Compound, mixture, liquid crystal composition, cured product, optically anisotropic body, and reflective film

文档序号：788641 发布日期：2021-04-09 浏览：26次中文

阅读说明：本技术 化合物、混合物、液晶组合物、固化物、光学各向异性体、反射膜 (Compound, mixture, liquid crystal composition, cured product, optically anisotropic body, and reflective film ) 是由小玉启祐铃木优子加藤峻也于 2019-09-04 设计创作，主要内容包括：本发明的课题在于,提供一种通过利用紫外线等光照射的曝光来增加HTP的强度的化合物及含有上述化合物的混合物。并且,本发明的另一课题在于,提供一种液晶组合物、固化物、光学各向异性体及反射膜。本发明的化合物由下述通式(1)表示。(The present invention addresses the problem of providing a compound that increases the intensity of an HTP by exposure to light such as ultraviolet light, and a mixture containing the compound. Another object of the present invention is to provide a liquid crystal composition, a cured product, an optically anisotropic body, and a reflective film. The compound of the present invention is represented by the following general formula (1).)

1. A compound represented by the general formula (1),

in the general formula (1), R¹～R⁶Each independently represents a hydrogen atom or a substituent having a valence of 1, wherein R¹～R⁶At least one of them represents a substituent having a valence of 1 represented by the following general formula (2), the portion of the solid line parallel to the dotted line represents a single bond or a double bond, R¹And R²May be bonded to each other to form a ring structure,

in the general formula (2), Ar¹Represents an n +1 valent aromatic hydrocarbon ring group, C^ARepresents a carbon atom, R⁷And R⁸Each independently represents a hydrogen atom, a cyano group, a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group or a C1-10 aliphatic hydrocarbon group, RⁱRepresents a substituent having a valence of 1, n represents an integer of 0 to 5, and L¹Represents a single bond or a 2-valent linking group represented by the following general formula (3), represents a bonding position with the binaphthyl skeleton in the general formula (1),

when n is 2 or more, a plurality of RⁱMay be the same or different from each other,

*—L²—Ar²—**

(3)

in the general formula (3), L²Represents a single bond or a 2-valent linking group, Ar²An aromatic hydrocarbon ring group having a valence of 2, wherein the aromatic hydrocarbon ring group represents a bonding position with the binaphthyl skeleton in the general formula (1), and the aromatic hydrocarbon ring group represents a bonding position with the C in the general formula (2)^AThe bonding site of (3).

2. The compound of claim 1, wherein,

said L¹Represents a single bond.

3. The compound according to claim 1 or 2, wherein,

is selected from the group consisting of said R¹The R is³And said R⁵One or more of the groups represents a substituent having a valence of 1 represented by the general formula (2), and is selected from the group consisting of the R²The R is⁴And said R⁶One or more of the groups represents a substituent having a valence of 1 represented by the general formula (2).

4. The compound according to any one of claims 1 to 3, wherein,

the R is¹And said R²Bonded to each other to form a ring structure.

5. The compound according to any one of claims 1 to 4, wherein,

said L¹Represents a 2-valent linking group represented by the general formula (3), or the RⁱIs represented by^S1-aromatic hydrocarbon ring group, or said R¹And said R²Are bonded to each other to represent^S2-2-valent aromatic hydrocarbon ring radical-L^S2-, in addition, L^S1And L^S2Each independently represents a single bond or a 2-valent linking group, and represents a bonding position.

6. The compound according to any one of claims 1 to 5, wherein,

the R is⁷And said R⁸Represents a hydrogen atom.

7. The compound according to any one of claims 1 to 6, wherein,

ar is¹Represents a benzene ring group.

8. The compound according to any one of claims 1 to 7, wherein,

the R is¹-said R⁶Each represents a substituent having a valence of 1 other than the substituent having a valence of 1 represented by the following general formula (4),

in the general formula (4), Ar³Represents an m +1 valent aromatic hydrocarbon ring group, C^BRepresents a carbon atom, R⁹And R¹⁰Each independently represents a hydrogen atom, a cyano group, a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group or a 1-valent C1-10Aliphatic hydrocarbon group of R^jRepresents a substituent having a valence of 1, m represents an integer of 0 to 5, L³Represents a single bond or a 2-valent linking group represented by the following general formula (5) and represents a bonding position with the binaphthyl skeleton in the general formula (1),

when m is 2 or more, a plurality of R^jMay be the same or different from each other,

*—L⁴—Ar⁴—**

(5)

in the general formula (5), Ar⁴Represents a 2-valent aromatic hydrocarbon ring group, L⁴Represents a single bond or a 2-valent linking group, represents a bonding position with the binaphthyl skeleton in the general formula (1), and represents a bonding position with the C in the general formula (4)^BThe bonding site of (3).

9. A mixture comprising the compound according to claim 8 and a compound represented by the following general formula (Y1),

in the general formula (Y1), R¹¹～R¹⁶Each independently represents a hydrogen atom or a substituent having a valence of 1, wherein R¹¹～R¹⁶At least one of them represents a substituent having a valence of 1 represented by the following general formula (6), the portion of the solid line parallel to the dotted line represents a single bond or a double bond, R¹¹And R¹²May be bonded to each other to form a ring structure,

in the general formula (6), Ar⁵Represents an aromatic hydrocarbon ring group having a valence of l +1, C^CRepresents a carbon atom, R¹⁷And R¹⁸Each independently represents a hydrogen atom, a cyano group, a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group or a carbon atom1 to 10 of a 1-valent aliphatic hydrocarbon group, R^kRepresents a substituent having a valence of 1, L represents an integer of 0 to 5, and L⁵Represents a single bond or a 2-valent linking group represented by the following general formula (7), represents a bonding position to the binaphthyl skeleton in the general formula (Y1),

when l is 2 or more, a plurality of R^kMay be the same or different from each other,

*—L⁶—Ar⁶—**

(7)

in the general formula (7), Ar⁶Represents a 2-valent aromatic hydrocarbon ring group, L⁶Represents a single bond or a 2-valent linking group, represents a bonding position with the binaphthyl skeleton in the general formula (Y1), and represents a bonding position with the C in the general formula (6)^CThe bonding site of (3).

10. The mixture according to claim 9, wherein,

the ratio of the content of the 1-valent substituent represented by the general formula (2) to the content of the 1-valent substituent represented by the general formula (6) is 5 or more.

11. A liquid crystal composition comprising a liquid crystalline compound and a compound according to any one of claims 1 to 8 or a mixture according to claim 9 or 10.

12. A cured product obtained by curing the liquid crystal composition according to claim 11.

13. An optically anisotropic body formed using the liquid crystal composition according to claim 11.

14. A reflective film formed using the liquid crystal composition according to claim 11.

Technical Field

The present invention relates to a compound, a mixture, a liquid crystal composition, a cured product, an optically anisotropic body, and a reflective film.

Background

A compound exhibiting liquid crystallinity (hereinafter, also referred to as a "liquid crystalline compound") can be used for various applications. For example, the liquid crystalline compound is suitable for production of an optically anisotropic body typified by a retardation film or production of a reflection film in which a cholesteric liquid crystal phase is fixed.

Generally, cholesteric liquid crystal phases are formed by adding a chiral compound to a nematic liquid crystal. Among them, as a chiral compound having a strong Helical Twisting Power (HTP), a binaphthyl derivative is generally used.

Patent document 1 discloses, as an intermediate of a binaphthyl derivative, a binaphthyl derivative including a stilbene structure in the molecule. In addition, in the synthesis method described in the example column of patent document 1, binaphthol derivatives containing only a trans-stilbene structure as a stilbene structure are selectively synthesized.

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 2003-055315

Disclosure of Invention

Technical problem to be solved by the invention

On the other hand, in recent years, a chiral compound which increases the intensity of HTP by exposure to light irradiation with ultraviolet rays or the like has been demanded. The present inventors have studied the binaphthol derivative described in patent document 1, and as a result, have found that the intensity of HTP is reduced by exposure, and the desired requirements cannot be satisfied.

Accordingly, an object of the present invention is to provide a compound that increases the intensity of HTP by exposure to light such as ultraviolet light, and a mixture containing the compound.

Another object of the present invention is to provide a liquid crystal composition, a cured product, an optically anisotropic body, and a reflective film.

Means for solving the technical problem

The present inventors have found that the above problems can be solved by a compound represented by the following general formula (1), and have completed the present invention.

That is, the following configuration was found to solve the above problems.

[ 1] A compound represented by the following general formula (1).

[ 2] the compound according to [ 1], wherein L is¹Represents a single bond.

[ 3] the compound according to [ 1] or [ 2], wherein R is selected from the group consisting of the above-mentioned R¹R is as defined above³And the above R⁵One or more of the groups (A) represents a substituent having a valence of 1 represented by the general formula (2), and is selected from the group consisting of the above-mentioned R²R is as defined above⁴And the above R⁶One or more of the groups (a) and (b) represent a substituent having a valence of 1 represented by the general formula (2).

[ 4] the compound according to any one of [ 1] to [ 3], wherein R is as defined above¹And the above-mentioned R²Bonded to each other to form a ring structure.

[ 5] the compound according to any one of [ 1] to [ 4], wherein L is¹Represents a 2-valent linking group represented by the general formula (3), or the above RⁱIs represented by^S1-aromatic hydrocarbon ring group, or the above R¹And the above R²Are bonded to each other to represent^S2-2-valent aromatic hydrocarbon ring radical-L^S2- *. In addition, L^S1And L^S2Each independently represents a single bond or a 2-valent linking group, and represents a bonding position.

[ 6] the compound according to any one of [ 1] to [ 5], wherein R is as defined above⁷And the above R⁸Represents a hydrogen atom.

[ 7] the compound according to any one of [ 1] to [ 6], wherein Ar is¹Represents a benzene ring group.

[ 8] the compound according to any one of [ 1] to [ 7], wherein R is as defined above¹R is as defined above⁶Each represents a valence of 1 represented by the general formula (4) described laterA substituent having a valence of 1 other than the substituent(s).

[ 9] A mixture comprising the compound according to [ 8] and a compound represented by the general formula (Y1) described later.

[ 10] A mixture according to [ 9], wherein the ratio of the content of the 1-valent substituent represented by the above general formula (2) to the content of the 1-valent substituent represented by the above general formula (6) is 5 or more.

[ 11] A liquid crystal composition comprising a liquid crystalline compound and the compound of any one of [ 1] to [ 8] or the mixture of [ 9] or [ 10 ].

A cured product obtained by curing the liquid crystal composition according to [ 11 ].

An optically anisotropic body formed using the liquid crystal composition according to [ 11 ].

[ 14] A reflective film formed using the liquid crystal composition according to [ 11 ].

Effects of the invention

According to the present invention, a compound that increases the intensity of HTP by exposure to light such as ultraviolet light and a mixture containing the compound can be provided.

Further, the present invention can provide a liquid crystal composition, a cured product, an optically anisotropic body, and a reflective film.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements is made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, a numerical range represented by "to" means a range including numerical values before and after "to" as a lower limit value and an upper limit value.

In the present specification, "(meth) acryloyl group" means an acryloyl group or a methacryloyl group.

[ Compound represented by the general formula (1) ]

The compound represented by the general formula (1) (hereinafter, also referred to as "specific compound") may be characterized by R¹～R⁶At least one of the above (a) and (b) contains a substituent having a valence of 1 represented by the general formula (2) described later. In other words, the specific compound introduces the cis-stilbene derivative structure into the molecule by containing a substituent having a valence of 1 represented by the general formula (2) described later. When irradiated with energy such as ultraviolet light, the 1-valent substituent represented by the general formula (2) described later is photoisomerized into a trans-stilbene derivative structure, and as a result, the intensity of HTP of a specific compound is increased.

And, as will be described later, R in a specific compound¹And R²When the cyclic structures are formed by bonding to each other, the specific compound suppresses the rotation of the binaphthyl skeleton, and thus the HTP has low temperature dependence (in other words, the HTP is less likely to change with temperature), and the HTP after exposure is high.

In the present specification, the "binaphthyl skeleton" represents R in the general formula (1) described later¹～R⁶Other structural parts (structural parts described below). That is, it corresponds to R in the general formula (1-1) and the general formula (1-2) described later¹～R⁶The term "structural part" is used generically.

[ chemical formula 1]

The specific compound will be described in detail below.

[ chemical formula 2]

In the general formula (1), R¹～R⁶Each independently represents a hydrogen atom or a substituent having a valence of 1. Wherein R is¹～R⁶At least one of them represents a substituent having a valence of 1 represented by the general formula (2) described later.

As a group consisting of R¹～R⁶The substituent having a valence of 1 represented by the formula (I) includes, for example: 1-valent substituents such as alkyl, alkoxy, aryl, arylcarbonyloxy, aryloxycarbonyl, arylamido, alkoxycarbonyl, alkylcarbonyloxy, and cinnamoyloxy; a substituent having a valence of 1 represented by the following general formula (2); a substituent having a valence of 1 represented by the general formula (4) described later.

As a result of the above-mentioned R¹～R⁶The alkyl group in the alkyl group and the alkylcarbonyloxy group may be any of linear, branched and cyclic, and examples thereof include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

As a result of the above-mentioned R¹～R⁶The alkoxy group and the alkoxy group in the alkoxycarbonyl group may be any of linear, branched and cyclic, and examples thereof include alkoxy groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

As a result of the above-mentioned R¹～R⁶Examples of the aryl group and the aryl group in the arylcarbonyloxy group, aryloxycarbonyl group and arylamido group include aryl groups having 6 to 18 carbon atoms (e.g., phenyl groups).

The 1-valent substituent such as the alkyl group, the alkoxy group, the aryl group, the arylcarbonyloxy group, the aryloxycarbonyl group, the arylamido group, the alkoxycarbonyl group, the alkylcarbonyloxy group, the cinnamoyloxy group, or the like may further have a substituent.

The substituent is not particularly limited, and examples thereof include an alkoxy group having 1 to 10 carbon atoms, a phenoxy group, and a group containing the following polymerizable group.

Examples of the polymerizable group in the group containing a polymerizable group include known polymerizable groups, and from the viewpoint of reactivity, a functional group capable of addition polymerization is preferable, and a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group is more preferable. Examples of the polymerizable group include a (meth) acryloyloxy group, a (meth) acryloylamino group, a vinyl group, a maleimido group, an acetyl group, a styryl group, an allyl group, an epoxy group, an oxetanyl group, and a group containing these groups. The hydrogen atom in each of the above groups may be substituted with another substituent such as a halogen atom.

Preferred examples of the polymerizable group include groups represented by the following general formulae (P-1) to (P-21). In addition, a bonding site is represented by × (x) in the following formula. And Ra represents a hydrogen atom or a methyl group. Me represents a methyl group, and Et represents an ethyl group.

[ chemical formula 3]

[ chemical formula 4]

The group containing the polymerizable group is not particularly limited as long as it has the polymerizable group, and examples thereof include a group represented by the following general formula (PA).

*-L^A-P (PA)

In the general formula (PA), L^ARepresents a single bond or a 2-valent linking group. P represents a group represented by the general formulae (P-1) to (P-21). Denotes the bonding site.

As the linking group having a valence of 2 represented by the above LA, for example, preferred is a C1-10 linear or branched alkylene group or one or more-CH groups among C1-10 linear or branched alkylene groups₂Is selected from the group consisting of-O-, -S-, -NH-, -N (CH)₃) A 2-valent linking group substituted with one or more groups selected from the group consisting of-CO-, -OCO-, and-COO-.

The 2-valent linking group represented by LA is more preferably-CH-which is at least one of linear or branched alkylene groups having 1 to 10 carbon atoms₂-a group substituted by-O-.

As the group represented by the general formula (PA), preferred is a group represented by ". about. -O- (CH)₂)_k-P (k represents an integer of 1 to 10)'.

In addition, for example, in the group consisting of R¹～R⁶Aryl carbonyloxy, aryloxy group represented byWhen the carbonyl group or the arylamide group has a substituent, examples of the arylcarbonyloxy group having a substituent, the aryloxycarbonyl group having a substituent, and the arylamide group having a substituent include a group represented by the following general formula (T1).

[ chemical formula 5]

In the general formula (T1), L₁₁represents-O-CO-, -CO-O-, -N (R)_b) -CO-or-CO-N (R)_b)-。R_bRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

L^AAnd the meaning of P is the same as L in the above formula (PA)^AAnd P have the same meanings, and the preferred embodiments are also the same.

R¹¹Represents a substituent having a valence of 1. As a group consisting of R¹¹The substituent having a valence of 1 is, for example, an alkoxy group having 1 to 3 carbon atoms.

S11 and S12 each independently represent an integer of 0 to 5. Wherein, 1 is less than or equal to S11 and S12 is less than or equal to 5.

Wherein as represented by R¹～R⁶The substituent having a valence of 1 as represented by the above formula (2) is preferably an alkoxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, an arylamido group or a substituent having a valence of 1 as represented by the above formula (2). And, as will be described later, R¹And R²May be bonded to each other to form a ring structure.

The following describes the 1-valent substituent represented by the above general formula (2) and the 1-valent substituent represented by the above general formula (4).

First, a substituent having a valence of 1 represented by the above general formula (2) will be described.

The specific compound introduces a cis-stilbene derivative structure into a molecule by containing a substituent having a valence of 1 represented by the general formula (2). Specifically, L in the substituent having a valence of 1 represented by the general formula (2)¹When it represents a single bond, it is clearly shown in the formula (2) as the double bond site of the olefin (C)^AAr explicitly shown in formula (2) at ═ C), and¹and general formula(1) The benzene ring contained in the binaphthyl skeleton (which means a benzene ring bonded to a substituent having a valence of 1 represented by the general formula (2)) is in a cis-configuration, and a cis-stilbene derivative structure is formed. And L in the substituent having a valence of 1 represented by the general formula (2)¹When a 2-valent linking group represented by the general formula (3) is represented, the double bond site (C) of the olefin clearly shown in the general formula (2)^AAr explicitly shown in formula (2) at ═ C), and¹and Ar explicitly shown in the general formula (3)²The cis-stilbene derivative is in cis-configuration to form a cis-stilbene derivative structure.

[ chemical formula 6]

In the general formula (2), Ar¹Represents an n +1 valent aromatic hydrocarbon ring group.

The aromatic hydrocarbon ring constituting the aromatic hydrocarbon ring group is not particularly limited, and examples thereof include an aromatic hydrocarbon ring having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and among them, a benzene ring (i.e., Ar)¹Preferably a benzene ring group).

C^ARepresents a carbon atom.

R⁷And R⁸Each independently represents a hydrogen atom, a cyano group, a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group or a 1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

As a group consisting of R⁷And R⁸Examples of the substituted boron group include those represented by^X1R^X2(R^X1And R^X2Each independently represents a hydrogen atom or a substituent having a valence of 1. Wherein R is^X1And R^X2Wherein one or more of the substituents represents a substituent having a valence of 1. In addition, R^X1And R^X2May be bonded to each other to form a ring structure. ) The group shown.

As a group consisting of R^X1And R^X2The substituent having a valence of 1 is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms (which may be substituted by a substituent having a valence of 1The polymer may be linear, branched or cyclic. ) Phenyl group or C1-10 alkoxy group.

As a group consisting of R⁷And R⁸Examples of the substituted silyl group include^X3R^X4R^X5(R^X3～R^X5Each independently represents a substituent having a valence of 1. ) The group shown.

As a group consisting of R^X3～R^X5The 1-valent substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms (which may be linear, branched, or cyclic), a phenyl group, and the like.

As a group consisting of R⁷And R⁸Substituted aluminum radicals represented by^X5R^X6(R^X5And R^X6Each independently represents a hydrogen atom or a substituent having a valence of 1. Wherein R is^X5And R^X6Wherein one or more of the substituents represents a substituent having a valence of 1. In addition, R^X5And R^X6May be bonded to each other to form a ring structure. ) The group shown.

As a group consisting of R^X5And R^X6The 1-valent substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms (which may be linear, branched, or cyclic), a phenyl group, and the like.

As a group consisting of R⁷And R⁸Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As a group consisting of R⁷And R⁸The alkyl group in the alkoxycarbonyl group may be any of linear, branched and cyclic, and examples thereof include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). The alkoxycarbonyl group may further have a substituent.

As a group consisting of R⁷And R⁸The alkyl group in the alkylcarbonyl group may be any of linear, branched and cyclic, and examples thereof include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). The alkylcarbonyl group may further have a substituent.

As byR⁷And R⁸The 1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms may be any of linear, branched, and cyclic.

The C1-10 aliphatic hydrocarbon group having a valence of 1 includes an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms), an alkenyl group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), and an alkynyl group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms). The 1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms may further have a substituent.

Wherein, as R⁷And R⁸Preferably a hydrogen atom.

RⁱRepresents a substituent having a valence of 1.

As a group consisting of RⁱThe substituent having a valence of 1 is not particularly limited, and examples thereof include substituents having a valence of 1 such as an alkyl group, an alkoxy group, an aryl group, an arylcarbonyloxy group, an aryloxycarbonyl group, an arylamido group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and a cinnamoyloxy group.

From the above RⁱThe alkyl, alkoxy, aryl, arylcarbonyloxy, aryloxycarbonyl, arylamido, alkoxycarbonyl and alkylcarbonyloxy groups represented by the above formula (1) and R¹～R⁶The alkyl group, alkoxy group, aryl group, arylcarbonyloxy group, aryloxycarbonyl group, arylamido group, alkoxycarbonyl group, and alkylcarbonyloxy group are each the same as defined above, and the preferred embodiments are also the same.

As a group consisting of RⁱThe substituent having a valence of 1 as represented herein is preferably an alkoxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, an arylamido group or an alkoxycarbonyl group.

In the general formula (2), when n is 2 or more, a plurality of RⁱMay be the same or different.

n represents an integer of 0 to 5.

The number of n is not particularly limited, but is preferably an integer of 0 to 3, more preferably an integer of 1 to 3.

L¹Represents a single bond or a 2-valent linking group represented by the following general formula (3)And (4) clustering. And represents a bonding position to the binaphthyl skeleton in the general formula (1).

In addition, at L¹When it represents a single bond, represented by C^AThe carbon atom represents a bonding site to the binaphthyl skeleton in the general formula (1).

Among these, L is L from the viewpoint of increasing the HTP rate more¹Preferably a single bond.

The linking group having a valence of 2 represented by the above general formula (3) will be described below.

[ chemical formula 7]

*-L²-Ar²-**

(3)

In the general formula (3), L²Represents a single bond or a 2-valent linking group.

As a result of L²The linking group having a valence of 2 is not particularly limited, and examples thereof include aliphatic hydrocarbon groups having a valence of 2 (which may be linear, branched or cyclic, and preferably have 1 to 20 carbon atoms), O-, -S-, -SO, and alkylene, alkenylene and alkynylene groups)₂-、-NR^A-、-CO-(-C(＝O)-)、-COO-(-C(＝O)O-)、-OCO-(-OC(＝O)-)、-NR^A-CO-、-CO-NR^A-、-SO₃-、-SO₂NR^A-、-NR^ASO₂-, -N ═ N-, -CH ═ N-, -N ═ CH-, and a combination of two or more thereof. Herein, R is^ARepresents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

The hydrogen atom in the above-mentioned linking group having a valence of 2 may be substituted with another substituent such as a halogen atom.

Wherein as represented by L²The 2-valent linking group is preferably-O-, -CO-, -COO-or-OCO-, more preferably-COO-or-OCO-.

Ar²Represents a 2-valent aromatic hydrocarbon ring group.

In the general formula (3), a bonding position to the binaphthyl skeleton in the general formula (1) is represented. Is represented by the above C in the above general formula (2)^AThe bonding site of the carbon atom is shown.

Next, the substituent having a valence of 1 represented by the above general formula (4) will be described.

The specific compound can introduce a trans-stilbene derivative structure into a molecule by containing a substituent having a valence of 1 represented by the general formula (4). Specifically, L in the substituent having a valence of 1 represented by the general formula (4)³When it represents a single bond, it is clearly shown in the olefinic double bond site (C) in the general formula (4)^BAr explicitly shown in formula (4) at ═ C), and³and a benzene ring contained in the binaphthyl skeleton in the general formula (1) (which means a benzene ring bonded to a substituent having a valence of 1 represented by the general formula (4)) is in a trans configuration, thereby forming a trans stilbene derivative structure. And L in the substituent having a valence of 1 represented by the general formula (4)³When a 2-valent linking group represented by the general formula (5) is represented, the double bond site (C) of the olefin shown clearly in the general formula (4)^BAr explicitly shown in formula (4) at ═ C), and³and Ar explicitly shown in the general formula (5)⁴The trans-stilbene derivative structure is formed by trans-configuration.

[ chemical formula 8]

In the general formula (4), Ar³Represents an aromatic hydrocarbon ring group having a valence of m + 1.

C^BRepresents a carbon atom.

R⁹And R¹⁰Each independently represents a hydrogen atom, a cyano group, a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group or a carbon atomA number of 1 to 10 of aliphatic hydrocarbon groups having a valence of 1.

As a group consisting of R⁹And R¹⁰The substituted boron group, the substituted silyl group, the substituted aluminum group, the halogen atom, the alkoxycarbonyl group, the alkylcarbonyl group and the C1-10 aliphatic hydrocarbon group represented by the formula (2)⁷And R⁸The preferred embodiment of the compound represented by the formula (I) is the same as the compound represented by the formula (I) wherein the group is a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group, or a 1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Wherein, as R⁹And R¹⁰Preferably a hydrogen atom.

R^jRepresents a substituent having a valence of 1.

As a group consisting of R^jThe substituent having a valence of 1 represented by the formula (2) is exemplified by RⁱThe same substituents as those having 1-valent substituents are also preferred.

In the general formula (4), when m is 2 or more, a plurality of R' s^jMay be the same or different.

m represents an integer of 0 to 5.

The number of m is not particularly limited, but is preferably an integer of 0 to 3, more preferably an integer of 1 to 3.

L³Represents a single bond or a 2-valent linking group represented by the following general formula (5). And represents a bonding position to the binaphthyl skeleton in the general formula (1).

In addition, at L³When it represents a single bond, represented by C^BThe carbon atom represents a bonding site to the binaphthyl skeleton in the general formula (1).

Wherein as L³Preferably a single bond.

The linking group having a valence of 2 represented by the above general formula (5) will be described below.

[ chemical formula 9]

*-L⁴-Ar⁴-**

(5)

In the general formula (5), L⁴Represents a single bond or a 2-valent linkageAnd (3) a linking group.

As a result of L⁴The 2-valent linking group represented by the formula (3)²The substituents having the valences of 2 are the same, and the preferable modes thereof are also the same.

Ar⁴Represents a 2-valent aromatic hydrocarbon ring group.

As by Ar⁴The 2-valent aromatic hydrocarbon ring group represented by (A) is represented by Ar in the general formula (3)²The preferred embodiment of the substituent is the same as that of the 2-valent aromatic hydrocarbon ring group.

In the general formula (5), a represents a bonding position to the binaphthyl skeleton in the general formula (1). And C in the above general formula (4)^BThe bonding site of the carbon atom is shown.

In the general formula (1), as represented by R¹～R⁶The substituent having a valence of 1 represented by the above general formula (4) is preferably a group other than the substituent having a valence of 1 from the viewpoint that the HTP increasing rate becomes higher.

In the general formula (1), R is preferably R from the viewpoint that HTP after exposure is large and the HTP increasing rate becomes larger¹～R⁶Two or more of them are 1-valent substituents represented by the above general formula (2). Among them, preferably, selected from the group consisting of R¹、R³And R⁵One or more of the groups (A) represents a substituent having a valence of 1 represented by the general formula (2), and is selected from the group consisting of R²、R⁴And R⁶One or more of the groups (a) represents a substituent having a valence of 1 represented by the general formula (2).

In addition, the specific compound preferably satisfies one or more modes selected from the following mode (a), the following mode (B), and the following mode (C) from the viewpoint that the HTP becomes larger after exposure.

Mode (a): in the substituent having a valence of 1 represented by the above general formula (2), L¹Represents a 2-valent linking group represented by the general formula (3).

Mode (B): in the substituent having a valence of 1 represented by the above general formula (2), RⁱIs represented by^S1-an aromatic hydrocarbon ring group having a valence of 1.

Mode (C): in the general formula (1)R of (A) to (B)¹And R²Are bonded to each other to represent^S2-2-valent aromatic hydrocarbon ring radical-L^S2-*。

L^S1And L^S2Each independently represents a single bond or a 2-valent linking group. From L^S1And L^S2The meaning of the 2-valent linking group represented by the formula (3)²The meaning of the 2-valent linking group is the same. As L^S1And L^S2A single bond or a 2-valent aliphatic hydrocarbon group (which may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, and examples thereof include alkylene, alkenylene and alkynylene), -O-, -CO-, -NH-CO-, -CO-NH-, -COO-and-OCO-.

The aromatic hydrocarbon ring constituting the 1-valent aromatic hydrocarbon ring group shown in the embodiment (B) is not particularly limited, and examples thereof include an aromatic hydrocarbon ring having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and more preferably a benzene ring.

The aromatic hydrocarbon ring constituting the 2-valent aromatic hydrocarbon ring group shown in the embodiment (C) is not particularly limited, and examples thereof include an aromatic hydrocarbon ring having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and more preferably a benzene ring.

In particular, the specific compound is preferably represented by the general formula (1-2) described later and satisfies one or more modes selected from the above-mentioned mode (a), the above-mentioned mode (B), and the above-mentioned mode (C), from the viewpoint that the HTP becomes larger after exposure.

In the case of the above configuration, the specific compound includes a structure in which three or more aromatic hydrocarbon ring groups are connected via a single bond or a 2-valent linking group (not including the connection of naphthalene rings in a binaphthyl skeleton), and this structure is presumed to be one of factors for increasing the HTP after exposure to light.

Specifically, the specific compound of the embodiment (A) includes a naphthalene ring contained in a binaphthyl skeleton, and Ar clearly shown in the general formula (3)²And Ar explicitly shown in the general formula (2)¹A structure linked via a single bond or a 2-valent linking group. The specific compound of the embodiment (B) includes a naphthalene ring contained in a binaphthyl skeleton and is clearly shown in the general formula (2)) Ar in (1)¹And the above RⁱThe aromatic hydrocarbon rings in (1) are linked via a single bond or a 2-valent linking group. And, the specific compound of the mode (C) includes two naphthalene rings and R contained in the binaphthyl skeleton¹And R²Are bonded to each other to form^S2-2-valent aromatic hydrocarbon ring radical-L^S2A structure in which aromatic hydrocarbon rings are connected via a single bond or a 2-valent linking group.

In the general formula (1), R is preferably R from the viewpoint of large HTP after exposure and less temperature dependence of HTP¹And R²Bonded to each other to form a ring structure.

The ring structure is not particularly limited, and may be any of an aromatic ring and a non-aromatic ring, preferably a non-aromatic ring, and may contain a hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom.

The number of the ring members of the above-mentioned ring structure is not particularly limited, and is, for example, 5 to 12. In addition, the above-mentioned number of membered rings is a number including four carbon atoms explicitly shown in the general formula (1).

In the general formula (1), the portion where the solid line is parallel to the broken line represents a single bond or a double bond. The specific compound corresponds to a compound represented by the following general formula (1-1) when the portion where the solid line and the broken line are parallel is a single bond, and corresponds to a compound represented by the following general formula (1-2) when the portion where the solid line and the broken line are parallel is a double bond. Among them, the specific compound is preferably a compound represented by the following general formula (1-2) from the viewpoint of further improving the effect of the present invention.

In addition, R in the following general formula (1-1) and the following general formula (1-2)¹～R⁶With R in the general formula (1)¹～R⁶Respectively, and the preferred modes are the same.

[ chemical formula 10]

Among them, as the specific compound, a compound represented by the following general formula (X1) is preferable.

[ chemical formula 11]

In the general formula (X1), R^X1～R^X6Each independently represents a hydrogen atom or a substituent having a valence of 1. Wherein R is^X1～R^X6At least one of them represents a substituent having a valence of 1 represented by the above general formula (2). And, R^X1～R^X6Has no substituent having a valence of 1 represented by the above general formula (4).

As a group consisting of R^X1～R^X6The substituent having a valence of 1 represented by the formula (I) includes, for example: 1-valent substituents such as alkyl, alkoxy, aryl, arylcarbonyloxy, aryloxycarbonyl, arylamido, alkoxycarbonyl, alkylcarbonyloxy, and cinnamoyloxy; a substituent having a valence of 1 represented by the above general formula (2); and the like.

From the above R^X1～R^X6The alkyl, alkoxy, aryl, arylcarbonyloxy, aryloxycarbonyl, arylamido, alkoxycarbonyl and alkylcarbonyloxy groups represented by the above formula (1) and R¹～R⁶The alkyl group, alkoxy group, aryl group, arylcarbonyloxy group, aryloxycarbonyl group, arylamido group, alkoxycarbonyl group, and alkylcarbonyloxy group are each the same as defined above, and the preferred embodiments are also the same.

Wherein as represented by R^X1～R^X6The substituent having a valence of 1 as represented by the above formula (2) is preferably an alkoxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, an arylamido group or a substituent having a valence of 1 as represented by the above formula (2). And, as will be described later, R^X1And R^X2May be bonded to each other to form a ring structure.

In the general formula (X1), R is preferably R from the viewpoint that the HTP after exposure is large and the HTP increase rate becomes larger^X1～R^X6Two or more of them are 1-valent substituents represented by the above general formula (2). Among them, preferably, selected from the group consisting of R^X1、R^X3And R^X5One or more substituents in the group (A) represent a 1-valent substituent represented by the general formula (2), and are selected fromComprising R^X2、R^X4And R^X6One or more of the groups (a) represents a substituent having a valence of 1 represented by the general formula (2).

In addition, the compound represented by the general formula (X1) preferably satisfies one or more modes selected from the following modes (a), (B), and (C) from the viewpoint that the HTP becomes larger after exposure.

Mode (a): in the substituent having a valence of 1 represented by the above general formula (2), L¹Represents a 2-valent linking group represented by the above general formula (3).

Mode (B): in the substituent having a valence of 1 represented by the above general formula (2), RⁱIs represented by^S1-an aromatic hydrocarbon ring group having a valence of 1.

Mode (C): r in the general formula (1)¹And R²Are bonded to each other to represent^S2-2-valent aromatic hydrocarbon ring radical-L^S2-*。

In particular, from the viewpoint that the HTP becomes larger after exposure, the compound represented by the general formula (X1) preferably has the same structure as that represented by the general formula (1-2) (in other words, the portions of the general formula (X1) in which the solid line and the broken line are parallel each represent a double bond) and satisfies one or more modes selected from the above-described mode (a), the above-described mode (B), and the above-described mode (C).

In the case of the above-described structure, the compound represented by the general formula (X1) includes a structure in which three or more aromatic hydrocarbon ring groups are linked via a single bond or a 2-valent linking group (not including the linkage of naphthalene rings in a binaphthyl skeleton), and this structure is presumed to be one of factors that make the HTP after exposure larger. Specifically, the compound represented by the general formula (X1) of the embodiment (a) includes a naphthalene ring contained in a binaphthyl skeleton, and Ar clearly shown in the general formula (3)²And Ar explicitly shown in the general formula (2)¹A structure linked by a single bond or a 2-valent linking group. The compound represented by the general formula (X1) in the embodiment (B) includes a naphthalene ring contained in a binaphthyl skeleton, and Ar clearly shown in the general formula (2)¹And the above RⁱThe aromatic hydrocarbon rings in (1) are linked via a single bond or a 2-valent linking group. The compound represented by the general formula (X1) according to the embodiment (C) includes two naphthalene rings and R contained in the binaphthyl skeleton¹And R²Are bonded to each other to form^S2-2-valent aromatic hydrocarbon ring radical-L^S2A structure in which aromatic hydrocarbon rings are connected via a single bond or a 2-valent linking group.

In the general formula (X1), R is preferably R from the viewpoint of large HTP after exposure and less temperature dependence of HTP^X1And R^X2Bonded to each other to form a ring structure.

The number of the ring members of the above-mentioned ring structure is not particularly limited, and is, for example, 5 to 12. In addition, the above-mentioned number of the membered ring is a number including four carbon atoms explicitly shown in the general formula (X1).

In the specific compound, the content of the 1-valent substituent represented by the above general formula (2) (hereinafter also referred to as "X1 (mol)") and the content represented by the above general formula (4) are the sameThe content of the 1-valent substituent (hereinafter also referred to as "Y1 (mol)") can be determined by¹H NMR (nuclear magnetic resonance). When the specific compound contains a substituent having a valence of 1 represented by the above general formula (2) and a substituent having a valence of 1 represented by the above general formula (4), X1/Y1 is preferably 5 or more, and more preferably 10 or more.

The specific compound can be synthesized by a known method. For example, the compound can be synthesized by a production method including a step of reducing a binaphthol derivative having a tolane structure by catalytic reduction, a production method including a step of preparing a substituted olefin by hydrogenating and metallizing a binaphthol derivative having a tolane structure, or the like.

The specific compound may be the R isomer, the S isomer, or a mixture of the R isomer and the S isomer.

Specific examples of the specific compound are shown below, but the specific compound is not limited thereto. In addition, the following compounds are sometimes exemplified by only the R isomer or the S isomer, but the corresponding S isomer and R isomer may also be used.

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ use ]

As the so-called chiral agent, the above-mentioned specific compound can be suitably used for various purposes. For example, a cholesteric liquid crystal phase can be formed by using a liquid crystal composition in which a specific compound and a liquid crystalline compound are mixed.

[ mixture ]

The mixture of the present invention contains a compound represented by the above general formula (X1) and a compound represented by the following general formula (Y1).

Hereinafter, the compound represented by the following general formula (Y1) will be described in detail.

[ chemical formula 28]

In the general formula (Y1), R¹¹～R¹⁶Each independently represents a hydrogen atom or a substituent having a valence of 1. Wherein R is¹¹～R¹⁶At least one of them represents a substituent having a valence of 1 represented by the general formula (6) described later.

As a group consisting of R¹¹～R¹⁶The substituent having a valence of 1 represented by the formula (I) includes, for example: alkyl, alkoxy, aryl, arylcarbonyloxy, aryl1-valent substituents such as oxycarbonyl, arylamido, alkoxycarbonyl, alkylcarbonyloxy and cinnamoyloxy; a substituent having a valence of 1 represented by the above general formula (2); a substituent having a valence of 1 represented by the following general formula (6); and the like.

From the above R¹¹～R¹⁶The alkyl, alkoxy, aryl, arylcarbonyloxy, aryloxycarbonyl, arylamido, alkoxycarbonyl and alkylcarbonyloxy groups are as defined above for R in the general formula (1)¹～R⁶The alkyl group, alkoxy group, aryl group, arylcarbonyloxy group, aryloxycarbonyl group, arylamido group, alkoxycarbonyl group, and alkylcarbonyloxy group are each the same as defined above, and the preferred embodiments are also the same.

Wherein as represented by R¹¹～R¹⁶The substituent having a valence of 1 as represented by the above formula (6) is preferably an alkoxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, an arylamido group or a substituent having a valence of 1 as represented by the above formula (6). And, as will be described later, R¹¹And R¹²May be bonded to each other to form a ring structure.

The substituent having a valence of 1 represented by the above general formula (6) will be described below.

The compound represented by the general formula (Y1) introduces the trans stilbene derivative structure into the molecule by containing a substituent having a valence of 1 represented by the general formula (6). Specifically, L in the substituent having a valence of 1 represented by the general formula (6)⁵When it represents a single bond, it is clearly shown in the double bond site (C) of the olefin in the general formula (6)^CAr shown explicitly in formula (6) at ═ C), and⁵and a benzene ring contained in the binaphthyl skeleton in the general formula (Y1) (which means a benzene ring bonded to a substituent having a valence of 1 represented by the general formula (6)) is in a trans configuration, thereby forming a trans stilbene derivative structure. And L in the substituent having a valence of 1 represented by the general formula (6)⁵When a 2-valent linking group represented by the general formula (7) is represented, the double bond site (C) of the olefin shown clearly in the general formula (6)^CAr shown explicitly in formula (6) at ═ C), and⁵and Ar explicitly shown in the general formula (7)⁶The trans-stilbene derivative structure is formed by trans-configuration.

[ chemical formula 29]

In the general formula (6), Ar⁵Represents an aromatic hydrocarbon ring group having a valence of l + 1.

C^CRepresents a carbon atom.

R¹⁷And R¹⁸Each independently represents a hydrogen atom, a cyano group, a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group or a 1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

As a group consisting of R¹⁷And R¹⁸The substituted boron group, the substituted silyl group, the substituted aluminum group, the halogen atom, the alkoxycarbonyl group, the alkylcarbonyl group or the C1-10 aliphatic hydrocarbon group represented by the formula (2)⁷And R⁸The preferred embodiment of the compound represented by the formula (I) is the same as the compound represented by the formula (I) wherein the group is a substituted boron group, a substituted silyl group, a substituted aluminum group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyl group, or a 1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Wherein, as R¹⁷And R¹⁸Preferably a hydrogen atom.

R^kRepresents a substituent having a valence of 1.

The substituent having a valence of 1 represented by Rk is represented by R in the general formula (2)ⁱThe same substituents as those having 1-valent substituents are also preferred.

In the general formula (6), when 1 is 2 or more, a plurality of R^kMay be the same or different.

1 represents an integer of 0 to 5.

The number l is not particularly limited, but is preferably an integer of 0 to 3, more preferably an integer of 1 to 3.

L⁵Represents a single bond or a 2-valent linking group represented by the following general formula (7). And represents a bonding position to the binaphthyl skeleton in the general formula (Y1).

In addition, at L⁵When it represents a single bond, represented by C^CThe carbon atom represents a bonding site to the binaphthyl skeleton in the general formula (Y1).

Wherein as L⁵Preferably a single bond.

The linking group having a valence of 2 represented by the above general formula (7) will be described below.

[ chemical formula 30]

*-L⁶Ar⁶-**

(7)

In the general formula (7), L⁶Represents a single bond or a 2-valent linking group.

As a result of L⁶The 2-valent linking group represented by the formula (3)²The substituents having the valences of 2 are the same, and the preferable modes thereof are also the same.

Ar⁶Represents a 2-valent aromatic hydrocarbon ring group.

As by Ar⁶The 2-valent aromatic hydrocarbon ring group represented by (A) is represented by Ar in the general formula (3)²The preferred embodiment of the substituent is the same as that of the 2-valent aromatic hydrocarbon ring group.

In the general formula (7), a bonding site to the binaphthyl skeleton in the general formula (Y1) is represented. Represents the same as the above C in the above general formula (6)^CThe bonding site of (3).

In the general formula (Y1), R is preferably¹¹～R¹⁶Two or more of them are 1-valent substituents represented by the above general formula (6). Among them, preferably, selected from the group consisting of R¹¹、R¹³And R¹⁵One or more of the groups (A) represents a substituent having a valence of 1 represented by the general formula (6), and is selected from the group consisting of R¹²、R¹⁴And R¹⁶One or more of the groups (a) represents a substituent having a valence of 1 represented by the general formula (6).

Further, from the viewpoint of less temperature dependence of HTP, the general formulaIn (Y1), R is preferred¹¹And R¹²Bonded to each other to form a ring structure.

The number of the ring members of the above-mentioned ring structure is not particularly limited, and is, for example, 5 to 12. The number of the above-mentioned membered ring is a number including four carbon atoms explicitly shown in the general formula (Y1).

In the general formula (Y1), the portion where the solid line is parallel to the broken line represents a single bond or a double bond. The compound represented by the general formula (Y1) corresponds to the compound represented by the following general formula (Y1-1) in the case where the portion parallel to the dotted line is a single bond, and the chiral compound represented by the general formula (Y1) corresponds to the compound represented by the following general formula (Y1-2) in the case where the portion parallel to the dotted line is a double bond.

R in the following general formula (Y1-1) and the following general formula (Y1-2)¹¹～R¹⁶With R in the general formula (Y1)¹¹～R¹⁶Respectively, and the preferred modes are the same.

[ chemical formula 31]

The mixing ratio of the compound represented by the general formula (X1) and the compound represented by the general formula (Y1) in the mixture is not particularly limited, and the compounds may be mixed in an arbitrary ratio so that the initial HTP and the increase rate of HTP are expected. In other words, by adjusting the mixing ratio of the compound represented by the general formula (X1) to the compound represented by the general formula (Y1), the mixture can be set to a desired initial HTP and HTP increase rate.

Among these, from the viewpoint that the HTP increase rate becomes larger, the content ratio of the 1-valent substituent represented by the general formula (2) (hereinafter also referred to as "X2 (mol)") to the 1-valent substituent represented by the general formula (6) (hereinafter also referred to as "Y2 (mol)") in the mixture (the content of the 1-valent substituent represented by the general formula (2) to the content of the 1-valent substituent represented by the general formula (6) (X2/Y2)) is preferably 5 or more, and more preferably 10 or more.

In addition, in the mixture, the content of the substituent having a valence of 1 represented by the general formula (2) and the content of the substituent having a valence of 1 represented by the general formula (6) may be adjusted by¹H NMR (nuclear magnetic resonance).

In the mixture, the combination of the compound represented by the general formula (X1) and the compound represented by the general formula (Y1) is preferably a combination that satisfies both the following requirement (a) and the following requirement (B).

Requirement (a):

in the mixture, in both the general formula (X1) and the general formula (Y1), the portions where the solid lines and the broken lines are parallel represent double bonds, or in both the general formula (X1) and the general formula (Y1), the portions where the solid lines and the broken lines are parallel represent single bonds.

Requirement (B):

in the compound represented by the above general formula (X1), R^X1And R^X2Case where the ring structures are not bonded to each other:

in the mixture, R in the compound represented by the above general formula (X1)^X1In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹¹Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X2In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹²Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X3In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹³Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X4In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹⁴Represents a valence of 1 represented by the general formula (6)In the compound represented by the above general formula (X1), R^X5In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹⁵Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X6In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹⁶Represents a substituent having a valence of 1 represented by the general formula (6).

In the above embodiment, L in the general formula (2) is preferably L¹、R⁷、R⁸、Ar¹、RⁱAnd n and L in the formula (6)⁵、R¹⁷、R¹⁸、Ar⁵Rk and 1 are the same and represent R of a compound other than the 1-valent substituent represented by the general formula (2) among the compounds represented by the general formula (X1)^X1～R^X6And R which represents a compound other than the 1-valent substituent represented by the general formula (6) among the compounds represented by the general formula (Y1)¹¹～R¹⁶Are respectively the same.

In the compound represented by the above general formula (X1), R^X1And R^X2Case of bonding to each other to form a ring structure:

in the mixture, R in the compound represented by the above general formula (X1)^X3In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹³Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X4In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹⁴Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X5In the case where the substituent having a valence of 1 represented by the general formula (2) is represented, R in the compound represented by the above general formula (Y1)¹⁵Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the general formula (X1)^X6When the substituent having a valence of 1 represented by the general formula (2) is represented, the compound represented by the general formula (Y1)R¹⁶Represents a substituent having a valence of 1 represented by the general formula (6), and R in the compound represented by the above general formula (Y)¹¹And R¹²Bonded to each other to represent a ring structure.

In the above embodiment, L in the general formula (2) is preferably L¹、R⁷、R⁸、Ar¹、RⁱAnd n and L in the formula (6)⁵、R¹⁷、R¹⁸、Ar⁵、R^kAnd l are the same and each represents R of a compound other than the 1-valent substituent represented by the general formula (2) among the compounds represented by the general formula (X1)^X3～R^X6And R which represents a compound other than the 1-valent substituent represented by the general formula (6) among the compounds represented by the general formula (Y1)¹³～R¹⁶Are the same and R in the compound represented by the above general formula (X1)^X1And R^X2A ring structure formed by bonding with each other and R in the compound represented by the above general formula (Y)¹¹And R¹²The ring structures bonded to each other to form the same.

[ use ]

As so-called chiral reagents, the above-mentioned mixtures can be adapted to various uses. For example, a cholesteric liquid crystal phase can be formed by using a liquid crystal composition obtained by mixing the mixture and a liquid crystal compound.

[ liquid Crystal composition ]

Next, the liquid crystal composition of the present invention will be described.

The liquid crystal composition of the present invention contains a liquid crystalline compound and the above specific compound or the above mixture.

Hereinafter, each component contained in the liquid crystal composition of the present invention will be described.

[ liquid crystalline Compound ]

The liquid crystalline compound is a compound exhibiting liquid crystallinity. The compound exhibits liquid crystallinity, and when the temperature is changed, the compound has a property of exhibiting an intermediate phase between a crystal phase (low temperature side) and an isotropic phase (high temperature side). As a specific observation method, optical anisotropy and fluidity derived from a liquid crystal phase can be confirmed by observing the compound under a polarizing microscope while heating or cooling the compound using a hot-stage system FP90 manufactured by METTLER TOLEDO.

The liquid crystalline compound is not particularly limited as long as it has liquid crystallinity, and examples thereof include a rod-like nematic liquid crystalline compound.

Examples of the rod-like nematic liquid crystal compound include azomethines, azoxides, cyanobiphenyls, cyanobenzenes, benzoates, cyclohexanecarboxylates, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitrile. In addition, not only a low molecular liquid crystalline compound but also a high molecular liquid crystalline compound may be used.

The liquid crystalline compound may be a polymerizable compound or a non-polymerizable compound.

Various documents (e.g., y.goto et al, mol.crystal.liq.crystal.1995, vol.260, pp.23-28) describe rod-like liquid crystalline compounds having no polymerizable group.

On the other hand, the polymerizable rod-like liquid crystalline compound is obtained by introducing a polymerizable group into a rod-like liquid crystalline compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an azetidinyl group, and the like, and an unsaturated polymerizable group is preferable, and an ethylenically unsaturated polymerizable group is more preferable. The polymerizable group can be introduced into the molecule of the rod-like liquid crystalline compound by various methods. The number of the polymerizable groups in the polymerizable rod-like liquid crystalline compound is preferably 1 to 6, and more preferably 1 to 3. Two or more polymerizable rod-like liquid crystalline compounds may be used simultaneously. When two or more polymerizable rod-like liquid crystalline compounds are used simultaneously, the alignment temperature can be lowered.

The liquid crystal compound is preferably a liquid crystal compound having at least one polymerizable group, and more preferably a liquid crystal compound having at least two polymerizable groups, from the viewpoint of fixing the cholesteric liquid crystal phase.

The liquid crystalline compound is preferably a compound represented by the following general formula (LC).

[ chemical formula 32]

In the general formula (LC), P¹¹And P¹²Each independently represents a hydrogen atom or a polymerizable group. Wherein, P¹¹And P¹²At least one of them represents a polymerizable group. L is¹¹And L¹²Each independently represents a single bond or a 2-valent linking group. A. the¹¹～A¹⁵Each independently represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent. Z¹¹～Z¹⁴Each independently represents a single bond or a 2-valent linking group. m is³And m⁴Each independently represents an integer of 0 or 1.

In the general formula (LC), as represented by P¹¹And P¹²The polymerizable group represented by the formula (I) is not particularly limited, and examples thereof include polymerizable groups represented by the general formulae (P-1) to (P-21).

P¹¹And P¹²At least one of them represents a polymerizable group, and preferably both represent polymerizable groups.

In the general formula (LC), as represented by L¹¹And L¹²The 2-valent linking group is not particularly limited, and examples thereof include-CH-which is one or more than two selected from the group consisting of a linear or branched alkylene group having 1 to 20 carbon atoms and a linear or branched alkylene group having 1 to 20 carbon atoms₂-a linking group of the group of groups substituted by-O-, -S-, -NH-, -N (CH3) -, -CO-, -OCO-or-COO-. As a result of L¹¹And L¹²The 2-valent linking group is preferably one or more-CH groups in a linear or branched alkylene group having 1 to 20 carbon atoms₂-a group substituted by-O-.

In the general formula (LC), A¹¹～A¹⁵Respectively independently represent a toolAn aromatic hydrocarbon ring group or an aromatic heterocyclic group having a substituent.

The number of the aromatic hydrocarbon ring groups is not particularly limited, and is, for example, 5 to 10.

The aromatic hydrocarbon ring constituting the aromatic hydrocarbon ring group may be a monocyclic structure or a polycyclic structure.

The number of carbon atoms of the aromatic hydrocarbon ring is not particularly limited, but is preferably 6 to 18, and more preferably 6 to 10. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, benzene ring is preferable. The aromatic hydrocarbon ring is an aromatic hydrocarbon ring group formed by removing two hydrogen atoms on the ring.

The number of the aromatic heterocyclic group-containing rings is, for example, 5 to 10.

The aromatic heterocyclic group constituting the aromatic heterocyclic group may have a monocyclic structure or a polycyclic structure.

Examples of the hetero atom contained in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of carbon atoms of the aromatic heterocycle is not particularly limited, but is preferably 5 to 18. Specific examples of the aromatic heterocyclic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, and an imidazole ring. The aromatic heterocyclic group is an aromatic heterocyclic group formed by removing two hydrogen atoms from the ring.

The aromatic hydrocarbon ring group and the aromatic heterocyclic group may have a substituent. The kind of the substituent is not particularly limited, and known substituents can be mentioned. Examples thereof include a halogen atom, an alkyl group, an alkoxy group, an aryl group, a hydroacid group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonamide group, an acyl group, an acyloxy group, a cyano group, a nitro group and an alkoxycarbonyl group. Each of the above groups may be further substituted with a substituent. For example, a hydrogen atom in an alkyl group may be substituted with a fluorine atom. The number of substituents is not particularly limited, and the aromatic hydrocarbon ring group and the aromatic heterocyclic group may have one substituent or may have a plurality of substituents.

Among them, from the viewpoint of further improving the solubility of the compound represented by the general formula (LC), the substituent is preferably a fluorine atom, a chlorine atom, a fluoroalkyl group, an alkoxy group, or an alkyl group, and more preferably a fluoroalkyl group, an alkoxy group, or an alkyl group.

The number of carbon atoms in the fluoroalkyl group and the alkyl group and the number of carbon atoms in the alkyl group in the alkoxy group are not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 1.

The fluoroalkyl group means a group in which at least one hydrogen atom is substituted with a fluorine atom, and preferably all hydrogen atoms are substituted with a fluorine atom (a so-called perfluoroalkyl group is preferable).

A¹¹～A¹⁵The aromatic hydrocarbon ring group may have a substituent is preferable, and phenylene groups bonded at the 1-and 4-positions are more preferable.

In the general formula (LC), as represented by Z¹¹～Z¹⁴The linking group having a valence of 2 is not particularly limited, and examples thereof include aliphatic hydrocarbon groups having a valence of 2 (which may be linear, branched or cyclic, preferably having 1 to 20 carbon atoms, and may include alkylene, alkenylene and alkynylene), O-, -S-, -SO₂-、-NR¹-、-CO-(-C(＝O)-)、-COO-(-C(＝O)O-)、-OCO-(-OC(＝O)-)、-NR¹-CO-、-CO-NR¹-、-SO₃-、-SO₂NR¹-、-NR¹SO₂-, -N ═ N-, -CH ═ N-, -N ═ CH-, and a combination of two or more thereof. Herein, R1 represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). The hydrogen atom in the above-mentioned linking group having a valence of 2 may be substituted with another substituent such as a halogen atom.

Wherein as Z¹¹～Z¹⁴preferably-COO-, -OCO-or-CH ═ CH-.

In the general formula (LC), m³And m⁴Each independently represents an integer of 0 or 1, preferably 0.

The compound represented by the general formula (LC) can be synthesized by a known method.

Specific examples of the compound represented by the above general formula (LC) are shown below, but the present invention is not limited thereto.

[ chemical formula 33]

[ chemical formula 34]

[ chemical formula 35]

The compound represented by the general formula (LC) may be used alone or in combination of two or more.

The content of the liquid crystalline compound in the liquid crystal composition of the present invention is preferably 5 to 99% by mass, more preferably 25 to 98% by mass, even more preferably 65 to 98% by mass, and particularly preferably 70 to 98% by mass, based on the total mass of the liquid crystal composition.

[ particular Compounds or mixtures ]

The liquid crystal composition of the present invention contains a specific compound or a mixture thereof. Specific compounds and mixtures are described above. The specific compound may be used alone or in combination of two or more.

The content of the specific compound or the mixture in the liquid crystal composition of the present invention is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 2 to 10% by mass, based on the total mass of the liquid crystal compounds.

[ polymerization initiator ]

The liquid crystal composition may contain a polymerization initiator.

The polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation. Examples of the photopolymerization initiator include α -carbonyl compounds, acyloin ethers, α -hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, phenazine compounds, and oxadiazole compounds.

The content of the polymerization initiator in the liquid crystal composition is not particularly limited, and is preferably 0.1 to 20% by mass, and more preferably 1 to 8% by mass, based on the total mass of the liquid crystalline compound.

In addition to the above, the liquid crystal composition may contain other additives such as a solvent, an alignment control agent, an antioxidant, an ultraviolet absorber, a sensitizer, a stabilizer, a plasticizer, a chain transfer agent, a polymerization inhibitor, a defoaming agent, a leveling agent, a thickener, a flame retardant, a surfactant, a dispersant, a polymerizable monomer, and a coloring material such as a dye and a pigment.

[ use ]

The liquid crystal composition can be suitably used for various purposes. For example, a screen, an optically anisotropic body, or a reflective film may be formed using the liquid crystal composition. In addition, for example, in the case where the liquid crystalline compound has a polymerizable group, a cured product can be obtained by subjecting the liquid crystalline composition to a curing treatment (light irradiation treatment, heat treatment, or the like), and the cured product can be preferably applied to an optically anisotropic body or a reflective film.

The optically anisotropic body is a substance having optical anisotropy.

The reflective film corresponds to a layer in which a cholesteric liquid crystal phase is fixed, and can reflect light in a predetermined reflection band. The reflective film may be preferably applied to a transparent screen, for example.

Hereinafter, a method for curing the liquid crystal composition will be described.

The method for curing (polymerization curing) the liquid crystal composition is not particularly limited, and a known method can be used. For example, the method includes the following steps: a step X of bringing a predetermined substrate into contact with the liquid crystal composition to form a composition layer on the substrate; a step Y of exposing the composition layer; and a step Z of curing the composition layer.

According to this embodiment, the liquid crystalline compound can be fixed in an aligned state, and a layer in which a so-called optically anisotropic material or a cholesteric liquid crystal phase is fixed can be formed.

The sequence of steps X to Z will be described in detail below.

The step X is a step of bringing the substrate and the liquid crystal composition into contact with each other to form a composition layer on the substrate. The type of the substrate used is not particularly limited, and known substrates (for example, a resin substrate, a glass substrate, a ceramic substrate, a semiconductor substrate, and a metal substrate) can be used.

The method of bringing the substrate and the liquid crystal composition into contact is not particularly limited, and examples thereof include a method of coating the liquid crystal composition on the substrate and a method of immersing the substrate in the liquid crystal composition.

After the substrate and the liquid crystal composition are brought into contact with each other, a drying treatment may be performed as necessary to remove the solvent from the composition layer on the substrate. Further, in order to promote the alignment of the liquid crystalline compound to bring it into a liquid crystal phase state, heat treatment may be performed.

The step Y is a step of subjecting the composition layer to exposure treatment using i-ray or the like.

The above specific compound causes photoisomerization by exposure treatment, resulting in an increase in HTP. As a result, the liquid crystalline compound in the composition layer is aligned to form a cholesteric liquid crystal phase.

In addition, in the exposure process, the degree of change in HTP can be adjusted by appropriately adjusting the exposure amount, the exposure wavelength, and the like. After the exposure, a heat treatment may be performed to further promote the alignment of the liquid crystalline compound to bring it into a liquid crystal phase state.

Step Z is a step of applying a curing treatment to the composition layer subjected to step Y.

The method of the curing treatment is not particularly limited, and examples thereof include a photo-curing treatment and a thermosetting treatment. Among them, the photo-curing treatment is preferable.

When the photo-curing treatment is performed as the curing treatment, the liquid crystal composition preferably contains a photopolymerization initiator. The wavelength of the irradiation light in the photocuring process is preferably different from the wavelength of the irradiation light in the exposure process.

The layer in which the cholesteric liquid crystal phase is fixed is formed by the curing treatment. Further, the layer in which the cholesteric liquid crystal phase is fixed does not need to exhibit liquid crystallinity. More specifically, for example, the most typical and preferable mode for "fixing" the state of the cholesteric liquid crystal phase is a state in which the alignment of the liquid crystal compound formed into the cholesteric liquid crystal phase is maintained. More specifically, the temperature is usually in the range of 0 to 50 ℃ (more severe conditions, and-30 to 70 ℃), and the following conditions are preferred: the layer has no fluidity, and the alignment state is not changed by an external field or an external force, and the fixed alignment state can be stably and continuously maintained.

Examples

The present invention will be described in further detail below with reference to examples. Hereinafter, materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the examples may be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed restrictively by the examples shown below.

[ example 1]

[ Synthesis of Compound CD-1 ]

[ chemical formula 36]

< Synthesis of intermediate 1 >

After 65.0g of (R) -binaphthol (manufactured by KANTO KAGAKU) and 500mL of butyl acetate (manufactured by Wako Pure Chemical Corporation) were placed in a 2L three-necked flask, 100g of bromine (manufactured by Wako Pure Chemical Corporation) was added dropwise at 0 ℃ and stirred for 5 hours. The obtained reaction solution was washed with sodium bisulfite (manufactured by Wako Pure Chemical Corporation) 21.7g and water 290mL), water 325mL, and sodium bicarbonate (manufactured by Wako Pure Chemical Corporation) 13.0g and water 300mL) in this order. After the washed solution was dried over magnesium sulfate, the solvent was distilled off under reduced pressure and transferred to a three-necked flask.

Subsequently, 80.2g of DMF (N, N-dimethylformamide, manufactured by Wako Pure Chemical Corporation), 78.0g of potassium carbonate (manufactured by Wako Pure Chemical Corporation), 75.0g of butyl acetate (manufactured by Wako Pure Chemical Corporation), and 43.5g of dibromomethane (manufactured by Wako Pure Chemical Corporation) were added to the three-necked flask, and stirred at 90 ℃ for 4 hours. After the resulting reaction solution was cooled to room temperature, a solid was filtered off. After the solid was filtered out, 170mL of ethyl acetate (manufactured by Wako Pure Chemical Corporation) and 550mL of methanol (manufactured by Wako Pure Chemical Corporation) were added to the solution, and the resultant solid was filtered out. Then, the obtained solid was air-dried at 40 ℃ for 12 hours to obtain intermediate 1(66.0g, yield: 75%).

< Synthesis of intermediate 2 >

120.0 g of intermediate, 17.4g of ethynylanisole (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.08g of copper iodide (manufactured by Wako Pure Chemical Corporation), 0.22g of triphenylphosphine palladium dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 120mL of triethylamine (manufactured by Wako Pure Chemical Corporation) and 40mL of pyridine (manufactured by Wako Pure Chemical Corporation) were put in a 500mL three-necked flask and stirred at 90 ℃ for 3 hours. Subsequently, the obtained reaction solution was cooled to 0 ℃ and then 400mL of methanol (manufactured by Wako Pure Chemical Corporation) was added thereto, and the resultant solid was filtered off. Then, the obtained solid was air-dried at 40 ℃ for 12 hours to obtain intermediate 2(22.0g, yield: 90%).

< Synthesis of Compound CD-1 >

100mL of intermediate 220.0g, Lindlar catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0g, quinoline (manufactured by Wako Pure Chemical Corporation) 9.2g, and 1, 4-dioxane (manufactured by Wako Pure Chemical Corporation) were placed in a 300mL three-necked flask, replaced with hydrogen, and stirred at 80 ℃ for 6 hours. The solid was filtered off by Celite filtration, and after purifying the resulting solution by column chromatography, it was air-dried at 40 ℃ for 12 hours to obtain Compound CD-1(18.0g, yield: 90%).

Of the Compound CD-1¹H NMR (heavy solvent: DMSO (Dimethyl sulfoxide)) -d₆)：δ8.01(2H、d)、7.94(2H、s)、7.52(2H、d)、7.16(8H、m)、6.76(4H、d)、6.67(4H、d)、5.70(2H、s)、3.57(6H、s)

From compoundsOf CD-1¹As a result of H NMR measurement, it was confirmed that: the compound CD-1 contains a substituent having a valence of 1 represented by the above general formula (2), and does not contain a substituent having a valence of 1 represented by the above general formula (4).

[ evaluation of initial HTP, HTP after exposure, and increase rate of HTP by exposure ]

The initial (unexposed) helical twisting power (initial HTP), the post-exposure helical twisting power (post-exposure HTP), and the increase rate of HTP by exposure were evaluated using compound CD-1.

< preparation of sample solution >

A liquid crystalline compound LC-1 represented by the following structure and a compound CD-1 (chiral compound) were mixed, and then a solvent was added to the resulting mixture to prepare a sample solution having the following composition.

100 parts by mass of a liquid crystalline compound LC represented by the following structure

15 parts by mass of Compound CD-15

Solvent (MEK (methyl ethyl ketone)/cyclohexanone 90/10 (mass ratio))

The solute concentration is 30 mass%

[ chemical formula 37]

< production of liquid Crystal layer 1 >

Subsequently, a polyimide alignment film SE-130 (manufactured by Nissan Chemi cal Corporation) was coated on the cleaned glass substrate to form a coating film. After the obtained coating film was calcined, a substrate with an alignment film was produced by rubbing treatment. After 30. mu.L of the sample solution was spin-coated on the rubbed surface of the alignment film at 1000rpm for 10 seconds, the resultant was aged at 90 ℃ for 1 minute to obtain a liquid crystal layer 1.

< evaluation >

(initial HTP)

The central reflection wavelength of the liquid crystal layer 1 was measured, and the initial HTP was determined by the following formula (1).

Formula (1): HTP ═ (average refractive index of liquid crystalline compound)/{ (concentration (mass%) of chiral compound with respect to liquid crystalline compound) x (central reflection wavelength (nm)) } [ μm^-1]

In the formula (1), the calculation was performed on the assumption that "the average refractive index of the liquid crystalline compound" was 1.55. The "center reflection wavelength" was measured using a spectroscope (UV-3100 manufactured by Shimadzu Corporation).

(post-exposure HTP)

Irradiating the liquid crystal layer 1 with 365nm light to make the exposure amount to be 100mJ/cm²After that, the central reflection wavelength of the liquid crystal layer 1 after exposure was measured. Next, the post-exposure HTP is obtained by the above formula (1).

(HTP increasing rate)

From the obtained initial HTP and the HTP after exposure, the HTP increase rate was calculated by the following formula (2).

Formula (2): HTP increase rate { (HTP after exposure) - (HTP before exposure) }/(HTP before exposure) × 100 [% ]

The initial HTP, the post-exposure HTP, and the increase rate of the HTP by exposure were evaluated according to the following evaluation criteria. The results are shown in Table 1.

< evaluation Standard (initial HTP) >)

"A": initial HTP was 50[ mu ] m^-1]The above.

"B": initial HTP was 25[ mu ] m^-1]More than and less than 50[ mu ] m^-1]。

"C": initial HTP less than 25[ mu ] m^-1]。

< evaluation Standard (post-Exposure HTP) >)

"AA": HTP after exposure was 70[ mu ] m^-1]The above.

"A": HTP after exposure was 50[ mu ] m^-1]More than and less than 70[ mu ] m^-1]。

"B": HTP after exposure was 30[ mu ] m^-1]More than and less than 50[ mu ] m^-1]。

"C": HTP after exposure is less than 30[ mu ] m^-1]。

< evaluation criterion (HTP increase rate) >)

"AA": the HTP increase rate is 200% or more.

"A": the HTP increase rate is 150% or more and less than 200%.

"B": the HTP increase rate is 100% or more and less than 150%.

"C": the HTP increase is less than 100%.

"D": the HTP did not increase.

[ evaluation of temperature dependence of HTP ]

The HTPs at 40 ℃ and 90 ℃ of the liquid crystal layer 1 (when not exposed) were calculated from the above formula (1).

The "central reflection wavelength at each temperature (40 ℃ C., 90 ℃ C.), was measured using a microscope (manufactured by Nikon Corporation, ECLIPSE E600-POL) and a spectrophotometer (manufactured by OCEAN OPTICS Co., Ltd., USB-4000/USB4H09800) in a state where liquid crystal layers prepared by hot-stage (manufactured by METTLER TOLEDO, FP90/FP82HT) were heated at 40 ℃ C. and 90 ℃ C., respectively.

(calculation of the rate of temperature Change of HTP)

The temperature dependence of HTP was evaluated by calculating the rate of change in HTP temperature by the following formula (3).

Formula (3): temperature change rate { (HTP at 40 ℃ C.) - (HTP at 90 ℃ C.) }/(HTP at 40 ℃ C.). times.100 [% ]

The evaluation of the temperature dependence of the HTP was performed according to the following evaluation criteria using the value calculated by the above equation (3). The results are shown in Table 1.

< evaluation Standard (HTP temperature dependence) >)

"A": the temperature change rate is less than 2 percent.

"B": the temperature change rate is 2% or more and less than 5%.

"C": the temperature change rate is more than 5%.

[ example 2]

Compound CD-2 was synthesized in the same manner as described above for compound CD-1. The following shows a method for synthesizing the compound CD-2.

[ chemical formula 38]

From compound CD-2¹H NMR(DMSO-d⁶) As a result of the measurement, it was confirmed that: the compound CD-2 contains both the 1-valent substituent represented by the above general formula (2) and the 1-valent substituent represented by the above general formula (4), and the content ratio (X1/Y1) of the content (X1 mol) of the 1-valent substituent represented by the general formula (2) to the content (Y1 mol) of the 1-valent substituent represented by the general formula (4) is 1.

Subsequently, the same evaluation as in example 1 was carried out using the above compound CD-2. The results are shown in Table 1.

Examples 3 to 13 and comparative examples 1 to 2

Compounds CD-3 to CD-13 and comparative compounds CCD-1 to CCD-2 were synthesized in the same manner as the above compound CD-1. Next, using the above-described compounds, the same evaluation as in example 1 was performed. The results are shown in Table 1.

[ example 14]

[ Synthesis of Compound CD-14 ]

Compound CD-14 was synthesized in the same manner as compound CD-1 described above and in the methods described in Advanced Synthesis and analysis, 356, 179-188 (2014). Next, using the above-described compounds, the same evaluation as in example 1 was performed. The results are shown in Table 1.

[ chemical formula 39]

[ example 15]

[ Synthesis of Compound CD-15 ]

The compound CD-15 was synthesized in the same manner as the above-mentioned compound CD-1, by the method described in Tetrahedron, 72, 1553-1540(2016) and the method described in Organic Chemistry, 9, 1883-1890 (2013). Next, using the above-described compounds, the same evaluation as in example 1 was performed. The results are shown in Table 1.

[ chemical formula 40]

[ examples 16 to 18]

[ Synthesis of Compound CCD-3 ]

The compound CCD-3 was synthesized in the same manner as the above-mentioned compounds CD-1 and CD-2.

[ chemical formula 41]

From compound CCD-3¹H NMR(DMSO-d⁶) As a result of the measurement, it was confirmed that: the compound CCD-3 does not contain a substituent having a valence of 1 represented by the above general formula (2), and contains a substituent having a valence of 1 represented by the above general formula (6). The compound CCD-3 corresponds to the compound represented by the above general formula (Y1).

[ example 16]

< preparation of sample solution >

A mixture was prepared by mixing the above compound CD-1 and compound CD-2 at the mixing ratio shown in Table 1. Next, the liquid crystalline compound LC-1 and the mixture containing two chiral compounds are mixed, and then a solvent is added to the resulting mixture, thereby preparing a sample solution having the following composition.

LC-1100 parts by mass of a liquid crystalline compound

5 parts by mass of a mixture of the Compound CD-1 and the Compound CD-2

Solvent (MEK (methyl ethyl ketone)/cyclohexanone 90/10 (mass ratio))

The solute concentration is 30 mass%

Next, a liquid crystal layer was produced by the same method as the method for producing the liquid crystal layer 1 of example 1, except that the sample solution was used. Further, evaluation was performed by the same method as in example 1. The results are shown in Table 2.

[ example 17]

A liquid crystal layer was produced in the same manner as in example 16, except that the compound CD-1 and the compound CD-2 were mixed at the mixing ratio shown in table 1. Further, evaluation was performed by the same method as in example 1. The results are shown in Table 2.

[ example 18]

A liquid crystal layer was produced in the same manner as in example 16, except that the compound CD-1 and the compound CCD-3 were mixed at the mixing ratio shown in table 1. Further, evaluation was performed by the same method as in example 1. The results are shown in Table 2.

Tables 1 and 2 are shown below.

In table 1, the "content ratio X1/Y1" refers to the content ratio of the 1-valent substituent represented by the general formula (2) (X1 mol) to the 1-valent substituent represented by the general formula (4) (Y1 mol) in the compound, and represents a value obtained by dividing X1 by Y1.

In Table 1, compound CD-1 and compounds CD-3 to CD-15 correspond to the above general formula (X1).

In table 2, "content ratio X2/Y2" refers to the content ratio of the 1-valent substituent represented by the general formula (2) (X2 mol) to the 1-valent substituent represented by the general formula (6) (Y2 mol) in the mixture, and represents the value obtained by dividing X2 by Y2.

In Table 2, the compound CD-1 and the compound CD-2 represent the compound CD-1 used in example 1 and the compound CD-2 used in example 2.

In Table 2, the compound CD-2 and the compound CCD-3 correspond to the above general formula (Y1).

[ Table 4]

From the results of table 1, it was confirmed that: the compound of the example increases the intensity of HTP by exposure to light irradiation with ultraviolet rays or the like, and the HTP increase rate thereof is also excellent.

From a comparison of example 1 and example 2, it can be confirmed that: in the case where the specific compound does not contain a substituent represented by the general formula (4), the HTP increasing rate is large.

Further, from a comparison of example 1 and example 6, it was confirmed that: l in a particular Compound¹In the case of a single bond, the HTP increase rate is large.

Further, from the comparison between example 1 and examples 7 and 8, it was confirmed that: r in specific compounds¹And R²When the ring structures are formed by bonding to each other, the HTP after exposure is large and the temperature dependence of the HTP is small. Further, from the comparison between example 1 and examples 7 to 10, it was also confirmed that: r in specific compounds¹And R²When the ring structures are formed by bonding to each other, the HTP after exposure is large and the temperature dependence of the HTP is small.

Further, from a comparison of example 1 and example 11, it was confirmed that: selected from among specific compounds including R¹、R³And R⁵Is a substituent having a valence of 1 represented by the general formula (2) and is selected from the group consisting of R²、R⁴And R⁶When at least one of the substituents in the group (2) is a substituent having a valence of 1 represented by the general formula (2), the HTP and the HTP increase rate after exposure is large.

Further, from comparison between example 1 and examples 4 to 6, it is clear that: in the case where the specific compound includes a structure in which three or more aromatic hydrocarbon ring groups are connected via a single bond or a 2-valent linking group (not including the connection of naphthalene rings in a binaphthyl skeleton), the HTP after exposure is large.

Further, from a comparison of example 1 and example 13, it was confirmed that: ar in the general formula (2)¹In the case of benzene ring, the HTP increase rate is large.

Further, from a comparison of example 1 with examples 14 and 15, it was confirmed that: r in the formula (2)⁷And R⁸In the case of hydrogen atoms, the HTP and HTP increase rates after exposure are large.

Further, from comparison of examples 16 to 18 in Table 2, it was confirmed that: when the value of X2/Y2 in the mixture is 5 or more (preferably 10 or more), the HTP increase rate is large.

On the other hand, it is also known that: the smaller the value of X2/Y2 in the mixture, the greater the HTP of the mixture prior to exposure. Therefore, in the case where the specific compound not containing the substituent represented by the general formula (4) (corresponding to the compound represented by the above general formula (X1)) and the compound represented by the general formula (Y1) are mixed in an arbitrary ratio, the resulting mixture can be set to a desired initial HTP and HTP increase rate.

Example 19: production of reflective film

[ preparation of liquid Crystal composition ]

The liquid crystal composition was prepared in the following formulation.

The surfactant S-1 is a compound described in Japanese patent No. 5774518, and has the following structure.

[ chemical formula 42]

[ production of reflective film ]

A polyimide alignment film material SE-130 (manufactured by Nissan Chemical Corporation) was coated on the cleaned glass substrate to form a coating film. After the obtained coating film was calcined, a substrate with an alignment film was produced by rubbing treatment. The liquid crystal composition (40. mu.L) was spin-coated on the rubbed surface of the alignment film at 1500rpm for 10 seconds to form a composition layer, and the composition layer was dried (cured) at 90 ℃ for 1 minute to align the liquid crystal compound in the composition layer (in other words, to bring the composition into a state of a cholesteric liquid crystal phase).

Next, the film was irradiated from a light source (2 UV transilluminator, manufactured by UVP Co.) at 3.0mW/cm through a mask having an opening²The composition layer after the alignment of the liquid crystalline compound was irradiated with 365nm light for 30 seconds (corresponding to the treatment for increasing the HTP of CD-1). Due to the difference between the opening and the non-opening of the mask, the composition layer was in a state where there were a portion irradiated with light having a wavelength of 365nm and a portion not irradiated.

Next, in a state where the mask was removed, the temperature was 25 ℃ and the nitrogen atmosphere was 500mJ/cm²The composition layer was irradiated with ultraviolet light (EXECURE 3000-W, manufactured by HOYA-SCHOTT) at the irradiation dose of (1) to cure the composition layer, thereby forming a reflective film (a layer corresponding to a fixed cholesteric liquid crystal phase).

Confirming that: in the obtained reflective film, the portion irradiated with light having a wavelength of 365nm showed short-wavelength reflection, the portion not irradiated showed long-wavelength reflection, and the selective reflection wavelengths were different (the pitch of the spiral of the cholesteric layer was different).

42页详细技术资料下载

上一篇：一种医用注射器针头装配设备

下一篇：多胺的季铵碱

Compound, mixture, liquid crystal composition, cured product, optically anisotropic body, and reflective film

相关技术

网友询问留言