JP6965570B2 - Stabilizer compounds, liquid crystal compositions and display devices - Google Patents

Description

The present invention relates to stabilizer compounds.

Liquid crystal display elements are used in various electric devices for food, various measuring devices, automobile panels, word processors, electronic organizers, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and IPS (inplane switching). Types, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence type), VA (vertical orientation) type, CSH (color superhomeotropic) type and the like can be mentioned. Further, as the drive method, a static drive, a multiplex drive, a simple matrix method, an active matrix (AM) method driven by a TFT (thin film transistor), a TFD (thin film diode), or the like can be mentioned.

Among these, display methods such as IPS type and VA type driven by AM are used for high-speed, high-viewing-angle melting display elements, such as televisions.

The nematic liquid crystal composition used in these display methods is required to have a low voltage drive, a high-speed response, and a wide operating temperature range. That is, a large absolute value of Δε, a low viscosity (η), and a high nematic phase-isotropic liquid phase transition temperature (T _ni ) are required. Further, from the setting of Δn × d, which is the product of the refractive index anisotropy (Δn) and the 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 a liquid crystal display element is applied to a television or the like, high-speed response is emphasized, so that a liquid crystal composition having a _{low viscosity (η) and a small γ 1 is required.}

In addition to the requirements for the physical characteristics of these liquid crystal compositions, the liquid crystal composition used for the liquid crystal display element is required to be stable to external stimuli such as moisture, air, heat, and light. If the stability against external stimuli is impaired, display defects such as burn-in and display unevenness occur on the liquid crystal display element. It is considered essential to have a high voltage retention rate (VHR) in order to obtain a liquid crystal composition and a liquid crystal display element that do not cause or are unlikely to cause display defects such as burn-in and display unevenness. For example, it is known that VHR can be maintained high by adding an antioxidant, an ultraviolet absorber or a light stabilizer to the liquid crystal composition (see Patent Documents 1 to 3).

From the above, there is a demand for a liquid crystal composition that achieves a high VHR while satisfying the requirements for the physical characteristics of the liquid crystal composition. In achieving this, a new antioxidant and an ultraviolet absorber that suppress the decrease in VHR are required. Alternatively, a light stabilizer is required.

Special table 2004-507607 JP-A-2002-256267 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.

As a result of diligent studies to solve the above problems, the inventor of the present application has completed the invention of the present application.
That is, the present invention has 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 I ²⁵ are independent hydrogen atoms, halogen atoms, hydroxyl groups, cyano groups, chlorine. Atomic, 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 independently -O-, -S-, -CO-, and-, respectively. 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- , Transformers 1, 4 It may be substituted with a-cyclohexylene group, 1,4-phenylene group or naphthalene-2,6-diyl group, and one or more hydrogen atoms in the alkyl group are independently halogen atoms or cyano groups, respectively. in may be ^{substituted, R I11, R I12, R} I13, R I14, R I15, R I21, R I22, R I23, all ^{R I24} and ^{R I25} is never represents a hydrogen atom.)
Provided is an additive for a liquid crystal composition having a compound represented by.

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. 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.

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 I ²⁵ are hydrogen atoms from the viewpoint of compatibility with the liquid crystal composition. , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a fluorine atom, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkenyl having 3 to 8 carbon atoms. It is more preferably a group or a hydrogen atom. The hydrogen atom, alkyl group or alkenyl group is preferably linear or branched, preferably linear. From the viewpoint of ease of production, a fluorine atom, a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms is particularly preferable. Furthermore, the enhanced photodegradation preventing ability ^{R I11, R I12, R I13} , R I14, R I15, R I21, R I22, R I23, of ^{R I24} and ^{R I25,} 1 connected to eight but is hydroxyl It is preferable that 1 to 6 are hydroxyl groups, 1 to 4 are hydroxyl groups, 1 to 2 are hydroxyl groups, and 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} preferably represents an R ^{I22, R I13} and ^{R I23, R I14} and any one or more sets are different groups selected from ^{R I24} and ^{R I15} and ^{R I25.}

Further, from the viewpoint of compatibility with the liquid crystal ^{composition, R I11, R I12, R} I13, R I14, R I15, R I21, R I22, R I23, 1 or is selected from ^{R I24} and ^{R I25} or 2 It is preferable that one or more groups represent a fluorine atom.

From the viewpoint of affinity and photodegradation ability of preventing the ^alignment layer 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 preferable that one or more groups represent an alkyl group having 4 to 20 carbon atoms. The alkyl group is preferably linear or branched, preferably linear. The number of carbon atoms of the alkyl group is preferably 4 to 15, preferably 4 to 10, and preferably 4 to 8. The compound represented by the general formula (I) is preferably a compound represented by the general formulas (I-1) to (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.)
The compound represented by the general formula (I) is a compound represented by the general formulas (I-67) to (I-109) from the viewpoint of ease of synthesis and compatibility with the liquid crystal composition. Is preferable.

(In the formula, _n in C n H _{(2n + 1)} represents an integer from 0 to 8.)
Further, the compound represented by the general formula (I) is preferably a compound represented by the general formulas (I-110) to (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 from 0 to 8.)
In the present invention, the compound represented by the general formula (I) can be produced as follows. Of course, the gist 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} A compound in which R ^I15 and R ^I25 each represent the same group is represented by the general formula (Ia). In the following formulas, R ¹ , R ² , R ³ , R ⁴ and R ^{5 are R I 11} and R I ²¹ , R ^{I 12} and R I ²² , R I ¹³ and R I ²³ , R I ¹⁴ and R I ^{24 in the} general formula (I). It has the same meaning as ^{R I15} and R ^{I25, respectively.}

(Production Method 1) A method for producing a compound (Ia) represented by the 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. By allowing sodium borohydride to act on the compound represented by the general formula (S-2), the compound represented by the general formula (Ia) can be obtained. In addition to this, the general formula (Ia) can be obtained by various functional group conversions. In addition, for example, Experimental Chemistry Course (edited by Japan Chemical Society, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Belstein Handbook of Organic Chemistry Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) as described in the literature, such as or SciFinder (Chemical Abstracts Service, American Chemical Society), Reaxys (Elsevier By using the reaction conditions listed in a database such as Ltd.), it is possible to derive a compound represented by the general formula (Ia).

(Production method 2) Method for producing a compound represented by the 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 binding 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) can be used. The compound represented can be obtained. By allowing dimethyl sulfoxide to act on the general formula (S-5) in the presence of a palladium catalyst and a copper catalyst, the compound represented by the general formula (S-6) can be obtained. By allowing sodium borohydride to act on the compound represented by the general formula (S-6), the compound represented by the general formula (Ib) can be obtained. In addition to this, the general formula (Ib) can be obtained by various functional group conversions. In addition, for example, Experimental Chemistry Course (edited by Japan Chemistry Society, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Belstein Handbook of Organic Chemistry Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) as described in the literature, such as or SciFinder (Chemical Abstracts Service, American Chemical Society), Reaxys (Elsevier By using the reaction conditions listed in the database such as Ltd.), the compounds represented by the general formulas (S-3) and (S-4) can be supplied from the corresponding compounds, and the general formula (I-b) can be supplied. ) Can be derived.

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

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

Deterioration of the liquid crystal composition can be prevented by adding the compound represented by the general formula (I) to the liquid crystal composition. The compound represented by the general formula (I) is considered to function as a stabilizer for suppressing deterioration of the liquid crystal composition due to stimuli such as light and heat. Further, 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 the 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 value 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 preferably 0.07% by mass. % Or more, preferably 0.1% by mass or more, preferably 0.15% by mass or more, preferably 0.2% by mass or more, and 0.25% by mass or more. It is preferably contained, preferably 0.3% by mass or more, preferably 0.5% by mass or more, and preferably 1% by mass or more. Further, as an upper limit value, it is preferably contained in an amount of 5% by mass or less, preferably 3% by mass or less, preferably 1% by mass or less, preferably 0.5% by mass or less, and 0.45% or less. It is preferably contained in an amount of mass% or less, preferably 0.4% by mass or less, preferably 0.35% by mass or less, preferably 0.3% by mass or less, and 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, and preferably 0.07% by mass or less. It is preferable that the content is 0.05% by mass or less, and 0.03% by mass or less is preferable.

More specifically, it is preferably contained in an amount of 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, and even more preferably 0.02 to 0.3% by mass. It is particularly preferably 0.05 to 0.25% by mass. More specifically, when the suppression of precipitation at low temperature is emphasized, the content thereof 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. May be contained.

The composition containing the compound represented by the general formula (I) preferably further contains the compound represented by the following general formula (i) or general formula (ii).

^{(Wherein, R i0} a hydrogen atom, a hydroxyl group, -O ·, or an alkyl group having 1 to 20 carbon atoms, existing in the alkyl group one or not-adjacent two or more -CH ₂ -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 may be substituted in R ⁱ⁰ . One or more hydrogen atoms of the above may be independently substituted with a fluorine atom, a chlorine atom or a cyano group, respectively.
R ⁱ¹ , R ⁱ² , R ⁱ³ and R ⁱ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and the R ⁱ¹ and R ⁱ² and / or R ⁱ³ and R ⁱ⁴ are bonded to each other to form a ring. May be
^{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, If ^{R i3, R i4, R i5} , R i6, R i7, R i8 and ^{n i} is plurally present, they may be the same or different. )

^{(Wherein, R ii0} is a hydrogen atom, a hydroxyl group, -O ·, or an alkyl group having 1 to 20 carbon atoms, existing in the alkyl group one or not-adjacent two or more -CH ₂ -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 may be substituted in ^Rii0 . One or more hydrogen atoms of the above may be independently substituted with a fluorine atom, a chlorine atom or a cyano group, respectively.
^{R ii1,} R ii2, R ⁱⁱ³ and ^{R ii4} each independently represent an alkyl group having 1 to 12 carbon atoms, said ^{R ii1} and ^{R ii2} and / or ^{R ii3} and ^{R ii4,} taken together form a ring May be
ⁿⁱⁱ 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. )
Formula (i) and general formula ^(ii), from the viewpoint of the compatibility with ^{R i0} and ^{R ii0} liquid crystal composition, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms 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. From the viewpoint of ease of production, a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms is particularly preferable. Further, in order to enhance the photodegradation prevention ability, 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, preferably ^{R ii3} and ^{R ii4} are each independently an alkyl group having 1 to 4 carbon atoms, easy availability of raw materials and A methyl group is particularly preferable from the viewpoint of compound stability. Further, in order to facilitate the removal of polar impurities mixed in during production, it is preferable that ^Ri1 and ^Ri2 and / or ^Ri3 and ^Ri4 are bonded to each other to form a ring structure. ^{Similarly, R ii1} and ^{R ii2} and / or ^{R ii3} and ^{R ii4} is preferably bonded together 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, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. It is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group from the viewpoint of easy 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)

^{(Z 1} , Z ² and Z ³ in the equation are independently -O-, -S-, -CH = CH-, -C≡C-, -CO-, -CO-O-, -O, respectively. Represents -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 are independent of each other. Replaced with -O-, -S-, -CH = CH-, -C≡C-, -CO-, -CO-O-, -O-CO-, -OCF _2- or -CF ₂ O- You may.
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 independent of each other. It may be substituted with −O−, −S−, −CH = CH−, −C≡C−, −CO−O−, −O−CO−, 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. )
The structure represented by is preferable in order to enhance compatibility with the liquid crystal composition and storage stability.

Here, from the viewpoint of ease of production and availability of raw materials, ^{it is preferable that at least one of Z 1} , Z ² and Z ³ represents -O-, -CO-O- or a single bond, and Z ¹ , It is particularly preferred that all of Z ² and Z ³ represent -O-, -CO-O- or single bonds. Further, Sp ¹ , Sp ² and Sp ³ preferably represent a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 8 carbon atoms, and a single bond. Alternatively, it is more preferable to represent an alkylene group having 1 to 4 carbon atoms. The alkylene group is unsubstituted, or one or more -CH _2- present in the alkylene group are 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 -, It is particularly preferable that it is an unsubstituted alkylene group or a single bond having 1 to 4 carbon atoms.

^{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 independent of each other. The structure represented by −O−, −S−, −CH = CH−, −C≡C−, −CO−O− or −O−CO−) is the liquid crystal. It is more preferable to enhance compatibility with the composition and storage stability. Here, due to the ease of production and the availability of raw materials, R ⁸ is a hydrogen atom, -OH, an alkyl group having 2 to 10 carbon atoms, and -O-CO-R ⁹ (R ⁹ is 1 carbon atom). (Representing an alkyl group of ~ 9) is preferable, and it is particularly preferable to represent 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 formulas represents the same meaning as ^{R i0} of independently in the general formula (i).)
The compound represented by the general formula (i) is preferably a compound represented by the following general formula (i-1).

In the general formula (i-1), ^Ris independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but a hydrogen atom is particularly preferable. In the case of an alkyl group, the number of carbon atoms is preferably 1 to 8, preferably 1 to 5, preferably 1 to 3, and preferably 1 carbon atom. More preferred. When ^{there are a plurality of RHS} , they may be the same or different.

^MiS represents an alkyl group having 1 to 15 carbon atoms when ^miS represents 1, and represents an alkylene group having 1 to 15 carbon atoms when ^miS represents an integer of 2 to 6, and is present in ^MiS. One or more −CH ₂ −s are −O−, −CH = CH−, −C≡C−, −CO−, −OCO−, −COO−, trans-1,4-cyclohexylene groups, 1 , 4-Phenylene group, Naphthalene-2,6-Diyl group may be substituted, but considering the viscosity given to the liquid crystal composition and its own volatility, ^MiS is an alkyl group having 2 to 10 carbon atoms or an alkyl group. 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. The ^MiS may be linear or branched.

^miS represents an integer from 1 to 6, but is preferably 2 to 4.

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

(In the formula, ^RH11 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.)

^{(Wherein, R IS} and ^{R i11} are each independently represents hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
When ^miS represents 2, the compound represented by the general formula (i-1) is preferably a compound represented by the general formula (i-2).

(In the formula, ^RH1 and ^RH2 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, which are present in M. 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 the general formula (i-2), it is particularly preferable that ^RH1 and ^{RH2 are hydrogen atoms.} In the case of an alkyl group, the number of carbon atoms is preferably 1 to 8, preferably 1 to 5, preferably 1 to 3, and preferably 1 carbon atom. More preferred.
In the general formula (i-2), M represents an alkylene group having 1 to 15 carbon atoms, but considering the viscosity given to the liquid crystal composition and its own volatility, M represents an alkylene group having 2 to 10 carbon atoms. Preferably, an alkylene having 4 to 8 carbon atoms is preferable, and an alkylene having 6 or 8 carbon atoms is preferable.
Specific examples thereof include compounds represented by the general formula (i-24), the general formula (i-26) and the general formula (i-28). The ^{R H1} and ^{R H2} in these formulas are as previously described.

When ^miS represents an integer of 3 to 6, the compound represented by the general formula (i-1) is preferably a compound represented by the general formula (i-3).

(In the formula, ^RH3 , ^RH4 and ^RH5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N ^H1 and n ^H2 independently represent 0 or 1, respectively. ^H3 represents an integer from 1 to 4. n When ^H3 is 2, 3 or 4, and ^{there are a plurality of RH5} , they may be the same or different.)
In the general formula (i-3), ^RH3 , ^RH4 and ^RH5 are particularly preferably hydrogen atoms. In the case of an alkyl group, the number of carbon atoms is preferably 1 to 8, preferably 1 to 5, preferably 1 to 3, and preferably 1 carbon atom. More preferred.

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

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

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

(In the formula, R ^{ii 10} represents a hydrogen atom or a hydroxyl group, and R ^{ii 12} represents a hydrogen atom or a monovalent organic group.
Sp ⁱⁱ¹ represents a single bond or an alkylene group having a carbon number of from 12, one -CH ₂ present in the alkylene group - or nonadjacent two or more -CH ₂ - is -O -, - It 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 done.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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 with -N =).
It is a group selected from the group consisting of, and the above groups (a), groups (b) and groups (c) are independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group or a methoxy group, respectively. R ⁱⁱ¹¹ may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a general formula (ie).

(In the formula, 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 − or adjacent to the alkylene group is present. no more than one _-CH 2 - is -O -, - COO -, - OCO -, - CH = CH- or -C≡C- may be replaced by, 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- may be replaced.
n ⁱⁱ¹ represents 0 or ^{1, p ii} each represents 0, 1, or ^{2, if p ii} represents 2, may be the same or different and are more present Spii1 and Aii2 each independently .. )

(In the formula, R ⁱⁱ¹⁰ and R ⁱⁱ²¹ represent a hydrogen atom or a hydroxyl group, and ⁿⁱⁱ² , l, o and r independently represent 0 or 1, respectively.)
Further, the composition containing the compound represented by the general formula (I) is preferably further contained a hindered phenol-based compound. The hindered phenolic 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 more -CH _2- in the hydrocarbon is -O-, -CO- so that oxygen atoms are not directly adjacent to each other. , -COO-, -OCO- may be substituted.), 1,4-phenylene group, trans-1,4-cyclohexylene group, and the 1,4-phenylene group has an arbitrary hydrogen atom of fluorine. May be replaced by atoms
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- , 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, It represents a 4-phenylene group and a trans-1,4-cyclohexylene group, and the 1,4-phenylene group may have any hydrogen atom substituted with a fluorine atom, and l represents an integer of 2 to 6. )
Examples of the antioxidant represented by the general formula (H1) include the following general formula (H1-I).

(In the formula, M ^x is a hydrocarbon having 1 to 25 carbon atoms (one or more -CH _2- in the hydrocarbon is -O-, -CO- so that oxygen atoms are not directly adjacent to each other. , -COO-, may be substituted with -OCO-), where X is an alkylene group having 1 to 15 carbon atoms (one or two or more -CH _2- in the alkylene group is oxygen. It may be replaced with -O-, -CO-, -COO-, -OCO- so that the atoms are not directly adjacent to each other), -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-cyclohexylene group, and the 1,4-phenylene group has any hydrogen atom as a fluorine atom. , A, b, c, and d each independently represent 0 or 1, but a + b + c + d represents 2 or more).

M ^x is a hydrocarbon having 2 to 15 carbon atoms (one or more -CH _2- in the hydrocarbon is -O-, -CO-, -COO- so that oxygen atoms are not directly adjacent to each other. , -OCO- may be substituted), where X is an alkylene group having 2 to 15 carbon atoms (one or two or more -CH ₂ − in the alkylene group is directly adjacent to an oxygen atom. It may be substituted with -O-, -CO-, -COO-, -OCO- so as not to prevent), single bond, 1,4-phenylene group, trans-1,4-cyclohexylene group are preferable. , A + b + c + d is more preferably 2 to 4, and particularly preferably 2.

^{M x} in the general formula (HI) is more preferably an alkylene group having 1 to 15 carbon atoms, a large number of carbon atoms is preferable in consideration of volatility, and the carbon number is not too large in consideration of viscosity. Is preferable. From the above, M ^x is 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), ^RH21 represents a linear alkyl group or a branched alkyl group having 1 to 22 carbon atoms, and one or more -CH _2- in the alkyl group is an oxygen atom. May be replaced with -O-, -CH = CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O- or -OCF _{2- so that} ,
a ^H2 represents 0, 1 or 2,
M ^H21 is (a) trans-1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O- or -S- May be replaced with),
(B) A 1,4-phenylene group (one -CH = or two or more non-adjacent -CH = present in this group may be replaced with -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 above groups (a), (b) or group (c). The hydrogen atom may be substituted with a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, respectively. When a ^H2 represents 2 and ^{a plurality of MH21s} are present, the plurality of ^MH21s present are 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- or it represents a ^{-OCO-, if Z H21} represents ^{a H2} 2 there are a plurality, ^{Z H21} may be different even with the same presence of a plurality. )
Specifically, the compound represented by the general formula (H1) and the general formula (H2) is preferably represented by the general formula (H-1) to the general formula (H-4).

In the general formulas (H-1) to (H-4), ^RH1 is 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 an alkenyl group having 2 to 10 carbon atoms. 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 more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom, respectively. More specifically, it may be 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. It is preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
In the general formula (H-4), ^MH4 is an alkylene group having 1 to 15 carbon atoms (one or more -CH ₂ − in the alkylene group is-CH 2 − so that oxygen atoms are not directly adjacent to each other. It may be replaced with O-, -CO-, -COO-, -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, 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or trans-1,4-cyclohexylene group. It is expressed that it is preferably an alkylene group having 1 to 14 carbon atoms, and a large number of carbon atoms is preferable in consideration of volatility, but it is preferable that the number of carbon atoms is not too large in consideration of viscosity. The number of carbon atoms is more preferably 2 to 12, the number of carbon atoms is 3 to 10, the number of carbon atoms is 4 to 10, the number of carbon atoms is 5 to 10, and the number of carbon atoms is 6 to 10.
In the general formula (H-1) to the general formula (H-4), one in the 1,4-phenylene group or two or more non-adjacent -CH = may be replaced by -N =. Further, the hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.
In the general formula (H-1) to the general formula (H-4), one in the 1,4-cyclohexylene group or two or more non-adjacent −CH ₂ − are replaced by −O− or −S−. It may have been done. Further, the hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.
More specifically, for example, formulas (H-11) to formulas (H-15) can be mentioned.

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 0.001% as the lower limit value with respect to the total mass of the composition. It is preferably contained in an amount of 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. It is preferably contained, preferably 0.02% or more, preferably 0.03% or more, preferably 0.04% or more, and preferably 0.05% or more. It is preferably contained in an amount of 0.06% or more, preferably 0.07% or more, preferably 0.08% or more, preferably 0.09% or more, and 0.10% or more. It is preferable to contain 0.11% or more, preferably 0.12% or more, preferably 0.13% or more, preferably 0.14% or more, and 0. .15% or more is preferable, 0.20% or more is preferably contained, 0.25% or more is preferably contained, 0.30% or more is preferably contained, and 0.35% or more is contained. It is preferably contained in an amount of 0.40% or more, preferably 0.50% or more, and preferably 1% or more. Further, as an upper limit value, it is preferably contained in an amount of 5% or less, preferably 3% or less, preferably 2% or less, preferably 1.5% or less, and preferably 1% or less. Preferably, it is preferably contained in an amount of 0.9% or less, preferably 0.8% or less, preferably 0.7% or less, preferably 0.6% or less, and preferably 0.5%. It is preferably contained below, preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, and preferably 0.3% or less. , 0.25% or less, preferably 0.2% or less, preferably 0.15% or less, preferably 0.1% or less, 0.07% or less. It is preferably contained, preferably 0.05% or less, and preferably 0.03% or less.

More specifically, the content is preferably 0.01 to 2% by mass, preferably 0.01 to 1% by mass, further preferably 0.01 to 0.2% by mass, and 0. It is particularly preferably 01 to 0.15% by mass. More specifically, when the suppression of precipitation at low temperature is emphasized, the content thereof is preferably 0.01 to 0.1% by mass.

In the liquid crystal composition of the present invention, the total content 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). The ratio to the total amount of is preferably in the range of 1: 100 to 10000: 1, more preferably in the range of 1: 10 to 1000: 1, and 1: 1 to 1: 500. : 1 to 1: 100 is preferable.

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

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. “%” In the compositions of the following Examples and Comparative Examples means “% by mass”. Compound purity was analyzed by GC or UPLC. Abbreviations for 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)) Under a nitrogen atmosphere, metallic magnesium (75 g) and THF (40 ml) were added to a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and the compound (S) was added thereto. A solution of −I-1) in THF (260 ml) was slowly added dropwise, and then the mixture was stirred for 1 hour so as not to exceed 30 ° C. Then, DMF was slowly added dropwise so that the internal temperature did not exceed 40 ° C., and the mixture was further stirred at 30 ° C. or lower for 1 hour. While cooling in an ice bath, add 10% hydrochloric acid (420 ml), separate the organic layer and the aqueous layer, extract from the aqueous layer with toluene (200 ml), combine the organic layers, and wash this with saturated saline (400 ml). Then, it was dried with 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)) Compound (S-2-1) (20 g) and 3-benzyl-5- (20 g) were placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube under a nitrogen atmosphere. A solution of 2-hydroxyethyl) -4-methylthiazolium chloride (1.8 g) in ethanol (90 ml) was added, and the mixture was stirred at room temperature, and triethylamine (5.6 ml) was added thereto. Then, the mixture was stirred under heating under reflux for 7 hours, cooled to room temperature, and then water (200 ml) and ethyl acetate (200 ml) were slowly added. The organic layer and the aqueous layer were separated, extracted from the obtained aqueous layer 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. However, 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, in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, THF (80 ml) / methanol of compound (S-3-1) (19 g) ( 20 ml) The solution was added and stirred under ice-cooling. Sodium borohydride (1.5 g) was slowly added thereto while paying attention to the generation of hydrogen, and the mixture was further stirred for 1 hour. Slowly add saturated aqueous ammonium chloride solution (100 ml), separate the organic layer and the aqueous layer, extract from the obtained aqueous layer with hexane (80 ml) / THF (80 ml), combine the organic layers, and use saturated brine (200 ml). The mixture was washed, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and toluene (20 ml) / hexane (20 ml) was added to the obtained residue, washed in a suspended state, and collected by filtration. -1-1) (11 g) was obtained.
GC-MS: m / z 298.19 [M ⁺ ]
(Examples 2 to 135)
Examples 2 (Compound (I-2-1)) to Example 135 (Compound (I-105-3)) using the same reaction 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)) Compound (S-4-1) (14 g) and tetrakistriphenylphosphine palladium (0) were placed in a reaction vessel equipped with a stirrer, a thermometer and a cooling tube under a nitrogen atmosphere. ) (1.3 g,), copper (I) iodide (0.44 g) and triethylamine (40 ml) in DMF (80 ml) are added, and the mixture is stirred at 75 ° C., wherein compound (S-5-1) is added. The DMF (40 ml) solution of No. 1 was slowly added dropwise, and then the mixture was stirred for 1 hour so as not to exceed 75 ° C. After cooling to room temperature, water (80 ml) and toluene (80 ml) are added, the organic layer and the aqueous layer are separated, extracted from the aqueous layer with toluene (40 ml), the organic layers are combined, and this is saturated saline (saturated saline solution). After washing twice with 80 ml), it was dried over anhydrous sodium sulfate. The obtained solution was concentrated under reduced pressure, dissolved in hexane (80 ml) / toluene (50 ml), passed through a silica gel column (filled with 15 g of silica gel), and then 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)) Compound (S-6-1) (16 g) and palladium (II) acetate (II) (1. A solution of 2 g) and copper (II) bromide (1.2 g) in dimethyl sulfoxide (120 ml) was added, and the mixture was stirred at 120 ° C. for 6 hours. After cooling to room temperature, water (200 ml) and ethyl acetate (200 ml) were added slowly. The organic layer and the aqueous layer were separated, extracted from the obtained aqueous layer 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. However, a brown oily compound (S-7-1) (12 g) was obtained.

(Production of Compound (I-111-5)) Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, THF (80 ml) / methanol of compound (S-7-1) (12 g) ( 20 ml) The solution was added and stirred under ice-cooling. Sodium borohydride (2.2 g) was slowly added thereto while paying attention to the generation of hydrogen, and the mixture was further stirred for 1 hour. Slowly add saturated aqueous ammonium chloride solution (100 ml), separate the organic layer and the aqueous layer, extract from the obtained aqueous layer with hexane (80 ml) / THF (80 ml), combine the organic layers, and use saturated brine (200 ml). The mixture was washed, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and toluene (20 ml) / hexane (20 ml) was added to the obtained residue, washed in a suspended state, and collected by filtration. −111-5) (7.3 g) was obtained.
GC-MS: m / z 301.17 [M-18 ⁺ ]
(Examples 137 to 247)
Examples 137 (Compound (I-110-1)) to Example 247 (Compound (I-145-3)) using the same reaction as in Example 136 and, if necessary, a method according to a known method. ) Was manufactured.

The measured characteristics of the liquid crystal composition containing any of the compounds obtained in Examples 1 to 247 are as follows.

VHR: The voltage holding ratio (%) at 333K was evaluated on a three-point scale 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-resistant VHR: The liquid crystal composition is irradiated with ^{ultraviolet rays at 180 J / m 2} using an ultra-high pressure mercury lamp through a glass having a thickness of 0.5 mm. The voltage retention of the liquid crystal after irradiation with ultraviolet rays is measured by the same method as the above-mentioned VHR measurement. However, the irradiation intensity was 0.1 W / m ^{2 at} 366 nm. The evaluation was performed in the following three stages.

A: 90% or more to 100%
B: 75% or more and less than 90% C: less than 75% Compatibility: Visually evaluate the state of dissolution when 500 ppm of any of the compounds obtained in Examples 1 to 247 is added to the liquid crystal composition in three stages. bottom.

A: All dissolved B: Slightly not dissolved and separated C: Partially not dissolved and separated Storage stability: The liquid crystal composition is stored at -20 ° C for 1 week, and the presence or absence of precipitates is visually observed. Was evaluated on a three-point scale.

A: No precipitate B: Slightly cloudy 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 parent liquid crystal display (H), 500 ppm of the compound (I-1-1) obtained in Example 1 was added.
The measured characteristics of the composition examples in the examples are as follows.

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

(Comparative Example 1)
As a comparative example, the results of measuring the characteristics of the parent liquid crystal display (H) without adding any further compound are as follows.

VHR: A
Lightproof 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 results of the measurement obtained by adding 500 ppm of the compound (R-1) to the parent liquid crystal display (H) are as follows.

VHR: A
Lightproof VHR: A
Compatibility: B
Storage stability: C
(Comparative Examples 3 and 4)
Hereinafter, the results of the measurements of 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 by light.

Claims (7)

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 I ²⁵ are independent hydrogen atoms, halogen atoms, hydroxyl groups, cyano groups, chlorine. Atomic, 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 independently -O-, -S-, -CO-, and-, respectively. 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- , Transformers 1, 4 It may be substituted with a-cyclohexylene group, 1,4-phenylene group or naphthalene-2,6-diyl group, and one or more hydrogen atoms in the alkyl group are independently halogen atoms or cyano groups, respectively. in may be ^{substituted, R I11, R I12, R} I13, R I14, R I15, R I21, R I22, R I23, all ^{R I24} and ^{R I25} is never represents a hydrogen atom.)
An additive for a liquid crystal composition having a compound represented by. In the general formula ^(I), the liquid crystal composition according to claim ^{1, 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} represent the same group, respectively Additives for products. In the general formula ^(I), the ^{R I11} and ^{R I21, R I12} and ^{R I22, R I13} and ^{R I23, R I14} and any one or more sets are different groups selected from ^{R I24} and ^{R I15} and ^{R I25} The additive for a liquid crystal composition according to claim 1. 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 a liquid crystal composition 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 a liquid crystal composition according to any one of claims 1 to 4, which represents an alkyl group having 4 to 20 atoms. In the general formula ^{(I), R I11, R} I12, R I13, R I14, R I15, R I21, R I22, 1 , or two or more groups selected from R ^{I23, R I24} and ^{R I25} is, The liquid crystal composition according to any one of claims 1 to 5, 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 for. Two or more groups selected from R ^I11 , R ^I12 , R ^I13 , R I ¹⁴ and R I ¹⁵ represent halogen atoms, cyano atoms or alkyl groups with 1 to 20 carbon atoms and / or R ^I21 , ^{R I22,} R I23, R ^I24 and two or more groups halogen atoms selected from ^{R I25,} according to any one of claims 1 to 6, a cyano group or an alkyl group having 1 to 20 carbon atoms Additives for liquid crystal compositions.