JP2018193488A - Stabilizer compound, liquid crystal composition and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent deterioration of a liquid crystal composition by adding it to the liquid crystal composition, to have high compatibility with the liquid crystal composition, and to impair the storage stability of the liquid crystal composition. It is an object of the present invention to provide a stabilizer compound which can be easily produced without any problem. The present invention provides a compound represented by the general formula (I) [Chemical formula 1]. The compound according to the present invention is useful as a constituent member of the liquid crystal composition because it prevents deterioration of the liquid crystal composition due to light, has high compatibility with the liquid crystal composition, and does not impair the storage stability of the liquid crystal composition. Is. Since the liquid crystal composition and the liquid crystal display element containing the compound of the present invention exhibit UV resistance and have high VHR, display defects such as seizure and display unevenness do not occur or are suppressed, and the display quality is excellent. A liquid crystal display element can be obtained. [Selection diagram] None

Description

  The present invention relates to stabilizer compounds.

  Liquid crystal display elements are used in clocks, calculators, various electric appliances for food, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, and the like. Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), and IPS (in-plane switching). Type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence type), VA (vertical alignment) type, CSH (color super homeotropic) type, and the like. Further, examples of the driving method include static driving, multiplex driving, simple matrix method, active matrix (AM) method driven by TFT (Thin Film Transistor), TFD (Thin Film Diode), and the like.

  Among these, display systems such as the IPS type and the VA type using the AM drive are used for display elements that are melted at a high speed and have a high viewing angle, such as televisions.

Nematic liquid crystal compositions used in these display systems are required to have low voltage driving, high-speed response, and a wide operating temperature range. That is, the absolute value of Δε is large, the viscosity (η) is low, and a high nematic phase-isotropic liquid phase transition temperature (T _ni ) is required. Further, from the setting of Δn × d, which is the product of refractive index anisotropy (Δn) and cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range according to the cell gap. In addition, when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a low viscosity (η) and a small γ ₁ is required.

  In addition to the requirements regarding the physical properties of these liquid crystal compositions, the liquid crystal compositions used for liquid crystal display elements are required to be stable against external stimuli such as moisture, air, heat and light. If the stability against external stimuli is impaired, display defects such as image sticking and display unevenness occur in the liquid crystal display element. In order to obtain a liquid crystal composition and a liquid crystal display element in which display defects such as image sticking and display unevenness do not occur or hardly occur, it is considered that a high voltage holding ratio (VHR) is indispensable. For example, it is known that VHR can be maintained high by adding an antioxidant, an ultraviolet absorber, or a light stabilizer to a liquid crystal composition (see Patent Documents 1 to 3).

  In view of the above, there has been a demand for a liquid crystal composition that achieves a high VHR while satisfying the demands on the physical properties of the liquid crystal composition, and in achieving this, a novel antioxidant and ultraviolet absorber that suppresses a decrease in VHR Or there is a need for light stabilizers.

Special table 2004-507607 JP 2002-256267 A Special table 2014-505745 Special table 2014-505746

The problem to be solved by the present invention is a compound that prevents deterioration of the liquid crystal composition by being added to the liquid crystal composition, has high compatibility with the liquid crystal composition, and does not impair the storage stability of the liquid crystal composition Is to provide.

The inventor of the present application has intensively studied to solve the above problems, and as a result, the present invention has been completed.
That is, the present invention relates to the general formula (I)

(In the formula, R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are each independently a hydrogen atom, halogen atom, hydroxyl group, cyano group, chlorine Atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano Represents a group or an alkyl group having 1 to 20 carbon atoms, and one or two or more —CH ₂ — present in the alkyl group are each independently —O—, —S—, —CO—, — CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - C≡C -, - Si (CH 3) 2 -, Which may be substituted with a trans 1,4-cyclohexylene group, 1,4-phenylene group or naphthalene-2,6-diyl group, and one or more hydrogen atoms in the alkyl group are each independently R ¹¹¹ , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 may all be substituted with a halogen atom or a cyano group. (Do not represent.)
The additive for liquid crystal compositions which has a compound represented by these is provided.

The compound according to the present invention is useful as an additive for a liquid crystal composition because it prevents deterioration of the liquid crystal composition due to light, has high compatibility with the liquid crystal composition, and does not impair the storage stability of the liquid crystal composition. It is. The liquid crystal composition and the liquid crystal display element containing the compound of the present invention exhibit UV resistance and have a high VHR, so that display defects such as image sticking and display unevenness do not occur or are suppressed, and display quality is excellent. A liquid crystal display element can be obtained.

  The liquid crystal composition in the present invention contains one or more compounds represented by the general formula (I).

In the general formula (I), R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are hydrogen atoms from the viewpoint of compatibility with the liquid crystal composition. , Preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a fluorine atom, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl having 3 to 8 carbon atoms. More preferably, it is a group or a fluorine atom. The hydrogen atom, alkyl group or alkenyl group is preferably linear or branched, and is preferably linear. In view of ease of production, a fluorine atom, a hydrogen atom, or a linear alkyl group having 1 to 5 carbon atoms is particularly preferable. Further, in order to enhance the ability to prevent ^{photodegradation} , one to eight of R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are hydroxyl groups. Preferably, 1 to 6 are hydroxyl groups, preferably 1 to 4 are hydroxyl groups, preferably 1 to 2 are hydroxyl groups, and particularly preferably 2 are hydroxyl groups. In the ease of ^synthesis, it ^{R I1n} and ^R I2n (n = ^1~5) are equal, ^i.e., the ^{R I11} and ^{R I21, R I12} and ^{R I22, R I13} and ^{R I23, R I14} R It is preferred that ^I24 and R ^I15 and R ^I25 each represent the same group. Alternatively, from the viewpoint of compatibility with the liquid crystal ^composition, of the combination of ^{R I1n} and ^R I2n (n = ^1~5), that at least one pair are different from each other, ^i.e., the ^{R I11} and ^{R I21, R I12} It is preferable that any one or more sets selected from R ^I22 , R ^I13 and R ^I23 , R ^I14 and R ^I24, and R ^I15 and R ^I25 represent different groups.

From the viewpoint of compatibility with the liquid crystal composition, one or two selected from R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 It is preferable that at least one group represents a fluorine atom.

Further, from the viewpoint of the affinity with the alignment film and the ability to prevent ^{photodegradation} , it is selected from R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25. It is preferred that one or more groups represent an alkyl group having 4 to 20 carbon atoms. The alkyl group is preferably linear or branched, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 4 to 15, preferably 4 to 10, and preferably 4 to 8. The compound represented by General Formula (I) is preferably a compound represented by General Formula (I-1) to General Formula (I-66) from the viewpoint of ease of synthesis.

(In the formula, _n in C _n H _{(2n + 1)} represents an integer of 1 to 8.)
In addition, the compound represented by the general formula (I) is a compound represented by the general formula (I-67) to the general formula (I-109) from the viewpoint of easy synthesis and compatibility with the liquid crystal composition. It is preferable that

(In the formula, _n in C _n H _{(2n + 1)} represents an integer of 0 to 8.)
In addition, the compound represented by General Formula (I) is preferably a compound represented by General Formula (I-110) to General Formula (I-157) from the viewpoint of compatibility with the liquid crystal composition. .

(In the formula, _n in C _n H _{(2n + 1)} represents an integer of 0 to 8.)
In the present invention, the compound represented by the general formula (I) can be produced as follows. Of course, the spirit and scope of the present invention are not limited by these production examples.
Among the general formula ^{(I), R I1n} and ^R I2n (n = ^1~5) is equal to each other compounds, ^{i.e., R I11} and ^{R I21, R I12} and ^{R I22, R I13} and ^{R I23, R I14} and ^{R I24 And} a compound in which R ^I15 and R ^I25 each represent the same group is represented by formula (Ia). In the following formulae, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are R ^I11 and R ^I21 , R ^I12 and R ^I22 , R ^I13 and R ^I23 , R ^I14 and R ^{I24 in} general formula (I) and R ^I15 and R ^I25 each have the same meaning.

  (Production Method 1) Production Method of Compound (Ia) Represented by General Formulas (I-1) to (I-109)

The compound represented by the general formula (S-2) can be obtained by reacting the compound represented by the general formula (S-1) with a catalytic amount of potassium cyanide. The compound represented by the general formula (Ia) is obtained by allowing sodium borohydride to act on the compound represented by the general formula (S-2). In addition, general formula (Ia) is obtained by various functional group conversions. In addition, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publicization), Beilstein Handbook of Organic Chemistry (Beilstein Organic Chemistry (Beilstein Organic Chemistry). Springer-Verlag Berlin and Heidelberg GmbH & Co. K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.), etc. ce, American Chemical Society), by using the reaction conditions listed in databases such as Reaxys (Elsevier Ltd.), can be derived to the compound represented by formula (I-a).

  (Manufacturing method 2) Manufacturing method of compound represented by general formula (1-b)

The compound represented by the general formula (S-4) can be obtained by reacting the compound represented by the general formula (S-3) with triphenylphosphine and carbon tetrabromide and allowing butyllithium to act on the compound. By combining the compound represented by the general formula (S-4) and the compound represented by the general formula (S-7) (X = Br, I) by a coupling reaction, the general formula (S-5) The compounds represented can be obtained. The compound represented by general formula (S-6) can be obtained by allowing dimethyl sulfoxide to act on general formula (S-5) in the presence of a palladium catalyst and a copper catalyst. A compound represented by the general formula (Ib) is obtained by allowing sodium borohydride to act on the compound represented by the general formula (S-6). In addition, general formula (Ib) is obtained by various functional group conversions. In addition, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publicization), Beilstein Handbook of Organic Chemistry (Beilstein Organic Chemistry (Beilstein Organic Chemistry). Springer-Verlag Berlin and Heidelberg GmbH & Co. K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.), etc. compounds represented by general formulas (S-3) and (S-4) from the corresponding compounds by using reaction conditions listed in databases such as ce, American Chemical Society), and Reaxys (Elsevier Ltd.). And can be derived into a compound represented by formula (Ib).

  In each step, a reaction solvent can be appropriately used. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.

In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purification agent include silica gel, NH ₂ silica gel, alumina, activated carbon and the like.

  By adding the compound represented by the general formula (I) to the liquid crystal composition, deterioration of the liquid crystal composition can be prevented. The compound represented by the general formula (I) is considered to function as a stabilizer that suppresses deterioration of the liquid crystal composition due to stimulation such as light and heat. In addition, the compound represented by the general formula (I) has high compatibility with the liquid crystal composition and excellent storage stability, and is useful as an additive for the liquid crystal composition.

  The composition containing one or more compounds represented by general formula (I) preferably has a liquid crystal phase at room temperature. The compound represented by the general formula (I) preferably contains 0.001% by mass or more, preferably 0.005% by mass or more, as a lower limit with respect to the total mass of the composition. It is preferably contained in an amount of 01% by mass or more, preferably 0.02% by mass or more, preferably 0.03% by mass or more, preferably 0.05% by mass or more, and 0.07% by mass. %, Preferably 0.1% by weight or more, preferably 0.15% by weight or more, preferably 0.2% by weight or more, preferably 0.25% by weight or more. It is preferable to contain, it is preferable to contain 0.3 mass% or more, it is preferable to contain 0.5 mass% or more, it is preferable to contain 1 mass% or more. Moreover, it is preferable to contain 5 mass% or less as an upper limit, It is preferable to contain 3 mass% or less, It is preferable to contain 1 mass% or less, It is preferable to contain 0.5 mass% or less, 0.45 It is preferably contained in an amount of not more than 0.4% by mass, preferably not more than 0.4% by mass, preferably not more than 0.35% by mass, preferably not more than 0.3% by mass, and more preferably 0.25% by mass. It is preferably contained below, preferably 0.2% by mass or less, preferably 0.15% by mass or less, preferably 0.1% by mass or less, preferably 0.07% by mass or less. It is preferable to contain 0.05 mass% or less, and it is preferable to contain 0.03 mass% or less.

  More specifically, the content is preferably 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.3% by mass, Particularly preferred is 0.05 to 0.25% by mass. More specifically, when emphasizing the suppression of precipitation at low temperatures, the content is preferably 0.01 to 0.1% by mass.

  The composition containing the compound represented by the general formula (I) may contain a compound having a liquid crystal phase in addition to the compound represented by the general formula (I), or a compound having no liquid crystal phase. It may contain.

  It is preferable that the composition containing the compound represented by the general formula (I) further contains a compound represented by the following general formula (i) or general formula (ii).

(In the formula, R ⁱ⁰ represents a hydrogen atom, a hydroxyl group, —O ·, or an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent —CH ₂ present in the alkyl group. -Is independently -O-, -S-, -CO-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-. , -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH- , —C≡C—, —Si (CH ₃ ) ₂ —, trans 1,4-cyclohexylene group, 1,4-phenylene group or naphthalene-2,6-diyl group, and R ⁱ⁰ 1 or 2 or more hydrogen atoms may be independently substituted with a fluorine atom, a chlorine atom or a cyano group. Ku,
R ⁱ¹ , R ⁱ² , R ⁱ³ and R ⁱ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ⁱ¹ and R ⁱ² and / or R ⁱ³ and R ⁱ⁴ are bonded to each other to form a ring. You may,
^{R i5,} R i6, R ⁱ⁷ and ^{R i8} is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms ^{independently,} when ^{R II5} and ^{R II6} and / or ^{the R II7} and ^{R II8} represents an alkyl group , wherein ^{R II5} and ^{R II6} and / or ^{R II7} and ^{R II8} may be bonded to each other to form a ring,
n ⁱ represents 0 or 1,
m ⁱ represents an integer of 1 to 6, ^{M i} represents a 1-6 valent organic radical, the valence of ^{M i} is the same number as the number represented by ^{m i, R i0, R i1} , R i2, When there are a plurality of R ⁱ³ , R ⁱ⁴ , R ⁱ⁵ , R ⁱ⁶ , R ⁱ⁷ , R ⁱ⁸ and n ⁱ , they may be the same or different. )

(Wherein R ⁱⁱ⁰ represents a hydrogen atom, a hydroxyl group, —O ·, or an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent —CH ₂ present in the alkyl group. -Is independently -O-, -S-, -CO-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-. , -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH- , —C≡C—, —Si (CH ₃ ) ₂ —, a trans 1,4-cyclohexylene group, a 1,4-phenylene group or a naphthalene-2,6-diyl group, in R ⁱⁱ⁰ 1 or 2 or more hydrogen atoms are each independently substituted with a fluorine atom, a chlorine atom or a cyano group It may be,
R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ and R ⁱⁱ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ⁱⁱ¹ and R ⁱⁱ² and / or R ⁱⁱ³ and R ⁱⁱ⁴ are bonded to each other to form a ring. You may,
n ⁱⁱ represents 0 or 1,
t represents 1 to 4, U represents a 2 × t-valent organic group forming a ring structure, R ⁱⁱ⁰ , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ , R ⁱⁱ⁴ , R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ , R ^{If ii8} and n ⁱⁱ there are a plurality, they may be different even in the same. )
In general formula (i) and general formula (ii), R ⁱ⁰ and R ⁱⁱ⁰ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms from the viewpoint of compatibility with the liquid crystal composition. It is preferably an alkoxy group or an alkenyl group having 2 to 20 carbon atoms, and is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms. Is more preferable. The alkyl group, alkoxy group or alkenyl group is preferably linear or molecular, and preferably linear. In view of ease of production, a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms is particularly preferable. In order to enhance the ability to prevent photodegradation, a hydrogen atom or a hydroxyl group is preferable, and a hydrogen atom is particularly preferable.

R ⁱ¹ , R ⁱ² , R ⁱ³ , R ⁱ⁴ , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ and R ⁱⁱ⁴ are preferably each independently an alkyl group having 1 to 4 carbon atoms, A methyl group is particularly preferred from the viewpoint of the stability of the compound. In order to facilitate removal of polar impurities mixed during production, R ⁱ¹ and R ⁱ² and / or R ⁱ³ and R ⁱ⁴ are preferably bonded to each other to form a ring structure. Similarly, R ⁱⁱ¹ and R ⁱⁱ² and / or R ⁱⁱ³ and R ⁱⁱ⁴ are preferably bonded to each other to form a ring structure.

R ⁱ⁵ , R ⁱ⁶ , R ⁱ⁷ , R ⁱ⁸ , R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ and R ⁱⁱ⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of availability of raw materials and stability of the compound.

In the compound represented by the general formula (i), ^{m i} is an integer of 1-6, ^{M i} represents a 1-6 valent organic group, as many valence of ^{M i} is represented by ^{n i} although, m ⁱ is 3, M ⁱ is preferably a trivalent organic group.

If m ⁱ represents 3, ^{M i} is the general formula (i-M)

(In the formula, Z ¹ , Z ² and Z ³ are each independently —O—, —S—, —CH═CH—, —C≡C—, —CO—, —CO—O—, —O. _{-CO -, - OCF 2 -,} - CF 2 O -, - NH- or a single bond.
Sp ¹ , Sp ² and Sp ³ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and one or more —CH ₂ — present in the alkylene group is independently Substituted with —O—, —S—, —CH═CH—, —C≡C—, —CO—, —CO—O—, —O—CO—, —OCF ₂ — or —CF ₂ O—. May be.
A is

(In the formula, R ⁸ represents a hydrogen atom, —OH or an alkyl group having 1 to 10 carbon atoms, and one or two or more —CH ₂ — present in the alkyl group are each independently -O-, -S-, -CH = CH-, -C≡C-, -CO-O-, -O-CO- may be substituted, and the hydrogen atom in the cyclic structure is a halogen atom or (It may be substituted with a cyano group.)
Represents a group selected from: )
In order to improve the compatibility with the liquid crystal composition and the storage stability, it is preferable.

Here, from the viewpoint of ease of production and availability of raw materials, at least one of Z ¹ , Z ² and Z ³ preferably represents —O—, —CO—O— or a single bond, Z ¹ , It is particularly preferred that all of Z ² and Z ³ represent —O—, —CO—O— or a single bond. Moreover, Sp ¹ , Sp ² and Sp ³ preferably represent a single bond or an alkylene group having 1 to 10 carbon atoms, preferably represent a single bond or an alkylene group having 1 to 8 carbon atoms, Or it is more preferable to represent a C1-C4 alkylene group. The alkylene group is unsubstituted or one or more —CH ₂ — present in the alkylene group is each independently —O—, —CO—, —CO—O— or —O—. It is preferably substituted with CO-, and more preferably unsubstituted. ^{Specifically,} Sp ^1, Sp ² and ^Sp 3 _{are, -CO -, - CH 2 -CO} -, - CH 2 -CH 2 -CO -, - CH 2 -O -, - CH 2 -CH 2 - _{O -, - CH 2 -CH 2} -CH 2 -O -, - CH 2 -O-CO -, - CH 2 -CH 2 -O-CO -, - CH 2 -CH 2 -CH 2 -O-CO -Is particularly preferably an unsubstituted alkylene group having 1 to 4 carbon atoms or a single bond.

^{Further, -Sp 1 -Z 1 -, -} Sp 2 -Z 2 - and ^-Sp 2 -Z ² - are each independently _{-CO-O -, - CH 2} -CO-O -, - CH 2 - _{CH 2 -CO-O -, -} CH 2 -CH 2 --CH 2 -CO-O -, - CH 2 -O -, - CH 2 -CH 2 -O -, - CH 2 -CH 2 -CH 2 _{-O -, - CH 2 -O-} CO-O -, - preferably CH 2 -CH 2 -O-CO- O- or _{-CH 2 -CH 2 -CH 2 -O-} CO-O- in which _{, -CO-O -, - CH} 2 -CO-O- or more preferably _-CH 2 _-CH 2 -CO-O- and which.

  A is

(In the formula, R ⁸ represents a hydrogen atom, —OH or an alkyl group having 1 to 10 carbon atoms, and one or two or more —CH ₂ — present in the alkyl group are each independently -O-, -S-, -CH = CH-, -C≡C-, -CO-O-, or -O-CO- may be substituted). It is more preferable to improve the compatibility with the composition and the storage stability. Here, R ⁸ is a hydrogen atom, —OH, an alkyl group having 2 to 10 carbon atoms, —O—CO—R ⁹ (R ⁹ is 1 carbon atom) because of ease of production and availability of raw materials. Represents an alkyl group of ˜9), and particularly preferably represents a hydrogen atom.

Specifically, ^{compounds n i} is 3 as a general formula (i) is a compound represented by the general formula (i-a1) ~ (i -a14) are particularly preferred.

(R ¹¹ , R ¹² and R ¹³ in the formula independently represent the same meaning as R ⁱ⁰ in the general formula (i).)
Moreover, as a compound represented by general formula (i), it is preferable that it is a compound represented by the following general formula (i-1).

In general formula (i-1), R ^is each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is particularly preferably a hydrogen atom. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and 1 carbon atom. Further preferred. When a plurality of ^RHS are present, they may be the same or different.

M ^iS represents an alkyl group having 1 to 15 carbon atoms when m ^iS represents 1, and represents an alkylene group having 1 to 15 carbon atoms when m ^iS represents an integer of 2 to 6, and is present in M ^iS One or more —CH ₂ — represents —O—, —CH═CH—, —C≡C—, —CO—, —OCO—, —COO—, trans-1,4-cyclohexylene group, , 4-phenylene group and naphthalene-2,6-diyl group may be substituted, but considering the viscosity given to the liquid crystal composition and its volatility, M ^iS is an alkyl group having 2 to 10 carbon atoms or An alkylene group is preferable, an alkyl group or alkylene group having 2 to 8 carbon atoms is preferable, an alkyl group or alkylene group having 4 to 8 carbon atoms is preferable, and an alkyl group or alkylene group having 6 or 8 carbon atoms is preferable. M ^iS may be linear or branched.

m ^iS represents an integer of 1 to 6, and preferably 2 to 4.

When ^miS represents 1, it is preferable that the compound represented by general formula (i-1) is a compound represented by general formula (i-11) or general formula (i-12).

(Wherein R ^H11 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and M represents an alkylene group having 1 to 13 carbon atoms.)

(In the formula, R ^is and R ⁱ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
When ^miS represents 2, it is preferable that the compound represented by general formula (i-1) is a compound represented by general formula (i-2).

(In the formula, R ^H1 and R ^H2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and M represents an alkylene group having 1 to 15 carbon atoms. One or more —CH ₂ — is —O—, —CH═CH—, —C≡C—, —CO—, —OCO—, —COO—, trans-1,4-cyclohexylene group, 1, (It may be substituted with a 4-phenylene group or a naphthalene-2,6-diyl group.)
In general formula (i-2), R ^H1 and R ^H2 are particularly preferably hydrogen atoms. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and 1 carbon atom. Further preferred.
In general formula (i-2), M represents an alkylene group having 1 to 15 carbon atoms. However, considering the viscosity given to the liquid crystal composition and its volatility, M is an alkylene having 2 to 10 carbon atoms. Preferably, alkylene having 4 to 8 carbon atoms is preferable, and alkylene having 6 or 8 carbon atoms is preferable.
Specific examples include compounds represented by general formula (i-24), general formula (i-26), and general formula (i-28). R ^H1 and R ^{H2 in} these formulas are as described above.

Moreover, when ^miS represents the integer of 3 to 6, it is preferable that the compound represented by general formula (i-1) is a compound represented by general formula (i-3).

(In the formula, R ^H3 , R ^H4 and R ^H5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N ^H1 and n ^H2 each independently represent 0 or 1 n. ^H3 represents an integer of 1 to 4. When n ^H3 is 2, 3 or 4, and a plurality of R ^H5 are present, they may be the same or different.
In general formula (i-3), R ^H3 , R ^H4 and R ^H5 are particularly preferably hydrogen atoms. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and 1 carbon atom. Further preferred.

In general formula (i-3), when ^nH3 represents 1, it is preferable to represent the said general formula (i-a1)-general formula (i-a3). Moreover, when ^nH3 represents 2 in general formula (i-3), the compound represented by the following general formula (i-31) and general formula (i-32) is preferable. R ^H3 , R ^H4 and R ^{H5 in} these formulas are as described above.

Examples of the compound n ⁱ represents 0 in the compound represented by the general formula (i), the following compounds are preferred.

  As a compound represented by general formula (ii), the compound represented by the following general formula (ii-1) or general formula (ii-2) is preferable.

(In the formula, R ⁱⁱ¹⁰ represents a hydrogen atom or a hydroxyl group, R ⁱⁱ¹² represents a hydrogen atom or a monovalent organic group,
^Spii1 represents a single bond or an alkylene group having 1 to 12 carbon atoms, and one —CH ₂ — present in the alkylene group or two or more non-adjacent —CH ₂ — are —O—, — May be replaced by COO-, -OCO-, -CH = CH- or -C≡C-
A ⁱⁱ¹ each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- May be.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH═ or two or more non-adjacent —CH═ may be replaced by —N═.
Each of the groups (a), (b) and (c) is independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group or a methoxy group. R ⁱⁱ¹¹ may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a general formula ( ^ie )

(Wherein R ^e1 represents a hydrogen atom or a hydroxyl group, ^Spie1 represents a single bond or an alkylene group having 1 to 12 carbon atoms, and one —CH ₂ — present in the alkylene group or adjacent thereto. And two or more —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—, and s1 represents 0 or 1.)
In represents a ^group represented by one -CH present in ^{R ii11} ₂ - or nonadjacent two or more -CH ₂ - is -O -, - S -, - COO -, - OCO- , -CO-, -CH = CH- or -C≡C-
n ⁱⁱ¹ represents 0 or 1, and p ⁱⁱ represents 0, 1 or 2, but when p ⁱⁱ represents 2, a plurality of Spii1 and Aii2 may be independently the same or different. . )

(In the formula, R ⁱⁱ¹⁰ and R ⁱⁱ²¹ each represent a hydrogen atom or a hydroxyl group, and n ⁱⁱ² , l, o, and r each independently represent 0 or 1)
Moreover, it is preferable that the composition containing the compound represented by the general formula (I) further contains a hindered phenol compound. The hindered phenol compound is preferably a compound represented by the general formula (H1).

(In the formula, X ^y is a hydrocarbon having 1 to 25 carbon atoms (one or two or more —CH ₂ — in the hydrocarbon is —O—, —CO— so that the oxygen atom is not directly adjacent) , -COO-, or -OCO- may be substituted.), Represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and an arbitrary hydrogen atom is fluorine. May be substituted by an atom,
M ^y is -CH ₂ 1, two or more of the alkylene group (the alkylene group having from 1 to 15 carbon atoms - as the oxygen atoms are not directly adjacent, -O -, - CO -, - COO- , it may be substituted in _{-OCO-), -. OCH 2 -} , - CH 2 O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CF 2 CF 2 - , —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —C≡C—, single bond, 1, A 4-phenylene group and a trans-1,4-cyclohexylene group are represented. In the 1,4-phenylene group, an arbitrary hydrogen atom may be substituted with a fluorine atom, and l represents an integer of 2 to 6. )
As the antioxidant represented by the general formula (H1), the following general formula (H1-I)

(In the formula, M ^x is a hydrocarbon having 1 to 25 carbon atoms (one or two or more —CH ₂ — in the hydrocarbon is —O—, —CO— , -COO -, -. the OCO- may be substituted in) represents, X is one of the alkylene group (the alkylene group having from 1 to 15 carbon atoms or two or more -CH ₂ -, the oxygen as atoms are not directly adjacent, -O -, - CO -, - COO -, - OCO- it may be substituted _{in), -. OCH 2 -,} - CH 2 O -, - COO -, - OCO _{-, - CF 2 O -,} - OCF 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, -CH = CH-, -C≡C-, single bond, 1,4-phenylene group, trans-1,4-cycl Represents a hexylene group, and a 1,4-phenylene group may have an arbitrary hydrogen atom substituted by a fluorine atom, and a, b, c and d each independently represents 0 or 1, but a + b + c + d is 2 or more Is more preferable.

M ^x is a hydrocarbon having 2 to 15 carbon atoms (one or more of —CH ₂ — in the hydrocarbon is —O—, —CO—, —COO— so that oxygen atoms are not directly adjacent to each other). X may be an alkylene group having 2 to 15 carbon atoms (one or more of —CH ₂ — in the alkylene group may be directly adjacent to an oxygen atom). And may be substituted with —O—, —CO—, —COO— or —OCO—), preferably a single bond, 1,4-phenylene group or trans-1,4-cyclohexylene group. , A + b + c + d is more preferably 2 to 4, and 2 is particularly preferable.

In the general formula (HI), M ^x is more preferably an alkylene group having 1 to 15 carbon atoms. In consideration of volatility, a large number is preferable, and in consideration of viscosity, the carbon number is not too large. Is preferred. From the above, M ^x has more preferably 2 to 15 carbon atoms, and particularly preferably 2 to 10 carbon atoms.

  Further, the compound B2 is preferably a compound represented by the general formula (H2).

(In the general formula (H2), R ^H21 represents a linear alkyl group having 1 to 22 carbon atoms or a branched alkyl group, and one or two or more —CH ₂ — in the alkyl group represents an oxygen atom. May be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O— or —OCF ₂ — so that they are not directly adjacent to each other. ,
a ^H2 represents 0, 1 or 2,
^MH21 represents (a) a trans-1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more —CH ₂ — not adjacent to each other is —O— or —S—). Or may be replaced by
(B) a 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =), and (c) ) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6 -Represents a group selected from the group consisting of a diyl group or a chroman-2,6-diyl group, but one or more of the groups (a), groups (b) or groups (c) each represents a hydrogen atom a fluorine atom, a trifluoromethyl group, may be substituted by a trifluoromethoxy group or a chlorine atom, if M ^H21 represents a ^H2 2 there are a plurality, M ^H21 there are a plurality had the same Can be different,
Z ^H21 is a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - COO- Alternatively, -OCO- is represented, but when a ^H2 represents 2 and a plurality of Z ^H21 are present, the plurality of Z ^H21 may be the same or different. )
Specifically, the compounds represented by general formula (H1) and general formula (H2) are preferably represented by general formula (H-1) to general formula (H-4).

In general formula (H-1) to general formula (H-4), R ^H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or It represents an alkenyloxy group having 2 to 10 carbon atoms, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O- or -S- In addition, one or two or more hydrogen atoms present in the group may be each independently substituted with a fluorine atom or a chlorine atom. More specifically, it is an alkyl group having 2 to 7 carbon atoms, an alkoxyl group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. An alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable.
In General Formula (H-4), ^MH4 represents an alkylene group having 1 to 15 carbon atoms (one or two or more —CH ₂ — in the alkylene group may be — O—, —CO—, —COO—, —OCO— may be substituted.), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, — _{OCF 2 -, - CF 2 CF} 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - C≡C—, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or a trans-1,4-cyclohexylene group. Preferably an alkylene group having 1 to 14 carbon atoms, In consideration of the viscosity, a large number of carbon atoms is preferable, but in consideration of the viscosity, the number of carbon atoms is preferably not too large. Therefore, the number of carbon atoms is more preferably 2 to 12, more preferably 3 to 10. 4 to 10 carbon atoms are more preferred, 5 to 10 carbon atoms are more preferred, and 6 to 10 carbon atoms are more preferred.
In general formulas (H-1) to (H-4), one or more non-adjacent —CH═ in the 1,4-phenylene group may be substituted by —N═. Further, each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.
In general formula (H-1) to general formula (H-4), one or two or more non-adjacent —CH ₂ — in the 1,4-cyclohexylene group is replaced by —O— or —S—. May be. In addition, each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.
More specifically, for example, the formulas (H-11) to (H-15) can be given.

  In the liquid crystal composition of the present invention, the total amount of the compounds represented by the general formula (i), the general formula (ii) and the general formula (H1) is set to 0.001% as a lower limit with respect to the total mass of the composition. Preferably, it is contained 0.002% or more, preferably 0.003% or more, preferably 0.004% or more, and preferably 0.005% or more. 0.006% or more, preferably 0.007% or more, preferably 0.008% or more, preferably 0.009% or more, 0.01% or more Preferably, contained 0.02% or more, preferably 0.03% or more, preferably 0.04% or more, 0.05% or more Preferably 0.06% or more, preferably 0.07% or more, preferably 0.08% or more, preferably 0.09% or more, 0 .10% or more, preferably 0.11% or more, preferably 0.12% or more, preferably 0.13% or more, preferably 0.14% or more It is preferable to contain 0.15% or more, preferably 0.20% or more, preferably 0.25% or more, preferably 0.30% or more. It is preferable to contain 35% or more, preferably 0.40% or more, preferably 0.50% or more, and preferably 1% or more. Further, the upper limit is preferably 5% or less, preferably 3% or less, preferably 2% or less, preferably 1.5% or less, and preferably 1% or less. Preferably, 0.9% or less, preferably 0.8% or less, preferably 0.7% or less, preferably 0.6% or less, 0.5% It is preferably contained below, preferably 0.45% or below, preferably 0.4% or below, preferably 0.35% or below, preferably 0.3% or below. , 0.25% or less, preferably 0.2% or less, preferably 0.15% or less, preferably 0.1% or less, 0.07 Preferably contains less, preferably it contains more than 0.05%, and preferably 0.03% or less.

  More specifically, the content is preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass, still more preferably 0.01 to 0.2% by mass. It is particularly preferably from 01 to 0.15% by weight. More specifically, when emphasizing the suppression of precipitation at low temperatures, the content is preferably 0.01 to 0.1% by mass.

  In the liquid crystal composition of the present invention, the total amount of the compound represented by the general formula (I) and the content of the compound represented by the general formula (i), the general formula (ii), and the general formula (H1) Is preferably in the range of 1: 100 to 10000: 1, more preferably in the range of 1:10 to 1000: 1, 1: 1 to 1: 500, : It is preferable that it is 1-1: 100.

  Contains a compound represented by general formula (I) and one or more compounds selected from the group of compounds represented by general formula (i), general formula (ii) and general formula (H1) By doing so, deterioration of the liquid crystal composition of the liquid crystal composition can be further prevented.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. “%” In the compositions of the following examples and comparative examples means “% by mass”. The purity of the compound was analyzed by GC or UPLC. Abbreviations of compounds and reaction solvents are as follows: tetrahydrofuran (THF), N, N-dimethylformamide (DMF)
Example 1 Production of Compound (I-1-1)

(Production of Compound (S-2-1)) Magnesium magnesium (75 g) and THF (40 ml) were added to a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube in a nitrogen atmosphere, and then compound (S -I-1) in THF (260 ml) was slowly added dropwise, followed by stirring for 1 hour so as not to exceed 30 ° C. Thereafter, DMF was slowly added dropwise so that the internal temperature did not exceed 40 ° C., and further stirred at 30 ° C. or lower for 1 hour. While cooling in an ice bath, 10% hydrochloric acid (420 ml) was added, the organic layer and the aqueous layer were separated, extracted from the aqueous layer with toluene (200 ml), the organic layers were combined, and this was washed with saturated brine (400 ml). Then, it was dried over anhydrous sodium sulfate. The obtained solution was concentrated under reduced pressure to obtain a yellow oily compound (S-2-1) (54 g).
GC-MS: m / z 148.09 [M ⁺ ]
(Production of Compound (S-3-1)) In a nitrogen atmosphere, a reaction vessel equipped with a stirrer, a thermometer and a condenser tube was charged with compound (S-2-1) (20 g) and 3-benzyl-5- ( A solution of 2-hydroxyethyl) -4-methylthiazolium chloride (1.8 g) in ethanol (90 ml) was added and stirred at room temperature, and triethylamine (5.6 ml) was added thereto. Thereafter, the mixture was stirred for 7 hours with heating under reflux, cooled to room temperature, and water (200 ml) and ethyl acetate (200 ml) were slowly added. The organic layer and the aqueous layer were separated, and the resulting aqueous layer was extracted with ethyl acetate (200 ml). The organic layers were combined, washed with saturated brine (200 ml), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. As a result, a brown oil compound (I-3-1) (19 g) was obtained.
GC-MS: m / z 296.18 [M ⁺ ]
(Production of Compound (I-1-1)) Under a nitrogen atmosphere, a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube was charged with THF (80 ml) / methanol (19 g) of Compound (S-3-1) (19 g). 20 ml) solution was added and stirred under ice cooling. Thereto, sodium borohydride (1.5 g) was slowly added while paying attention to the generation of hydrogen, and further stirred for 1 hour. Saturated aqueous ammonium chloride (100 ml) was slowly added, the organic layer and the aqueous layer were separated, and the resulting aqueous layer was extracted with hexane (80 ml) / THF (80 ml). The organic layers were combined, and saturated brine (200 ml) was added. After washing and drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure. Toluene (20 ml) / hexane (20 ml) was added to the resulting residue, and the mixture was washed in a suspended state and collected by filtration to give colorless crystalline compound (I -1-1) (11g) was obtained.
GC-MS: m / z 298.19 [M ⁺ ]
(Example 2 to Example 135)
Example 2 (Compound (I-2-1)) to Example 135 (Compound (I-105-3) were used in the same manner as in Example 1 and, if necessary, a method based on a known method. ) Was manufactured.

Example 136 Production of Compound (I-111-5)

(Production of Compound (S-6-1)) In a nitrogen atmosphere, a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube was charged with compound (S-4-1) (14 g), tetrakistriphenylphosphine palladium (0 ) (1.3 g), copper (I) iodide (0.44 g) and triethylamine (40 ml) in DMF (80 ml) were added, and the mixture was stirred at 75 ° C., and then compound (S-5-1) Of DMF (40 ml) was slowly added dropwise and stirred for 1 hour so as not to exceed 75 ° C. After cooling to room temperature, water (80 ml) and toluene (80 ml) were added, the organic layer and the aqueous layer were separated, extracted from the aqueous layer with toluene (40 ml), the organic layers were combined, and this was combined with saturated brine ( 80 ml) and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure, dissolved in hexane (80 ml) / toluene (50 ml), passed through a silica gel column (packed with 15 g of silica gel), and eluted with hexane (80 ml) / toluene (40 ml). When concentrated under reduced pressure, a yellow oily compound (S-6-1) (16 g) was obtained.
GC-MS: m / z 266.15 [M ⁺ ]
(Production of compound (S-7-1)) In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube in the atmosphere, compound (S-6-1) (16 g) and palladium (II) acetate (1. 2 g) and copper (II) bromide (1.2 g) in dimethyl sulfoxide (120 ml) were added and stirred at 120 ° C. for 6 hours. After cooling to room temperature, water (200 ml) and ethyl acetate (200 ml) were slowly added. The organic layer and the aqueous layer were separated, and the resulting aqueous layer was extracted with ethyl acetate (200 ml). The organic layers were combined, washed with saturated brine (200 ml), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. As a result, a brown oily compound (S-7-1) (12 g) was obtained.

(Production of Compound (I-111-5)) Under a nitrogen atmosphere, a reaction vessel equipped with a stirrer, a thermometer and a condenser tube was charged with THF (80 ml) / methanol (12 g) of Compound (S-7-1) (12 g). 20 ml) solution was added and stirred under ice cooling. Thereto, sodium borohydride (2.2 g) was slowly added while paying attention to the generation of hydrogen, and further stirred for 1 hour. Saturated aqueous ammonium chloride (100 ml) was slowly added, the organic layer and the aqueous layer were separated, and the resulting aqueous layer was extracted with hexane (80 ml) / THF (80 ml). The organic layers were combined, and saturated brine (200 ml) was added. After washing and drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure. Toluene (20 ml) / hexane (20 ml) was added to the resulting residue, and the mixture was washed in a suspended state and collected by filtration to give colorless crystalline compound (I -111-5) (7.3 g) was obtained.
GC-MS: m / z 301.17 [M-18 ⁺ ]
(Example 137 to Example 247)
Using a reaction similar to that of Example 136 and, if necessary, a method based on a known method, Example 137 (Compound (I-110-1)) to Example 247 (Compound (I-145-3)) ) Was manufactured.

  Regarding the liquid crystal composition containing any of the compounds obtained in Examples 1 to 247, the measured properties are as follows.

  VHR: The voltage holding ratio (%) at 333 K was evaluated in three stages under the conditions of a frequency of 60 Hz and an applied voltage of 1 V.

A: 98-100%
B: 95-98%
C: 95% or less Light resistance VHR: The liquid crystal composition is irradiated with ultraviolet rays at 180 J / m ² using an ultrahigh pressure mercury lamp through a glass having a thickness of 0.5 mm. The voltage holding ratio of the liquid crystal after ultraviolet irradiation is measured by the same method as the above VHR measurement. However, the irradiation intensity was 366 nm and 0.1 W / m ² . Evaluation was performed in the following three stages.

A: 90% to 100%
B: 75% or more to less than 90% C: less than 75% Compatibility: Three-stage evaluation of the state of dissolution when 500 ppm of any of the compounds obtained in Examples 1 to 247 was added to the liquid crystal composition. did.

A: All dissolved B: Slightly dissolved and separated C: Partially dissolved and separated Storage stability: The liquid crystal composition was stored at −20 ° C. for 1 week and visually checked for the presence or absence of precipitates It was evaluated in three stages.

A: No precipitate B: Slight cloudiness is observed C: Precipitate can be clearly confirmed (Example 248) Preparation of liquid crystal composition-1
A host liquid crystal composition (H) having the following composition was prepared.

To this base liquid crystal (H), 500 ppm of the compound (I-1-1) obtained in Example 1 was added.
The measured properties of the composition examples in the examples are as follows.

VHR: A
Light resistant VHR: A
Compatibility: C
Storage stability: C
(Examples 249 to 494)
Hereinafter, in the same manner as in Example 248, the results of measurement of Examples 249 to 494 using the compounds manufactured in Examples 2 to 247 are shown below.

(Comparative Example 1)
As a comparative example, the results of measuring the characteristics of the base liquid crystal (H) without particularly adding additional compounds are as follows.

VHR: A
Light resistant VHR: C
Storage stability: A
From this result, it can be seen that the compound of the present invention has an effect of preventing deterioration of the liquid crystal composition due to light.
(Comparative Example 2)
The result of adding 500 ppm of the compound (R-1) to the base liquid crystal (H) and measuring the results is as follows.

VHR: A
Light resistant VHR: A
Compatibility: B
Storage stability: C
(Comparative Examples 3 and 4)
Hereinafter, the results of measurement in Comparative Examples 3 and 4 in the same manner as in Comparative Example 2 are shown below.

  From this result, it can be seen that the compound of the present invention has high compatibility with the liquid crystal composition without impairing the storage stability of the liquid crystal composition, and has an effect of preventing deterioration of the liquid crystal composition due to light.

Claims (11)

Formula (I)

(In the formula, R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are each independently a hydrogen atom, halogen atom, hydroxyl group, cyano group, chlorine Atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano Represents a group or an alkyl group having 1 to 20 carbon atoms, and one or two or more —CH ₂ — present in the alkyl group are each independently —O—, —S—, —CO—, — CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - C≡C -, - Si (CH 3) 2 -, Which may be substituted with a trans 1,4-cyclohexylene group, 1,4-phenylene group or naphthalene-2,6-diyl group, and one or more hydrogen atoms in the alkyl group are each independently R ¹¹¹ , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 may all be substituted with a halogen atom or a cyano group. (Do not represent.)
The additive for liquid crystal compositions which has a compound represented by these. 2. The liquid crystal composition according to claim 1, wherein in general formula (I), R ^I11 and R ^I21 , R ^I12 and R ^I22 , R ^I13 and R ^I23 , R ^I14 and R ^I24, and R ^I15 and R ^I25 each represent the same group. Additives for products. In the general formula (I), any one or more groups selected from R ^I11 and R ^I21 , R ^I12 and R ^I22 , R ^I13 and R ^I23 , R ^I14 and R ^I24, and R ^I15 and R ^I25 are different groups. The additive for liquid crystal composition of Claim 1 represented. In the general formula (I), one or more groups selected from R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are fluorine. The additive for liquid crystal compositions according to any one of claims 1 to 3, which represents an atom. In the general formula (I), one or more groups selected from R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are carbon. The additive for liquid crystal compositions according to any one of claims 1 to 4, which represents an alkyl group having 4 to 20 atoms. In general formula (I), one or more groups selected from R ^I11 , R ^I12 , R ^I13 , R ^I14 , R ^I15 , R ^I21 , R ^I22 , R ^I23 , R ^I24 and R ^I25 are The liquid crystal composition according to claim 1, which represents a group having a trans 1,4-cyclohexylene group, a 1,4-phenylene group, or a naphthalene-2,6-diyl group in the group. Additives. Two or more groups selected from R ^I11 , R ^I12 , R ^I13 , R ^I14 and R ^I15 represent a halogen atom, a cyano atom or an alkyl group having 1 to 20 carbon atoms, and / or R ^I21 , 7 or more groups selected from R ^{< I22 >,} R ^{< I23 >,} R ^{< I24 >} and R ^<I25> represent a halogen atom, a cyano group, or a C1-C20 alkyl group. Liquid crystal composition additive.   The compound represented by the general formula (I) according to claim 1.   A composition comprising the compound according to claim 8. Furthermore, general formula (i) and general formula (ii)

(In the formula, R ⁱ⁰ represents a hydrogen atom, a hydroxyl group, —O ·, or an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent —CH ₂ present in the alkyl group. -Is independently -O-, -S-, -CO-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-. , -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH- , —C≡C—, —Si (CH ₃ ) ₂ —, trans 1,4-cyclohexylene group, 1,4-phenylene group or naphthalene-2,6-diyl group, and R ⁱ⁰ 1 or 2 or more hydrogen atoms may be independently substituted with a fluorine atom, a chlorine atom or a cyano group. Ku,
R ⁱ¹ , R ⁱ² , R ⁱ³ and R ⁱ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ⁱ¹ and R ⁱ² and / or R ⁱ³ and R ⁱ⁴ are bonded to each other to form a ring. You may,
^{R i5,} R i6, R ⁱ⁷ and ^{R i8} is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms ^{independently,} when ^{R II5} and ^{R II6} and / or ^{the R II7} and ^{R II8} represents an alkyl group , wherein ^{R II5} and ^{R II6} and / or ^{R II7} and ^{R II8} may be bonded to each other to form a ring,
n ⁱ represents 0 or 1,
m ⁱ represents an integer of 1 to 6, ^{M i} represents a 1-6 valent organic radical, the valence of ^{M i} is the same number as the number represented by ^{m i, R i0, R i1} , R i2, When there are a plurality of R ⁱ³ , R ⁱ⁴ , R ⁱ⁵ , R ⁱ⁶ , R ⁱ⁷ , R ⁱ⁸ and n ⁱ , they may be the same or different. )

(Wherein R ⁱⁱ⁰ represents a hydrogen atom, a hydroxyl group, —O ·, or an alkyl group having 1 to 20 carbon atoms, and one or two or more non-adjacent —CH ₂ present in the alkyl group. -Is independently -O-, -S-, -CO-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-. , -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH- , —C≡C—, —Si (CH ₃ ) ₂ —, a trans 1,4-cyclohexylene group, a 1,4-phenylene group or a naphthalene-2,6-diyl group, in R ⁱⁱ⁰ 1 or 2 or more hydrogen atoms are each independently substituted with a fluorine atom, a chlorine atom or a cyano group It may be,
R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ and R ⁱⁱ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ⁱⁱ¹ and R ⁱⁱ² and / or R ⁱⁱ³ and R ⁱⁱ⁴ are bonded to each other to form a ring. You may,
n ⁱⁱ represents 0 or 1,
t represents 1 to 4, U represents a 2 × t-valent organic group forming a ring structure, R ⁱⁱ⁰ , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ , R ⁱⁱ⁴ , R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ , R ^{If ii8} and n ⁱⁱ there are a plurality, they may be different even in the same. )
The composition of Claim 9 which contains 1 type, or 2 or more types of compounds selected from the compound group represented by these.   The display element using the composition of Claim 9 or 10.