JP6853347B2 - Method for producing organic film, organic film and liquid crystal composition - Google Patents

Description

The present invention relates to a method for producing an organic film, an organic film and a liquid crystal composition.

A triphenylene derivative that forms a uniform periodic structure over a large area has been reported (Non-Patent Document 1). According to this document, by substituting an alkoxycarbonyl group as a substituent on the triphenylene ring, the interaction between the triphenylene rings is enhanced, a column composed of a triphenylene derivative is formed (columnar phase), and the interaction between the columns increases the interaction between the columns. , While the column stands perpendicular to the substrate, a large domain assembled in a hexagonal structure is formed. At this time, the π plane of the triphenylene ring is oriented parallel to the in-plane direction of the substrate, and exhibits an anisotropically large electron transport capability in the column axis, that is, the out-of-plane direction.

Angew. Chem. Int. Ed. 2012, 51, 7990

However, as a result of repeated studies on the method for producing an organic film described in the above document, the present inventors have suppressed the occurrence of focal conic defects and uniformly has a large domain (for example, 1 cm square or more). It was found that it is necessary to avoid quenching of the liquid crystal composition and to lower the temperature from the isotropic phase at a very slow rate of about 0.5 ° C. per minute.

Therefore, an object of the present invention is to provide a method for producing an organic film in which the occurrence of focal conic defects is suppressed and a large domain is uniformly present when the temperature is lowered at a high rate of 2 ° C. or more per minute. .. It is also an object of the present invention to provide an organic film and a liquid crystal composition.

As a result of diligent studies on the above problems, the present inventor added a fluorine-based alignment agent to the liquid crystal composition when producing an organic film using the liquid crystal composition, thereby forming a coating film of the liquid crystal composition every time. We have found that it is possible to provide a method for producing an organic film having a large domain uniformly while suppressing the occurrence of focal conic defects even when the temperature is lowered at a high rate of 2 ° C. or more, and the present invention has been made.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1]
A step of forming a coating film of a liquid crystal composition containing a triphenylene derivative and a fluorine-based alignment agent, and
The step of heating the coating film to a temperature at which the triphenylene derivative is transferred to an isotropic phase, and
It has a step of lowering the temperature of the coating film after heating until the triphenylene derivative is transferred to the columnar liquid crystal phase to form an organic film.
In the organic film, the triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and the organic film is the organic film of the column in which the triphenylene rings are stacked in the thin film X-ray diffraction measurement. A method for producing an organic film, which shows a peak derived from a periodic structure in the in-plane direction of.
[2]
The method for producing an organic film according to [1], wherein the triphenylene derivative contains a triphenylene derivative represented by the formula (1) described later.
In the formula (1) described later, R ¹ may independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent. Represents an unsaturated hydrocarbon group having 1 to 20 carbon atoms. Here, ^{one or more carbon atoms among the carbon atoms contained in R 1} may be substituted with an oxygen atom or a carbonyl group.
[3]
The method for producing an organic film according to [2], wherein the triphenylene derivative represented by the above formula (1) has an unsaturated hydrocarbon group.
[4]
The fluorine-based alignment agent is at least one compound selected from the group consisting of compounds represented by the formulas (2), (3), (4), (5) and (6) described later. The method for producing an organic film according to any one of [1] to [3], which comprises.
In the formula (2) described later, L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , and L ¹⁶ are independently single-bonded, -O-, -S-, and -C (O)-, respectively. , -C (O) O-, -OC (O)-, -C (O) S-, -SC (O)-, -NRC (O)-, or -C (O) NR- R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Sp ¹¹ , Sp ¹² , Sp ¹³ and Sp ¹⁴ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. A ¹¹ and A ¹² represent aromatic hydrocarbon groups, Hb ¹¹ and Hb ¹² each independently represent a perfluoroalkyl group having 2 to 30 carbon atoms, and m11 and n11 independently represent 0 to 3, respectively. And m11 + n11 ≧ 1, where T ¹¹ is a divalent group or divalent heterocycle selected from the group consisting of the formulas (T-1) to (T-15) described later. Represents a group.
In the formulas (T-1) to (T-15) described later, X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, and Ya, Yb, Yc and Yd are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and o and p each independently represent an integer of 0 or more.
In the formula (3) described later, X ³¹ , X ³² and X ³³ independently represent -NH-, -O- or -S-, and Y ³¹ , Y ³² and Y ³³ are independent of each other. In addition, at least two divalent linking groups selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _{2- or a group selected from the above group are combined.} Represents a divalent linking group, Rf ³¹ , Rf ³² and Rf ³³ _{independently represent a fluorine-substituted alkyl group having a CF 3} group or a CF ₂ H group at the end, and m31, m32 and m33 are independent, respectively. Represents an integer of 1-3.
In the formula (4) described later, Y ⁴¹ , Y ⁴² and Y ⁴³ are independently selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-. Represents a divalent linking group to be prepared or a divalent linking group in which at least two groups selected from the above group are combined, and Rf ⁴¹ , Rf ⁴² and Rf ⁴³ are independently terminated with ₃ CF groups or CFs, respectively. ₂ Represents a fluorine-substituted alkyl group having an H group.
In formula (5) described later, Y ⁵¹ is a divalent linking group selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _{2- or the above group.} represents a divalent linking group formed by combining at least two groups that are more selected, ^{Rf 51} represents a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the end, m51 is an integer of 1 to 3 Represents.
In formula (6) described later, Y ⁶¹ , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ are independently alkylene groups, -CO-, -NH-, -O-, -S- and, respectively. -SO ₂ - a divalent linking group or a group selected from the group selected from the group consisting of representing at least two combined divalent linking ^{group, Rf 61, Rf 62, Rf} 63, Rf 64, Rf ⁶⁵ and Rf ⁶⁶ each independently represent a fluorine-substituted alkyl group having a _{CF 3} group or a CF _{2 H group at the end.} However, ^{in at least one group of Y 61} , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ , the structure including the portion directly bonded to the triphenylene ring is -O- * and -O (O) C-. Represents a structure other than *. Note that * indicates the bonding position with the triphenylene ring.
[5]
The method for producing an organic film according to any one of [2] to [4], wherein the triphenylene derivative further contains a triphenylene derivative represented by the formula (7) described later.
In the formula (7) described later, ^{each of R 7} independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20. Here, ^{one or more carbon atoms among the carbon atoms contained in R 7} may be substituted with an oxygen atom or a carbonyl group.
[6]
The method for producing an organic film according to [5], wherein the triphenylene derivative represented by the above formula (7) has an unsaturated hydrocarbon group.
[7]
In the step of forming the organic film, any one of [1] to [6], wherein the temperature of the coating film is lowered and then the coating film is exposed to fix the orientation of the triphenylene ring. The method for producing an organic film according to one.
[8]
The production of the organic film according to any one of [1] to [7], wherein the orientation of the triphenylene ring is immobilized by a covalent bond between the triphenylene derivatives or immobilized by a binder. Method.
[9]
The method for producing an organic film according to any one of [1] to [8], wherein the liquid crystal composition contains a photopolymerization initiator.
[10]
An organic film containing at least one selected from the group consisting of a triphenylene derivative and a polymer of the above triphenylene derivative, and a fluorine-based orientation agent.
The triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and the peak derived from the periodic structure of the column in which the triphenylene rings are stacked is shown in the in-plane direction of the organic film in the thin film X-ray diffraction measurement. , Organic film.
[11]
A liquid crystal composition containing a triphenylene derivative and a fluorine-based orientation agent.
The triphenylene derivative contains a triphenylene derivative represented by the formula (1) described later, and contains the triphenylene derivative.
The fluorine-based alignment agent is at least one compound selected from the group consisting of compounds represented by the formulas (2), (3), (4), (5) and (6) described later. A liquid crystal composition containing.
In the formula (1) described later, R ¹ may independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent. Represents an unsaturated hydrocarbon group having 1 to 20 carbon atoms. Here, ^{one or more carbon atoms among the carbon atoms contained in R 1} may be substituted with an oxygen atom or a carbonyl group.
In the formula (2) described later, L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , and L ¹⁶ are independently single-bonded, -O-, -S-, and -C (O)-, respectively. , -C (O) O-, -OC (O)-, -C (O) S-, -SC (O)-, -NRC (O)-, or -C (O) NR- R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Sp ¹¹ , Sp ¹² , Sp ¹³ and Sp ¹⁴ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. A ¹¹ and A ¹² represent aromatic hydrocarbon groups, Hb ¹¹ and Hb ¹² each independently represent a perfluoroalkyl group having 2 to 30 carbon atoms, and m11 and n11 independently represent 0 to 3, respectively. Represents an integer of m11 + n11 ≧ 1, and T ¹¹ is a divalent group or a divalent aromatic complex selected from the group consisting of the following formulas (T-1) to (T-15). Represents a ring group.
In the formulas (T-1) to (T-15) described later, X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, and Ya, Yb, Yc and Yd are , Each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and o and p each independently represent an integer of 0 or more.
In the formula (3) described later, X ³¹ , X ³² and X ³³ independently represent -NH-, -O- or -S-, and Y ³¹ , Y ³² and Y ³³ are independent of each other. In addition, at least two divalent linking groups selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _{2- or a group selected from the above group are combined.} Rf ³¹ , Rf ³² and Rf ³³ each independently _{represent a fluorine-substituted alkyl group having a CF 3} group or a CF ₂ H group at the end, and m31, m32 and m33 are independent, respectively. Represents an integer of 1-3.
In the formula (4) described later, Y ⁴¹ , Y ⁴² and Y ⁴³ are independently selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-. Represents a divalent linking group to be prepared or a divalent linking group in which at least two groups selected from the above group are combined, and Rf ⁴¹ , Rf ⁴² and Rf ⁴³ are independently terminated with ₃ CF groups or CFs, respectively. ₂ Represents a fluorine-substituted alkyl group having an H group.
In formula (5) described later, Y ⁵¹ is a divalent linking group selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _{2- or the above group.} represents a divalent linking group formed by combining at least two groups that are more selected, ^{Rf 51} represents a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the end, m51 is an integer of 1 to 3 Represents.
In formula (6) described later, Y ⁶¹ , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ are independently alkylene groups, -CO-, -NH-, -O-, -S- and, respectively. -SO ₂ - a divalent linking group or a group selected from the group selected from the group consisting of representing at least two combined divalent linking ^{group, Rf 61, Rf 62, Rf} 63, Rf 64, Rf ⁶⁵ and Rf ⁶⁶ each independently represent a fluorine-substituted alkyl group having a _{CF 3} group or a CF _{2 H group at the end.} However, ^{in at least one group of Y 61} , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ , the structure including the portion directly bonded to the triphenylene ring is -O- * and -O (O) C-. Represents a structure other than *. Note that * indicates the bonding position with the triphenylene ring.
[12]
The liquid crystal composition according to [11], wherein the triphenylene derivative represented by the above formula (1) has an unsaturated hydrocarbon group.
[13]
The liquid crystal composition according to [11] or [12], wherein the triphenylene derivative further contains a triphenylene derivative represented by the formula (7) described later.
In the formula (7) described later ^{, each of R 7} may independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent. Represents an unsaturated hydrocarbon group having 1 to 20 carbon atoms. Here, ^{one or more carbon atoms among the carbon atoms contained in R 7} may be substituted with an oxygen atom or a carbonyl group.
[14]
The liquid crystal composition according to [13], wherein the triphenylene derivative represented by the above formula (7) has an unsaturated hydrocarbon group.
[15]
The liquid crystal composition according to any one of [11] to [14], further containing a photopolymerization initiator.

As shown below, according to the present invention, there is provided a method for producing an organic film in which the occurrence of focal conic defects is suppressed and a large domain is uniformly present when the temperature is lowered at a high rate of 2 ° C. or more per minute. can do. Further, according to the present invention, an organic film and a liquid crystal composition can also be provided.

The present invention will be described below.
In the present invention, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

[Manufacturing method of organic film]
In the method for producing an organic film of the present invention, a step of forming a coating film of a liquid crystal composition containing a triphenylene derivative and a fluorine-based alignment agent (hereinafter, also referred to as a "coating film forming step") and the above-mentioned triphenylene derivative are isotropic. The step of heating the coating film to a temperature at which the coating film changes to the phase (hereinafter, also referred to as “coating film heating step”) and the temperature of the coating film after heating are lowered until the triphenylene derivative transfers to the columnar liquid crystal phase. It also has a step of forming an organic film (hereinafter, also referred to as an “organic film forming step”).
Further, in the organic film, the triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and the organic film is the column in which the triphenylene rings are stacked in the thin film X-ray diffraction measurement. The peak derived from the periodic structure in the in-plane direction of the organic membrane is shown.
According to the method for producing an organic film of the present invention, even when the temperature of the coating film of the liquid crystal composition is lowered at a high rate of 2 ° C. or more per minute, the occurrence of focal conic defects is suppressed and a large domain is formed. An organic film having a uniform shape can be formed.
The details of this reason have not been clarified yet, but it is presumed to be due to the following reasons. That is, by adding the fluorine-based alignment agent to the liquid crystal composition, the fluorine-based alignment agent in the coating film of the liquid crystal composition rapidly moves to the air interface. It is presumed that this prevented the triphenylene derivative in the liquid crystal composition from causing orientation disorder at the air interface even when the coating film was rapidly cooled.

Hereinafter, the steps included in the method for producing an organic film of the present invention and the steps that can be included will be described.

[Coating film forming process]
The coating film forming step is a step of forming a coating film of a liquid crystal composition containing a triphenylene derivative and a fluorine-based aligning agent.
The coating film of the liquid crystal composition is formed, for example, by applying the liquid crystal composition to the substrate. The liquid crystal composition can be applied by a curtain coating method, a dip coating method, a spin coating method, a printing coating method, a spray coating method, a slot coating method, a roll coating method, a slide coating method, a blade coating method, a gravure coating method, and the like. , A known method such as a wire bar method.

The coating film forming step may include a drying treatment. By the drying treatment, components such as a solvent can be removed from the coating film. The drying treatment may be carried out by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by a method of heating and / or blowing air.
The coating film heating step described later may also serve as the drying treatment.

Examples of the substrate include a glass substrate and a plastic film. As the glass substrate, a non-alkali glass substrate for display applications is preferably used, and as the plastic film, for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polycarbonate film, polyether sulfone film, polysulfone film, polyarylate. Films, cyclic polyolefin films, polyimide films, acetyl cellulose-based films and the like are preferably used.

<Liquid crystal composition>
The liquid crystal composition used in the method for producing an organic film of the present invention contains a triphenylene derivative and a fluorine-based orientation agent.

(Triphenylene derivative)
The triphenylene derivative means a compound based on a triphenylene ring (structure).
The triphenylene derivative more preferably contains a triphenylene derivative represented by the following formula (1). By using the triphenylene derivative represented by the following formula (1), the triphenylene ring derived from the triphenylene derivative can be more easily oriented in the in-plane direction of the organic film, and the triphenylene ring is stacked in the thin film X-ray diffraction measurement. It becomes easier to obtain an organic film showing a peak derived from the periodic structure in the in-plane direction of the organic film.

In the above formula (1), R ¹ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20.
In the above formula (1), R ¹ at least one of a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent group or, carbon atoms that may have a substituent 1 to 20, It is preferable that it is an unsaturated hydrocarbon group of ¹ , and all R 1 may have a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. More preferably, it is an unsaturated hydrocarbon group having a number of 1 to 20.
The number of carbon atoms of the saturated hydrocarbon group and unsaturated hydrocarbon group R ¹ represents preferably 1 to 15, 1 to 10 is more preferable. The saturated hydrocarbon group and the unsaturated hydrocarbon group may be linear or branched, but linear is preferable.
When R ¹ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group and a cyano group.
When R ¹ is a saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, one or more carbon atoms among the carbon atoms are oxygen atoms or carbonyl groups. It may be replaced with. Specific examples of such a group include a group ^{represented by −R 11} −OC (O) −R ¹² , a group represented by − (R ¹¹ −O) _n1 −R ¹² , and −R. Examples include groups represented by ^11- C (O) -R ^12. In each formula, R ¹¹ and R ¹² each independently include a saturated hydrocarbon group which may have a substituent or an unsaturated hydrocarbon group which may have a substituent, and n1 is 1 or more. Represents an integer of.

Specific examples of the triphenylene derivative represented by the formula (1) are shown below.

Specifically, the triphenylene derivative preferably contains a triphenylene derivative represented by the following formula (7).
By using the triphenylene derivative represented by the formula (7) and the triphenylene derivative represented by the formula (1) in combination, not only the crystallization is suppressed, but also the isotropic phase transition temperature rises, and the phase is phased. It has the advantage of expanding the transition temperature range.

In the above formula (7), R ⁷ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20.
In the above formula (7), ^{at least one of R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 1 to 20 carbon atoms which may have a substituent. of preferably an unsaturated hydrocarbon group, all of R ⁷ is a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, or may have a substituent group having a carbon More preferably, it is an unsaturated hydrocarbon group having a number of 1 to 20.
The number of carbon atoms of the saturated hydrocarbon group and the unsaturated hydrocarbon group represented by ^{R 7 is preferably 1 to 15, and more preferably 1 to 10.} The saturated hydrocarbon group and the unsaturated hydrocarbon group may be linear or branched, but linear is preferable.
When R ⁷ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group and a cyano group.
When R ⁷ is a saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, one or more carbon atoms among the carbon atoms are oxygen atoms or carbonyl groups. It may be replaced with. Specific examples of such a group include a group ^{represented by -R 71-} OC (O) -R ⁷² , a group represented _by- ^{(R 71-} O) n7 -R ⁷² , and -R. Examples include groups represented by ^71- C (O) -R ^72. In each formula, R ⁷¹ and R ⁷² each independently include a saturated hydrocarbon group which may have a substituent or an unsaturated hydrocarbon group which may have a substituent, and n7 is 1 or more. Represents an integer of.

Specific examples of the triphenylene derivative represented by the formula (7) are shown below.

The triphenylene derivative in the present invention preferably has a polymerizable group from the viewpoint of promoting the immobilization of the orientation of the triphenylene ring in the organic film. As the polymerizable group, a polymerization having an ethylenically unsaturated group such as a vinyl group, a vinyloxy group, a styryl group, a p- (2-phenylethenyl) phenyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, etc. Examples thereof include a sex group, an epoxy group, and an oxetanyl group. As the polymerizable group, a radically polymerizable group and a cationically polymerizable group suitable for photopolymerization are preferable, and since they tend to be easy to handle and easy to produce, acryloyl group, metachloroyl group and acryloyl group are preferable. An oxy group or a methacryloyloxy group is preferred.
When the triphenylene derivative in the present invention contains at least one of the triphenylene derivative represented by the formula (1) and the triphenylene derivative represented by the formula (7), at least one of these triphenylene derivatives is the unsaturated hydrocarbon described above. It is preferable to have a group. In this case, by polymerizing the triphenylene derivatives during the production of the organic film of the present invention, the triphenylene derivatives are fixed by covalent bonds. That is, the orientation of the triphenylene ring can be easily fixed.

(Fluorine-based alignment agent)
The fluorine-based alignment agent has a function of controlling the orientation of the triphenylene derivative at the air interface. The fluorine-based alignment agent is not particularly limited as long as it is a compound having a fluorine atom having the above functions.
The fluorine-based alignment agent is preferably a compound having a fluoroalkyl group at the molecular terminal from the viewpoint of being able to exert the above functions more, and the following formulas (2), (3), (4), (5) and ( It is more preferable to contain at least one compound selected from the group consisting of the compounds represented by 6).

In formula (2), L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ and L ¹⁶ are independently single-bonded, -O-, -S-, -C (O)-,-, respectively. Represents C (O) O-, -OC (O)-, -C (O) S-, -SC (O)-, -NRC (O)-, or -C (O) NR-, where R stands for Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The alkyl group that R can take may be linear or branched. The alkyl group preferably has 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group.

In formula (2), Sp ¹¹ , Sp ¹² , Sp ¹³ and Sp ¹⁴ independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and are a single bond or an alkylene group having 1 to 7 carbon atoms. Is preferable, and a single bond or an alkylene group having 1 to 4 carbon atoms is more preferable. However, the hydrogen atom of the alkylene group may be substituted with a fluorine atom.
The alkylene group may or may not be branched, but a linear alkylene group is preferred. From a synthetic point of view, it is preferable that ^{Sp 11} and Sp ¹⁴ are the same, and Sp ¹² and Sp ^{13 are the same.}

In formula (2), A ¹¹ and A ¹² represent aromatic hydrocarbon groups. The ^{number of carbon atoms of the aromatic hydrocarbon group represented by A 11} and A ¹² is preferably 6 to 22, more preferably 6 to 14, further preferably 6 to 10, and particularly preferably 6. The aromatic hydrocarbon groups represented by ^{A 11} and A ^{12 may have a substituent.}
Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group, or an ester group. For the description and preferred ranges of these groups, reference to the corresponding description of the T ¹¹ below. Among these, the substituent is preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, or a cyano group.
Since a molecule having a large amount of perfluoroalkyl moiety in the molecule can orient the liquid crystal with a small amount of addition, A ¹¹ and A ¹² are trivalent or tetravalent so as to have many perfluoroalkyl groups in the molecule. Is preferable, and tetravalent is more preferable.
From a synthetic point of view, it is preferable that ^{A 11} and A ^{12 are the same.}

Hb ¹¹ and Hb ¹² each independently represent a perfluoroalkyl group having 2 to 30 carbon atoms, preferably a perfluoroalkyl group having 3 to 20 carbon atoms, and more preferably a perfluoroalkyl group having 3 to 10 carbon atoms. .. The perfluoroalkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.

m11 and n11 each independently represent an integer of 0 to 3, and m11 + n11 ≧ 1.
When m11 or n11 in the formula (2) is 2 or more, the structures in a plurality of parentheses may be the same or different from each other, but it is preferable that they are the same. M11 and n11 in the formula (2) ^is determined by the valence of ^{A 11} and ^{A 12,} the preferred range is also determined by the valency of the preferred range of ^{A 11} and ^{A 12.}

T ¹¹ represents a divalent group or a divalent heterocyclic group selected from the group consisting of the following formulas (T-1) to (T-15), and represents the following formulas (T-1) to (T-15). A divalent group selected from the group consisting of -15) is preferable, and the following formula (T-1), formula (T-4), formula (T-13), formula (T-14), or formula (T-14) is preferable. The divalent group represented by T-15) is more preferable, and the divalent group represented by the following formula (T-1) is further preferable.

In the above formulas (T-1) to (T-15), X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, and Ya, Yb, Yc and Yd are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The ^{number of carbon atoms of the alkyl group that X contained in T 11} can take is 1 to 8, preferably 1 to 5, and more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched. As the alkyl group, a methyl group, an ethyl group, an n-propyl group and an isopropyl group are preferable, and a methyl group is more preferable.
The alkyl moiety of the alkoxy group X contained in the T ¹¹ can take, can refer to the description and the preferred range of the alkyl group X contained in the T ¹¹ can take.
Examples of the ^{halogen atom that X contained in T 11} can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable.
Examples of the ^{ester group that X contained in T 11} can take include a group represented by R'COO-. As R', an alkyl group having 1 to 8 carbon atoms can be mentioned. For the description and preferable range of the alkyl group that R'can take, the description of the alkyl group that X contained in ^{T 11 can take and the preferable range can be referred to.} Specific examples of the ester group include CH ₃ COO- and C ₂ H ₅ COO-.
The alkyl groups having 1 to 4 carbon atoms that can be taken by Ya, Yb, Yc, and Yd may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group can be mentioned.
O and p contained in T ¹¹ independently represent integers of 0 or more, and when o and p are 2 or more, a plurality of X's may be the same or different from each other. The ^{o contained in T 11} is preferably 1 or 2. The ^{p contained in T 11} is preferably an integer of 1 to 4, and more preferably 1 or 2.

The ^{divalent heterocyclic group represented by T 11} preferably has a 5-membered, 6-membered or 7-membered heterocycle. Of these, a 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is even more preferable. As the complex atom constituting the heterocycle, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. The heterocycle is preferably an aromatic heterocycle. Aromatic heterocycles are generally unsaturated heterocycles. Unsaturated heterocycles with the most double bonds are more preferred.
Examples of the heterocycle include a furan ring, a thiophene ring, a pyrrole ring, a pyrrolin ring, a pyrrolidine ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothazole ring, an imidazole ring, an imidazoline ring, an imidazoline ring, a pyrazole ring, a pyrazoline ring, Pyrazolidine ring, triazole ring, flazan ring, tetrazole ring, pyrazole ring, thine ring, pyridine ring, piperidine ring, oxazine ring, morpholin ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, and triazine ring. Can be mentioned.
The divalent heterocyclic group may have a substituent. For a description and preferred range of examples of such substituents, the description and description of possible substituents of the aromatic hydrocarbon groups ^{A 1} and A ^{2 above can be referred to.}

The compound represented by the formula (2) may have a molecular structure having symmetry or may not have symmetry. The symmetry here means one that corresponds to any of point symmetry, line symmetry, and rotational symmetry, and asymmetry does not correspond to any of point symmetry, line symmetry, and rotational symmetry. Means things.
The compound represented by the formula (2) includes the perfluoroalkyl groups (Hb ¹¹ and Hb ¹² ) described above, and the linking group-(-Sp ^11- L ^{11- Sp 12-} L ¹² ) m _11- A ^11- L. It is a compound in which ¹³ − and −L ¹⁴ −A ¹² − (L ¹⁵ − Sp ^{13 −} L ¹⁶ − Sp ¹⁴ −) n ₁₁ ^{− and T 11} which is a divalent group having an excluded volume effect are combined. When two or more perfluoroalkyl groups are present in the molecule, they are preferably the same, and the linking group-(-Sp ^11- L ^{11- Sp 12-} L ¹² ) m _11- A ^{11 in the molecule.} When both −L ¹³ − and −L ¹⁴ −A ¹² − (L ¹⁵ − Sp ^{13 −} L ¹⁶ − Sp ¹⁴ −) n ₁₁ − are present, it is preferable that these linking groups are also the same as each other. ..

End of ^{Hb 11 -Sp 11 -L 11 -Sp 12} - and ^-Sp 13 ^-L 16 ^-Sp 14 ^{-Hb 12} is preferably a group represented by any one of the following formulas.
(C _a F _{2a + 1} )-(C _b H _2b )-
(C _a F _{2a + 1} )-(C _b H _2b ) -O- (C _r H _2r )-
(C _a F _{2a + 1} )-(C _b H _2b ) -C (O) O- (C _r H _2r )-
(C _a F _{2a + 1} )-(C _b H _2b ) -OC (O)-(C _r H _2r )-
In the above formula, a is preferably 2 to 30, more preferably 3 to 20, and even more preferably 3 to 10. b is preferably 0 to 20, more preferably 0 to 10, and even more preferably 0 to 5. a + b is 3 to 30. r is preferably 1 to 10, more preferably 1 to 4. However, in the above _{formula, - (C r H 2r)} - if there is is, b is 10 or less.
^{Furthermore, Hb 11 -Sp 11 -L 11 -Sp} 12 -L 12 end of the equation (2) - and ^{-L 15 -Sp 13 -L 16 -Sp 14} -Hb 12 , the table in either of the following formulas It is preferable that it is a group to be used.
(C _a F _{2a + 1} )-(C _b H _2b ) -O-
(C _a F _{2a + 1} )-(C _b H _2b ) -C (O) O-
_{(C a F 2a + 1)} - (C b H 2b) -O- (C r H 2r) -O-
(C _a F _{2a + 1} )-(C _b H _2b ) -C (O) O- (C _r H _2r ) -C (O) O-
_{(C a F 2a + 1)} -OC (O) - (C r H 2r) -C (O) O-
The definitions of a, b and r in the above equation are the same as the definitions described above.

Specific examples of the compound represented by the formula (2) include the compounds described in paragraphs [0020] to [0031] described in JP2013-47204A.

In the above formula (3), X ³¹ , X ³² and X ³³ independently represent -NH-, -O- or -S-, and Y ³¹ , Y ³² and Y ³³ independently represent, respectively. , An alkylene group, a divalent linking group selected from the group consisting of -CO-, -NH-, -O-, -S- and -SO _2- , or at least two groups selected from this group. Represents a combined divalent linking group, a divalent linking group selected from the group consisting of an alkylene group, -NH- and -O-, or at least two divalent linking groups selected from this group. A combined group is preferable, and a divalent linking group selected from the group consisting of an alkylene group and —O—, or a group in which at least two divalent linking groups selected from this group are combined is more preferable.
m31, m32 and m33 each independently represent an integer of 1 to 3, preferably 2.
Rf ^{31, Rf 32} and ^{Rf 33} independently represents a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the terminal. The _{alkyl group having a CF 3} group or a CF ₂ H group at the terminal may be linear or branched chain, preferably having 4 to 20 carbon atoms, and more preferably 4 to 16 carbon atoms. It is more preferably 6 to 16. Further, a group other than the terminal group of the fluorine-substituted alkyl group (that is, an alkylene group) may have a substituent.
Alkyl group having a CF ₃ group or CF 2 _H group at the end is an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms contained in the alkyl group. It is preferable that 50% or more of the hydrogen atoms in the alkyl group are substituted with fluorine atoms, more preferably 60% or more are substituted, and even more preferably 70% or more are substituted. Examples of alkyl groups (Rf1 to Rf12) having _{CF 3} groups or CF ₂ H groups at the ends represented by Rf ¹ , Rf ² and Rf ^{3 are shown below.}

_{Rf1: n-C 8 F 17} -
_{Rf2: n-C 6 F 13} -
_{Rf3: n-C 4 F 9} -
_{Rf4: n-C 8 F 17} - (CH 2) 2 -
_{Rf5: n-C 6 F 13} - (CH 2) 2 -
_{Rf6: n-C 4 F 9} - (CH 2) 2 -
_{Rf7: H- (CF 2) 8} -
Rf8: H- (CF ₂ ) _{6-
Rf9: H- (CF 2) 4} -
_{Rf10: H- (CF 2) 8} - (CH 2) -
Rf11: H- (CF ₂ ) _6- (CH ₂ )-
_{Rf12: H- (CF 2) 4} - (CH 2) -

In the above formula (4), Y ⁴¹ , Y ⁴² and Y ⁴³ are independently selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-. Represents a divalent linking group or a divalent linking group in which at least two groups selected from this group are combined, and is selected from the group consisting of an alkylene group, -NH-, -O- and -S-. A divalent linking group or a group in which at least two divalent linking groups selected from this group are combined is preferable, and a divalent linking group selected from the group consisting of an alkylene group, -NH- and -O- A linking group or a group in which at least two divalent linking groups selected from this group are combined is more preferable, and -NH-, -O-, or -NH (CH _{2 ) n-} O- (in the formula). , N represents an integer of 1 to 8, preferably 3; more preferably, a nitrogen atom is bonded to the triazine ring).
Rf ⁴¹ , Rf ⁴² and Rf ⁴³ each independently represent a fluorine-substituted alkyl group having a _{CF 3} group or a CF ₂ H group at the end, and are synonymous with ^{Rf 31} , Rf ³² and Rf ^{33 in the formula (3).} , The preferred range is also the same.

In the above formula (5), Y ⁵¹ is a divalent linking group selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _{2-, or a divalent linking group thereof.} Represents a divalent linking group that combines at least two groups selected from the group. Y ^{51 has the same meaning as Y 31} , Y ³² and Y ³³ in the formula (3), and the preferred range thereof is also the same.
Rf ⁵¹ represents a fluorine-substituted alkyl group having a _{CF 3} group or a CF ₂ H group at the terminal, ^{and is synonymous with Rf 31} , Rf ³² and Rf ³³ in the formula (3), and the preferable range thereof is also the same.
m51 represents an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

In the above formula (6), Y ⁶¹ , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ are independently alkylene groups, -CO-, -NH-, -O-, -S- and-, respectively. It represents a divalent linking group selected from the group consisting of SO _2- , or a divalent linking group obtained by combining at least two groups selected from this group. Y ⁶¹ , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ^{66 are synonymous with Y 31} , Y ³² and Y ³³ in formula (3), and their preferred ranges are also the same. However, ^{in at least one group of Y 61} , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ , the structure including the portion directly bonded to the triphenylene ring is -O- * and -O (O) C-. Represents a structure other than *. Note that * indicates the bonding position with the triphenylene ring.
Rf ⁶¹ , Rf ⁶² , Rf ⁶³ , Rf ⁶⁴ , Rf ⁶⁵ and Rf ⁶⁶ each independently represent a fluorine-substituted alkyl group having a _{CF 3} group or a CF ₂ H group at the end, and ^{Rf 31} in formula (3), It is synonymous with Rf ³² and Rf ³³ , and the preferred range thereof is also the same.

Specific examples of the compound represented by the formula (3), the formula (4) or the formula (5) are shown below, but the fluorine-based aligning agent is not limited thereto. In the specific examples below, No. I-1 to 27 are the formulas (3), No. I-28 to 39 are the formulas (4), No. I-40 to 50 are examples of compounds represented by the formula (5).

Among the above-mentioned fluorine-based orientation agents, the fluorine-based alignment agent preferably contains a compound represented by the above formula (3) from the viewpoint of further exerting the effect of the present invention.

In the liquid crystal composition, the content of the fluorine-based alignment agent is preferably 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass with respect to the content (100 parts by mass) of the triphenylene derivative in the liquid crystal composition. Parts are more preferable, and 0.1 to 5 parts by mass is further preferable.
The fluorine-based alignment agent may be used alone or in combination of two or more. When two or more kinds are used in combination, two or more kinds of compounds represented by the formulas (2) to (6) may be used in combination, or the compounds represented by the formulas (2) to (6) may be used in combination. , Other known compounds may be used in combination. As the compound that can be used in combination, for example, the fluoroaliphatic-containing polymer described in paragraphs [0043] to [0055] of JP-A-2008-46436 can be preferably used. These fluoroaliphatic-containing polymers can also be used alone.

(Photopolymerization initiator)
The liquid crystal composition used in the method for producing an organic film of the present invention is a photopolymerization initiator from the viewpoint of promoting the immobilization of the orientation of the triphenylene ring when the component contained in the liquid crystal composition has a polymerizable group. May be contained.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrances. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents). 35493667 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), and acyl. Examples thereof include phosphine oxide compounds (described in JP-A-63-40799, JP-A-5-29234, JP-A-10-95788, JP-A-10-29997).
When the liquid crystal composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 20% by mass with respect to the total solid content (100% by mass) of the liquid crystal composition. , 1 to 8% by mass, more preferably.

(Polymerizable monomer)
The liquid crystal composition used in the method for producing an organic film of the present invention may contain a polymerizable monomer from the viewpoint of promoting the immobilization of the orientation of the triphenylene ring.
Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. The polymerizable monomer is a compound having a polymerizable group as a functional group, which is a component different from the above-mentioned triphenylene derivative. Specific examples of the polymerizable group are as described in the section on triphenylene derivatives.
The polymerizable monomer may be either a monofunctional monomer having one polymerizable group or a polyfunctional monomer having two or more polymerizable groups, but it efficiently forms a polymer network and stabilizes the orientation of the liquid crystal. A polyfunctional monomer is preferable in terms of causing it to occur. As the polymerizable monomer, for example, known (meth) acrylate monomers described in JP-A-2015-43073 [0117] to [0119] can be used.
When the liquid crystal composition contains a polymerizable monomer, the content of the polymerizable monomer is preferably 0.1 to 30% by mass, preferably 1 to 20% by mass, based on the total solid content (100% by mass) of the liquid crystal composition. % Is more preferable.

(binder)
The liquid crystal composition used in the method for producing an organic film of the present invention may contain a binder from the viewpoint of promoting the immobilization of the orientation of the triphenylene ring.
Examples of the binder include polymers such as polymethylmethacrylate, and those having a crosslinkable group are also preferable.
When the liquid crystal composition contains a binder, the content of the binder is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total solid content (100% by mass) of the liquid crystal composition. ..

(Other ingredients)
The liquid crystal composition used in the method for producing an organic film of the present invention may contain components other than the above, and examples thereof include known components such as an organic solvent and a sensitizer.

[Coating film heating process]
The coating film heating step is a step of heating the coating film to a temperature at which the triphenylene derivative is transferred to an isotropic phase.
The heating temperature is not particularly limited as long as it is the temperature at which the triphenylene derivative in the coating film transitions to an isotropic phase, but is preferably 50 to 300 ° C, more preferably 70 to 250 ° C, and even more preferably 80 to 200 ° C.
The heating means is not particularly limited, and a known device (for example, a heating device such as a hot plate and a dryer) can be used.

[Organic film forming process]
The organic film forming step is a step of lowering the temperature of the heated coating film until the triphenylene derivative is transferred to the columnar liquid crystal phase to form an organic film. As a result, in the organic film, the triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and the organic film is the organic film of the column in which the triphenylene rings are stacked in the thin film X-ray diffraction measurement. It shows the peak derived from the periodic structure in the in-plane direction of.

The temperature lowering rate in the temperature lowering treatment is preferably -2 ° C./min or less (that is, the coating film is lowered by 2 ° C./min or more), more preferably -5 ° C./min or less (that is, the coating film is 5 ° C./min / min). To decrease above). Since the liquid crystal composition used in the method for producing an organic film of the present invention contains the above-mentioned fluorine-containing alignment agent, focal conic defects occur even when the temperature of the coating film is lowered at such a high speed. It is possible to obtain an organic film that is suppressed and has a large domain uniformly.
The lower limit of the temperature lowering rate is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, from the viewpoint of more exerting the effect of the present invention.
The temperature lowering treatment means is not particularly limited, and a known device having a temperature control function can be used.

In the organic film forming step, after the temperature of the coating film is lowered, the coating film may be exposed to an exposure treatment to fix the orientation of the triphenylene ring.
The exposure treatment is preferably used when the liquid crystal composition has a polymerizable group. The exposure treatment accelerates the polymerization reaction by the polymerizable group.
The exposure means used for the exposure process is not particularly limited, and a known exposure apparatus may be used. Further, the exposure treatment is preferably carried out by irradiation with ultraviolet rays.

<Orientation of triphenylene ring>
According to the method for producing an organic film of the present invention, the triphenylene ring is oriented in the in-plane direction of the organic film. "The triphenylene ring is oriented in the in-plane direction of the organic film" means that the plane (disk-shaped surface) of the triphenylene ring is oriented in the in-plane direction of the organic film.
The orientation of the triphenylene ring in the present invention can be estimated from observation with a polarizing microscope. Specifically, when the coating film containing the triphenylene derivative transferred to the isotropic phase is optically observed with a polarizing microscope with a hot stage (FP90 manufactured by Metrator Toledo) or a device equivalent thereto while lowering the temperature. , When a leaf branch-like domain called a dendric texture is formed in the liquid crystal phase and in-plane anisotropy is not confirmed over the entire domain, the triphenylene ring is oriented in the in-plane direction of the organic film. It is estimated to be.
Here, the column represents a state in which a plurality of triphenylene rings are stacked with their axes aligned. Therefore, when the triphenylene rings are oriented in the in-plane direction of the organic film, the plurality of triphenylene rings constituting the column are stacked in the thickness direction of the organic film, and the column is oriented in the thickness direction of the organic film. It can be said that.
The fact that a plurality of triphenylene rings are stacked in the thickness direction of the organic film means that when the organic film is measured by the thin film X-ray diffraction method described later, the peak derived from the π association between the triphenylene rings is generated. It is also indicated by being detected. In particular, when a peak corresponding to a period of 0.35 to 0.37 nm is detected, it can be said that the positional relationship between the triphenylene rings is good and the column is well formed.

<Confirmation of periodicity between multiple columns in the in-plane direction>
According to the method for producing an organic film of the present invention, the obtained organic film shows a peak derived from a periodic structure in the in-plane direction of the organic film of the column in thin film X-ray diffraction measurement. That is, in the obtained organic film, it is shown that a plurality of columns are periodically arranged in the in-plane direction of the organic film.
The peak derived from the periodic structure described above may be a 6-fold symmetric peak corresponding to a period of 1.6 to 3.0 nm derived from the fact that a plurality of columns form a hexagonal lattice in the in-plane direction. preferable. As a result, it can be said that the columns are arranged in a good positional relationship in the in-plane direction of the organic film.
Here, the thin film X-ray diffraction measurement is performed using an X-ray diffractometer of the RIKEN Center for Radiological Science, and an organic film that has been sufficiently cooled to room temperature or whose orientation has been fixed by polymerization is used. Is preferable. The above thin film X-ray diffraction measurement can also be performed using a general X-ray diffractometer (for example, a nanoviewer manufactured by Rigaku Co., Ltd.), but from the viewpoint of accuracy, the Center for Radiological Sciences, RIKEN An X-ray diffractometer is preferable.

[Organic film]
The organic film of the present invention contains at least one selected from the group consisting of a triphenylene derivative and a polymer of the above triphenylene derivative, and a fluorine-based orientation agent. Further, in the organic film of the present invention, the triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and in the thin film X-ray diffraction measurement, the in-plane direction of the organic film of the column on which the triphenylene rings are stacked. The peak derived from the periodic structure in.
The organic film of the present invention has an excellent property that the occurrence of focal conic defects is suppressed by the action of the fluorine-based orienting agent and the large domain is uniformly held.

The organic film of the present invention is preferably obtained by the above-mentioned method for producing an organic film of the present invention from the viewpoint of better expressing the above-mentioned properties. The properties of the organic film of the present invention and the components constituting the organic film are as described in the above-mentioned "Method for producing an organic film", and thus the description thereof will be omitted.
Here, the polymer of the triphenylene derivative is intended to be in the form of polymerizing the triphenylene derivative described in the above-mentioned "Method for producing an organic film". For example, when the triphenylene derivative contains a triphenylene derivative represented by the formula (1) and / or a triphenylene derivative represented by the formula (3), and these triphenylene derivatives have an unsaturated hydrocarbon group, unsaturated carbonization A polymer of a triphenylene derivative is formed with a hydrogen group as a polymerization point.

The use of the organic film of the present invention is not particularly limited, but is used, for example, as an optical film. In particular, from the viewpoint of the orientation of the triphenylene derivative and / or the polymer of the triphenylene derivative contained in the organic film, it can be suitably used as a negative C plate.
Other uses of the organic membrane of the present invention include Angew. Chem. Int. Ed. Examples thereof include the organic semiconductors described in 2012, 51 and 7990.

[Liquid crystal composition]
The liquid crystal composition of the present invention is a liquid crystal composition containing a triphenylene derivative and a fluorine-based orientation agent, wherein the triphenylene derivative contains a triphenylene derivative represented by the above formula (1), and the fluorine-based orientation agent is used. , At least one compound selected from the group consisting of the compounds represented by the above formulas (2), (3), (4), (5) and (6).
According to the liquid crystal composition of the present invention, the occurrence of focal conic defects is further suppressed even when the temperature of the coating film of the liquid crystal composition is lowered at a high speed of 2 ° C. or more per minute during the production of the organic film. It is possible to form an organic film having a large domain more uniformly.
The components contained in the liquid crystal composition of the present invention and the components that can be contained are as described in the above-mentioned "Method for producing an organic film", and thus the description thereof will be omitted.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to this.

[Example 1]
A liquid crystal composition 1 having the following composition was prepared, and the liquid crystal composition 1 was spin-coated on a glass substrate washed with alkali to form a coating film of the liquid crystal composition 1. Next, the coating film was heated to 100 ° C. using a polarizing microscope with a hot stage (FP90 manufactured by METTLER TOLEDO), and then the coating film was optically observed while the temperature was lowered from 100 ° C. to 2 ° C. per minute. It was. At 95 ° C, dislocations from the isotropic phase to the columnar phase were observed, leaf branch-like domain formation called dendric texture (domain size: 1 cm square or more) was observed, and the triphenylene ring was oriented in the in-plane direction of the organic membrane. An oriented organic film 1 was obtained.
When thin film X-ray diffraction measurement was performed on the obtained organic film 1, a peak corresponding to a period of 0.35 to 0.37 nm and a 6-fold symmetry corresponding to a period of 1.6 to 3.0 nm were performed. The peak was confirmed.
Here, the peak corresponding to the period of 0.35 to 0.37 nm is a peak derived from the π association between the triphenylene rings, and the triphenylene ring is 0.35 to 0.37 nm with respect to the thickness direction of the organic film. It is shown that the columns are formed by stacking in the cycle of.
The 6-fold symmetric peak corresponding to the period of 1.6 to 3.0 nm is a peak derived from the hexagonal columnar phase, and the columns have a period of 1.6 to 3.0 nm in the in-plane direction of the organic film. Indicates that they are arranged in.
――――――――――――――――――――――――――――――
Composition of liquid crystal composition 1 ――――――――――――――――――――――――――――――
・ The following triphenylene derivative 1-4 3.98 parts by mass ・ The following fluorine-based air interface alignment agent I-6 0.02 parts by mass ・ Chloroform 96.0 parts by mass ――――――――――――――― ―――――――――――――――

In the above formula (1-4), "*" indicates a bond position with -O-, and in the above formula (I-6), "*" represents a bond position with a benzene ring.

[Example 2]
A liquid crystal composition 2 having the following composition was prepared, and the liquid crystal composition 2 was spin-coated on a glass substrate washed with alkali to form a coating film of the liquid crystal composition 2. After raising the temperature of the coating film to 150 ° C. with a polarizing microscope equipped with a hot stage (FP90 manufactured by METTLER TOLEDO), the coating film was optically observed while the temperature was lowered from 150 ° C. to 2 ° C. per minute. At 138 ° C, dislocations from the isotropic phase to the columnar phase were observed, leaf branch-like domain formation called dendric texture (domain size: 1 cm square or more) was observed, and the triphenylene ring was oriented in the in-plane direction of the organic membrane. An oriented organic film 2 was obtained.
When the obtained organic film 2 was subjected to thin film X-ray diffraction measurement, a peak corresponding to a period of 0.35 to 0.37 nm and a 6-fold symmetry corresponding to a period of 1.6 to 3.0 nm were performed. The peak was confirmed. The details of each peak are as described in Example 1.
Further, the isotropic phase transition temperature of compound 7-2 is 90 ° C., and the mixing of compound 1-4 and compound 7-2 significantly raises the isotropic phase transition temperature and stabilizes the columnar phase. I understood.
――――――――――――――――――――――――――――――
Composition of liquid crystal composition 2 ――――――――――――――――――――――――――――――
-The above triphenylene derivative 1-4 1.9 parts by mass-The following triphenylene derivative 7-2 1.99 parts by mass-The above fluorine-based aligning agent 1 0.02 parts by mass-Chloroform 96.0 parts by mass ――――――― ―――――――――――――――――――――――

In the above formula (7-2), "*" indicates the bonding position with -O-.

[Comparative Example 1]
A liquid crystal composition 3 having the following composition was prepared, and the liquid crystal composition 3 was spin-coated on a glass substrate washed with alkali to form a coating film of the liquid crystal composition 3. After raising the temperature of the coating film to 100 ° C. with a polarizing microscope equipped with a hot stage (FP90 manufactured by METTLER TOLEDO), optical observation of the coating film was performed while lowering the temperature from 100 ° C. to 2 ° C. per minute. At 95 ° C., a dislocation from the isotropic phase to the columnar phase was observed, and an optical structure in which the column was randomly oriented, called focal conic, was observed.
――――――――――――――――――――――――――――――
Composition of liquid crystal composition 3 ――――――――――――――――――――――――――――――
・ The above triphenylene derivative 1-4 4.00 parts by mass ・ Chloroform 96.0 parts by mass ――――――――――――――――――――――――――――――

Claims (14)

A step of forming a coating film of a liquid crystal composition containing a triphenylene derivative and a fluorine-based alignment agent, and
A step of heating the coating film to a temperature at which the triphenylene derivative is transferred to an isotropic phase, and
It comprises a step of lowering the temperature of the heated coating film to form an organic film until the triphenylene derivative is transferred to the columnar liquid crystal phase.
In the organic film, the triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and the organic film is the organic film of a column in which the triphenylene rings are stacked in a thin film X-ray diffraction measurement. A method for producing an organic film, which shows a peak derived from a periodic structure in the in-plane direction of. The method for producing an organic film according to claim 1, wherein the triphenylene derivative contains a triphenylene derivative represented by the following formula (1).

In the above formula (1), R ¹ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20. Here, ^{one or more carbon atoms among the carbon atoms contained in R 1} may be substituted with an oxygen atom or a carbonyl group. The method for producing an organic film according to claim 2, wherein the triphenylene derivative represented by the formula (1) has an unsaturated hydrocarbon group. The fluorine-based alignment agent is at least one compound selected from the group consisting of the compounds represented by the following formulas (2), (3), (4), (5) and (6). The method for producing an organic film according to any one of claims 1 to 3, which comprises.

In the above formula (2), L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ and L ¹⁶ are independently single-bonded, -O-, -S-, -C (O)-, respectively. Represents -C (O) O-, -OC (O)-, -C (O) S-, -SC (O)-, -NRC (O)-, or -C (O) NR-, and R Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Sp ¹¹ , Sp ¹² , Sp ¹³ and Sp ¹⁴ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. ¹¹ and A ¹² represent aromatic hydrocarbon groups, Hb ¹¹ and Hb ¹² each independently represent a perfluoroalkyl group having 2 to 30 carbon atoms, and m11 and n11 independently represent 0 to 3, respectively. It represents an integer and m11 + n11 ≧ 1, and T ¹¹ is a divalent group or a divalent heterocyclic group selected from the group consisting of the following formulas (T-1) to (T-15). Represent.

In the formulas (T-1) to (T-15), X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, and Ya, Yb, Yc and Yd are respectively. Independently, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and o and p each independently represent an integer of 0 or more.

In the above formula (3), X ³¹ , X ³² and X ³³ independently represent -NH-, -O-, or -S-, and Y ³¹ , Y ³² and Y ³³ independently represent, respectively. , An alkylene group, a divalent linking group selected from the group consisting of -CO-, -NH-, -O-, -S- and -SO _2-, or a combination of at least two groups selected from the group. represents a divalent linking ^group, each Rf 31, ^{Rf 32} and ^{Rf 33} independently represents a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the end, m31, m32 and m33 each independently , Represents an integer of 1-3.

In the above formula (4), Y ⁴¹ , Y ⁴² and Y ⁴³ are independently selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-. Represents a divalent linking group consisting of at least two divalent linking groups or a combination of at least two groups selected from the group, and Rf ⁴¹ , Rf ⁴² and Rf ⁴³ _{independently have 3} CF groups or CF ₂ at the ends, respectively. Represents a fluorine-substituted alkyl group having an H group.

In the formula (5), Y ⁵¹ is a divalent linking group selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-, or a divalent linking group selected from the group. a group selected represents at least two combined divalent linking group, ^{Rf 51} represents a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the end, m51 is 1-3 integer Represent.

In the above formula (6), Y ⁶¹ , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ are independently alkylene groups, -CO-, -NH-, -O-, -S- and-, respectively. Represents a divalent linking group selected from the group consisting of SO _2- or a divalent linking group obtained by combining at least two groups selected from the group, Rf ⁶¹ , Rf ⁶² , Rf ⁶³ , Rf ⁶⁴ , Rf. ⁶⁵ and Rf ⁶⁶ each independently represent a fluorine-substituted alkyl group having a _{CF 3} group or a CF _{2 H group at the end.} However, ^{in at least one group of Y 61} , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ , the structure including the portion directly bonded to the triphenylene ring is -O- * and -O (O) C-. Represents a structure other than *. Note that * indicates the bonding position with the triphenylene ring. The method for producing an organic film according to any one of claims 2 to 4, wherein the triphenylene derivative further contains a triphenylene derivative represented by the following formula (7).

In the above formula (7), R ⁷ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents 1 to 20 unsaturated hydrocarbon groups. Here, ^{one or more carbon atoms among the carbon atoms contained in R 7} may be substituted with an oxygen atom or a carbonyl group. The method for producing an organic film according to claim 5, wherein the triphenylene derivative represented by the formula (7) has an unsaturated hydrocarbon group. Any one of claims 1 to 6, wherein in the step of forming the organic film, the temperature of the coating film is lowered and then the coating film is exposed to fix the orientation of the triphenylene ring. The method for producing an organic film according to. The method for producing an organic film according to any one of claims 1 to 7, wherein the orientation of the triphenylene ring is immobilized by a covalent bond between the triphenylene derivatives or immobilized by a binder. The method for producing an organic film according to any one of claims 1 to 8, wherein the liquid crystal composition contains a photopolymerization initiator. An organic film containing at least one selected from the group consisting of a triphenylene derivative and a polymer of the triphenylene derivative, and a fluorine-based orientation agent.
The triphenylene ring derived from the triphenylene derivative is oriented in the in-plane direction of the organic film, and the peak derived from the periodic structure of the column in which the triphenylene rings are stacked is shown in the in-plane direction of the organic film in the thin film X-ray diffraction measurement. And
An organic film in which the triphenylene derivative contains a triphenylene derivative represented by the following formula (1) and a triphenylene derivative represented by the following formula (7).

In the above formula (1), R ¹ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20. Here, ^{one or more carbon atoms among the carbon atoms contained in R 1} may be substituted with an oxygen atom or a carbonyl group.

In the above formula (7), R ⁷ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20. Here, ^{one or more carbon atoms among the carbon atoms contained in R 7} may be substituted with an oxygen atom or a carbonyl group. A liquid crystal composition containing a triphenylene derivative and a fluorine-based orientation agent.
The triphenylene derivative contains a triphenylene derivative represented by the following formula (1) and a triphenylene derivative represented by the following formula (7).
The fluorine-based alignment agent is at least one compound selected from the group consisting of the compounds represented by the following formulas (2), (3), (4), (5) and (6). Liquid crystal composition, including.

In the above formula (1), R ¹ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20. Here, ^{one or more carbon atoms among the carbon atoms contained in R 1} may be substituted with an oxygen atom or a carbonyl group.

In the above formula (2), L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ and L ¹⁶ are independently single-bonded, -O-, -S-, -C (O)-, respectively. Represents -C (O) O-, -OC (O)-, -C (O) S-, -SC (O)-, -NRC (O)-, or -C (O) NR-, and R Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Sp ¹¹ , Sp ¹² , Sp ¹³ and Sp ¹⁴ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. ¹¹ and A ¹² represent aromatic hydrocarbon groups, Hb ¹¹ and Hb ¹² each independently represent a perfluoroalkyl group having 2 to 30 carbon atoms, and m11 and n11 independently represent 0 to 3, respectively. Representing an integer and m11 + n11 ≧ 1, T ¹¹ is a divalent group or a divalent aromatic heterocycle selected from the group consisting of the following formulas (T-1) to (T-15). Represents a group.

In the formulas (T-1) to (T-15), X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or an ester group, and Ya, Yb, Yc and Yd are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and o and p each independently represent an integer of 0 or more.

In the above formula (3), X ³¹ , X ³² and X ³³ independently represent -NH-, -O-, or -S-, and Y ³¹ , Y ³² and Y ³³ independently represent, respectively. , An alkylene group, a divalent linking group selected from the group consisting of -CO-, -NH-, -O-, -S- and -SO _2-, or a combination of at least two groups selected from the group. It represents a divalent linking ^group, Rf 31, ^{Rf 32} and ^{Rf 33} each independently represent a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the end, m31, m32 and m33 each independently , Represents an integer of 1-3.

In the above formula (4), Y ⁴¹ , Y ⁴² and Y ⁴³ are independently selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-. Represents a divalent linking group consisting of at least two divalent linking groups or a combination of at least two groups selected from the group, and Rf ⁴¹ , Rf ⁴² and Rf ⁴³ _{independently have 3} CF groups or CF ₂ at the ends, respectively. Represents a fluorine-substituted alkyl group having an H group.

In the formula (5), Y ⁵¹ is a divalent linking group selected from the group consisting of an alkylene group, -CO-, -NH-, -O-, -S- and -SO _2-, or a divalent linking group selected from the group. a group selected represents at least two combined divalent linking group, ^{Rf 51} represents a fluorine-substituted alkyl group having a CF ₃ group or CF ₂ H group at the end, m51 is 1-3 integer Represent.

In the above formula (6), Y ⁶¹ , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ are independently alkylene groups, -CO-, -NH-, -O-, -S- and-, respectively. Represents a divalent linking group selected from the group consisting of SO _2- or a divalent linking group obtained by combining at least two groups selected from the group, Rf ⁶¹ , Rf ⁶² , Rf ⁶³ , Rf ⁶⁴ , Rf. ⁶⁵ and Rf ⁶⁶ each independently represent a fluorine-substituted alkyl group having a _{CF 3} group or a CF _{2 H group at the end.} However, ^{in at least one group of Y 61} , Y ⁶² , Y ⁶³ , Y ⁶⁴ , Y ⁶⁵ and Y ⁶⁶ , the structure including the portion directly bonded to the triphenylene ring is -O- * and -O (O) C-. Represents a structure other than *. Note that * indicates the bonding position with the triphenylene ring.

In the above formula (7), R ⁷ independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents an unsaturated hydrocarbon group of numbers 1 to 20. Here, ^{one or more carbon atoms among the carbon atoms contained in R 7} may be substituted with an oxygen atom or a carbonyl group. The liquid crystal composition according to claim 11, wherein the triphenylene derivative represented by the formula (1) has an unsaturated hydrocarbon group. The liquid crystal composition according to claim 11 or 12 , wherein the triphenylene derivative represented by the formula (7) has an unsaturated hydrocarbon group. The liquid crystal composition according to any one of claims 11 to 13 , further comprising a photopolymerization initiator.