composition. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total content is preferably within the above range.

The surfactant is not particularly limited, and known surfactants can be used.
As surfactant, a silicone type surfactant and a fluorine type surfactant are mentioned, for example, A fluorine type surfactant is preferable.

  Specific examples of the surfactant include compounds described in paragraphs 0082 to 0090 of JP-A-2014-119605, compounds described in paragraphs 0031-0034 of JP-A-2012-203237, and JP-A-2005-99248. Compounds described in paragraphs 0092 and 0093, compounds described in paragraphs 0076 to 0078 and 0082 to 0085 of JP-A-2002-129162, and JP-A-2007-272185, paragraphs 0018 to 0043 Compounds etc. may be mentioned.

[Laminated body (second embodiment)]
The laminate according to the second embodiment of the present invention further includes a second substrate (second substrate) on the liquid crystal layer, and the first substrate and the second substrate are a laminate facing each other through the liquid crystal layer. .
A schematic cross-sectional view of a laminate according to a second embodiment of the present invention is shown in FIG. The laminate 200 includes a first substrate 101, a first alignment film 102, a liquid crystal layer 103, a second alignment film (hereinafter also referred to as a “second alignment film”) 201, and a second substrate 202. Prepare in this order.
The laminate 200 of FIG. 2 includes the second alignment film 201 between the liquid crystal layer 103 and the second substrate 202, but the laminate according to the present embodiment does not contain the second alignment film 201. May be

The form of the second alignment film 201 and the second substrate 202 in the laminate 200 is as described above as the form of the first alignment film 102 and the first substrate 101 in the first embodiment.
In addition, other materials and the like are as described above as the form of each layer according to the first embodiment.

[Method of Manufacturing Laminate (Second Embodiment)]
It does not restrict | limit especially as a manufacturing method of a laminated body, A well-known method can be used. As a method for producing a laminate, a composition for forming an alignment film containing a triptycene derivative is used on the first substrate and the second substrate in that the laminate can be produced more efficiently. Step of forming a first alignment film and a second alignment film (alignment film forming step), and a gap formed by arranging two substrates provided with a triptycene alignment film so that the triptycene alignment films face each other It is preferable to contain the process (liquid crystal layer formation process 2) of forming a liquid crystal layer using a liquid crystal composition in this order. Below, each said process is demonstrated.

<Alignment film formation process>
The alignment film forming step is a step of forming a first alignment film and a second alignment film on the first substrate and the second substrate using the composition for forming an alignment film containing a triptycene derivative. .
The method of forming a triptycene alignment film on each substrate and the form of the composition for forming an alignment film are as described above as the method of manufacturing a laminate according to the first embodiment.

<Liquid Crystal Layer Forming Step 2>
The liquid crystal layer forming step 2 is a step of forming a liquid crystal layer using a liquid crystal composition in a gap formed by arranging two substrates having a triptycene alignment film so that the triptycene alignment films face each other.
It does not restrict | limit especially as a method to form a liquid-crystal layer in a space | gap using a liquid-crystal composition, A well-known method can be used. Typically, a spacer and a sealing agent are disposed on one substrate or on a triptycene alignment film, and after bonding two substrates, a liquid crystal composition is injected into the formed void. Can be mentioned. In addition, arrangement | positioning of a spacer may be performed before the alignment film formation process. Further, as another embodiment, after dropping the liquid crystal composition on the triptycene alignment film in advance, a method of bonding two substrates and pressing may be used.
The spacers and the sealing agent are not particularly limited, and known ones can be used. The spacer has a function of equalizing the thickness of the space formed by the two substrates, and for example, the spacer described in paragraph 0024 and paragraph 0029 of JP-A-2016-164617 can be used. , The content of which is incorporated herein.
The sealing agent holds the two substrates integrally and has a function of preventing the liquid crystal composition from leaking. For example, the sealing agent described in paragraphs 0010 to 0041 of JP-A-2007-79588 can be used. The above content is incorporated herein.
The liquid crystal layer formation step 2 may further include a heating / exposure step and / or a ripening step, the form of which is as already described as the method of manufacturing a laminate according to the first embodiment. It is.
The form of the liquid crystal composition that can be used in the liquid crystal layer forming step 2 is as described above as the liquid crystal composition that can be used in the liquid crystal layer forming step 1.

[Laminated body (third embodiment)]
The laminate according to the third embodiment of the present invention has at least one site selected from the group consisting of: between the first substrate and the first alignment film, and between the second substrate and the second alignment film. Furthermore, it is a laminated body provided with a transparent electrode layer.
A schematic cross-sectional view of a laminate according to a third embodiment of the present invention is shown in FIG. The laminate 300 includes a first substrate 101, a transparent electrode layer 301, a first alignment film 102, a liquid crystal layer 103, a second alignment film 201, a transparent electrode layer 302, and a second substrate 202. Prepare in order. In addition, although the laminated body 300 of FIG. 3 is provided with two layers of transparent electrode layers, as a laminated body which concerns on this embodiment, one transparent electrode layer may be sufficient.
When the laminate according to the above embodiment contains a liquid crystal compound, particularly a liquid crystal compound not containing a polymerizable group, the alignment state of the liquid crystal compound can be changed by applying a voltage to the liquid crystal layer 103 by the transparent electrode layer. For example, it is possible to control the transmission amount of light (external light) incident from the outside on the laminate.

The material of the transparent electrode constituting the transparent electrode layers 301 and 302 is not particularly limited, and for example, indium tin oxide (ITO: Indium Tin Oxide), zinc oxide (ZnO), indium zinc oxide (IZO: Indium Zinc Oxide), Gallium zinc oxide (GZO: Gallium Zinc Oxide), and aluminum zinc oxide (Aluminium Zinc Oxide), etc. may be mentioned.
Moreover, as a transparent electrode layer other than the above, the transparent conductive film as described in Unexamined-Japanese-Patent No.2016-197336, or 0012-0078 paragraphs, or a transparent electrode can also be used, for example, The said content is integrated in this specification. Be

The thickness of the transparent electrode layers 301 and 302 is not particularly limited, but generally 0.01 to 1.0 μm is preferable.
The transparent electrode layer may be formed of a transparent electrode (in other words, may be a transparent electrode film), may be formed of a transparent electrode in the form of a pattern, or both may be used in combination.
When the transparent electrode layer contains a pattern-like transparent electrode, the patterning of the transparent electrode can be appropriately selected according to the material of the transparent electrode, and a photolithographic method, a resist mask screen printing-etching method, an inkjet method, and And printing methods can be used.

[Method of manufacturing laminate]
It does not restrict | limit especially as a manufacturing method of the laminated body which concerns on this embodiment, A well-known manufacturing method can be used. Typically, a pattern-like or film-like transparent electrode layer is formed on each substrate by a known method (sputtering, vapor deposition, photolithography, printing, etc.), and the method described above is formed thereon. Form a triptycene alignment film. Then, a laminated body can be manufactured by forming a liquid-crystal layer by the method already demonstrated as a manufacturing method of the laminated body which concerns on 2nd embodiment.

[Use of laminate]
The laminate according to each embodiment of the present invention can be used as a liquid crystal display device, a light control device, a retardation film, and the like.
Among them, when at least one substrate selected from the group consisting of the first substrate and the second substrate is made of a transparent resin, particularly when the first substrate and the second substrate are made of a transparent resin, The body has more excellent flexibility and can be used for a three-dimensional liquid crystal display device or the like.
In the light control device, foreign light is shielded or transmitted by changing the alignment state of the liquid crystal compound in the liquid crystal layer (typically, changing the alignment state by applying a voltage). Devices (so-called electronic blinds, etc.).

  Hereinafter, the present invention will be described in more detail based on examples. Materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

<Production of Laminate 1>
A 1 mass% chloroform solution (Composition 1 for forming an alignment film) of Compound 1 represented by the following formula is spin coated on an alkali-cleaned glass substrate, heated on a hot plate at 100 ° C. for 1 minute, and then at room temperature. Then, a triptycene alignment film was obtained. As described above, a laminate 1 was produced in which a triptycene alignment film containing Compound 1 was provided on a glass substrate.

<Production of Laminate 2>
The same as the laminate 1 except that a PET (polyethylene terephthalate, corresponding to a transparent resin) film provided with a transparent electrode layer (ITO; Indium Tin Oxide) is used in place of the glass substrate in the preparation of the laminate 1. Then, a laminate 2 was produced. In addition, the alignment film was formed on the surface at the side of the transparent electrode layer of PET.

<Preparation of Laminate 3>
A 1 mass% chloroform solution (Composition 2 for forming an alignment film) of Compound 2 represented by the following formula is spin coated on an alkali-cleaned glass substrate, heated on a hot plate at 160 ° C. for 1 minute, and then at room temperature. Then, a triptycene alignment film was obtained. As described above, a laminate 3 was produced, which was provided with a triptycene alignment film containing the compound 2 on a glass substrate.

<Production of Laminate 4>
A 1 mass% chloroform solution (Composition 3 for forming an alignment film) of Compound 3 represented by the following formula is spin coated on an alkali-cleaned glass substrate, heated on a hot plate at 80 ° C. for 1 minute, and then at room temperature. Then, a laminate 4 comprising a layer containing compound 3 on a glass substrate was produced.

Preparation of Liquid Crystal Composition 1
The following liquid crystal compounds LC1 to 5 (containing no polymerizable group), the following polymerizable liquid crystal compound 1 and a polymerization initiator (Irgacure 819) were mixed according to the following composition to prepare a liquid crystal composition 1.
-LC1 15.6 parts by mass-LC2 25.0 parts by mass-LC3 18.8 parts by mass-LC4 18.8 parts by mass-LC5 12.5 parts by mass-polymerizable rod-like liquid crystal compound 1 9.1 parts by mass-polymerization start Agent IRGACURE 819 (BASF) 0.3 part by mass

Preparation of Liquid Crystal Composition 2
A liquid crystal composition 2 was prepared by mixing a commercially available liquid crystal for driving MLC-6608 (a liquid crystal compound containing no polymerizable group) and a commercially available dichroic dye G-241 according to the following composition.
-MLC-6608 (manufactured by Merck) 99.9 parts by mass-G-241 (manufactured by Japan Photosensitive Dye Research Institute) 0.1 parts by mass

<Production of Liquid Crystal Cell 1>
After preparing two sheets of the laminate 1 and placing the triptycene alignment films of the laminate 1 so as to face each other with the 8 μm bead spacer interposed therebetween, in the space formed by the spacer and the two laminates. The liquid crystal composition 1 was injected at room temperature. After the liquid crystal composition 1 is injected, it is left at room temperature for 1 minute, and then 300 mJ / cm ² of UV (ultraviolet) light is irradiated using EXECURE 3000-W manufactured by Hoya-Schott Co., Ltd. to manufacture the liquid crystal cell 1 did. When the liquid crystal cell 1 was observed under crossed nicols using a polarization microscope, it became a dark field, and it was found that the liquid crystal compound was vertically aligned. The birefringence of the liquid crystal cell 1 was measured using AXOSCAN manufactured by AXOMETRICS. As a result, it was confirmed that the liquid crystal cell 1 had large birefringence in the out-of-plane direction (film thickness direction) and the liquid crystal compound was vertically aligned. It was done.

<Production of Liquid Crystal Cell 2>
A liquid crystal cell 2 was produced in the same manner as the liquid crystal cell 1 production method except that the UV light was not irradiated in the production of the liquid crystal cell 1. When the liquid crystal cell 2 was observed under crossed nicols using a polarization microscope, it became a dark field, and it was found that the liquid crystal compound was vertically aligned. The birefringence was measured using AXOSCAN manufactured by AXOMETRICS. As a result, it was confirmed that the birefringence of the liquid crystal cell 2 in the out-of-plane direction (film thickness direction) was large, and the liquid crystal compound was vertically aligned.

<Production of Liquid Crystal Cell 3>
A liquid crystal cell 3 was produced in the same manner as the liquid crystal cell 1 production method except that a glass substrate was used in place of the laminate 1 in the production of the liquid crystal cell 1. When the liquid crystal cell 3 was observed under crossed nicols using a polarization microscope, the texture due to the random alignment of the liquid crystal compound was observed, and it was found that the liquid crystal compound was not vertically aligned.

<Production of Liquid Crystal Cell 4>
After preparing the two laminates 2 above and setting the triptycene alignment films of the laminate 1 so as to face each other with the 8 μm bead spacer interposed, in the air gap formed by the spacer and the two laminates. The liquid crystal composition 2 was injected at room temperature to prepare a liquid crystal cell 4. It was found that the color density of the liquid crystal cell 4 is higher when observed obliquely than when observed from the front, and the dichroic dye is vertically aligned with the liquid crystal. In addition, it was found that by performing wiring processing on the upper and lower transparent electrodes of the liquid crystal cell 4 and applying a voltage, the transmittance was changed, and the alignment of the dichroic dye was changed with the driving of the liquid crystal. .

<Production of Liquid Crystal Cell 5>
A liquid crystal cell 5 was produced in the same manner as the liquid crystal cell 1 except that the laminate 3 was used instead of the laminate 1 in the production of the liquid crystal cell 1. When the liquid crystal cell 5 is observed under crossed nicols using a polarization microscope, a dark field is obtained, and it is found that the liquid crystal compound is vertically aligned. The birefringence was measured using AXOSCAN manufactured by AXOMETRICS. As a result, it was confirmed that the birefringence of the liquid crystal cell 5 in the out-of-plane direction (film thickness direction) was large, and the liquid crystal compound was vertically aligned.

<Production of Liquid Crystal Cell 6>
A liquid crystal cell 6 was produced in the same manner as in the liquid crystal cell 1 except that the laminate 4 was used instead of the laminate 1 in the production of the liquid crystal cell 1. When the liquid crystal cell 6 is observed under crossed nicols using a polarization microscope, a dark field is obtained, and it is found that the liquid crystal compound is vertically aligned. The birefringence was measured using AXOSCAN manufactured by AXOMETRICS. As a result, it was confirmed that the birefringence of the liquid crystal cell 6 in the out-of-plane direction (film thickness direction) was large, and the liquid crystal compound was vertically aligned.

<Heat resistance test>
The liquid crystal cell 1 and the liquid crystal cell 2 were placed on a hot plate at 100 ° C. and left for a fixed time (to be described later). Thereafter, each liquid crystal cell was returned to room temperature, and a change in alignment was observed. When the liquid crystal cell 2 was placed on a hot plate at 100 ° C. for 1 minute, the alignment state was disturbed and the vertical alignment was lost. On the other hand, it was found that the liquid crystal cell 1 did not disturb the alignment state even after being placed on a hot plate at 100 ° C. for 30 minutes, and the vertical alignment was maintained.

100, 200, 300 laminate 101 first substrate 102 first alignment film 103 liquid crystal layer 201 second alignment film 202 second substrate 301, 302 transparent electrode layer

Claims (13)

  A laminate comprising a first substrate, a first alignment film containing a triptycene derivative, and a liquid crystal layer in this order. The laminated body of Claim 1 whose said triptycene derivative is a compound represented by General formula (1).
In the general formula (1), R ¹ represents a saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms, and the hydrocarbon group may contain one or more substituents. Also, preferably, one or more carbon atoms in the hydrocarbon group are an oxygen atom, a sulfur atom, a silicon atom, or -NR ^5- (wherein R ⁵ represents a hydrogen atom, 1 carbon atom To 10 alkyl groups or aryl groups having 6 to 30 carbon atoms).
In general formula (1), R ² represents a group -R ¹ -Z, a hydrogen atom, or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
In general formula (1), R ³ represents a group -R ¹ -Z, a hydrogen atom, or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
In the general formula (1), three R ^{4 s} may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, a monoalkyl substituted amino group, a dialkyl substitution An amino group, an alkyl group having 1 to 10 carbon atoms which may contain a substituent, an alkenyl group having 2 to 10 carbon atoms which may contain a substituent, 2 to 10 carbon atoms which may contain a substituent Alkynyl group, an alkoxy group having 1 to 10 carbon atoms which may contain a substituent, an alkylthio group having 1 to 10 carbon atoms which may contain a substituent, a formyl group, a carbon which may contain a substituent The alkylcarbonyl group having a number of 1 to 10, the alkoxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, the alkylcarbonyloxy group having 1 to 10 carbon atoms which may have a substituent, and a substituent May It contains 1 to 5 at least one hetero atom selected from the group consisting of an aryl group having 6 to 30 carbon atoms, or a nitrogen atom, an oxygen atom, and a sulfur atom, and contains 2 to 10 carbon atoms And a 5- to 8-membered heteroaryl group which may have a substituent.
In the general formula (1), X may be the same or different, and each independently represents 1 to 5 selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, carbon atom, and silicon atom And a linker group consisting of a divalent atom group composed of atoms and hydrogen atoms.
In the general formula (1), Z represents a hydrogen atom, a group which can be bonded or adsorbed to the surface of a solid substrate, or a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, a phosphorus atom, a halogen atom and a silicon atom And 1 to 15 atoms selected from the group consisting of: and a terminal group consisting of a monovalent atomic group consisting of hydrogen atoms.
In the general formula (1), when one or both of R ² and R ³ are a group -R ¹ -Z, a plurality of R ¹ and Z may be the same or different.   The laminate according to claim 1, further comprising a second substrate on the liquid crystal layer, wherein the first substrate and the second substrate face each other through the liquid crystal layer.   The laminate according to claim 3, further comprising a second alignment film containing the triptycene derivative between the second substrate and the liquid crystal layer.   A transparent electrode layer is further provided at at least one location selected from the group consisting of: between the first substrate and the first alignment film, and between the second substrate and the second alignment film. The laminated body of Claim 4.   The laminate according to any one of claims 3 to 5, wherein at least one substrate selected from the group consisting of the first substrate and the second substrate is made of a transparent resin.   The liquid crystal layer according to any one of claims 1 to 6, wherein the liquid crystal layer contains a liquid crystal compound having a negative dielectric anisotropy or a liquid crystal compound having a negative dielectric anisotropy. The laminated body as described in a term.   The laminate according to any one of claims 1 to 7, wherein the liquid crystal layer contains a polymer obtained by polymerizing a polymerizable compound.   The laminate according to claim 8, wherein the polymerizable compound is a polymerizable rod-like liquid crystal compound.   The laminate according to any one of claims 1 to 9, wherein the liquid crystal layer further contains a dichroic dye.   Composition for alignment film formation containing a triptycene derivative. The composition for alignment film formation of Claim 11 whose said triptycene derivative is a compound represented by General formula (1).
In the general formula (1), R ¹ represents a saturated or unsaturated divalent hydrocarbon group having 2 to 60 carbon atoms, and the hydrocarbon group may contain one or more substituents. Also, preferably, one or more carbon atoms in the hydrocarbon group are an oxygen atom, a sulfur atom, a silicon atom, or -NR ^5- (wherein R ⁵ represents a hydrogen atom, 1 carbon atom To 10 alkyl groups or aryl groups having 6 to 30 carbon atoms).
In general formula (1), R ² represents a group -R ¹ -Z, a hydrogen atom, or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
In general formula (1), R ³ represents a group -R ¹ -Z, a hydrogen atom, or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
In the general formula (1), three R ^{4 s} may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, a monoalkyl substituted amino group, a dialkyl substitution An amino group, an alkyl group having 1 to 10 carbon atoms which may contain a substituent, an alkenyl group having 2 to 10 carbon atoms which may contain a substituent, 2 to 10 carbon atoms which may contain a substituent Alkynyl group, an alkoxy group having 1 to 10 carbon atoms which may contain a substituent, an alkylthio group having 1 to 10 carbon atoms which may contain a substituent, a formyl group, a carbon which may contain a substituent The alkylcarbonyl group having a number of 1 to 10, the alkoxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, the alkylcarbonyloxy group having 1 to 10 carbon atoms which may have a substituent, and a substituent May It contains 1 to 5 at least one hetero atom selected from the group consisting of an aryl group having 6 to 30 carbon atoms, or a nitrogen atom, an oxygen atom, and a sulfur atom, and contains 2 to 10 carbon atoms And a 5- to 8-membered heteroaryl group which may have a substituent.
In General Formula (1), X is a divalent atom composed of 1 to 5 atoms selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, carbon atom, and silicon atom, and hydrogen atom. Represents a linker group consisting of
In the general formula (1), Z represents a hydrogen atom, a group which can be bonded or adsorbed to the surface of a solid substrate, or a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, a phosphorus atom, a halogen atom and a silicon atom And 1 to 15 atoms selected from the group consisting of: and a terminal group consisting of a monovalent atomic group consisting of hydrogen atoms.
In the general formula (1), when one or both of R ² and R ³ are a group -R ¹ -Z, a plurality of R ¹ and Z may be the same or different.   An alignment film formed using the composition for forming an alignment film according to claim 11 or 12.