JP2017002201A - Liquid crystalline composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystalline composition capable of reducing phase transition temperature Tfrom a crystal phase to a nematic phase, good in orientation property and capable of suppressing generation of phase separation.SOLUTION: There is provided a liquid crystalline composition containing a polymerizable liquid crystal compound capable of exhibiting reverse wavelength dispersible double refraction and having molecular weight of 540 or more and a (meth)acrylate compound having SP value of less than 19.0 and molecular weight of 220 or more and less than 540.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal composition.

  When an optical film is produced using a liquid crystal compound, a liquid crystal composition containing the liquid crystal compound is coated on an appropriate substrate such as a resin film to form a layer, and the liquid crystal compound is formed in the layer of the liquid crystal composition. A desired optical film may be obtained by aligning and curing the layer while maintaining the alignment of the liquid crystal compound. In addition, the liquid crystal composition used in such a method can contain a solvent and an additive in combination with the liquid crystal compound (see Patent Documents 1 to 5).

JP 2004-277487 A JP 2000-281628 A JP 2010-241814 A JP 2004-231638 A International Publication No. 2012/147904

When aligning a liquid crystal compound, the temperature of the layer of the liquid crystalline composition is usually adjusted to a predetermined temperature at which the liquid crystal compound becomes a liquid crystal phase. This temperature is generally a temperature _{equal to} or higher than the phase transition temperature TCN from the crystal phase to the nematic phase of the liquid crystal composition. Therefore, when the phase transition temperature _TCN is high, it is required to increase the temperature of the liquid crystal composition layer when aligning the liquid crystal compound.

In general, when a liquid crystal composition layer is heated to increase the temperature of the liquid crystal composition layer, a large amount of heat is also applied to the base material supporting the layer. When such a large heat is applied, the base material is distorted, and the resulting optical film may be deformed such as wrinkles and undulations. Such deformation can cause deterioration of the quality of the optical film. Therefore, development of a technique capable of reducing the phase transition temperature _TCN of the liquid crystal composition is required.

  Moreover, in order to make the optical characteristics of the manufactured optical film uniform, it is desirable that the liquid crystalline composition has good orientation and the occurrence of phase separation is suppressed.

The present invention has been made in view of the problems described above, can be lowered phase transition temperature T _CN from the crystal phase to the nematic phase, orientation is good, and, which can suppress the occurrence of phase separation, An object is to provide a liquid crystal composition.

As a result of intensive studies to solve the above problems, the present inventor has a predetermined molecular weight polymerizable liquid crystal compound capable of developing reverse wavelength dispersive birefringence having a SP value and a molecular weight within a predetermined range (meta). by combining the acrylate compound, they found to be able to lower the phase transition temperature T _CN while suppressing the occurrence of orientation decreases and phase separation, and completed the present invention.
That is, the present invention is as follows.

（前記式（Ｉ）において、
Ｙ^１〜Ｙ^８は、それぞれ独立して、化学的な単結合、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ^１−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^１−、−Ｏ−Ｃ（＝Ｏ）−ＮＲ^１−、−ＮＲ^１−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ^１−Ｃ（＝Ｏ）−ＮＲ^１−、−Ｏ−ＮＲ^１−、又は、−ＮＲ^１−Ｏ−を表す。ここで、Ｒ^１は、水素原子又は炭素数１〜６のアルキル基を表す。
Ｇ^１及びＧ^２は、それぞれ独立して、置換基を有していてもよい、炭素数１〜２０の二価の脂肪族基を表す。また、前記脂肪族基には、１つの脂肪族基当たり１以上の−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ^２−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ^２−、−ＮＲ^２−、又は、−Ｃ（＝Ｏ）−が介在していてもよい。ただし、−Ｏ−又は−Ｓ−がそれぞれ２以上隣接して介在する場合を除く。ここで、Ｒ^２は、水素原子又は炭素数１〜６のアルキル基を表す。
Ｚ^１及びＺ^２は、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素数２〜１０のアルケニル基を表す。
Ａ^ｘは、芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数２〜３０の有機基を表す。
Ａ^ｙは、水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基、置換基を有していてもよい炭素数３〜１２のシクロアルキル基、置換基を有していてもよい炭素数２〜２０のアルキニル基、−Ｃ（＝Ｏ）−Ｒ^３、−ＳＯ_２−Ｒ^４、−Ｃ（＝Ｓ）ＮＨ−Ｒ^９、又は、芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数２〜３０の有機基を表す。ここで、Ｒ^３は、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基、置換基を有していてもよい炭素数３〜１２のシクロアルキル基、又は、炭素数５〜１２の芳香族炭化水素基を表す。Ｒ^４は、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、フェニル基、又は、４−メチルフェニル基を表す。Ｒ^９は、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基、置換基を有していてもよい炭素数３〜１２のシクロアルキル基、又は、置換基を有していてもよい炭素数５〜２０の芳香族基を表す。前記Ａ^ｘ及びＡ^ｙが有する芳香環は、置換基を有していてもよい。また、前記Ａ^ｘとＡ^ｙは、一緒になって、環を形成していてもよい。
Ａ^１は、置換基を有していてもよい三価の芳香族基を表す。
Ａ^２及びＡ^３は、それぞれ独立して、置換基を有していてもよい炭素数３〜３０の二価の脂環式炭化水素基を表す。
Ａ^４及びＡ^５は、それぞれ独立して、置換基を有していてもよい、炭素数６〜３０の二価の芳香族基を表す。
Ｑ^１は、水素原子、又は、置換基を有していてもよい炭素数１〜６のアルキル基を表す。
ｍ及びｎは、それぞれ独立に、０又は１を表す。） [1] Liquid crystallinity comprising a polymerizable liquid crystal compound having a molecular weight of 540 or more capable of developing reverse wavelength dispersive birefringence, and a (meth) acrylate compound having an SP value of less than 19.0 and having a molecular weight of 220 or more and less than 540 Composition.
[2] The liquid crystalline composition according to [1], wherein the (meth) acrylate compound is a non-liquid crystal compound.
[3] The liquid crystalline composition according to [1] or [2], wherein the (meth) acrylate compound has two or more (meth) acryloyl groups per molecule.
[4] The liquid crystalline composition according to any one of [1] to [3], wherein a phase transition temperature from a crystal phase to a nematic phase of the liquid crystalline composition is 98 ° C. or lower.
[5] Any one of [1] to [4], wherein the polymerizable liquid crystal compound includes a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in a molecule of the polymerizable liquid crystal compound. The liquid crystal composition according to item.
[6] The liquid crystalline composition according to any one of [1] to [5], wherein the polymerizable liquid crystal compound is represented by the following formula (I).

(In the formula (I),
Y ^{1 to} Y ⁸ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C. (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (= O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O— is represented. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G ¹ and G ² each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent. The aliphatic group includes one or more —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C per one aliphatic group. Even if (═O) —O—, —NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or —C (═O) — are present. Good. However, the case where two or more of -O- or -S- are adjacent to each other is excluded. Here, R < ² > represents a hydrogen atom or a C1-C6 alkyl group.
Z ¹ and Z ² each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
A ^x represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
A ^y has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. A cycloalkyl group having 3 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, —C (═O) —R ³ , —SO ₂ —R ⁴ , —C ( = S) NH-R ⁹ or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Here, R ³ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Or a C3-C12 cycloalkyl group or a C5-C12 aromatic hydrocarbon group. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R ⁹ is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted carbon. The C3-C12 cycloalkyl group or the C5-C20 aromatic group which may have a substituent is represented. The aromatic ring which said ^Ax and ^Ay have may have a substituent. A ^x and A ^y may be combined to form a ring.
A ¹ represents a trivalent aromatic group which may have a substituent.
A ² and A ³ each independently represent a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent.
A ⁴ and A ⁵ each independently represent a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent.
Q ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
m and n each independently represents 0 or 1. )

According to the present invention, can be lowered phase transition temperature T _CN from the crystal phase to the nematic phase, orientation is good, and, which can suppress the occurrence of phase separation, it is possible to provide a liquid crystal composition.

  Hereinafter, the present invention will be described in detail with reference to examples and embodiments. However, the present invention is not limited to the following exemplifications and embodiments, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

  In the following description, the term “(meth) acrylate” includes both “acrylate” and “methacrylate” unless otherwise specified. In the following description, the term “(meth) acryloyl group” includes both “acryloyl group” and “methacryloyl group” unless otherwise specified.

  In the following description, the term “polarizing plate” and the term “wave plate” include flexible films and sheets such as resin films, unless otherwise specified.

  In the following description, a resin having a positive intrinsic birefringence value means a resin having a refractive index in the stretching direction that is greater than a refractive index in a direction perpendicular thereto. Further, the resin having a negative intrinsic birefringence value means a resin having a refractive index in the stretching direction that is smaller than a refractive index in a direction perpendicular thereto. The intrinsic birefringence value can be calculated from the dielectric constant distribution.

  In the following description, the retardation of a certain layer represents in-plane retardation Re unless otherwise specified. This in-plane retardation Re is a value represented by Re = (nx−ny) × d unless otherwise specified. Here, nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the layer and giving the maximum refractive index. ny represents the refractive index in the in-plane direction of the layer and perpendicular to the nx direction. d represents the thickness of the layer. The measurement wavelength of retardation is 550 nm unless otherwise specified.

  In the following description, the direction of the slow axis of a certain layer means the direction of the slow axis in the in-plane direction unless otherwise specified.

  In the following description, unless the direction of the element is “parallel” or “vertical”, the range is within a range that does not impair the effect of the present invention, for example, ± 5 °, preferably ± 3 °, more preferably ± 1. An error within the range of ° may be included.

[1. Overview of liquid crystalline composition]
The liquid crystalline composition of the present invention contains a polymerizable liquid crystal compound capable of developing reverse wavelength dispersive birefringence and a (meth) acrylate compound. In the following description, a polymerizable liquid crystal compound that can exhibit reverse wavelength dispersive birefringence may be referred to as “reverse wavelength polymerizable liquid crystal compound” as appropriate. The reverse wavelength polymerizable liquid crystal compound has a molecular weight in a predetermined range. The (meth) acrylate compound has an SP value within a predetermined range and a molecular weight within a predetermined range. The phase transition temperature T _CN from the crystal phase to the nematic phase of such a liquid crystal composition is lower than the phase transition temperature T _CN from the crystal phase to the nematic phase of the reverse wavelength polymerizable liquid crystal compound alone. In the following description, the phase transition temperature T _CN from the crystal phase to the nematic phase may be referred to as “liquid crystallizing temperature” T _CN as appropriate. Moreover, such a liquid crystalline composition is excellent in orientation and the occurrence of phase separation is suppressed.

[2. Reverse wavelength polymerizable liquid crystal compound]
The reverse wavelength polymerizable liquid crystal compound is a liquid crystal compound having polymerizability. Since the reverse wavelength polymerizable liquid crystal compound is a liquid crystal compound having liquid crystallinity, a liquid crystal phase can be exhibited when the reverse wavelength polymerizable liquid crystal compound is aligned. Further, since the reverse wavelength polymerizable liquid crystal compound is a compound having polymerizability, it can be polymerized while exhibiting a liquid crystal phase as described above, and can be a polymer while maintaining the molecular orientation in the liquid crystal phase.

  Further, the reverse wavelength polymerizable liquid crystal compound is a compound that can exhibit reverse wavelength dispersive birefringence. Here, the compound capable of exhibiting reverse wavelength dispersive birefringence refers to a compound in which the obtained polymer exhibits reverse wavelength dispersive birefringence when used as a polymer as described above.

Reverse wavelength dispersive birefringence refers to birefringence in which birefringence Δn (450) at a wavelength of 450 nm and birefringence Δn (650) at a wavelength of 650 nm satisfy the following formula (D1). The above-mentioned reverse wavelength polymerizable liquid crystal compound capable of exhibiting such reverse wavelength dispersive birefringence can usually exhibit greater birefringence as the measurement wavelength is longer. Therefore, normally, the birefringence of the polymer obtained by polymerizing the reverse wavelength polymerizable liquid crystal compound as described above satisfies the following formula (D2). In the following formula (D2), Δn (550) represents birefringence at a measurement wavelength of 550 nm.
Δn (450) <Δn (650) (D1)
Δn (450) <Δn (550) <Δn (650) (D2)

The molecular weight of the reverse wavelength polymerizable liquid crystal compound is usually 540 or more, more preferably 800 or more, and particularly preferably 1000 or more. In general, the reverse wavelength polymerizable liquid crystal compound having such a large molecular weight tends to have a high liquid crystallizing temperature _TCN . On the other hand, in the liquid crystalline composition of the present invention, since the specific (meth) acrylate compound is combined with the reverse wavelength polymerizable liquid crystal compound, the liquid crystallizing temperature T _CN can be lowered as the entire liquid crystalline composition. . The upper limit of the molecular weight of the reverse wavelength polymerizable liquid crystal compound is not particularly limited, but is preferably 1800 or less, more preferably 1600 or less, and particularly preferably 1400 or less. When the molecular weight of the reverse wavelength polymerizable liquid crystal compound is not more than the above upper limit value, the coating property of the liquid crystalline composition can be particularly improved, so that the optical film can be easily produced.

From the viewpoint of effectively utilizing the effect that the liquid crystallizing temperature _TCN can be lowered, it is preferable to use a reverse wavelength polymerizable liquid crystal compound having a high liquid crystallizing temperature _TCN by itself. . The specific liquid crystallizing temperature T _CN of the reverse wavelength polymerizable liquid crystal compound alone is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and particularly preferably 100 ° C. or higher. Although there is no particular limitation on the upper limit of the liquid crystallizing temperature T _CN of the reverse wavelength polymerizable liquid crystal compound alone, it is preferably 180 ° C. or less, more preferably 150 ° C. or less, and particularly preferably 120 ° C. from the viewpoint of handleability. It is as follows.

  As such a reverse wavelength polymerizable liquid crystal compound, a compound containing a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in the molecule of the reverse wavelength polymerizable liquid crystal compound can be used. In the reverse wavelength polymerizable liquid crystal compound containing a main chain mesogen and a side chain mesogen, the side chain mesogen can be aligned in a direction different from the main chain mesogen in a state where the reverse wavelength polymerizable liquid crystal compound is aligned. Therefore, in the polymer obtained by polymerizing the reverse wavelength polymerizable liquid crystal compound while maintaining such orientation, the main chain mesogen and the side chain mesogen can be oriented in different directions. In such a case, birefringence appears as the difference between the refractive index corresponding to the main chain mesogen and the refractive index corresponding to the side chain mesogen, and as a result, the reverse wavelength polymerizable liquid crystal compound and the polymer thereof have the reverse wavelength. Dispersive birefringence can be expressed.

As described above, the three-dimensional shape of the compound having the main chain mesogen and the side chain mesogen is a specific shape different from the three-dimensional shape of a general forward wavelength dispersive liquid crystal compound. Here, the “normal wavelength polymerizable liquid crystal compound” refers to a polymerizable liquid crystal compound capable of exhibiting birefringence with a normal wavelength dispersion. The forward wavelength dispersive birefringence represents birefringence in which the absolute value of the birefringence decreases as the measurement wavelength increases. According to the study of the present inventor, the fact that the reverse wavelength polymerizable liquid crystal compound has a specific three-dimensional shape as described above is a decrease in orientation and phase separation when combined with a specific (meth) acrylate compound. It is presumed that this contributes to the effect that the liquid crystallizing temperature _TCN can be lowered while suppressing the generation. However, the technical scope of the present invention is not limited by the above estimation.

  One type of the reverse wavelength polymerizable liquid crystal compound may be used alone, or two or more types may be used in combination at any ratio.

  Preferable specific examples of the reverse wavelength polymerizable liquid crystal compound include compounds represented by the following formula (I). In the following description, the compound represented by the formula (I) may be referred to as “compound (I)” as appropriate.

Compound (I) is usually, as represented by the following formula, based ^{-Y 5 -A 4 - (Y 3} -A 2) n -Y 1 -A 1 -Y 2 - (A 3 -Y 4) m - It includes two mesogenic skeletons of a main chain mesogen 1a composed of A ⁵ -Y ^6- and a side chain mesogen 1b composed of a group> A ¹ -C (Q ¹ ) = NN (A ^x ) A ^y . The main chain mesogen 1a and the side chain mesogen 1b cross each other. Although the main chain mesogen 1a and the side chain mesogen 1b can be combined into one mesogen, in the present invention, they are divided into two mesogens.

  The refractive index in the major axis direction of the main chain mesogen 1a is n1, and the refractive index in the major axis direction of the side chain mesogen 1b is n2. At this time, the absolute value and the wavelength dispersion of the refractive index n1 usually depend on the molecular structure of the main chain mesogen 1a. Further, the absolute value and wavelength dispersion of the refractive index n2 usually depend on the molecular structure of the side chain mesogen 1b. Here, in the liquid crystal phase, the reverse wavelength polymerizable liquid crystal compound normally performs a rotational motion with the major axis direction of the main chain mesogen 1a as the rotation axis, and the refractive indexes n1 and n2 referred to here are the refraction as a rotating body. Represents the rate.

  Due to the molecular structure of the main chain mesogen 1a and the side chain mesogen 1b, the absolute value of the refractive index n1 is larger than the absolute value of the refractive index n2. Furthermore, the refractive indexes n1 and n2 usually show forward wavelength dispersion. Here, the forward wavelength dispersive refractive index represents a refractive index in which the absolute value of the refractive index decreases as the measurement wavelength increases. Since the refractive index n1 of the main chain mesogen 1a has a small forward wavelength dispersion, the refractive index measured at a long wavelength is not significantly smaller than the refractive index measured at a short wavelength. On the other hand, since the refractive index n2 of the side chain mesogen 1b has a large forward wavelength dispersion, the refractive index measured at a long wavelength is significantly smaller than the refractive index measured at a short wavelength. Therefore, when the measurement wavelength is short, the difference Δn between the refractive index n1 and the refractive index n2 is small, and when the measurement wavelength is long, the difference Δn between the refractive index n1 and the refractive index n2 is large. In this way, the reverse wavelength dispersive birefringence can be developed from the main chain mesogen 1a and the side chain mesogen 1b.

In the formula (I), Y ^{1 to} Y ⁸ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —. O—, —O—C (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (═O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O— is represented.

Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Examples of the alkyl group having 1 to 6 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, An n-hexyl group may be mentioned.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the compound (I), Y ^{1 to} Y ⁸ are each independently a chemical single bond, —O—, —O—C (═O) —, —C (═O) —O—, or , —O—C (═O) —O— is preferable.

In the formula (I), G ¹ and G ² each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent.
Examples of the divalent aliphatic group having 1 to 20 carbon atoms include a divalent aliphatic group having a chain structure such as an alkylene group having 1 to 20 carbon atoms and an alkenylene group having 2 to 20 carbon atoms; And divalent aliphatic groups such as a cycloalkanediyl group having 3 to 20 carbon atoms, a cycloalkenediyl group having 4 to 20 carbon atoms, and a divalent alicyclic fused ring group having 10 to 30 carbon atoms.

Examples of the substituent for the divalent aliphatic group represented by G ¹ and G ² include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, n-propoxy group, isopropoxy group , An n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, or the like, or an alkoxy group having 1 to 6 carbon atoms. Of these, a fluorine atom, a methoxy group, and an ethoxy group are preferable.

The aliphatic group includes one or more —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C per one aliphatic group. Even if (═O) —O—, —NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or —C (═O) — are present. Good. However, the case where two or more of -O- or -S- are adjacent to each other is excluded. Here, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom or a methyl group.
As the group intervening in the aliphatic group, —O—, —O—C (═O) —, —C (═O) —O—, and —C (═O) — are preferable.

Specific examples of the aliphatic group mediated by these groups include, for example, —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ —, — _{CH 2 -CH 2 -O-C (} = O) -CH 2 -CH 2 -, - CH 2 -CH 2 -C (= O) -O-CH 2 -CH 2 -, - CH 2 -CH 2 - C (═O) —O—CH ₂ —, —CH ₂ —O—C (═O) —O—CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —NR ² —C (═O) —CH _{2 -CH 2 -, - CH 2} -CH 2 -C (= O) -NR 2 -CH 2 -, - CH 2 -NR 2 -CH 2 -CH 2 -, - CH 2 -C (= O) - CH ₂ — may be mentioned.

Among these, G ¹ and G ² are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or the like, from the viewpoint of better expressing the desired effect of the present invention. A divalent aliphatic group having a chain structure is preferable, and a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group [— (CH ₂ ) ₁₀ - a] and the like, more preferably an alkylene group having 1 to 12 carbon atoms, a tetramethylene group [- _{(CH 2) 4} -], hexamethylene group [- _{(CH 2) 6} -], octamethylene [- ( CH ₂ ) ₈ —] and decamethylene group [— (CH ₂ ) ₁₀ —] are particularly preferred.

In the formula (I), Z ¹ and Z ² each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
As carbon number of this alkenyl group, 2-6 are preferable. Examples of the halogen atom that is a substituent of the alkenyl group of Z ¹ and Z ² include a fluorine atom, a chlorine atom, a bromine atom, and the like, and a chlorine atom is preferable.

Specific examples of the alkenyl group having 2 to 10 carbon atoms of Z ¹ and Z ² include CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH ₂ ═CH—CH ₂ —, CH ₃ —CH═. _{CH-, CH 2 = CH-CH} 2 -CH 2 -, CH 2 = C (CH 3) -CH 2 -CH 2 -, (CH 3) 2 C = CH-CH 2 -, (CH 3) 2 C _{= CH-CH 2 -CH 2 -} , CH 2 = C (Cl) -, CH 2 = C (CH 3) -CH 2 -, CH 3 -CH = CH-CH 2 - and the like.

Especially, from a viewpoint of expressing the desired effect of the present invention better, Z ¹ and Z ² are each independently CH ₂ = CH-, CH ₂ = C (CH ₃ )-, CH ₂ = _{C (Cl) -, CH 2} = CH-CH 2 -, CH 2 = C (CH 3) -CH 2 -, _{or, CH 2 = C (CH 3} ) -CH 2 -CH 2 - are preferred, CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) — is more preferable, and CH ₂ ═CH— is particularly preferable.

In the formula (I), A ^x represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. “Aromatic ring” means a cyclic structure having a broad sense of aromaticity according to the Huckle rule, that is, a cyclic conjugated structure having (4n + 2) π electrons, and sulfur, oxygen, typified by thiophene, furan, benzothiazole, etc. It means a cyclic structure in which a lone electron pair of a hetero atom such as nitrogen is involved in the π-electron system and exhibits aromaticity.

Of A ^x, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic organic group having 2 to 30 carbon atoms may be those having a plurality of aromatic rings And having both an aromatic hydrocarbon ring and an aromatic heterocycle.

  Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the aromatic heterocyclic ring include monocyclic aromatic heterocyclic rings such as a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring; Benzothiazole ring, benzoxazole ring, quinoline ring, phthalazine ring, benzimidazole ring, benzopyrazole ring, benzofuran ring, benzothiophene ring, thiazolopyridine ring, oxazolopyridine ring, thiazolopyrazine ring, oxazolopyrazine ring, thia And a condensed aromatic heterocycle such as a zolopyridazine ring, an oxazolopyridazine ring, a thiazolopyrimidine ring, and an oxazolopyrimidine ring.

The aromatic ring of A ^x may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and carbon number 2 such as vinyl group and allyl group. -6 alkenyl groups; C 1-6 halogenated alkyl groups such as trifluoromethyl groups; substituted amino groups such as dimethylamino groups; C 1-6 alkoxys such as methoxy groups, ethoxy groups, and isopropoxy groups group; a nitro group; a phenyl group, an aryl group such as phenyl or ^{naphthyl; -C (= O) -R 5} ; -C (= O) -OR 5; -SO 2 R 6; and the like. Here, R ⁵ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms, and R ⁶ is the same carbon as R ⁴ described later. An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group is represented.

Further, the aromatic ring within A ^x may have a plurality of identical or different substituents, bonded two adjacent substituents together may form a ring. The ring formed may be a monocycle, a condensed polycycle, an unsaturated ring, or a saturated ring.
Furthermore, the “carbon number” of the organic group having 2 to 30 carbon atoms of A ^x means the total carbon number of the whole organic group not including the carbon atom of the substituent (the same applies to A ^y described later). .

Of A ^x, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic ring, examples of the organic group having 2 to 30 carbon atoms, for example, an aromatic hydrocarbon ring group, aromatic A heterocyclic group; an alkyl group having 3 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group; an aromatic hydrocarbon ring group and an aromatic heterocyclic ring An alkenyl group having 4 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of a group; having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group, And an alkynyl group having 4 to 30 carbon atoms.

Preferred specific examples of A ^x are shown below. However, ^Ax is not limited to the following. In the following formulae, “-” represents a bond extending from any position of the ring (the same applies hereinafter).
(1) Aromatic hydrocarbon ring group

  (2) Aromatic heterocyclic group

In the above formula, E represents NR ^6a , an oxygen atom or a sulfur atom. Here, R ^6a represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group.

In the above formula, X, Y and Z each independently represent NR ⁷ , oxygen atom, sulfur atom, —SO— or —SO ₂ — (provided that oxygen atom, sulfur atom, —SO—, -SO ₂ - is, unless the respective adjacent).. R ⁷ represents the same hydrogen atom as R ^6a ; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group.

(In the above formula, X represents the same meaning as described above.)
(3) An alkyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group

  (4) An alkenyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group

  (5) An alkynyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group

Among the A ^x as described above, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or is preferably an aromatic heterocyclic group having 4 to 30 carbon atoms, more preferably one of the groups shown below .

Further, A ^x is more preferably any of the groups shown below.

Ring within A ^x may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and carbon number 2 such as vinyl group and allyl group. -6 alkenyl groups; C 1-6 halogenated alkyl groups such as trifluoromethyl groups; substituted amino groups such as dimethylamino groups; C 1-6 alkoxys such as methoxy groups, ethoxy groups, and isopropoxy groups Group; nitro group; aryl group such as phenyl group and naphthyl group; -C (= O) -R ⁸ ; -C (= O) -OR ⁸ ; -SO ₂ R ⁶ ; Here, R ⁸ represents an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; or an aryl group having 6 to 14 carbon atoms such as a phenyl group. Especially, as a substituent, a halogen atom, a cyano group, a C1-C6 alkyl group, and a C1-C6 alkoxy group are preferable.

The ring of A ^x may have a plurality of the same or different substituents, and two adjacent substituents may be bonded together to form a ring. The ring formed may be a single ring or a condensed polycycle.
The “carbon number” of the organic group having 2 to 30 carbon atoms of A ^x means the total number of carbon atoms of the entire organic group not including the carbon atom of the substituent (the same applies to A ^y described later).

In the formula (I), A ^y is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having from 3 to 12 carbon atoms which may have a substituent, which may have a substituent group an alkynyl group having a carbon number of ^{2~20, -C (= O) -R} 3, -SO 2 An organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of —R ⁴ , —C (═S) NH—R ⁹ , or an aromatic hydrocarbon ring and an aromatic heterocyclic ring; Represent. Here, R ³ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Or a C3-C12 cycloalkyl group or a C5-C12 aromatic hydrocarbon group. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R ⁹ is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted carbon. The C3-C12 cycloalkyl group or the C5-C20 aromatic group which may have a substituent is represented.

Of A ^y, the alkyl group having 1 to 20 carbon atoms an alkyl group having 1 to 20 carbon atoms that may have a substituent, such as methyl group, ethyl group, n- propyl group, an isopropyl radical, n -Butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group are mentioned. The carbon number of the alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably 1 to 12, and more preferably 4 to 10.

Examples of the alkenyl group having 2 to 20 carbon atoms that may have a substituent in A ^y include, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, and an isobutenyl group. Pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group. It is preferable that carbon number of the C2-C20 alkenyl group which may have a substituent is 2-12.

Of A ^y, a cycloalkyl group having 3 to 12 carbon atoms a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, A cyclooctyl group is mentioned.

Of A ^y, the alkynyl group having 2 to 20 carbon atoms alkynyl group having carbon atoms of 2 to 20 which may have a substituent, such as ethynyl group, propynyl group, 2-propynyl group (propargyl group), Butynyl, 2-butynyl, 3-butynyl, pentynyl, 2-pentynyl, hexynyl, 5-hexynyl, heptynyl, octynyl, 2-octynyl, nonanyl, decanyl, 7-decanyl Is mentioned.

Examples of the substituent of the alkyl group having 1 to 20 carbon atoms that may have a substituent and the alkenyl group having 2 to 20 carbon atoms that may have a substituent of A ^y include, for example, a fluorine atom Halogen atom such as chlorine atom; cyano group; substituted amino group such as dimethylamino group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group; methoxymethoxy group, methoxyethoxy group A C1-C12 alkoxy group substituted with a C1-C12 alkoxy group; a nitro group; an aryl group such as a phenyl group or a naphthyl group; a carbon number such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group A cycloalkyl group having 3 to 8 carbon atoms; a cycloalkyloxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; A cyclic ether group having 2 to 12 carbon atoms such as a ru group, a tetrahydropyranyl group, a dioxolanyl group and a dioxanyl group; an aryloxy group having 6 to 14 carbon atoms such as a phenoxy group and a naphthoxy group; a trifluoromethyl group and pentafluoroethyl A fluoroalkoxy group having 1 to 12 carbon atoms in which at least one is substituted with a fluorine atom, such as a group, —CH ₂ CF ₃ ; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzodioxanyl group; _{^{(= O) -R 7a; -C}} (= O) -OR 7a; alkoxy group ^{-SR 10} carbon atoms substituted with ^{1~12;; -SO 2 R 8a;} -SR 10 hydroxyl; and the like. Here, R ^7a and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 6 to 12 carbon atoms. Represents an aromatic hydrocarbon group. R ^8a represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group, similar to R ⁴ described above.

Examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms that may have a substituent for A ^y include, for example, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group Groups: alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy groups; nitro groups; phenyl groups, naphthyl groups, and the like A cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; —C (═O) —R ^7a ; —C (═O) —OR ^7a ; —SO ₂ R ^8a A hydroxyl group. Here, R ^7a and R ^8a represent the same meaning as described above.

Examples of the substituent of the alkynyl group having 2 to 20 carbon atoms that may have a substituent of A ^y include, for example, an alkyl group having 1 to 20 carbon atoms that may have a substituent, and substitution. The same substituent as the substituent of the C2-C20 alkenyl group which may have a group is mentioned.

In the group of A ^y represented by —C (═O) —R ³ , R ³ may have a substituent, an alkyl group having 1 to 20 carbon atoms, or a substituent. It represents a good alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 5 to 12 carbon atoms. Specific examples of these include an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and a substituent of the above ^Ay. The thing similar to what was mentioned as an example of a C3-C12 cycloalkyl group which you may have is mentioned.

Of A ^y, in the group represented by _-SO 2 -R ^{4, R 4} is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group Represent. Specific examples of the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of R ⁴ include the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of the above ^Ay . The thing similar to what was mentioned as an example is mentioned.

In the group of A ^y represented by —C (═S) NH—R ⁹ , R ⁹ has an optionally substituted alkyl group having 1 to 20 carbon atoms and a substituent. May be an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic group having 5 to 20 carbon atoms which may have a substituent. Represents. Specific examples of these include an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and a substituent of the above ^Ay. The thing similar to what was mentioned as an example of a C3-C12 cycloalkyl group which you may have is mentioned.

Of A ^y, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic ring, examples of the organic group having 2 to 30 carbon atoms, the same as those described in the A ^x Is mentioned.

Among these, as ^Ay , a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and a substituent A cycloalkyl group having 3 to 12 carbon atoms which may have an alkynyl group having 2 to 20 carbon atoms which may have a substituent, —C (═O) —R ³ , —SO ₂ —R ⁴ or a group represented by an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Further, ^Ay includes a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. An optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, and an aromatic carbon atom having 6 to 12 carbon atoms that may have a substituent. A group represented by a hydrogen group, an optionally substituted aromatic heterocyclic group having 3 to 9 carbon atoms, —C (═O) —R ³ , or —SO ₂ —R ⁴ is more preferable. Here, R ³ and R ⁴ represent the same meaning as described above.

^Ay , an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted carbon As a substituent of the alkynyl group having 2 to 20 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms, phenyl group, a cyclohexyl group, a cyclic ether group having 2 to 12 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxyl group, benzodioxanyl group, phenylsulfonyl group, 4-methyl phenylsulfonyl group, a benzoyl group, ^{-SR 10} Is preferred. Here, R ¹⁰ represents the same meaning as described above.

^Ay has an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and a substituent. As the substituent of the aromatic heterocyclic group having 3 to 9 carbon atoms, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group are preferable.

A ^x and A ^y may be combined to form a ring. Examples of such a ring include an unsaturated heterocyclic ring having 4 to 30 carbon atoms and an unsaturated carbocyclic ring having 6 to 30 carbon atoms, which may have a substituent.

The unsaturated heterocyclic ring having 4 to 30 carbon atoms and the unsaturated heterocyclic ring having 6 to 30 carbon atoms are not particularly limited and may or may not have aromaticity.
Examples of the ring formed by combining A ^x and A ^y include the rings shown below. In addition, the ring shown below is the one in the formula (I).

  The part represented as is shown.

(In the formula, X, Y and Z have the same meaning as described above.)
Moreover, these rings may have a substituent. Such substituent groups include the same as those described as substituents of the aromatic ring within A ^x.

The total number of π electrons contained in A ^x and A ^y is preferably 4 or more, more preferably 6 or more, preferably 24 or less, more preferably from the viewpoint of better expressing the desired effect of the present invention. 20 or less, particularly preferably 18 or less.

As a preferable combination of A ^x and A ^y ,
(Α) A ^x is an aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 30 carbon atoms, A ^y is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, (halogen atom, cyano group, An aromatic hydrocarbon group having 6 to 12 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms) as a substituent. , (Halogen atom, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, cyano group) which may have as a substituent a C 3-9 aromatic heterocyclic group or substituent An optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted substituent having 2 to 20 carbon atoms. And the substituent is a halogen atom, a cyano group, or 1 to 2 carbon atoms. 0 alkoxy group, C1-C12 alkoxy group substituted with C1-C12 alkoxy group, phenyl group, cyclohexyl group, C2-C12 cyclic ether group, C6-C14 aryloxy group, a hydroxyl group, benzodioxanyl group, benzenesulfonyl group, the combination is either a benzoyl group, and -SR ^10, and,
(Β) A combination in which A ^x and A ^y together form an unsaturated heterocyclic ring or an unsaturated carbocyclic ring,
Is mentioned. Here, R ¹⁰ represents the same meaning as described above.

As a more preferable combination of ^Ax and ^Ay ,
(Γ) A ^x is any of the groups having the following structure, and A ^y is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, (a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, carbon An aromatic hydrocarbon group having 6 to 12 carbon atoms which may have an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms as a substituent, (halogen atom, 1 to 6 carbon atoms) An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group) as an optionally substituted aromatic heterocyclic group having 3 to 9 carbon atoms or an optionally substituted carbon atom having 1 substituent. An -20 alkyl group, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted alkynyl group having 2 to 20 carbon atoms, wherein the substituent is , Halogen atom, cyano group, alkoxy group having 1 to 20 carbon atoms, carbon number C1-C12 alkoxy group substituted with 1-12 alkoxy group, phenyl group, cyclohexyl group, C2-C12 cyclic ether group, C6-C14 aryloxy group, hydroxyl group, benzodioxa group, a benzenesulfonyl group, a combination is either a benzoyl group, -SR ^10. Here, R ¹⁰ represents the same meaning as described above.

(In the formula, X and Y have the same meaning as described above.)
As a particularly preferred combination of A ^x and A ^y ,
(Δ) A ^x is any of the groups having the following structure, and A ^y is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, (a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, carbon An aromatic hydrocarbon group having 6 to 12 carbon atoms which may have an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms as a substituent, (halogen atom, 1 to 6 carbon atoms) An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group) as an optionally substituted aromatic heterocyclic group having 3 to 9 carbon atoms or an optionally substituted carbon atom having 1 substituent. An -20 alkyl group, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted alkynyl group having 2 to 20 carbon atoms, wherein the substituent is , Halogen atom, cyano group, alkoxy group having 1 to 20 carbon atoms, carbon number C1-C12 alkoxy group substituted with 1-12 alkoxy group, phenyl group, cyclohexyl group, C2-C12 cyclic ether group, C6-C14 aryloxy group, hydroxyl group, benzodioxa group, a benzenesulfonyl group, a benzoyl group, and a combination of any of -SR ^10. In the following formula, X represents the same meaning as described above. Here, R ¹⁰ represents the same meaning as described above.

In the formula (I), A ¹ represents a trivalent aromatic group which may have a substituent. The trivalent aromatic group may be a trivalent carbocyclic aromatic group or a trivalent heterocyclic aromatic group. From the viewpoint of better expressing the desired effect of the present invention, a trivalent carbocyclic aromatic group is preferable, a trivalent benzene ring group or a trivalent naphthalene ring group is more preferable, and a trivalent represented by the following formula: The benzene ring group or trivalent naphthalene ring group is more preferable. In the following formula, the substituents Y ¹ and Y ² are described for convenience in order to clarify the bonding state (Y ¹ and Y ² represent the same meaning as described above, and the same applies hereinafter). .

Among these, the ^{A 1,} and more preferably a group represented by the formula (A11) ~ (A25) shown below, equation (A11), (A13), (A15), in (A19), (A23) Groups represented by formulas (A11) and (A23) are particularly preferred.

Of A ^1, as a trivalent substituent which may be possessed by the aromatic group, the same as those described as substituents of the aromatic groups of the A ^X and the like. A ¹ preferably has no substituent.

In the formula (I), A ² and A ³ each independently represent a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. Examples of the divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include a cycloalkanediyl group having 3 to 30 carbon atoms and a divalent alicyclic condensed ring group having 10 to 30 carbon atoms.

  Examples of the cycloalkanediyl group having 3 to 30 carbon atoms include cyclopropanediyl group; cyclobutanediyl group such as cyclobutane-1,2-diyl group and cyclobutane-1,3-diyl group; cyclopentane-1,2- Cyclopentanediyl group such as diyl group, cyclopentane-1,3-diyl group; cyclohexanediyl group such as cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group Groups: cycloheptane-1,2-diyl group, cycloheptane-1,3-diyl group, cycloheptanediyl group such as cycloheptane-1,4-diyl group; cyclooctane-1,2-diyl group, cyclooctane Cyclooctane such as -1,3-diyl group, cyclooctane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Cyclodecane-1, 2-diyl group, cyclodecane-1,3-diyl group, cyclodecane-1,4-diyl group, cyclodecane-1,5-diyl group and the like; cyclododecane-1, Cyclododecanediyl groups such as 2-diyl group, cyclododecane-1,3-diyl group, cyclododecane-1,4-diyl group, cyclododecane-1,5-diyl group; cyclotetradecane-1,2-diyl group Cyclotetradecane-1,3-diyl group, cyclotetradecane-1,4-diyl group, cyclotetradecane-1,5-diyl group, cyclotetradecane-1,7-diyl group and the like; cycloeicosane And cycloeicosanediyl groups such as -1,2-diyl group and cycloeicosane-1,10-diyl group.

  Examples of the divalent alicyclic fused ring group having 10 to 30 carbon atoms include decalindiyl groups such as decalin-2,5-diyl group and decalin-2,7-diyl group; adamantane-1,2-diyl group An adamantanediyl group such as an adamantane-1,3-diyl group; a bicyclo [2.2.1] heptane-2,3-diyl group, a bicyclo [2.2.1] heptane-2,5-diyl group And bicyclo [2.2.1] heptanediyl group such as bicyclo [2.2.1] heptane-2,6-diyl group.

These divalent alicyclic hydrocarbon groups may have a substituent at any position. Examples of the substituent include the same as those described as substituents of the aromatic groups of the A ^X.

Among these, the ^{A 2} and ^{A 3,} preferably a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably a cycloalkane-diyl group having 3 to 12 carbon atoms, following formula (A31) ~ A group represented by (A34) is more preferred, and a group represented by the following formula (A32) is particularly preferred.

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms is based on a difference in configuration of carbon atoms bonded to Y ¹ and Y ³ (or Y ² and Y ⁴ ). Stereoisomers can exist. For example, in the case of a cyclohexane-1,4-diyl group, as shown below, a cis-type isomer (A32a) and a trans-type isomer (A32b) may exist.

  The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms may be cis, trans, or a mixture of cis and trans isomers. Of these, the trans-type or cis-type is preferable because the orientation is good, and the trans-type is more preferable.

In the formula (I), A ⁴ and A ⁵ each independently represent a C 6-30 divalent aromatic group which may have a substituent. The aromatic groups of A ⁴ and A ⁵ may be monocyclic or polycyclic. Preferable specific examples of A ⁴ and A ⁵ include the following.

The divalent aromatic groups of A ⁴ and A ⁵ may have a substituent at any position. Examples of the substituent include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a —C (═O) —OR ^8b group. Can be mentioned. Here, R ^8b is an alkyl group having 1 to 6 carbon atoms. Especially, a halogen atom, a C1-C6 alkyl group, and an alkoxy group are preferable. Moreover, as a halogen atom, a fluorine atom is more preferable, As a C1-C6 alkyl group, a methyl group, an ethyl group, and a propyl group are more preferable, As a alkoxy group, a methoxy group and an ethoxy group are more preferable.

Among these, from the viewpoint of better expressing the desired effect of the present invention, A ⁴ and A ⁵ may each independently have a substituent, and the following formulas (A41) and (A42) Or the group represented by (A43) is more preferable, and the group represented by the formula (A41) which may have a substituent is particularly preferable.

In the formula (I), Q ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. The alkyl group has also a good 1 to 6 carbon atoms have a substituent, the same as those described in the A ^X and the like. Among these, Q ¹ is preferably an alkyl group having a hydrogen atom and 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group.

  In the formula (I), m and n each independently represents 0 or 1. Among these, m is preferably 1, and n is preferably 1.

  Compound (I) can be produced, for example, by the reaction shown below.

^{(Wherein, Y 1 ~Y 8, G 1} , G 2, Z 1, Z 2, A x, A y, A 1 ~A 5, Q 1, m and n are as defined above.)

  As shown in the above reaction formula, compound (I) can be produced by reacting the hydrazine compound represented by formula (3) with the carbonyl compound represented by formula (4). Hereinafter, the hydrazine compound represented by the formula (3) may be referred to as “hydrazine compound (3)” as appropriate. In addition, the carbonyl compound represented by the formula (4) may be referred to as “carbonyl compound (4)” as appropriate.

  In the above reaction, the molar ratio of “hydrazine compound (3): carbonyl compound (4)” is preferably 1: 2 to 2: 1, more preferably 1: 1.5 to 1.5: 1. By reacting at such a molar ratio, the target compound (I) can be produced with high selectivity and high yield.

  In this case, the reaction system may contain an acid catalyst such as an organic acid such as (±) -10-camphorsulfonic acid and paratoluenesulfonic acid; an inorganic acid such as hydrochloric acid and sulfuric acid; By using an acid catalyst, the reaction time may be shortened and the yield may be improved. The amount of the acid catalyst is usually 0.001 mol to 1 mol with respect to 1 mol of the carbonyl compound (4). Moreover, an acid catalyst may be mix | blended with a reaction system as it is, and may be mix | blended as a solution dissolved in the appropriate solution.

  As a solvent used in this reaction, a solvent inert to the reaction can be used. Examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol; diethyl ether, tetrahydrofuran, 1, Ether solvents such as 2-dimethoxyethane, 1,4-dioxane and cyclopentyl methyl ether; ester solvents such as ethyl acetate, propyl acetate and methyl propionate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; n -Aliphatic hydrocarbon solvents such as pentane, n-hexane and n-heptane; amide solvents such as N, N-dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide; dimethyl sulfoxide, sulfolane and the like Sulfur-containing solvents; and mixed solvents of two or more thereof; and the like. Among these, alcohol solvents, ether solvents, and mixed solvents of alcohol solvents and ether solvents are preferable.

  The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-100g normally with respect to 1g of hydrazine compounds (3).

  The reaction can usually proceed smoothly in a temperature range of −10 ° C. or higher and lower than the boiling point of the solvent used. The reaction time for each reaction depends on the reaction scale, but is usually from several minutes to several hours.

  The hydrazine compound (3) can be produced as follows.

(In the formula, A ^x and A ^y represent the same meaning as described above. X ^a represents ^a leaving group such as a halogen atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group.)

  As shown in the above reaction formula, the corresponding hydrazine compound (3a) can be obtained by reacting the compound represented by formula (2a) with hydrazine (1) in an appropriate solvent. The molar ratio of “compound (2a): hydrazine (1)” in this reaction is preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10. Furthermore, the hydrazine compound (3) can be obtained by reacting the hydrazine compound (3a) with the compound represented by the formula (2b).

  As the hydrazine (1), a monohydrate can be usually used. As the hydrazine (1), a commercially available product can be used as it is.

  As a solvent used in this reaction, a solvent inert to the reaction can be used. Examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol; diethyl ether, tetrahydrofuran, 1, Ether solvents such as 2-dimethoxyethane, 1,4-dioxane and cyclopentyl methyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic carbonization such as n-pentane, n-hexane and n-heptane Hydrogen solvents; amide solvents such as N, N-dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; and a mixed solvent composed of two or more of these solvents Cited . Among these, alcohol solvents, ether solvents, and mixed solvents of alcohol solvents and ether solvents are preferable.

  The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-100g normally with respect to 1g of hydrazine.

  The reaction can usually proceed smoothly in a temperature range of −10 ° C. or higher and lower than the boiling point of the solvent used. The reaction time for each reaction depends on the reaction scale, but is usually from several minutes to several hours.

  The hydrazine compound (3) can also be produced by reducing the diazonium salt (5) using a known method as follows.

In formula (5), A ^x and A ^y represent the same meaning as described above. X ^b− represents an anion which is a counter ion for diazonium. Examples of ^Xb- include inorganic anions such as hexafluorophosphate ion, borofluoride ion, chloride ion, sulfate ion; polyfluoroalkylcarboxylate ion, polyfluoroalkylsulfonate ion, tetraphenylborate Organic anions such as ions, aromatic carboxylate ions, and aromatic sulfonate ions.

  As a reducing agent used for the said reaction, a metal salt reducing agent is mentioned, for example. The metal salt reducing agent is generally a compound containing a low-valent metal, or a compound comprising a metal ion and a hydride source (“Organic Synthesis Experiment Handbook” 1990, published by Maruzen Co., Ltd., edited by the Society of Synthetic Organic Chemistry, Japan 810). Page).

Examples of the metal salt reducing agent include NaAlH ₄ , NaAlH _p (Or) _q (p and q each independently represent an integer of 1 to 3, and p + q = 4. R is 1 to 6 carbon atoms. And LiAlH ₄ , iBu ₂ AlH, LiBH ₄ , NaBH ₄ , SnCl ₂ , CrCl ₂ , and TiCl ₃ . Here, “iBu” represents an isobutyl group.

In the reduction reaction, known reaction conditions can be employed. For example, the reaction can be performed under the conditions described in Japanese Patent Application Laid-Open No. 2005-336103, New Experimental Chemistry Course, 1978, published by Maruzen Co., Ltd., Volume 14; Experimental Chemistry Course, 1992, published by Maruzen Co., Ltd., Vol.
The diazonium salt (5) can be produced from a compound such as aniline by a conventional method.

  The carbonyl compound (4) includes, for example, an ether bond (—O—), an ester bond (—C (═O) —O—, —O—C (═O) —), a carbonate bond (—O—C (= O) -O-) and amide bond (-C (= O) -NH-, -NH-C (= O)-) are arbitrarily combined to appropriately combine a plurality of known compounds having a desired structure. It can be produced by binding to and modifying.

Formation of an ether bond can be performed as follows.
(I) A compound represented by the formula: D1-hal (hal represents a halogen atom; the same shall apply hereinafter) and a formula: D2-OMet (Met represents an alkali metal (mainly sodium). The same) is mixed and condensed (Williamson synthesis). In the formula, D1 and D2 represent arbitrary organic groups (the same applies hereinafter).
(Ii) A compound represented by the formula: D1-hal and a compound represented by the formula: D2-OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
(Iii) A compound represented by the formula: D1-J (J represents an epoxy group) and a compound represented by the formula: D2-OH in the presence of a base such as sodium hydroxide or potassium hydroxide, Mix and condense.
(Iv) A compound represented by the formula: D1-OFN (OFN represents a group having an unsaturated bond) and a compound represented by the formula: D2-OMet, such as sodium hydroxide, potassium hydroxide, etc. In the presence of a base, they are mixed and subjected to an addition reaction.
(V) A compound represented by the formula: D1-hal and a compound represented by the formula: D2-OMet are mixed and condensed in the presence of copper or cuprous chloride (Ullman condensation).

Formation of ester bonds and amide bonds can be performed as follows.
(Vi) formula: a compound represented by D1-COOH, wherein: the D2-OH or D2-NH is represented by ₂ compounds, dehydrated in the presence of a dehydrating condensing agent (N, N-dicyclohexylcarbodiimide, etc.) Allow to condense.
(Vii) A compound represented by the formula: D1-CO-hal is obtained by allowing a halogenating agent to act on the compound represented by the formula: D1-COOH, and this is combined with the formula: D2-OH or D2- The compound represented by NH ₂ is reacted in the presence of a base.
(Viii) Formula: by the action of an acid anhydride to a compound represented by D1-COOH, after obtaining a mixed acid anhydride, the ones with the formula: D2-OH or a compound represented by D2-NH ₂ And react.
(Ix) formula: a compound represented by D1-COOH, wherein: the D2-OH or a compound represented by D2-NH _2, dehydration condensation in the presence of an acid catalyst or base catalyst.

  More specifically, the carbonyl compound (4) can be produced by the method shown in the following reaction formula.

(Wherein, Y ^{1 to} Y ⁸ , G ¹ , G ² , Z ¹ , Z ² , A ^{1 to} A ⁵ , Q ¹ , m and n represent the same meaning as described above. L ¹ and L ² are Each independently represents a leaving group such as a hydroxyl group, a halogen atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, etc. -Y ^1a represents a group that can react with -L ¹ to become -Y ^1- ; -Y ^2a reacts with -L ² -Y ² - represents a and becomes capable group).

  As shown in the above reaction formula, an ether bond (—O—), an ester bond (—C (═O) —O—, —O—C (═O) —), or a carbonate bond (—O—). By using the formation reaction of C (═O) —O—), the compound represented by the formula (6d) is converted into the compound represented by the formula (7a), and then the compound represented by the formula (7b). The carbonyl compound (4) can be produced by reaction.

As a specific example, Y ¹ is a group represented by the formula: Y ¹¹ —C (═O) —O—, and the formula: Z ² —Y ⁸ —G ² —Y ⁶ —A ⁵ — (Y ⁴ -A ³⁾ _m -Y ² - is a group represented by the ^{formula: Z 1 -Y 7 -G 1 -Y} 5 -A 4 - is represented by _{^{- (Y 3 -A 2) n}} -Y 1 The production method of compound (4 ′), which is the same as the group, is shown below.

(Wherein Y ³ , Y ⁵ , Y ⁷ , G ¹ , Z ¹ , A ¹ , A ² , A ⁴ , Q ¹ , n and L ¹ represent the same meaning as described above. Y ¹¹ represents Y ^11. -C (= O) -O- represents a group that becomes Y ^1. Y ¹ represents the same meaning as described above.

  As shown in the above reaction formula, the compound by reacting the dihydroxy compound represented by formula (6) (compound (6)) and the compound represented by formula (7) (compound (7)) is obtained. (4 ′) can be produced. The molar ratio of “compound (6): compound (7)” in this reaction is preferably 1: 2 to 1: 4, more preferably 1: 2 to 1: 3. By reacting at such a molar ratio, the target compound (4 ') can be obtained with high selectivity and high yield.

When compound (7) is a compound (carboxylic acid) in which L ¹ is a hydroxyl group, in the presence of a dehydration condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride or dicyclohexylcarbodiimide. The target product can be obtained by reacting with. The amount of the dehydrating condensing agent to be used is generally 1 mol-3 mol with respect to 1 mol of compound (7).

When the compound (7) is a compound (carboxylic acid) in which L ¹ is a hydroxyl group, sulfonyl halides such as methanesulfonyl chloride and p-toluenesulfonyl chloride, and triethylamine, diisopropylethylamine, pyridine, 4- ( The target product can also be obtained by reacting in the presence of a base such as (dimethylamino) pyridine. The usage-amount of a sulfonyl halide is 1 mol-3 mol normally with respect to 1 mol of compounds (7). Moreover, the usage-amount of a base is 1 mol-3 mol normally with respect to 1 mol of compounds (7). In this case, in the formula (7), a compound (mixed acid anhydride) in which L ¹ is a sulfonyloxy group may be isolated and the following reaction may be performed.

Furthermore, when the compound (7) is a compound (acid halide) in which L ¹ is a halogen atom, the desired product can be obtained by reacting in the presence of a base. Examples of the base include organic bases such as triethylamine and pyridine; and inorganic bases such as sodium hydroxide, sodium carbonate, and sodium bicarbonate. The amount of the base to be used is generally 1 mol to 3 mol per 1 mol of compound (7).

Examples of the solvent used in the above reaction include chlorine solvents such as chloroform and methylene chloride; amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and hexamethylphosphate triamide; Ether solvents such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-octane; Alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and mixed solvents composed of two or more of these solvents; It is done.
The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-50g normally with respect to 1g of hydroxy compounds (6).

  Most of the compound (6) is a known substance and can be produced by a known method. For example, it can be produced by the method shown in the following reaction formula (see International Publication No. 2009/042544 and The Journal of Organic Chemistry, 2011, 76, 8082-8087, etc.). What is marketed as compound (6) may be purified if desired.

(Wherein A ¹ and Q ¹ represent the same meaning as described above, A ^1a represents a divalent aromatic group that can be converted to A ¹ by formylation or acylation, and R ′ represents methyl. And a hydroxyl-protecting group such as an alkyl group having 1 to 6 carbon atoms such as a group and an ethyl group, and an alkoxyalkyl group having 2 to 6 carbon atoms such as a methoxymethyl group.)

As shown in the above reaction formula, the hydroxy group of the dihydroxy compound (1,4-dihydroxybenzene, 1,4-dihydroxynaphthalene, etc.) represented by the formula (6a) is alkylated to represent the formula (6b). Then, the ortho-position of the OR ′ group is formylated or acylated by a known method to obtain a compound represented by the formula (6c), which is deprotected (dealkylated). ) To produce the target compound (6).
In addition, as the compound (6), a commercially available product may be used as it is or after purification as desired.

  Many of the compounds (7) are known compounds such as an ether bond (—O—), an ester bond (—C (═O) —O—, —O—C (═O) —), a carbonate bond (— A plurality of compounds having a desired structure by arbitrarily combining the formation reaction of O—C (═O) —O—) and amide bond (—C (═O) —NH—, —NH—C (═O) —) Can be produced by appropriately binding and modifying the known compounds.

  For example, when the compound (7) is a compound represented by the following formula (7 ′) (compound (7 ′)), a dicarboxylic acid represented by the formula (9 ′) (compound (9 ′)) Can be used as follows.

(Wherein Y ⁵ , Y ⁷ , G ¹ , Z ¹ , A ² , A ⁴ and Y ¹¹ represent the same meaning as described above. Y ¹² represents —O—C (═O) —Y ¹² represents Y. .R representing the ³ become group, an alkyl group such as a methyl group, an ethyl group, represents a); phenyl, p- aryl group which may have a substituent such as a methyl phenyl group.

First, the compound (9 ′) is reacted with a sulfonyl chloride represented by the formula (10) in the presence of a base such as triethylamine or 4- (dimethylamino) pyridine. Next, the reaction is performed by adding the compound (8) and a base such as triethylamine or 4- (dimethylamino) pyridine to the reaction mixture.
The amount of sulfonyl chloride to be used is generally 0.5 equivalent to 0.7 equivalent relative to 1 equivalent of compound (9 ′).
Moreover, the usage-amount of a compound (8) is 0.5 equivalent-0.6 equivalent normally with respect to 1 equivalent of compound (9 ').
The usage-amount of a base is 0.5 equivalent-0.7 equivalent normally with respect to 1 equivalent of compounds (9 ').
The reaction temperature is 20 ° C. to 30 ° C., and the reaction time is several minutes to several hours depending on the reaction scale and the like.

As a solvent used for the said reaction, what was illustrated as a solvent which can be used when manufacturing the said compound (4 ') is mentioned. Of these, ether solvents are preferred.
The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-50g normally with respect to 1g of compounds (9 ').

In any reaction, after the reaction is completed, normal post-treatment operations in organic synthetic chemistry can be performed. If desired, the desired product can be isolated by applying known separation and purification means such as column chromatography, recrystallization method, distillation method and the like.
The structure of the target compound can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.

[3. (Meth) acrylate compound]
The (meth) acrylate compound is an ester compound having a (meth) acryloyl group. Since it has a (meth) acryloyl group, the (meth) acrylate compound has polymerizability and can be polymerized with a reverse wavelength polymerizable liquid crystal compound. The liquid crystalline composition of the present invention uses a (meth) acrylate compound having an SP value in a predetermined range and a molecular weight in a predetermined range.

Specifically, the SP value of the (meth) acrylate compound is usually less than 19.0, preferably 18.7 or less. By using a (meth) acrylate compound having an SP value in such a range, the liquid crystallizing temperature _TCN can be lowered while suppressing the deterioration of the orientation of the liquid crystalline composition and the occurrence of phase separation. The lower limit of the SP value of the (meth) acrylate compound is not particularly limited, but is preferably 16.0 or more, more preferably 17.0 or more. A (meth) acrylate compound having an SP value equal to or higher than the above lower limit can be easily obtained.

  The SP value refers to a Hildebrand solubility parameter (Hildebrand solubility parameter). This SP value can be measured by SP value calculation software “HSPiP ver. 4.1.7” (http://www.hansen-solution.com/index.html).

The molecular weight of the (meth) acrylate compound is smaller than the molecular weight of the reverse wavelength polymerizable liquid crystal compound, and is usually 220 or more, preferably 225 or more, and usually less than 540, preferably 520 or less. By using a (meth) acrylate compound having a molecular weight in such a range, the liquid crystallizing temperature _TCN can be lowered while suppressing the deterioration of the orientation of the liquid crystalline composition and the occurrence of phase separation.

One molecule of the (meth) acrylate compound may have one (meth) acryloyl group, or two or more. Among them, the (meth) acrylate compound preferably has two or more (meth) acryloyl groups per molecule. By using a (meth) acrylate compound having two or more (meth) acryloyl groups per molecule, the liquid crystallizing temperature _TCN of the liquid crystal composition can be effectively lowered. Furthermore, when a compound having two or more polymerizable groups per molecule as in the compound (I) is used as the reverse wavelength polymerizable liquid crystal compound, an optical film produced using the liquid crystalline composition is used. Physical properties such as mechanical strength can be enhanced.

  Moreover, the (meth) acrylate compound may have an acryloyl group, may have a methacryloyl group, and may have a combination of an acryloyl group and a methacryloyl group.

  Further, the (meth) acrylate compound may be a liquid crystal compound having liquid crystallinity or a non-liquid crystal compound having no liquid crystallinity, but from the viewpoint that there are many commercially available products and they are easily available. Is preferably a non-liquid crystal compound having no liquid crystallinity.

  Preferred (meth) acrylate compounds include, for example, alkanediol diacrylates such as 1,6-hexanediol diacrylate and 1,9-nonanediol diacrylate; 1,2-butanediol dimethacrylate, 1,3- Alkanediol dimethacrylates such as butanediol dimethacrylate, 1,4-butanediol dimethacrylate, neopentanediol dimethacrylate, 1,6-hexanediol dimetallate; ethylene glycol diacrylate such as tetraethylene glycol diacrylate Dipropylene glycol diacrylates such as dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate; dioxane glycol Diacrylate; ethylene glycol dimethacrylates such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate; propylene glycol dimethacrylate such as dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate Methacrylates; Bisphenol ethoxylate diacrylates such as bisphenol A ethoxylate diacrylate; Trimethylolpropane triacrylate; Trimethylolpropane trimethacrylate; Trimethylolpropane ethoxylate triacrylate; Trimethylolpropane ethoxylate trimethacrylate; Trimethylolpropane Propo Shi triacrylate; trimethylolpropane propoxylate trimethacrylate; glycerol ethoxylate triacrylate; glycerol propoxylate triacrylate; pentaerythritol ethoxylate tetraacrylate; and the like. Among these, acrylate compounds are preferable. Moreover, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

The amount of the (meth) acrylate compound is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and particularly preferably 15 parts by weight with respect to 100 parts by weight of the total of the reverse wavelength polymerizable liquid crystal compound and the (meth) acrylate compound. Part or more, preferably 50 parts by weight or less, more preferably 45 parts by weight or less, and particularly preferably 35 parts by weight or less. By setting the amount of the (meth) acrylate compound to be equal to or higher than the lower limit of the above range, the liquid crystallizing temperature T _CN of the liquid crystalline composition can be effectively lowered. Moreover, the orientation of a liquid crystalline composition can be improved effectively by making it below the upper limit of the said range, or the phase separation of a liquid crystalline composition can be suppressed effectively.

[4. solvent]
The liquid crystal composition may contain a solvent. As the solvent, those capable of dissolving the reverse wavelength polymerizable liquid crystal compound are preferable. As such a solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone; acetate solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; 1 , 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,2-dimethoxyethane, and other ether solvents; and toluene, xylene, mesitylene, and other aromatic hydrocarbon solvents. Moreover, a solvent may be used individually by 1 type and may be used as a mixed solvent which combined 2 or more types by arbitrary ratios.

  The boiling point of the solvent is preferably 60 ° C. to 250 ° C., more preferably 60 ° C. to 150 ° C., from the viewpoint of excellent handleability.

  The amount of the solvent is preferably 200 parts by weight or more, more preferably 250 parts by weight or more, and particularly preferably 300 parts by weight or more with respect to a total of 100 parts by weight of the reverse wavelength polymerizable liquid crystal compound and the (meth) acrylate compound. The amount is preferably 650 parts by weight or less, more preferably 550 parts by weight or less, and particularly preferably 450 parts by weight or less. By setting the amount of the solvent to be equal to or higher than the lower limit value of the range, the generation of foreign matters can be suppressed, and by setting the amount of the solvent to be equal to or lower than the upper limit value of the range, the drying load can be reduced.

[5. Arbitrary ingredients]
The liquid crystalline composition may further contain optional components in combination with the reverse wavelength polymerizable liquid crystal compound, the (meth) acrylate compound and the solvent. Examples of optional components include polymerizable compounds other than reverse wavelength polymerizable liquid crystal compounds and (meth) acrylate compounds; metals; metal complexes; metal oxides such as titanium oxide; colorants such as dyes and pigments; Luminescent materials such as phosphorescent materials, leveling agents, thixotropic agents, gelling agents, polysaccharides, surfactants, polymerization initiators, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.

  The amount of the optional component can be arbitrarily set within a range that does not significantly impair the effects of the present invention. Specifically, the amount of the optional component may be 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the reverse wavelength polymerizable liquid crystal compound and the (meth) acrylate compound.

[6. Physical properties of liquid crystal composition]
(LCD temperature)
Liquid crystal composition of the present invention have a low liquid crystal temperature T _CN than that of the liquid crystal temperature T _CN in the reverse wavelength polymerizable liquid crystal compound alone that the liquid crystal composition comprises. Temperature difference [Delta] T _CN in the liquid crystal temperature T _CN in the liquid crystal temperature T _CN and the liquid crystal compound alone of the liquid crystal composition is preferably larger. Specifically, the temperature difference ΔT _CN is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 15 ° C. or higher. Although there is no special restriction | limiting in the upper limit of the said temperature difference (DELTA) _TCN , Usually, it is 50 degrees C or less.

The liquid crystallizing temperature _TCN of the liquid crystalline composition of the present invention is preferably a low temperature. The specific liquid crystallizing temperature T _CN of the liquid crystalline composition is preferably 98 ° C. or lower, more preferably 93 ° C. or lower, and particularly preferably 88 ° C. or lower. Since the liquid crystalline composition having such a low liquid crystallizing temperature T _CN does not require a large amount of heat for alignment, it is possible to suppress the occurrence of distortion of the base material when manufacturing the optical film. The lower limit of the liquid crystallizing temperature _TCN of the liquid crystalline composition is not particularly limited, but is usually 53 ° C. or higher.

The liquid crystallizing temperature T _CN of the liquid crystal composition can be measured by the following method.
A sample plate having a liquid crystal composition layer formed on a glass plate is prepared. Moreover, a polarizing optical microscope in which the polarizing plate is set to crossed Nicols is prepared, and a sample plate is placed on the polarizing optical microscope. Thereafter, the optical structure of the layer of the liquid crystalline composition is observed while raising the temperature of the sample plate, and the liquid crystallizing temperature T _{CN at} which the liquid crystalline composition contained in the layer causes a phase transition from the crystal phase to the nematic phase is set. It can be measured.

(Orientation)
Generally, when a certain liquid crystal compound is mixed with another compound, the orientation of the liquid crystal compound tends to decrease. However, in the liquid crystalline composition of the present invention in which the reverse wavelength polymerizable liquid crystal compound and the (meth) acrylate compound are combined as described above, such a decrease in orientation is suppressed. Therefore, the liquid crystalline composition of the present invention is excellent in orientation. Specifically, the liquid crystalline composition of the present invention has few alignment defects when the reverse wavelength polymerizable liquid crystal compound contained in the liquid crystalline composition is aligned to form a nematic phase, and the reverse wavelength polymerizable liquid crystal There is little variation in the orientation direction of the compound.

The orientation of the liquid crystal composition can be evaluated by the following method.
A sample plate having a liquid crystal composition layer formed on a glass plate is prepared. Moreover, a polarizing optical microscope in which the polarizing plate is set to crossed Nicols is prepared, and a sample plate is placed on the polarizing optical microscope. Thereafter, the liquid crystal composition is made into a nematic phase to align the liquid crystal compound, and in this state, the position of the sample plate is set to (i) the extinction position, and (ii) the slow axis of the liquid crystal composition layer is the extinction position. Observe at a position shifted by several degrees from. And the orientation of a liquid crystalline composition can be evaluated from the degree of the orientation defect observed and the state of leakage light.

(Phase separation)
Generally, when a certain liquid crystal compound is mixed with another compound, it tends to cause phase separation. However, the occurrence of such phase separation is suppressed in the liquid crystal composition of the present invention in which the reverse wavelength polymerizable liquid crystal compound and the (meth) acrylate compound are combined as described above.

The phase separation of the liquid crystal composition can be evaluated by the following method.
A sample plate having a liquid crystal composition layer formed on a glass plate is prepared. Moreover, a polarizing optical microscope in which the polarizing plate is set to crossed Nicols is prepared, and a sample plate is placed on the polarizing optical microscope. Thereafter, the liquid crystal composition is made into a nematic phase to align the liquid crystal compound, and in this state, the position of the sample plate is set to (i) the extinction position, and (ii) the slow axis of the liquid crystal composition layer is the extinction position. Observe at a position shifted by several degrees from. Then, phase separation can be evaluated from the observed image.

(Other physical properties)
The liquid crystalline composition of the present invention may be fluid or solid. The state of the liquid crystal composition can be adjusted according to the use mode of the liquid crystal composition. For example, when a liquid crystal composition is applied on a substrate to form a layer of the liquid crystal composition, the liquid crystal composition is preferably fluid. For example, when aligning the reverse wavelength polymerizable liquid crystal compound contained in the layer of the liquid crystal composition, the liquid crystal composition is preferably fluid.

[7. Manufacturing method of optical film]
By using the liquid crystalline composition of the present invention, an optical film can be produced. Examples of the method for producing an optical film using the liquid crystalline composition of the present invention include, for example, a step of forming a liquid crystalline composition layer on a substrate, and a reverse wavelength polymerizable liquid crystalline compound contained in the liquid crystalline composition layer. And a production method including a step of polymerizing a reverse wavelength polymerizable liquid crystal compound contained in the layer of the liquid crystalline composition. Hereinafter, this manufacturing method will be specifically described.

  As the substrate, a resin film is usually used. As the resin, a thermoplastic resin is usually used. Among them, a resin having a positive intrinsic birefringence value is preferable as the resin from the viewpoints of high orientation regulating force, high mechanical strength, and low cost. Furthermore, it is preferable to use a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin because it is excellent in transparency, low hygroscopicity, dimensional stability, and lightness. If a suitable example of resin contained in a base material is given by a trade name, “ZEONOR 1420” and “ZEONOR 1420R” manufactured by Nippon Zeon Co., Ltd. may be mentioned as norbornene resins.

Moreover, it is preferable that the glass transition temperature of resin contained in a base material is higher than liquid crystallizing temperature _TCN of a liquid crystalline composition. The resin contained in the base material has a glass transition temperature higher than the liquid crystallizing temperature _TCN of the liquid crystalline composition, thereby effectively suppressing distortion of the base material due to heat in the step of aligning the reverse wavelength polymerizable liquid crystal compound. it can.

  Of the surfaces of the base material, the surface on which the layer of the liquid crystalline composition is formed is sometimes referred to as “applied surface” as appropriate. The coating surface preferably has an alignment regulating force in order to promote the alignment of the reverse wavelength polymerizable liquid crystal compound in the liquid crystalline composition layer. The alignment regulating force refers to the property of the coated surface that can align the reverse wavelength polymerizable liquid crystal compound in the liquid crystalline composition. Examples of the treatment for generating the orientation regulating force on the coated surface include a photo-alignment treatment, a rubbing treatment, an alignment film forming treatment, and a stretching treatment. Of these, stretching is preferred.

  By subjecting the substrate to stretching under appropriate conditions, the polymer molecules contained in the substrate can be oriented. Thereby, the alignment control force which orientates the reverse wavelength polymerizable liquid crystal compound in the alignment direction of the molecules of the polymer contained in the substrate can be imparted to the coated surface of the substrate. In particular, in such a stretching process, the molecular director is substantially uniformly oriented over the entire thickness direction of the substrate. For this reason, the stretching process is more time-dependent due to environmental influences (heat, light, oxygen, etc.) than the method of imparting alignment regulating force to the substrate only by molecular orientation near the surface of the substrate, such as rubbing treatment. It is difficult to relax the orientation regulating force. Furthermore, the stretching treatment can suppress dust generation, scratches, and foreign matter contamination.

  The stretching of the base material is preferably performed so that anisotropy is imparted to the base material and the slow axis is expressed in the base material. Thereby, usually, an alignment regulating force for aligning the reverse wavelength polymerizable liquid crystal compound in a direction parallel or perpendicular to the slow axis of the substrate is imparted to the surface of the substrate. For example, when a resin having a positive intrinsic birefringence value is used as the material of the base material, the slow axis parallel to the stretching direction is usually obtained by orienting the polymer molecules contained in the base material in the stretching direction. Since it is expressed, an alignment regulating force for aligning the reverse wavelength polymerizable liquid crystal compound in a direction parallel to the slow axis of the substrate is imparted to the surface of the substrate. Therefore, the extending direction of the substrate can be set according to the desired alignment direction in which the reverse wavelength polymerizable liquid crystal compound is to be aligned. In addition, the stretching may be performed only in one direction or in two or more directions. Such stretching can be performed using a stretching machine such as a tenter stretching machine.

  After preparing a base material, the process of forming the layer of a liquid crystalline composition on the base material is performed. Usually, a liquid crystalline composition is applied to the coated surface of the substrate to form the liquid crystalline composition layer. Examples of the method for applying the liquid crystalline composition include curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, and gravure. Examples thereof include a coating method, a die coating method, a cap coating method, and a dipping method.

  The method for producing an optical film shown in this example includes a step of forming a liquid crystal composition layer on a substrate and a step of polymerizing a reverse wavelength polymerizable liquid crystal compound, if necessary. A step of drying the layer of the object may be included. Such drying can be achieved by a drying method such as natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying. By such drying, the solvent can be removed from the liquid crystal composition layer.

  After forming the liquid crystal composition layer, a step of aligning the reverse wavelength polymerizable liquid crystal compound contained in the liquid crystal composition layer is performed. In this step, the reverse wavelength polymerizable liquid crystal compound is aligned in a direction according to the alignment regulating force of the substrate by performing an alignment treatment on the layer of the liquid crystalline composition.

The alignment treatment is usually performed by adjusting the temperature of the liquid crystal composition layer to a predetermined alignment temperature. The alignment temperature can be a temperature _{equal to} or higher than the liquid crystallizing temperature TCN of the liquid crystalline composition. Thereby, the reverse wavelength polymerizable liquid crystal compound contained in the layer of the liquid crystalline composition can be effectively aligned by causing the liquid crystalline composition to undergo a phase transition to a liquid crystal phase such as a nematic phase. At this time, the orientation temperature is preferably a temperature lower than the glass transition temperature of the resin contained in the substrate. Thereby, generation | occurrence | production of the distortion of the base material by an orientation process can be suppressed. Moreover, the processing time of the alignment treatment can be set to, for example, 30 seconds to 5 minutes.

  After aligning the reverse wavelength polymerizable liquid crystal compound, a step of polymerizing the reverse wavelength polymerizable liquid crystal compound is performed. As a polymerization method of the reverse wavelength polymerizable liquid crystal compound, a method suitable for the properties of the components contained in the liquid crystal composition can be selected. Examples of the polymerization method include a method of irradiating active energy rays and a thermal polymerization method. Among them, the method of irradiating with active energy rays is preferable because heating is unnecessary and the polymerization reaction can proceed at room temperature. Here, the irradiated active energy rays can include light such as visible light, ultraviolet light, and infrared light, and arbitrary energy rays such as electron beams.

Among these, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple. The temperature during ultraviolet irradiation is preferably not higher than the glass transition temperature of the substrate, preferably not higher than 150 ° C., more preferably not higher than 100 ° C., particularly preferably not higher than 80 ° C. The lower limit of the temperature during ultraviolet irradiation can be 15 ° C. or higher. The irradiation intensity of ultraviolet rays is preferably 0.1 mW / cm ² or more, more preferably 0.5 mW / cm ² or more, preferably 1000 mW / cm ² or less, more preferably 600 mW / cm ² or less.

  Thereby, since the optically anisotropic layer containing the polymer of a reverse wavelength polymerizable liquid crystal compound is formed on a base material, a multilayer film provided with a base material and an optically anisotropic layer is obtained. By the above polymerization, the liquid crystal phase of the reverse wavelength polymerizable liquid crystal compound is usually lost, and the optically anisotropic layer is formed as a cured layer. In the optically anisotropic layer, the polymer of the reverse wavelength polymerizable liquid crystal compound maintains the alignment state of the reverse wavelength polymerizable liquid crystal compound. Therefore, the optically anisotropic layer can have optical characteristics corresponding to the alignment state of the reverse wavelength polymerizable liquid crystal compound.

  As described above, the multilayer film may be used as an optical film as it is by utilizing the optical characteristics of the optically anisotropic layer. Moreover, you may obtain an optical film by forming arbitrary layers in the said multilayer film further. Furthermore, the substrate may be peeled from the optically anisotropic layer of the multilayer film, and the optically anisotropic layer may be used as an optical film having a single layer structure.

  In the optical film obtained as described above, since the distortion of the base material due to heat for the alignment treatment is suppressed, it is possible to suppress variations in optical characteristics. Moreover, since the orientation of the liquid crystalline composition is good and the phase separation is suppressed, the optically anisotropic layer obtained from the liquid crystalline composition is of high quality and can be produced with a high yield. .

Since it contains a polymer obtained by polymerizing a reverse wavelength polymerizable liquid crystal compound, the optically anisotropic layer has birefringence with reverse wavelength dispersion. Accordingly, the optically anisotropic layer can have a reverse wavelength dispersion retardation. Here, the retardation of the inverse wavelength dispersion is a retardation Re (450) at a wavelength of 450 nm, a retardation Re (550) at a wavelength of 550 nm, and a retardation Re (650) at a wavelength of 650 nm. A retardation that satisfies the following formula (D4) is preferably satisfied. By having the retardation of reverse wavelength dispersion, the optically anisotropic layer can uniformly function in a wide wavelength band in optical applications such as a quarter-wave plate or a half-wave plate.
Re (450) <Re (650) (D3)
Re (450) <Re (550) <Re (650) (D4)

  The specific retardation range of the optically anisotropic layer can be arbitrarily set according to the use of the optically anisotropic layer. For example, when the optically anisotropic layer is desired to function as a quarter wavelength plate, the retardation Re (550) of the optically anisotropic layer is preferably 80 nm or more, more preferably 100 nm or more, and particularly preferably 120 nm. The thickness is preferably 180 nm or less, more preferably 160 nm or less, and particularly preferably 150 nm or less. For example, when the optically anisotropic layer is desired to function as a half-wave plate, the retardation Re (550) of the optically anisotropic layer is preferably 245 nm or more, more preferably 265 nm or more, particularly preferably. Is 270 nm or more, preferably 305 nm or less, more preferably 285 nm or less, and particularly preferably 280 nm or less.

  The thickness of the optically anisotropic layer can be appropriately set so that characteristics such as retardation can be in a desired range. Specifically, the thickness of the optically anisotropic layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 10 μm or less, more preferably 7 μm or less.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.
In the following description, “%” and “part” representing amounts are based on weight unless otherwise specified. In addition, the operations described below were performed under normal temperature and normal pressure conditions unless otherwise specified. Furthermore, in the following description, a polymerizable liquid crystal compound capable of developing forward wavelength dispersive birefringence may be appropriately referred to as “forward wavelength polymerizable liquid crystal compound”.

[Evaluation method]
[Evaluation Method for Lowering Effect of Liquid Crystallization Temperature _TCN ]
A polarizing optical microscope (“ECLIPSE LV100POL” manufactured by Nikon Corporation) was prepared. Two polarizing plates provided in this polarizing optical microscope were set to crossed Nicols, and a sample plate provided with a glass substrate and a layer of a liquid crystalline composition was installed in this polarizing optical microscope. Then, using a hot stage (“FP-80” manufactured by METTLER), the sample plate was heated from 40 ° C. to 200 ° C. while observing the optical structure of the layer of the liquid crystalline composition, and the liquid crystal contained in the layer. gender composition was measured crystal temperature T _CN caused a phase transition from crystalline phase to nematic phase.

LCD temperature T _CN in this manner measured liquid composition, the degradation temperature (temperature difference) [Delta] T _CN from the liquid crystal temperature T _CN in the liquid crystal compound alone was calculated and the following on the basis of the temperature decrease [Delta] T _CN Judged by the criteria of.
○: Decrease temperature ΔT _CN is 15 ° C. or higher.
Δ: Lowering temperature ΔT _CN is 5 ° C. or higher and lower than 15 ° C.
X: Lowering temperature ΔT _CN is less than 5 ° C.

(Evaluation method of orientation)
A polarizing optical microscope (“ECLIPSE LV100POL” manufactured by Nikon Corporation) was prepared. Two polarizing plates provided in this polarizing optical microscope were set to crossed Nicols, and a sample plate provided with a glass substrate and a layer of a liquid crystalline composition was installed in this polarizing optical microscope. The liquid crystal composition is made into a nematic phase and the liquid crystal compound is aligned, and in this state, the position of the sample plate is (i) the extinction position, and (ii) the slow axis of the liquid crystal composition layer is a number from the extinction position. The observation was made according to the shifted position. And the orientation was evaluated based on the following reference | standard from the grade of the observed orientation defect, and the state of leakage light.
○: No alignment defect is observed, and there is almost no leakage light at the extinction position.
(Triangle | delta): The alignment defect is seen slightly and there is slight leak light in a quenching position.
X: Orientation defects are clearly seen, and light leaks at the extinction position.

[Evaluation method of phase separation]
A polarizing optical microscope (“ECLIPSE LV100POL” manufactured by Nikon Corporation) was prepared. Two polarizing plates provided in this polarizing optical microscope were set to crossed Nicols, and a sample plate provided with a glass substrate and a layer of a liquid crystalline composition was installed in this polarizing optical microscope. The liquid crystal composition is in a nematic phase to align the liquid crystal compound. In this state, the position of the sample plate is (i) the extinction position, and (ii) the slow axis of the liquid crystal composition layer is several degrees from the extinction position. The observation was made according to the shifted position. From the observed images, phase separation was evaluated based on the following criteria.
○: Phase separation is not observed.
Δ: Slight phase separation is observed.
X: Clear phase separation is observed.

[Reference Example 1: Evaluation of liquid crystal compound (E1)]
100.0 parts of a reverse wavelength polymerizable liquid crystal compound (E1, molecular weight 1,170) represented by the following formula (E1) and 400.0 parts of 1,3-dioxolane (manufactured by Toho Chemical) as a solvent were mixed. A liquid crystal composition was produced.

  A glass substrate (manufactured by EHC Co.) having a rubbing-treated polyimide horizontal alignment film cut into 2.5 cm square was prepared. On the alignment film of this glass substrate, the liquid crystalline composition was applied by spin coating using a spin coater (“A-200” manufactured by Mikasa Co., Ltd.) to form a liquid crystalline composition layer. The coating conditions at this time were a rotation speed of 1100 rpm and a coating time of 5 seconds. Then, the solvent was removed from the liquid crystalline composition layer by air drying to obtain a sample plate having a glass substrate and a liquid crystal compound layer.

A polarizing optical microscope (“ECLIPSE LV100POL” manufactured by Nikon Corporation) was prepared. Two polarizing plates included in the polarizing microscope are set in crossed Nicols, and the sample plate is placed on the polarizing optical microscope. Then, the optical structure of the liquid crystal compound layer was observed while raising the temperature of the sample plate from 40 ° C. to 200 ° C. using a hot stage (“FP-80” manufactured by Mettler Co.), and the liquid crystal compound (E1) was in a crystalline phase. was measured crystal temperature T _CN caused a phase transition to a nematic phase from. As a result of the measurement, the reverse wavelength polymerizable liquid crystal compound (E1) alone had a liquid crystallizing temperature _TCN of 103 ° C.

  Further, in-plane retardation Re of the liquid crystal compound layer was measured in a state where the liquid crystal compound layer was aligned in a nematic phase. The in-plane retardation Re is measured at the measurement wavelengths of 450 nm and 650 nm, and the ratio of the in-plane retardation Re (450) at the measurement wavelength of 450 nm to the in-plane retardation Re (650) at the measurement wavelength of 650 nm is Re (450) / Re (650) was determined. As a result of the measurement, the in-plane retardation ratio Re (450) / Re (650) is 0.765, and it is confirmed that the reverse wavelength polymerizable liquid crystal compound (E1) can exhibit birefringence with reverse wavelength dispersion. It was done.

[Reference Example 2]
In the same manner as in Reference Example 1, except that the reverse wavelength polymerizable liquid crystal compound (E2, molecular weight 1,186) represented by the following formula (E2) was used instead of the reverse wavelength polymerizable liquid crystal compound (E1), The liquid crystallinity temperature _TCN and in-plane retardation ratio Re (450) / Re (650) of the wavelength polymerizable liquid crystal compound (E2) were measured.

As a result of the measurement, the liquid crystallinity temperature _TCN of the reverse wavelength polymerizable liquid crystal compound (E2) alone was 108 ° C.
Further, the in-plane retardation ratio Re (450) / Re (650) of the layer of the reverse wavelength polymerizable liquid crystal compound (E2) is 0.819, and the reverse wavelength polymerizable liquid crystal compound (E2) has the reverse wavelength dispersibility. It was confirmed that the birefringence of 1 can be expressed.

[Reference Example 3]
Using the normal wavelength polymerizable liquid crystal compound (X1) instead of the reverse wavelength polymerizable liquid crystal compound (E1), and changing the type of solvent from 1,3-dioxolane to methyl ethyl ketone (manufactured by Maruzen Petrochemical) Except for, and in the same manner as in Reference Example 1, the liquid crystallinity temperature _TCN and the in-plane retardation ratio Re (450) / Re (650) of this normal wavelength polymerizable liquid crystal compound (X1) were measured.

As a result of the measurement, the normal wavelength polymerizable liquid crystal compound (X1) alone had a liquid crystallizing temperature _TCN of 101 ° C.
Further, the ratio Re (450) / Re (650) of the in-plane retardation of the layer of the normal wavelength polymerizable liquid crystal compound (X1) is 1.188, and this normal wavelength polymerizable liquid crystal compound (X1) is distributed in the normal wavelength dispersion. It was confirmed that sex birefringence can be expressed.

[1. Example using 10% by weight of (meth) acrylate compound]
[Example 1-1 to Example 1-7 and Comparative Example C1-1 to Comparative Example C1-14]
90.0 parts of the reverse wavelength polymerizable liquid crystal compound of the type shown in Table 1, 10.0 parts of the (meth) acrylate compound shown in Table 1, and 400.0 parts of 1,3-dioxolane (manufactured by Toho Chemical) as the solvent Were mixed to produce a liquid crystal composition.

A glass substrate (manufactured by EHC Co.) having a rubbing-treated polyimide horizontal alignment film cut into 2.5 cm square was prepared. On the alignment film of this glass substrate, the liquid crystalline composition was applied by spin coating using a spin coater (“A-200” manufactured by Mikasa Co., Ltd.) to form a liquid crystalline composition layer. The coating conditions at this time were a rotation speed of 1100 rpm and a coating time of 5 seconds. Thereafter, the solvent was removed from the liquid crystalline composition layer by air drying to obtain a sample plate having a glass substrate and a liquid crystalline composition layer.
This sample plate was evaluated by the method described above.

[Comparative Example C1-15 to Comparative Example C1-17]
Mixing 90.0 parts of the forward wavelength polymerizable liquid crystal compound (X1), 10.0 parts of the (meth) acrylate compound shown in Table 1, and 400.0 parts of methyl ethyl ketone (manufactured by Maruzen Petrochemical Co., Ltd.) as a solvent, A liquid crystal composition was produced.

Using the liquid crystalline composition thus produced, a sample plate was produced in the same manner as in Example 1-1. That is, a glass substrate (manufactured by EHC Corporation) provided with a polyimide horizontal alignment film that had been rubbed and cut to 2.5 cm square was prepared. On the alignment film of this glass substrate, the liquid crystalline composition was applied by spin coating using a spin coater (“A-200” manufactured by Mikasa Co., Ltd.) to form a liquid crystalline composition layer. The coating conditions at this time were a rotation speed of 1100 rpm and a coating time of 5 seconds. Thereafter, the solvent was removed from the liquid crystalline composition layer by air drying to obtain a sample plate having a glass substrate and a liquid crystalline composition layer.
This sample plate was evaluated by the method described above.

[2. Example using 20% by weight of (meth) acrylate compound]
[Example 2-1 to Example 2-7 and Comparative Example C2-1 to Comparative Example C2-14]
Example 1-1 to Example 1-7 and Comparative Example C1 except that the amount of the reverse wavelength polymerizable liquid crystal compound was changed to 80.0 parts and the amount of the (meth) acrylate compound was changed to 20.0 parts. -1 In the same manner as in Comparative Example C1-14, a sample plate including a glass substrate and a liquid crystal composition layer was produced and evaluated.

[Comparative Example C2-15 to Comparative Example C2-17]
Comparative Example C1-15 to Comparative Example C1-17 except that the amount of the forward wavelength polymerizable liquid crystal compound (X1) was changed to 80.0 parts and the amount of the (meth) acrylate compound was changed to 20.0 parts. Similarly, manufacture and evaluation of the sample board provided with the layer of a glass substrate and a liquid crystalline composition were performed.

[3. Example using 30% by weight of (meth) acrylate compound]
[Example 3-1 to Example 3-7 and Comparative Example C3-1 to Comparative Example C3-14]
Example 1-1 to Example 1-7 and Comparative Example C1 except that the amount of the reverse wavelength polymerizable liquid crystal compound was changed to 70.0 parts and the amount of the (meth) acrylate compound was changed to 30.0 parts. -1 In the same manner as in Comparative Example C1-14, a sample plate including a glass substrate and a liquid crystal composition layer was produced and evaluated.

[Comparative Example C3-15 to Comparative Example C3-17]
Comparative Example C1-15 to Comparative Example C1-17, except that the amount of the forward wavelength polymerizable liquid crystal compound (X1) was changed to 70.0 parts and the amount of the (meth) acrylate compound was changed to 30.0 parts. Similarly, manufacture and evaluation of the sample board provided with the layer of a glass substrate and a liquid crystalline composition were performed.

[result]
The results of Examples and Comparative Examples are shown in Tables 1 to 3 below. In the following table, the meanings of the abbreviations are as follows.
E1: Reverse wavelength polymerizable liquid crystal compound (E1).
E2: Reverse wavelength polymerizable liquid crystal compound (E2).
X1: Normal wavelength polymerizable liquid crystal compound (X1).
Wavelength dispersion: wavelength dispersion of a liquid crystal compound.
Reverse wavelength: Reverse wavelength dispersibility.
Forward wavelength: Forward wavelength dispersibility.
R-604: Dioxane glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.).
HX-220: 3-Hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate 6-hexanolide addition polymer (degree of polymerization 1-7) and esterified product of acrylic acid (Japan) Manufactured by Kayaku).
HX-620: 6-hexanolide addition polymer of 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate (degree of polymerization 1-7) and esterified product of acrylic acid (Japan) Manufactured by Kayaku).
R-712: Bisphenol F ethylene oxide-modified acrylate (manufactured by Nippon Kayaku Co., Ltd.).
TPA-330: Acrylic ester of a propion oxide adduct of trimethylolpropane (manufactured by Nippon Kayaku Co., Ltd.).
BP-4EAL: Bisphenol A ethylene oxide adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.).
UA-306I: pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.).
UA-306H: pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.).
UA-306T: pentaerythritol triacrylate toluene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.).
80MFA: Acrylic acid adduct of “Epolite 80MF” manufactured by Kyoeisha Chemical Co., Ltd. (manufactured by Kyoeisha Chemical Co., Ltd.).
3002A (N): Acrylic acid adduct of “Epolite 3002 (N)” manufactured by Kyoeisha Chemical Co., Ltd. (manufactured by Kyoeisha Chemical Co., Ltd.).
1,6-HX-A: 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.).
NP-A: Neopentyl glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.).
A-9300: Ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
A-9300-1CL: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
A-BPEF: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd.).
V # 260: 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Co., Ltd.).
V # 295: Trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Co., Ltd.).
V # 540: Bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Osaka Organic Chemical Co., Ltd.).
LR9000: a polymer of 2-hydroxyethyl acrylate and 1,6-diisocyanatohexane (manufactured by BASF).
Mw: Molecular weight of (meth) acrylate compound.
SP: SP value of (meth) acrylate compound.
Amount: Weight ratio of (meth) acrylate compound to 100% of total of liquid crystal compound and (meth) acrylate compound.
TCN: results of evaluation of the lowering effect of liquid crystallization temperature _{T CN.}
[Delta] T _CN: liquid crystal temperature T _CN in the liquid crystal composition, lowering the temperature from the liquid crystal temperature T _CN in the liquid crystal compound alone (temperature difference).

[Consideration]
As can be seen from the above table, in the liquid crystalline composition according to the example, the liquid crystallizing temperature T _CN is set by combining the reverse wavelength polymerizable liquid crystal compound and the (meth) acrylate compound having a predetermined molecular weight and SP value. The effect was obtained that it could be lowered, the orientation was good, and the occurrence of phase separation could be suppressed. Moreover, since the said effect is not acquired in the comparative example using a forward wavelength dispersible liquid crystal compound, it turns out that the said effect is an effect acquired specifically in a reverse wavelength polymerizable liquid crystal compound.

Claims (6)

  A liquid crystalline composition comprising a polymerizable liquid crystal compound having a molecular weight of 540 or more capable of developing reverse wavelength dispersive birefringence and a (meth) acrylate compound having an SP value of less than 19.0 and having a molecular weight of 220 to 540.   The liquid crystalline composition according to claim 1, wherein the (meth) acrylate compound is a non-liquid crystal compound.   The liquid crystalline composition according to claim 1 or 2, wherein the (meth) acrylate compound has two or more (meth) acryloyl groups per molecule.   The liquid crystalline composition according to any one of claims 1 to 3, wherein a phase transition temperature from a crystal phase to a nematic phase of the liquid crystalline composition is 98 ° C or lower.   The liquid crystal according to any one of claims 1 to 4, wherein the polymerizable liquid crystal compound contains a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in a molecule of the polymerizable liquid crystal compound. Sex composition. The liquid crystalline composition according to claim 1, wherein the polymerizable liquid crystal compound is represented by the following formula (I).

(In the formula (I),
Y ^{1 to} Y ⁸ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C. (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (= O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O— is represented. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G ¹ and G ² each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent. The aliphatic group includes one or more —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C per one aliphatic group. Even if (═O) —O—, —NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or —C (═O) — are present. Good. However, the case where two or more of -O- or -S- are adjacent to each other is excluded. Here, R < ² > represents a hydrogen atom or a C1-C6 alkyl group.
Z ¹ and Z ² each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
A ^x represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
A ^y has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. A cycloalkyl group having 3 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, —C (═O) —R ³ , —SO ₂ —R ⁴ , —C ( = S) NH-R ⁹ or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Here, R ³ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Or a C3-C12 cycloalkyl group or a C5-C12 aromatic hydrocarbon group. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R ⁹ is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted carbon. The C3-C12 cycloalkyl group or the C5-C20 aromatic group which may have a substituent is represented. The aromatic ring which said ^Ax and ^Ay have may have a substituent. A ^x and A ^y may be combined to form a ring.
A ¹ represents a trivalent aromatic group which may have a substituent.
A ² and A ³ each independently represent a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent.
A ⁴ and A ⁵ each independently represent a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent.
Q ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
m and n each independently represents 0 or 1. )