CN112080290A - Liquid crystal composition containing polymerizable compound and liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a polymerizable compound-containing liquid crystal composition capable of rapidly and sufficiently polymerizing, tilting by weak or low UV light, and realizing high tilt stability, and a liquid crystal display element using the same. The solution is as follows: the present invention provides a polymerizable compound-containing liquid crystal composition containing one or more compounds represented by the general formula (i) and one or more polymerizable compounds, and a polymerizable compound-containing liquid crystal composition using A liquid crystal display element of the polymerizable compound-containing liquid crystal composition. [hua 1]

Description

Polymerizable compound-containing liquid crystal composition and liquid crystal display element

technical field

The present invention relates to a liquid crystal composition containing a polymerizable compound and a liquid crystal display element using the same. In addition, in this specification, the liquid crystal composition containing a polymerizable compound is called the liquid crystal composition containing a polymerizable compound. In addition, the polymerizable compound refers to a compound having a polymerizable group.

Background technique

PSA (Polymer Sustained Alignment, polymer stabilized alignment) type liquid crystal display element has a structure in which a polymer structure is formed in the cell to control the pretilt angle of liquid crystal molecules. Because of its high-speed response and high contrast, it is gradually used as a liquid crystal display components are put into practical use.

A PSA-type liquid crystal display element is produced by injecting a liquid crystal composition containing a polymerizable compound between substrates, irradiating UV light with a voltage applied to align the liquid crystal molecules to polymerize the polymerizable compound, and fixing the alignment of the liquid crystal molecules.

In recent years, highly fine pixels are required in PSA type liquid crystal display elements such as 4K and 8K. Therefore, by increasing the area of the wiring and the light-shielding portion, a considerable amount of UV light is filtered out, and in the same UV irradiation process as the conventional one, the formation of inclination becomes insufficient, and the polymerizable compound becomes insufficient. Polymerization, a large amount of polymerizable compound remains, etc. In addition, from this, deterioration in response speed, image sticking due to deterioration in orientation, and display failures such as screen burn-in (IS) caused by the gradual polymerization of the remaining polymerizable compound and the change in inclination during driving were confirmed.

From the above, a liquid crystal composition that can be stably produced by UV light that is weaker or less than conventional is required for a high-definition PSA-type liquid crystal display element.

As a method based on a liquid crystal composition for polymerizing a liquid crystal composition containing a polymerizable compound using weaker or less UV light than in the past, Patent Document 1 and Patent Document 2 introduce A technique for shortening the polymerization reaction rate by using a liquid crystal compound of a furan skeleton.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2009/050869

Patent Document 2: Japanese Patent Laid-Open No. 2016-132779

SUMMARY OF THE INVENTION

The problem to be solved by the invention

As described above, in recent years, high-definition PSA-type liquid crystal display elements have been demanded for polymerizable compound-containing liquid crystal compositions that can be stably produced using UV light that is weaker or less than conventional ones. However, the polymerizable compound-containing liquid crystal compositions described in Patent Document 1 and Patent Document 2, which contain a liquid crystal compound having a terphenyl skeleton and a dibenzofuran skeleton, have a sufficient polymerization rate, but are not sufficiently inclined to form a slope. Stability is not high enough. Therefore, there is a need to improve the properties of the polymerizable compound-containing liquid crystal composition.

The problem to be solved by the present invention is to provide a polymerizable compound-containing liquid crystal composition that can be rapidly and sufficiently polymerized, can be tilted by weak or small UV light, and can realize high tilt stability, and a liquid crystal display element using the same .

Means for solving problems

As a result of intensive research on the above-mentioned problems, the present inventors found that the above-mentioned problems can be solved by a polymerizable compound-containing liquid crystal composition comprising a liquid crystal compound having a specific structure and a polymerizable compound, and completed the present invention.

That is, the present invention provides a polymerizable compound-containing liquid crystal composition containing one or more of the compounds represented by the general formula (i) and one or more of the polymerizable compounds.

[hua 1]

(in the formula, X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group or a trifluoromethoxy group,

Y ⁱ¹ and Y ⁱ² each independently represent -O-, -CF ₂ -, -CO- or -CX ⁱ³ X ⁱ⁴ -, any one or more of Y ⁱ¹ and Y ⁱ² represents -O-, and X ⁱ³ and X ⁱ⁴ respectively independently represents the same meaning as X ⁱ¹ ,

L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or a general the group represented by the formula (L ⁱ -1),

[hua 2]

(wherein, R ⁱ¹ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms base,

A ⁱ¹ represents a group selected from the group consisting of,

(a) 1,4-cyclohexylene group (One -CH ₂ - or two or more non-adjacent -CH ₂ - present in this group may be substituted with -O- or -S-.)

(b) 1,4-phenylene (1 -CH= present in the group or 2 or more non-adjacent -CH= may be substituted by -N=, 1 hydrogen present in the group Atoms may be replaced by fluorine atoms.)

(c) 1,4-cyclohexenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl groups (the hydrogen atoms present in these groups may be replaced by fluorine atoms, and in addition, one of the naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups -CH= or two or more non-adjacent -CH= may be replaced by -N=.)

Z ⁱ¹ represents -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH= CH-, -CF=CF-, -C≡C- or single bond,

When n ⁱ¹ represents 1 or 2, and n ⁱ¹ represents 2, and there are a plurality of A ⁱ¹ and Z ⁱ¹ , they may be the same or different. )

W ⁱ¹ represents a group represented by the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3),

[hua 3]

(wherein, the black dot (·) represents the point of attachment to ^{Li2 or Y i2 ,} * represents the point of attachment to the carbon atom adjacent to the carbon atom to which ^Li5 is attached, and L ⁱ⁶ , L ⁱ⁷ and L ⁱ⁸ are each independently Indicates the same meaning as ^Li1 .)

W ⁱ² for single key or -CL ⁱ⁹ L ⁱ¹⁰ -,

(L ⁱ⁹ and L ⁱ¹⁰ each independently represent the same meaning as L ⁱ¹ .)

One -CH ₂ - or two or more non-adjacent -CH ₂ - present in L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ may be Substituted by -C≡C-, -O-, -COO-, -OCO- or -CO-, in addition, the hydrogen atom present in the alkyl or alkenyl group may be replaced by a fluorine atom. )

In addition, the present invention provides a liquid crystal display element, a liquid crystal display element for active matrix driving, a liquid crystal display element for a PSA mode, a PSVA mode, a PS-IPS mode or a PS-FFS mode using a polymerizable compound-containing liquid crystal composition, the The polymerizable compound-containing liquid crystal composition contains one or more of the compounds represented by the general formula (i) and one or more of the polymerizable compounds.

Invention effect

According to the polymerizable compound-containing liquid crystal composition of the present invention, rapid and sufficient polymerization can be achieved, tilt can be formed with weak or small UV light, and high tilt stability can be realized. In addition, in the liquid crystal display element using the polymerizable compound-containing liquid crystal composition of the present invention, the residual amount of the unreacted polymerizable compound is small, the tilt can be formed by weak or small UV light, and the high-speed responsiveness and high With respect to tilt stability, display defects such as poor orientation and burn-in caused by changes in pretilt angle do not occur or are suppressed, and excellent display quality can be exhibited.

Detailed ways

Hereinafter, the polymerizable compound-containing liquid crystal composition of the present invention and a liquid crystal display element using the same will be described in detail. In addition, the compound represented by general formula (i) may be called the compound of general formula (i) or compound (i). The same applies to other compounds.

A. Liquid crystal composition containing polymerizable compound

The polymerizable compound-containing liquid crystal composition of the present invention contains one or more of the compounds represented by the general formula (i) and one or more of the polymerizable compounds.

[hua 4]

(in the formula, X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group or a trifluoromethoxy group,

Y ⁱ¹ and Y ⁱ² each independently represent -O-, -CF ₂ -, -CO- or -CX ⁱ³ X ⁱ⁴ -, any one or more of Y ⁱ¹ and Y ⁱ² represents -O-, and X ⁱ³ and X ⁱ⁴ respectively independently represents the same meaning as X ⁱ¹ ,

L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or a general the group represented by the formula (L ⁱ -1),

[hua 5]

(wherein, R ⁱ¹ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms base,

A ⁱ¹ represents a group selected from the group consisting of,

(a) 1,4-cyclohexylene group (One -CH ₂ - or two or more non-adjacent -CH ₂ - present in this group may be substituted with -O- or -S-.)

(b) 1,4-phenylene (1 -CH= present in the group or 2 or more non-adjacent -CH= may be substituted by -N=, 1 hydrogen present in the group Atoms may be replaced by fluorine atoms.)

(c) 1,4-cyclohexenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl groups (the hydrogen atoms present in these groups may be replaced by fluorine atoms, and in addition, one of the naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups -CH= or two or more non-adjacent -CH= may be replaced by -N=.)

Z ⁱ¹ represents -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH= CH-, -CF=CF-, -C≡C- or single bond,

When n ⁱ¹ represents 1 or 2, and n ⁱ¹ represents 2, and there are a plurality of A ⁱ¹ and Z ⁱ¹ , they may be the same or different. )

W ⁱ¹ represents a group represented by the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3),

[hua 6]

(wherein, the black dot (·) represents the point of attachment to ^{Li2 or Y i2 ,} * represents the point of attachment to the carbon atom adjacent to the carbon atom to which ^Li5 is attached, and L ⁱ⁶ , L ⁱ⁷ and L ⁱ⁸ are each independently Indicates the same meaning as ^Li1 .)

W ⁱ² represents a single bond or -CL ⁱ⁹ L ⁱ¹⁰ - (L ⁱ⁹ and L ⁱ¹⁰ independently represent the same meaning as L ⁱ¹ .),

One -CH ₂ - or two or more non-adjacent -CH ₂ - present in L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ may be Substituted by -C≡C-, -O-, -COO-, -OCO- or -CO-, in addition, the hydrogen atom present in the alkyl or alkenyl group may be replaced by a fluorine atom. )

According to the polymerizable compound-containing liquid crystal composition of the present invention, the liquid crystal composition containing the compound represented by the general formula (i) and the polymerizable compound can be rapidly and sufficiently polymerized, and can be formed by weak or low UV light Tilt, high tilt stability can be achieved. Therefore, the polymerizable compound-containing liquid crystal composition of the present invention can produce a liquid crystal display that has a small residual amount of unreacted polymerizable compounds, can form tilt by weak or small UV light, and achieves both high-speed responsiveness and high tilt stability. element. In addition, according to the polymerizable compound-containing liquid crystal composition of the present invention, a liquid crystal display element that exhibits excellent display quality without occurrence or suppression of display defects such as poor orientation and burn-in due to changes in pretilt angle can be produced.

Among them, in the production of high-definition PSA-type liquid crystal display elements such as 4K and 8K, when the UV irradiation time is prolonged, the production efficiency is remarkably deteriorated. On the other hand, according to the polymerizable compound-containing liquid crystal composition of the present invention, high-definition PSA-type liquid crystal display elements such as 4K and 8K can be produced in a short UV irradiation time, and therefore the industrial utility value is very high.

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

[1] The compound represented by the general formula (i)

In the general formula (i), at least one of X ⁱ¹ and X ⁱ² preferably represents a hydrogen atom or a fluorine atom, and it is particularly preferable that at least one is a fluorine atom. Specifically, in the case of increasing the absolute value (|Δε|) of the dielectric constant anisotropy (Δε) at 20° C., it is preferable that both X ⁱ¹ and X ⁱ² are fluorine atoms, and when the reliability is emphasized, Both X ⁱ¹ and X ⁱ² are preferably hydrogen atoms.

At least one of Y ⁱ¹ and Y ⁱ² is -O-, especially preferably one is -O- and the other is -CH ₂ - or both are -O-. When emphasis is placed on large |Δε|, polymerization rate and formation of inclination, Both Y ⁱ¹ and Y ⁱ² are preferably -O-.

L ⁱ¹ and L ⁱ² preferably each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and in order to reduce the rotational viscosity (γ ₁ ), they preferably have 1 to 8 carbon atoms. The alkyl group or the alkenyl group having 2 to 8 carbon atoms is particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. In addition, it is preferably linear. The hydrogen atoms present in L ⁱ¹ and L ⁱ² may be substituted by fluorine atoms, but are preferably not substituted by fluorine atoms.

In addition, in order to improve the miscibility with other liquid crystal components, it is preferable that L ⁱ¹ and L ⁱ² are different. Preferably, either one of L ⁱ¹ and L ⁱ² is an alkoxy group or an alkenyloxy group, more preferably L ⁱ¹ is an alkoxy group or an alkenyloxy group, further preferably L ⁱ¹ is an alkoxy group, particularly preferably L ⁱ¹ is an ethoxy group, propoxy or butoxy. This is because when L ⁱ¹ is an alkoxy group, in addition to the miscibility with the other liquid crystal components described above, |Δε| can be more easily obtained, inclination can be easily formed in a short time, and the polymerization speed can be increased. Effect.

In addition, in order to improve the miscibility with other liquid crystal components, L ⁱ² is preferably an alkyl group, more preferably an ethyl group, a propyl group or a butyl group, and still more preferably a propyl group or a butyl group. In particular, in order to improve γ1 of the liquid crystal composition, L ⁱ² is preferably a butyl group.

In addition, L ⁱ¹ and L ⁱ² preferably represent the following formulae.

[hua 7]

R ⁱ¹ is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkyl group having 2 to 5 carbon atoms in order to reduce γ ₁ . alkenyl. In addition, it is preferably linear. In order to increase |Δε|, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms or an alkoxy group having 2 to 2 carbon atoms is particularly preferable. 5 of the alkenyloxy. When a plurality of R ⁱ¹ are present, in order to improve the miscibility with other liquid crystal components, R ⁱ¹ is preferably different from each other, and any of the plurality of R ⁱ¹ present is preferably an alkoxy group or an alkenyloxy group, and it is particularly preferable that one of the R ⁱ¹ is present. R ⁱ¹ is an alkoxy group or an alkenyloxy group. The hydrogen atoms present in R ⁱ¹ may be substituted by fluorine atoms, but are preferably not substituted by fluorine atoms.

A ⁱ¹ preferably represents a group selected from the group consisting of the following.

[hua 8]

Specifically, A ¹ is preferably trans-1,4-cyclohexylene, unsubstituted 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3 in order to reduce γ ₁ . -Fluoro-1,4-phenylene, particularly preferably trans-1,4-cyclohexylene. In order to improve the miscibility with other liquid crystal components, trans-1,4-cyclohexylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene is preferable. In order to increase the nematic phase-isotropic liquid phase transition temperature (T _ni ), unsubstituted 1,4-phenylene, unsubstituted 1,4-cyclohexylene, and 1,4-cyclohexene are preferred or unsubstituted naphthalene-2,6-diyl. In order to exhibit a large negative Δε, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene are preferred. The total number of fluorine atoms present in A ⁱ¹ is preferably 1 to 4, and particularly preferably 1 to 3, in order to exhibit a large negative Δε while taking into account the miscibility with other liquid crystal components.

Z ⁱ¹ is preferably a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ - in order to reduce γ ₁ , and more preferably a single bond or -CH ₂ CH ₂ -. Z ⁱ¹ is preferably a single bond, -COO-, -OCO-, -CH=CH- or -C≡C- in order to increase T _ni , and more preferably a single bond, -CH=CH- or -C≡C -. In order to improve the miscibility with other liquid crystal components, a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ - is preferable. In order to improve the long-term reliability when forming a liquid crystal display element, a single bond is preferable.

When n ⁱ¹ represents 2, it is preferable that any one or more of Z ⁱ¹ present in a plurality represents a single bond. It is preferable that n ⁱ¹ be 1 when γ ₁ is emphasized. When T _ni is important, 2 is preferable.

W ⁱ¹ is preferably the general formula (W ⁱ¹ -1) or (W ⁱ¹ -3).

W ⁱ² is preferably a single bond.

L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ preferably each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, more preferably a hydrogen atom.

L ⁱ⁶ and L ⁱ⁷ preferably each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, preferably a hydrogen atom.

L ⁱ⁸ preferably represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms, preferably A hydrogen atom.

It is preferable that at least one of L ⁱ⁹ and L ⁱ¹⁰ represents a hydrogen atom, and it is more preferable that both L ⁱ⁹ and L ⁱ¹⁰ represent a hydrogen atom.

In addition, in the compound represented by general formula (i), the structure in which heteroatoms are connected directly is not formed.

Among the compounds represented by the general formula (i), the compounds represented by the following general formulae (i-1) to (i-48) are preferable. Among them, particularly preferred compounds are compounds represented by general formulae (i-1) to (i-12), compounds represented by general formulae (i-1) to (i-4), and compounds represented by general formula (i-1) ) and the compounds represented by (i-3) are compounds represented by the general formula (i-1).

[Chemical 9]

(In the formula, R ⁱ² and R ⁱ³ have the same meanings as R ⁱ¹ in the general formula (i).)

[Chemical 10]

(In the formula, R ⁱ² and R ⁱ³ have the same meanings as R ⁱ¹ in the general formula (i).)

[Chemical 11]

(In the formula, R ⁱ² and R ⁱ³ have the same meanings as R ⁱ¹ in the general formula (i).)

[Chemical 12]

(In the formula, R ⁱ² and R ⁱ³ have the same meanings as R ⁱ¹ in the general formula (i).)

The lower limit of the content of the compound of the general formula (i) in the polymerizable compound-containing liquid crystal composition of the present invention is preferably 0.1% by mass, preferably 0.2% by mass, preferably 0.3% by mass, preferably 0.5% by mass The mass % is preferably 1 mass %, preferably 2 mass %, preferably 3 mass %, and preferably 4 mass %. The upper limit of the content of the compound of the general formula (i) is preferably 20% by mass, preferably 15% by mass, preferably 13% by mass, preferably 10% by mass, preferably 9% by mass, and preferably It is 7 mass %, Preferably it is 5 mass %. As content range of the compound of general formula (i), 0.1-25 mass % is preferable, 0.1-20 mass % is more preferable, 0.1-15 mass % is further more preferable, 0.5-10 mass % is especially preferable. Hereinafter, mass % is described as %.

The content of the compound of the general formula (i) is preferably set to be small when emphasis is placed on reliability, and is preferably set to be high when emphasis is placed on the reaction rate of the polymerizable compound and the formation of inclination.

[2] Polymeric compound

The polymerizable compound-containing liquid crystal composition of the present invention contains one or two or more types of polymerizable compounds. As a polymerizable compound, the compound represented by general formula (P) is preferable.

[Chemical 13]

(In the above general formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or -Sp ^p2 -P ^p2 , and one of the alkyl groups or non-adjacent 2 More than one -CH ₂ - may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, one or two of the alkyl groups The above hydrogen atoms may be independently substituted by cyano, fluorine or chlorine atoms,

P ^p1 and P ^p2 each independently represent any one of the general formulae (P ^p1 -1) to (P ^p1 -9),

[Chemical 14]

(wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and W ^p11 represents a single bond, -O-, -COO-, In the alkylene group having 1 to 5 carbon atoms, t ^p11 represents 0, 1 or 2, and when a plurality of R ^p11 , R ^p12 , W ^p11 and/or t ^p11 are present in the molecule, they may be the same or different.)

Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer, respectively,

Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO- , -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CO-NR ^ZP1 -, -NR ^ZP1 -CO-, -SCH ₂ -, -CH ₂ S-, - CH=CR ^ZP1 -COO-,-CH=CR ^ZP1 -OCO-,-COO-CR ^ZP1 =CH-,-OCO-CR ^ZP1 =CH-,-COO-CR ^ZP1 =CH-COO-,-COO-CR ^ZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) _z -COO-, -(CH ₂ ) _z -OCO-, - OCO-(CH ₂ ) _z -, -(C=O)-O-(CH ₂ ) _z -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, - CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - or -C≡C- (wherein, z independently represent An integer of 1 to 4, R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple R ^ZP1 in the molecule, they may be the same or different. It should be noted that * in the formula Indicates the point of attachment to Sp ^p1 or Sp ^p2 .),

A ^p1 and A ^p2 each independently represent a group selected from the group consisting of,

(a ^p ) 1,4-cyclohexylene group (One -CH ₂ - or two or more non-adjacent -CH ₂ - present in this group may be substituted with -O-.)

(b ^p ) 1,4-phenylene (1 -CH= or non-adjacent 2 or more -CH= present in this group may be substituted by -N=.) and

(c ^p ) naphthalenediyl, 1,2,3,4-tetrahydronaphthalenediyl, decahydronaphthalenediyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl (among these groups Existing 1 -CH= or non-adjacent 2 or more -CH= may be replaced by -N=.)

A ^p3 represents a group selected from the group consisting of the above-mentioned group (a ^p ), group (b ^p ) and group (c ^p ), and a single bond,

In the above-mentioned group ( ^ap ), group ( ^bp ) and group ( ^cp ), the hydrogen atom present in the group can be independently replaced by a cyano group, a halogen atom, a group having 1 to 8 carbon atoms. Alkyl, alkoxy with 1 to 8 carbon atoms, alkenyl with 1 to 8 carbon atoms, or -Sp ^p2 -P ^p2 substituted,

m ^p1 represents 0, 1, 2 or 3, and when there are multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they may be the same or different,

When m ^p1 is 0 and A ^p1 is a group other than naphthalenediyl, phenanthrene-2,7-diyl, and anthracene-2,6-diyl, A ^p3 represents a group other than a single bond. )

In the above general formula (P), R ^p1 is preferably -Sp ^p2 -P ^p2 .

P ^p1 and P ^p2 are each independently preferably any one of the above-mentioned general formula (P ^p1 -1) to (P ^p1 -3), and preferably the above-mentioned general formula (P ^p1 -1).

R ^p11 and R ^p12 are each independently preferably a hydrogen atom or a methyl group.

t ^p11 is preferably 0 or 1.

W ^p11 is preferably a single bond or an alkylene group having 1 to 5 carbon atoms. As the above-mentioned alkylene group having 1 to 5 carbon atoms, a methylene group or an ethylene group is preferable.

m ^p1 is preferably 0, 1 or 2, preferably 0 or 1.

Z ^p1 and Z ^p2 are preferably each independently a single bond, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -CF ₂ -, -CF ₂ O-, -(CH ₂ ) _z -COO-, -(CH ₂ ) _z -OCO-, -OCO-(CH ₂ ) _z -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) _z -, -OCF ₂ - or -C≡C-, preferably single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, - OCO-(CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ - or -C≡C-, preferably present in Only 1 in the molecule is -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, - CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ - or -C≡C- and others are single bonds, preferably only One is -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO- or -OCO- and the others are all single bonds, preferably all are single bonds.

In addition, it is preferable that only one of Z ^p1 and Z ^p2 existing in the molecule is selected from the group consisting of -CH=CH-COO-, -COO-CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -O-CO-(CH ₂ ) ₂ -, -COO-(CH ₂ ) ₂ - is a linking group and the others are single bonds.

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer, and the spacer is preferably an alkylene group having 1 to 30 carbon atoms, and -CH ₂ - in the alkylene group may not directly connect oxygen atoms to each other. Substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C-, the hydrogen atom in the alkylene group may be replaced by a halogen atom. Among these, Sp ^p1 and Sp ^p2 are each independently preferably a linear alkylene group having 1 to 10 carbon atoms or a single bond, more preferably a single bond.

In the general formula (P), the total number of -Sp ^p1 -P ^p1 and Sp ^p2 -P ^p2 is preferably 2 or more, preferably 2 to 4, and preferably 2 to 3.

A ^p1 and A ^p2 each independently represent a group selected from the group consisting of the following.

(a ^p ) 1,4-cyclohexylene group (One -CH ₂ - or two or more non-adjacent -CH ₂ - present in this group may be substituted with -O-.)

(b ^p ) 1,4-phenylene (1 -CH= or non-adjacent 2 or more -CH= present in this group may be substituted by -N=.) and

(c ^p ) naphthalenediyl, 1,2,3,4-tetrahydronaphthalenediyl, decahydronaphthalenediyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl (among these groups Existing 1 -CH= or non-adjacent 2 or more -CH= may be replaced by -N=.)

In addition, A ^p3 represents a group selected from the group consisting of the above-mentioned group ( ^ap ), group ( ^bp ), and group ( ^cp ), and a single bond.

Here, the naphthalenediyl group and the 1,2,3,4-tetrahydronaphthalene diyl group that can be adopted by A ^p1 , A ^p2 and A ^p3 are groups connected at two positions selected from the 1-8 positions. Specifically, with regard to naphthalenediyl and 1,2,3,4-tetrahydronaphthalenediyl, in the case of A ^p1 , one of two positions selected from the 1 to 8 positions and Sp ^p1 A group connected to Z ^p1 or Z ^p2 at the other place, in the case of A ^p2 , is connected to Z ^p1 at one of two positions selected from the 1st to 8th positions, and at the other place A group linked to Z ^p1 or Z ^p2 at one position, in the case of A ^p3 , is linked to Z ^p2 at one of two positions selected from positions 1 to 8, and is linked to R ^p1 at the other position linked group.

In addition, the decahydronaphthalenediyl group that can be used for A ^p1 , A ^p2 and A ^p3 is a group connected at two positions selected from the 1-10 positions. Specifically, in the case of A ^p1 , the decahydronaphthalene diyl group is connected to Sp ^p1 at one of two positions selected from positions 1 to 10, and is connected to Z ^p1 or Z at the other position. The group to which ^p2 is linked, in the case of A ^p2 , is a group linked to Z ^p1 at one of two positions selected from positions 1 to 10, and linked to Z ^p1 or Z ^p2 at the other. , in the case of A ^p3 , is a group connected to Z ^p2 at one of two positions selected from positions 1 to 10, and a group connected to R ^p1 at the other position.

As a naphthalene diyl group, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl are mentioned, for example Diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl and the like. Among them, naphthalene-2,6-diyl is preferable.

As the 1,2,3,4-tetrahydronaphthalene diyl group, for example, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-1 , 4-diyl, 1,2,3,4-tetrahydronaphthalene-1,5-diyl, etc. Among them, 1,2,3,4-tetrahydronaphthalene-2,6-diyl is preferable.

As the decahydronaphthalene diyl group, decalin-2,6-diyl is preferable.

A ^p1 , A ^p2 and A ^p3 are each independently preferably 1,4-phenylene or 1,4-cyclohexylene, and from the viewpoint of reactivity, 1,4-phenylene is preferable. Regarding the 1,4-phenylene group, in order to improve compatibility with the liquid crystal compound, it is preferable that at least one hydrogen atom present in the 1,4-phenylene group be replaced by a fluorine atom, an alkyl group having 1 to 8 carbon atoms, or a carbon atom. The alkoxy group having 1 to 8 carbon atoms is substituted, and among these, it is preferably substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. This is because the residual amount of the polymerizable compound after UV light irradiation can be reduced by substituting at least one hydrogen atom present in the 1,4-phenylene group with these groups. When at least one hydrogen atom present in the 1,4-phenylene group is substituted with an alkoxy group having 1 to 8 carbon atoms, the above-described effects are more likely to be exhibited, which is particularly preferable. As an alkyl group, a methyl group is mentioned preferably, for example, As an alkoxy group, a methoxy group is mentioned preferably, for example.

When m ^p1 is 0 and A ^p1 is naphthalenediyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, A ^p3 may represent a single bond.

When m ^p1 is 0 and A ^p1 is a group other than naphthalenediyl, phenanthrene-2,7-diyl, and anthracene-2,6-diyl, A ^p3 represents a group other than a single bond, that is, a group selected from A group in the group consisting of the above-mentioned group ( ^ap ), group ( ^bp ) and group ( ^cp ).

The total content of the compounds represented by the general formula (P) is preferably in the range of 0.05 to 10%, and preferably in the range of 0.1 to 8% with respect to the total amount of the polymerizable compound-containing liquid crystal composition of the present invention. , preferably in the range of 0.1 to 5%, preferably in the range of 0.1 to 3%, preferably in the range of 0.2 to 2%, preferably in the range of 0.2 to 1.3%, preferably in the range of 0.2 to 1% , preferably in the range of 0.2 to 0.56%.

The preferable lower limit values of the total content of the compounds represented by the general formula (P) are 0.01% by mass, 0.03% by mass, 0.05% by mass, and 0.08% by mass relative to the total amount of the polymerizable compound-containing liquid crystal composition of the present invention. mass %, 0.1 mass %, 0.15 mass %, 0.2 mass %, 0.25 mass %, 0.3 mass %. The preferable upper limit values of the total content of the compounds represented by the general formula (P) are 10 mass %, 8 mass %, 5 mass %, 3 mass % with respect to the total amount of the polymerizable compound-containing liquid crystal composition of the present invention mass %, 1.5 mass %, 1.2 mass %, 1 mass %, 0.8 mass %, 0.5 mass %. When the content of the compound represented by the general formula (P) contained in the polymerizable compound-containing liquid crystal composition of the present invention is small, the following inconvenience is likely to occur in that it is difficult to express the compound represented by the general formula (P) by adding the compound represented by the general formula (P). As a result, the formation of inclination becomes insufficient, and the inclination stability is poor. In addition, problems such as weak alignment restraint force of the liquid crystal composition or weakening over time tend to occur. On the other hand, if the above-mentioned content is too large, problems such as an increase in the amount remaining after curing, a time-consuming curing, and a decrease in the reliability of the liquid crystal will occur. Therefore, the content is set in consideration of their balance.

As the compound represented by the general formula (P), for example, a compound represented by the following general formula (P-a1) or (P-a2) can be used.

[Chemical 15]

P ^p1a -Sp ^p1a -A ^p1a -Z ^p2a -A ^p3a -R ^p1a (P-a1)

P ^p1a -Sp ^p1a -A ^p1a -Z ^p1a -A ^p2a -Z ^p2a -A ^p3a -R ^p1a (P-a2)

(In the above general formulae (P-a1) and (P-a2), A ^p1a , A ^p2a and A ^p3a each independently represent a group selected from the group (a ^p ), the group (b ^p ) and the group (c A group in the group consisting of ^p ), in the above-mentioned group ( ^ap ), group ( ^bp ) and group ( ^cp ), the hydrogen atoms present in the group can each independently be replaced by a cyano group , halogen atom, alkyl group with 1 to 8 carbon atoms, alkoxy group with 1 to 8 carbon atoms, alkenyl group with 1 to 8 carbon atoms, or -Sp ^p2a -P ^p2a substituted,

In at least one of A ^p1a , A ^p2a and A ^p3a , at least one hydrogen atom in the ring is substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms,

P ^p1a , Sp ^p1a , Z ^p1a , Z ^p2a and R ^p1a , and Sp ^p2a and P ^p2a and P ^p1 , Sp ^p1 , Z ^p1 , Z ^p2 and R ^p1 , and Sp ^p2 and P in the general formula (P) above The definition of ^p2 is the same, and when there are multiple Sp ^p2a or P ^p2a in the molecule, they can be the same or different. )

The compounds represented by the above general formulae (P-a1) and (P-a2) contain two or three rings in the molecular structure, and at least one of these rings has an alkyl group or an alkoxy group. The compounds represented by the general formulae (P-a1) and (P-a2) can exhibit excellent solubility in liquid crystal compositions and excellent polymerization reactivity by having such a molecular structure, and thus can be used in the present invention. It is suitably used in the polymerizable compound-containing liquid crystal composition.

Moreover, as a compound represented by general formula (P), for example, the compound represented by following general formula (P-b) can be used.

[Chemical 16]

P ^p1b -Sp ^p1b -A ^p1b -Z ^p1b -A ^p2b -Z ^p2b -A ^p3b -R ^p1b (Pb)

(In the above general formula (Pb), A ^p1b , A ^p2b and A ^p3b each independently represent a 1,4-phenylene group or a naphthalenediyl group, and in these groups, the hydrogen atoms present in the group are each independently Can be substituted by a cyano group, a halogen atom, an alkyl group with 1 to 8 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an alkenyl group with 1 to 8 carbon atoms, or -Sp ^p2b -P ^p2b ,

P ^p1b , Sp ^p1b , Z ^p1b , Z ^p2b and R ^p1b , and Sp ^p2b and P ^p2b and P ^p1 , Sp ^p1 , Z ^p1 , Z ^p2 and R ^p1 , and Sp ^p2 and P in the general formula (P) above The definition of ^p2 is the same, and when there are multiple Sp ^p2b or P ^p2b in the molecule, they can be the same or different. )

The compound represented by the above-mentioned general formula (P-b) is required to have three ring structures in its molecular structure, and since it can exhibit excellent polymerization reactivity, it can be suitably used in the polymerizable compound-containing liquid crystal composition of the present invention .

As the naphthalene diyl group that can be used for A ^p1b , A ^p2b and A ^p3b , naphthalene-2,6-diyl group is preferable among them.

Moreover, as a compound represented by general formula (P), the compound represented by following general formula (P-c1) or (P-c2) can be used, for example.

[Chemical 17]

P ^p1c -Sp ^p1c -A ^p1c -Z ^p2c -A ^p3c -R ^p1c (P-c1)

P ^p1c -Sp ^p1c -A ^p1c -Z ^p1c -A ^p2c -Z ^p2c -A ^p3c -R ^p3c (P-c2)

(In the above general formulae (P-c1) and (P-c2), A ^p1c , A ^p2c and A ^p3c each independently represent a group selected from the group (a ^p ), the group (b ^p ) and the group (c A group in the group consisting of ^p ), in the above-mentioned group ( ^ap ), group ( ^bp ) and group ( ^cp ), the hydrogen atoms present in the group can each independently be replaced by a cyano group , halogen atom, alkyl group with 1 to 8 carbon atoms, alkoxy group with 1 to 8 carbon atoms, alkenyl group with 1 to 8 carbon atoms, or -Sp ^p2c -P ^p2c substituted,

P ^p1c , Sp ^p1c , Z ^p1c , Z ^p2c and R ^p1c , and Sp ^p2c and P ^p2c and P ^p1 , Sp ^p1 , Z ^p1 , Z ^p2 and R ^p1 , and Sp ^p2 and P in the general formula (P) above The definition of ^p2 is the same, when there are multiple Sp ^p2c or P ^p2c in the molecule, they can be the same or different,

In the above formula (P-c1), Z ^p2C is selected from -CH=CH-COO-, -COO-CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, A linker in the group consisting of -O-CO-(CH ₂ ) ₂ -, -COO-(CH ₂ ) ₂ -,

In the above formula (P-c2), at least one of Z ^p1C and Z ^p2C is selected from -CH=CH-COO-, -COO-CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -O-CO-(CH ₂ ) ₂ -, -COO-(CH ₂ ) ₂ - A linker in the group consisting of. ) are preferably the compounds represented above.

The compounds represented by the general formulae (P-c1) and (P-c2) can exhibit excellent solubility in liquid crystal compositions and excellent Because of its polymerization reactivity, it can be suitably used in the polymerizable compound-containing liquid crystal composition of the present invention.

As a preferable example of the compound represented by general formula (P), the polymerizable compound represented by following formula (P-1-1) - formula (P-1-46) is mentioned.

[Chemical 18]

[Chemical 19]

[hua 20]

[Chemical 21]

(In the formula, P ^p11 , P ^p12 , Sp ^p11 and Sp ^p12 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-2-1) to (P-2-9).

[Chemical 23]

(In the formula, P ^p21 , P ^p22 , Sp ^p21 and Sp ^p22 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferable examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-3-1) to (P-3-15).

[Chemical 24]

[Chemical 25]

(In the formula, P ^p31 , P ^p32 , Sp ^p31 and Sp ^p32 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

As a preferable example of the compound represented by general formula (P), the polymerizable compound represented by following formula (P-4-1) - formula (P-4-21) is mentioned.

[Chemical 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

(In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^p42 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulae (P-5-1) to (P-5-37).

[Chemical 30]

[Chemical 31]

[Chemical 32]

(In the formula, P ^p51 , P ^p52 , Sp ^p51 and Sp ^p52 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

[3] Liquid crystal compound

The polymerizable compound-containing liquid crystal composition of the present invention contains, in addition to the compound of the general formula (i) and the polymerizable compound, one or two or more types of liquid crystal compounds as constituent components. In addition, the composition which removes a polymerizable compound and an additive from the polymerizable compound-containing liquid crystal composition of this invention is called the liquid crystal composition in this invention. The liquid crystal composition in this invention contains 1 type or 2 or more types of compounds chosen from the compound group represented by general formula (NU-01) to general formula (NU-08).

[Chemical 33]

(where, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU81 and R ^NU82 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms.)

In further detail, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU81 and R ^NU82 is each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

On the other hand, when the response speed is important, at least one of R ^NU11 , R ^NU21 , R ^NU41 and R ^NU51 is preferably an alkenyl group having 2 to 8 carbon atoms. As the alkenyl group, the formula (R1) to the formula (R5) can be mentioned.

[Chemical 34]

(The black dots in each formula represent carbon atoms in the ring structure.) Among them, an alkenyl group having 2 to 3 carbon atoms is preferable, and an alkenyl group represented by formula (R1) or formula (R2) is preferable.

The compound having an alkenyl group selected from the compound group represented by the general formula (NU-01) to the general formula (NU-08) is preferably 30% or less, preferably 25% or less with respect to the total amount of the liquid crystal composition in the present invention , preferably 20% or less, preferably 15% or less, preferably 10% or less, preferably 5% or less. When emphasis is placed on high VHR, the compound having an alkenyl group is preferably 10% or less, preferably 5% or less, preferably 1% or less, and preferably not contained.

More specifically, R ^NU11 , R ^NU21 , R ^NU31 , R ^NU41 , R ^NU51 , R ^NU61 , R ^NU71 , and R ^NU81 are particularly preferably independently alkyl groups having 1 to 5 carbon atoms, R ^NU12 , R ^NU22 , R ^NU32 , R ^NU42 , R ^NU52 , R ^NU62 , R ^NU72 and R ^{NU82 are} particularly preferably alkyl groups having 1 to 5 carbon atoms or alkoxy groups having 1 to 5 carbon atoms.

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-01) and the compound represented by the general formula (NU-02).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-01) and the compound represented by the general formula (NU-03).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-03) and the compound represented by the general formula (NU-04).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-03) and the compound represented by the general formula (NU-05).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-01) and the compound represented by the general formula (NU-06).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-01) and the compound represented by the general formula (NU-07).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (NU-01) and the compound represented by the general formula (NU-08).

The liquid crystal composition in the present invention preferably contains a compound represented by general formula (NU-01), a compound represented by general formula (NU-02), and a compound represented by general formula (NU-04).

The liquid crystal composition in the present invention preferably contains a compound represented by general formula (NU-01), a compound represented by general formula (NU-03), and a compound represented by general formula (NU-05).

The liquid crystal composition in the present invention preferably contains a compound represented by general formula (NU-01), a compound represented by general formula (NU-02), a compound represented by general formula (NU-03), and a compound represented by general formula (NU The compound represented by -05).

The content of the compound represented by the general formula (NU-01) is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-03) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-04) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-05) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 3 to 20% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-06) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-07) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass in the total amount of the liquid crystal composition.

The content of the compound represented by the general formula (NU-08) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass in the total amount of the liquid crystal composition.

The liquid crystal composition in the present invention preferably contains one or two or more kinds selected from the group consisting of general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) A compound in the indicated compound group. These compounds correspond to compounds having negative dielectric anisotropy. The "compound having negative dielectric anisotropy" refers to a compound in which the sign of Δε is negative and the absolute value thereof shows a value greater than 2. In addition, the Δε of the compound is a value extrapolated from the measured value of the dielectric constant anisotropy of the composition in which the compound was added to a substantially dielectrically neutral composition at 20°C.

[Chemical 35]

(in the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 2 to 8 carbon atoms. alkenyloxy, Z ¹ independently represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ - or -CH ₂ O-, and m independently represents 1 or 2.)

R ²¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably an alkyl group having 2 to 4 carbon atoms. Among them, when Z ¹ represents other than a single bond, R ²¹ is preferably an alkyl group having 1 to 3 carbon atoms.

R ²² is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, even more preferably An alkoxy group having 1 to 4 carbon atoms.

When R ²¹ and R ²² are alkenyl groups, formula (R1) to formula (R5) are preferred,

[Chemical 36]

(The black dots in each formula represent carbon atoms in the ring structure.) The formula (R1) or the formula (R2) is more preferable.

Z ¹ is further preferably each independently a single bond, -CH ₂ CH ₂ - or -CH ₂ O-.

When m is 1, Z ¹ is preferably a single bond or -CH ₂ O-.

When m is 2, Z ¹ is preferably a single bond, -CH ₂ CH ₂ - or -CH ₂ O-.

In the liquid crystal composition of the present invention, as the compound represented by the general formula (N-01), it is preferable to contain one or more kinds selected from the group consisting of the general formula (N-01-1) to the general formula (N-01- 4) A compound of the compound group represented.

[Chemical 37]

(In the formula, R ²⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (N-01-1) and the compound represented by the general formula (N-01-4).

In the liquid crystal composition of the present invention, as the compound represented by the general formula (N-02), it is preferable to contain one or more kinds selected from the group consisting of the general formula (N-02-1) to the general formula (N-02- 3) A compound of the compound group represented.

[Chemical 38]

(In the formula, R ²⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (N-02-1) or the compound represented by the general formula (N-02-3).

The liquid crystal composition in the present invention preferably contains one or more compounds represented by the general formula (N-03-1) as the compound represented by the general formula (N-03).

[Chemical 39]

(In the formula, R ²⁴ represents an alkyl group having 1 to 5 carbon atoms, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition in the present invention preferably contains a compound represented by general formula (N-03-1).

The liquid crystal composition in the present invention preferably contains the compound represented by the general formula (N-03-1) and the compound represented by the general formula (N-01-4).

In the liquid-crystal composition in this invention, it is preferable to contain the compound represented by general formula (N-04-1) by 1 type or 2 or more types as a compound represented by general formula (N-04).

[Chemical 40]

(In the formula, R ²⁴ represents an alkyl group having 1 to 5 carbon atoms, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-04-1).

It is particularly preferable that the liquid crystal composition in the present invention contains the compound represented by the general formula (N-04-1) and the compound represented by the general formula (N-01-4).

It is particularly preferable that the liquid crystal composition in the present invention contains a compound represented by general formula (N-04-1), a compound represented by general formula (N-01-4), and a compound represented by general formula (N-03-1) compound.

The liquid crystal composition in the present invention may contain, as the compound represented by the general formula (N-05), a compound selected from the group of compounds represented by the formula (N-05-1) to the formula (N-05-3) .

[Chemical 41]

The lower limit of the preferable content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35 %, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35 %, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35 %, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by general formula (N-04) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35 %, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by formula (N-05) is 0%, 2%, 5%, 8%, 10%, 13%, 15% with respect to the total amount of the liquid crystal composition in the present invention. %, 17%, 20%, preferably the upper limit of the content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%.

The liquid crystal composition in the present invention may contain one or more compounds having positive dielectric anisotropy described in paragraphs 0236 to 0509 of Japanese Patent No. 6233550.

The liquid crystal composition in the present invention preferably does not contain a compound having a structure in which oxygen atoms, such as a peracid (-CO-OO-) structure, are connected to each other in the molecule. When importance is attached to the reliability and long-term stability of the liquid crystal composition, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less with respect to the total mass of the composition. , most preferably not substantially contained.

In the liquid crystal composition of the present invention, when the stability to UV irradiation is important, the content of the chlorine atom-substituted compound is preferably 15% or less, preferably 10% or less, based on the total mass of the composition. , preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably not substantially contained.

In the liquid crystal composition of the present invention, it is preferable to increase the content of the compound whose ring structure in the molecule is all 6-membered rings, and the content of the compound whose ring structure is all 6-membered rings in the molecule is preferably relative to the total mass of the composition. It is 80% or more, more preferably 90% or more, still more preferably 95% or more, and most preferably, the composition is composed of substantially only compounds whose intramolecular ring structures are all 6-membered rings.

In order to suppress deterioration due to oxidation of the liquid crystal composition, in the liquid crystal composition of the present invention, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group relative to the The total mass of the composition is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably not substantially contained.

When importance is attached to the improvement of viscosity and improvement of T _ni , in the liquid crystal composition of the present invention, it is preferable to reduce the content of the compound having 2-methylbenzene-1,4-diyl in which hydrogen atoms may be substituted by halogen in the molecule, The content of the compound having 2-methylbenzene-1,4-diyl in the molecule is preferably 10% or less, preferably 8% or less, and more preferably 5% based on the total mass of the composition. % or less, preferably 3% or less, and more preferably not substantially contained.

In addition, in this specification, "substantially not containing" means not containing except for the substance contained unintentionally.

The liquid crystal composition in the present invention may contain, in addition to the above-mentioned compounds, normal nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, and the like.

The nematic-isotropic liquid phase transition temperature (T _ni ) of the liquid crystal composition in the present invention is 60°C to 120°C, more preferably 70°C to 100°C, particularly preferably 70°C to 85°C. In addition, in this invention, 60 degreeC or more is expressed as high T _ni .

In the case of liquid crystal television applications, T _ni is preferably 70 to 80°C, in the case of mobile applications, T _ni is preferably 80 to 90° C. In the case of outdoor display applications such as PID (Public Information Display, public information display), T _ni is preferably 90 to 110°C.

The refractive index anisotropy (Δn) at 20° C. of the liquid crystal composition in the present invention is 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. More specifically, in the case of a thin cell gap, it is preferably 0.10 to 0.13, and in a case of a thick cell gap, it is preferably 0.08 to 0.10. In addition, it is especially preferable that the refractive index anisotropy (Δn) at 20 degreeC of the liquid crystal composition of this invention is 0.098-0.118.

The liquid crystal composition in the present invention has a rotational viscosity (γ ₁ ) at 20° C. of 50 to 160 mPa·s, preferably 55 to 160 mPa·s, preferably 60 to 160 mPa·s, preferably 80 to 150 mPa·s, preferably It is 90 to 140 mPa·s, preferably 90 to 130 mPa·s, preferably 90 to 115 mPa·s.

The Δε of the liquid crystal composition in the present invention is -1.7 to -4.0, preferably -2.5 to -3.8, more preferably -2.7 to -3.7, more preferably -2.6 to -3.6.

[4] Additives

The polymerizable compound-containing liquid crystal composition of the present invention may contain an antioxidant, an ultraviolet absorber, a light stabilizer, an infrared absorber, and the like. Among them, the polymerizable compound-containing liquid crystal composition of the present invention preferably contains an antioxidant so that polymerization does not occur in the heat treatment, which is one of the manufacturing steps of the liquid crystal display element.

The polymerizable compound-containing liquid crystal composition of the present invention preferably contains antioxidants represented by general formula (H-1) to general formula (H-4), and the lower limit of the content is preferably 10 mass ppm, preferably 20 mass ppm, preferably 50 mass ppm The upper limit of mass ppm is 10000 mass ppm, preferably 1000 mass ppm, preferably 500 mass ppm, preferably 100 mass ppm.

[Chemical 42]

In general formula (H-1) to general formula (H-3), R ^H1 each independently represents an alkyl group having 3 to 7 carbon atoms. More specifically, R ^H1 in the general formula (H-1) represents an alkyl group having 7 carbon atoms. R ^H1 in the general formula (H-2) represents an alkyl group having 3 carbon atoms. R ^H1 in the general formula (H-3) represents an alkyl group having 3 carbon atoms.

In the general formula (H-4), M ^H1 represents an alkylene group having 4 to 10 carbon atoms (one or more -CH ₂ - in the alkylene group may be - such that oxygen atoms are not directly adjacent to each other - COO- or -OCO- substituted.) single bond, 1,4-phenylene (any hydrogen atom in 1,4-phenylene may be substituted by fluorine atom.) or trans-1,4-cycloidene Hexyl, M ^H1 is preferably an alkylene group having 4 to 8 carbon atoms.

[5] Others

In the entire polymerizable compound-containing liquid crystal composition of the present invention, only the compound represented by the general formula (i) and the compound represented by the general formula (P) are selected from the group consisting of the general formulae (N-01) to (N-05 ) of the compound group represented by the compound group and the components selected from the compound group represented by the general formula (NU-01) to (NU-08) The upper limit of the ratio of the ratio of the components is preferably 100% by mass, 99% by mass %, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass %, 85 mass %, 84 mass %.

In addition, in the entire polymerizable compound-containing liquid crystal composition of the present invention, only the compound represented by the general formula (i), the compound represented by the general formula (P), selected from the group consisting of the general formulae (N-01) to (N -05) The lower limit value of the ratio of the components constituted by the compound represented by the compound group represented by the compound group and the compound selected from the compound group represented by the general formula (NU-01) to (NU-08) is preferably 78% by mass, 80 mass %, 81 mass %, 83 mass %, 85 mass %, 86 mass %, 87 mass %, 88 mass %, 89 mass %, 90 mass %, 91 mass %, 92 mass %, 93 mass %, 94 mass % %, 95% by mass, 96% by mass, 97% by mass, 98% by mass, 99% by mass.

Preferable values of T _ni , Δn, γ ₁ and Δε of the polymerizable compound-containing liquid crystal composition of the present invention can be set to be the same as the properties of the liquid crystal composition of the present invention described above.

B. Liquid crystal display element

Next, the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention is a liquid crystal display element using the polymerizable compound-containing liquid crystal composition described in the section "A. Polymerizable compound-containing liquid crystal composition". That is, the liquid crystal display element of the present invention is a liquid crystal using a polymerizable compound-containing liquid crystal composition containing one or more compounds represented by the general formula (i) and one or more polymerizable compounds. display element.

By using the above-mentioned polymerizable compound-containing liquid crystal composition, the liquid crystal display element of the present invention can obtain a sufficient tilt angle, the residual amount of the polymerizable compound in the liquid crystal display element after polymerization is small, and high-definition PSA type liquid crystals such as 4K and 8K can be obtained. Display failures such as burn-in (IS) of the display element do not occur or can be significantly suppressed. In addition, in the production of high-definition PSA type liquid crystal display elements such as 4K and 8K, if the UV irradiation time is prolonged, the production efficiency will be significantly deteriorated, but the liquid crystal display element of the present invention uses the above-mentioned polymerizable compound-containing liquid crystal Therefore, the composition can be used as a high-definition PSA-type liquid crystal display element using the UV irradiation time, and the industrial utility value is very high.

The liquid crystal display element of the present invention is particularly useful as a liquid crystal display element for active matrix driving, and can be used for a liquid crystal display element for a PSA mode, a PSVA mode, a VA mode, a PS-IPS mode, or a PS-FFS mode.

Since the liquid crystal display element of this invention uses the said polymerizable compound containing liquid crystal composition, it can be set as the liquid crystal display element which does not have an alignment film, ie, the mode generally called PI-less (PI-less). In this case, it is preferable to use a compound having spontaneous orientation in combination with the polymerizable compound-containing liquid crystal composition. Examples of compounds having spontaneous orientation include JP 2014-513150 A, JP 2014-524951 A, JP 06081361 A, JP 2016-501938 A, JP 2018-A Compounds having spontaneous orientation described in Gazette 023718, International Publication No. 2017/041893, Japanese Patent No. 06070973, International Publication No. 2017/047177, and the like.

The liquid crystal display element of the present invention preferably includes a first substrate and a second substrate arranged to face each other, a common electrode provided on the first substrate or the second substrate, and a common electrode provided on the first substrate or the second substrate The substrate has pixel electrodes of thin film transistors, and a liquid crystal layer provided between the first substrate and the second substrate. The liquid crystal layer contains at least the compound represented by the general formula (i), the liquid crystal composition contained in the polymerizable compound-containing liquid crystal composition, and the polymer of the polymerizable compound.

In the liquid crystal display element of the present invention, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the opposing surface side of at least one of the first substrate and the second substrate so as to contact the liquid crystal layer as necessary, The alignment film may not be provided on both the first substrate and the second substrate. As the alignment film, a vertical alignment film, a horizontal alignment film, etc. can be appropriately selected according to the driving mode of the liquid crystal display element, and a rubbing alignment film (for example, a polyimide alignment film), a photo alignment film (for example, a decomposable polyimide film) can be used. Alignment film) and other well-known alignment films. Further, a color filter may be appropriately provided on the first substrate or the second substrate, and a color filter may be provided on the pixel electrode and the common electrode.

The two substrates of the liquid crystal cell used in the liquid crystal display element of the present invention may be glass or a flexible transparent material such as plastic, or one of them may be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate, for example.

The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. A method for producing a color filter using a pigment dispersion method will be described as an example: the curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and then cured by heating or light irradiation. . By performing this process for each of the three colors of red, green, and blue, a pixel portion for a color filter can be produced. In addition, pixel electrodes provided with active elements such as TFTs, thin-film diodes, and metal-insulator-metal resistivity elements may be provided on the substrate.

It is preferable that the first substrate and the second substrate face each other so that the common electrode and the pixel electrode layer are on the inside.

The space|interval of a 1st board|substrate and a 2nd board|substrate can be adjusted by a spacer. At this time, it is preferable to adjust so that the thickness of the obtained liquid crystal layer may become 1-100 micrometers, More preferably, it is 1.5-10 micrometers. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarization axis of each polarizing plate may be adjusted, and the viewing angle and contrast may be adjusted so that the viewing angle and contrast become favorable. Furthermore, a retardation film for widening the viewing angle can also be used. As a spacer, a glass particle, a plastic particle, an alumina particle, a photoresist material, etc. are mentioned, for example. Then, sealants, such as an epoxy-type thermosetting composition, are screen-printed on this board|substrate so that a liquid crystal injection port may be provided, the board|substrates are bonded together, and the sealant is thermally cured by heating.

As a method of sandwiching the polymerizable compound-containing liquid crystal composition between two substrates, a general vacuum injection method, an ODF method, or the like can be used.

As a method for polymerizing the polymerizable compound contained in the polymerizable compound-containing liquid crystal composition, in order to obtain favorable alignment performance of the liquid crystal, a moderate polymerization rate is desired, so it is preferable to irradiate an active agent such as ultraviolet rays or electron beams singly or in combination or sequentially. A method of polymerizing with energy rays. In the case of using ultraviolet rays, a polarized light source may be used, or a non-polarized light source may be used. In addition, when polymerizing the polymerizable compound-containing liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiated surface side needs to be given appropriate transparency with respect to active energy rays. Alternatively, a method may be used in which only a specific portion is polymerized using a mask during light irradiation, and then the orientation state of the unpolymerized portion is changed by changing conditions such as electric field, magnetic field, and temperature, and further polymerization may be performed by irradiating active energy rays. In particular, in the case of UV exposure, it is preferable to perform UV exposure while applying an AC electric field to the polymerizable compound-containing liquid crystal composition. The applied alternating current field is preferably alternating current at a frequency of 10 Hz to 10 kHz, more preferably at a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the liquid crystal display element of the PSVA mode, it is preferable to control the pretilt angle within the range of 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used for polymerizing the polymerizable compound contained in the polymerizable compound-containing liquid crystal composition is not particularly limited. For example, when applying a polymerizable compound-containing liquid crystal composition to a liquid crystal display element including a substrate having an alignment film, it is preferably within a temperature range in which the liquid crystal state of the polymerizable compound-containing liquid crystal composition is maintained. The polymerization is preferably carried out at a temperature close to room temperature, that is, typically in the range of 15 to 35°C.

On the other hand, for example, when the liquid crystal composition containing a polymerizable compound is applied to a liquid crystal display element provided with a substrate without an alignment film, it may be the same as that applied to a liquid crystal display element provided with a substrate provided with an alignment film. The temperature range at the time of irradiation is wider than the temperature range.

As the lamp for generating ultraviolet rays, metal halide lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, etc. can be used, and ultra-high pressure UV lamps of USHIO and fluorescent ultraviolet lamps of TOSHIBA are preferable. Moreover, as a wavelength of the ultraviolet-ray to irradiate, it is preferable to irradiate the ultraviolet-ray whose wavelength range is not in the absorption wavelength region of the polymerizable compound-containing liquid crystal composition, and it is preferable to filter an ultraviolet-ray as needed and use. The intensity of the irradiated ultraviolet rays is preferably 0.1 mW/cm ² to 100 W/cm ² , more preferably 2 mW/cm ² to 50 W/cm ² . The amount of energy of the irradiated ultraviolet rays can be appropriately adjusted, but is preferably 10 mJ/cm ² to 500 J/cm ² , more preferably 100 mJ/cm ² to 200 J/cm ² . When irradiating ultraviolet rays, the intensity can be changed. The time of irradiation with ultraviolet rays is appropriately selected according to the intensity of ultraviolet rays to be irradiated, and is preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.

The present invention is not limited to the above-described embodiments. The above-described embodiments are examples, and technical solutions that have substantially the same configuration and achieve the same effects as the technical concept described in the claims of the present invention are also included in the technical scope of the present invention.

Example

The following examples are given to further describe the present invention in detail, but the present invention is not limited by these examples. In addition, in the following Examples and Comparative Examples, "%" means "mass %".

For the description of the compounds in the following Examples and Comparative Examples, the following abbreviations are used.

(side chain)

-nC _n H _2n+1 linear alkyl group with n carbon atoms

nC _n H _2n+1 - Linear alkyl group with n carbon atoms

-On-OC _n H _2n+1 linear alkoxy group with n carbon atoms

(linker)

-1O--CH ₂ -O-

(ring structure)

[Chemical 43]

The properties measured in the following Examples and Comparative Examples are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (°C)

Δn: Refractive index anisotropy at 20°C

η: Viscosity at 20°C (mPa·s)

γ ₁ : Rotational viscosity at 20°C (mPa·s)

Δε: Dielectric constant anisotropy at 20°C

K ₃₃ : Elastic constant K ₃₃ (pN) at 20°C

The manufacturing method and evaluation method of the liquid crystal display element in the following Examples and Comparative Examples are as follows.

(Manufacturing method of liquid crystal display element)

First, in a liquid crystal cell including a substrate with ITO obtained by applying a polyimide alignment film that induces vertical alignment and rubbing, and having a cell gap of 3.5 μm, a polymerizable compound-containing liquid crystal cell, which will be described later, is injected by a vacuum injection method. Liquid crystal composition. After that, the liquid crystal cell into which the polymerizable compound-containing liquid crystal composition was injected was irradiated with ultraviolet rays using a fluorescent UV lamp for an arbitrary period of time to obtain a liquid crystal display element. At this time, the fluorescent UV lamp was adjusted so that the illuminance measured under the condition of a center wavelength of 313 nm would be 3 mW/cm ² .

(Evaluation method of residual amount of polymerizable compound)

The residual amount [ppm] of the polymerizable compound in the liquid crystal display element after irradiating ultraviolet rays for 150 seconds under the above-mentioned irradiation conditions was measured. A method for measuring the residual amount of the polymerizable compound will be described. First, the decomposed liquid crystal display element and acetonitrile were put into the test tube, and the acetonitrile solution containing the elution components of the liquid crystal composition, the polymer, and the unreacted polymerizable compound was obtained by shaking filtration. This was analyzed by high performance liquid chromatography (column: reversed-phase non-polar column, developing solvent: mixed solvent of 70% acetonitrile and 30% water), and the peak area of each component was calculated. The amount of the remaining polymerizable compound was determined from the ratio of the peak area of the liquid crystal compound to the peak area of the unreacted polymerizable compound as an index. From this value and the amount of the initially added polymeric compound, the residual amount of the polymeric compound is determined. In addition, the detection limit of the residual amount of a polymerizable compound was 100 ppm.

(Evaluation method of pretilt angle change amount)

The pretilt angle change amount [°] of the liquid crystal display element before and after irradiation with ultraviolet rays for 50 seconds under the above irradiation conditions was measured.

First, the pretilt angle of the liquid crystal display element was measured, and it was set as a pretilt angle (initial state). The liquid crystal display element was irradiated with ultraviolet rays for 50 seconds while applying a voltage of 10 V at a frequency of 100 Hz. After that, the pretilt angle was measured and set as the pretilt angle (after UV). The value obtained by subtracting the pretilt angle (after UV) from the measured pretilt angle (initial) was used as the pretilt angle change amount [°]. The pretilt angle was measured using OPTIPRO manufactured by Shintec.

(Preparation and Physical Properties of Liquid Crystal Compositions)

The liquid crystal composition LC-001 before adding the compound of formula (i) and the polymerizable compound was prepared, and its physical property values were measured. The constitution of the liquid crystal composition LC-001 and the results of its physical properties are shown in Table 1.

[Table 1]

LC-001 3-Cy-Cy-2 18 3-Cy-Cy-4 8 3-Ph-Ph-1 13 3-Cy-Ph-Ph-2 6 5-Cy-Ph-Ph-2 4 3-Cy-1O-Ph5-O1 6 3-Cy-1O-Ph5-O2 7 2-Cy-Cy-1O-Ph5-O2 14 3-Cy-Cy-1O-Ph5-O2 3 3-Cy-Ph-Ph5-O3 6 3-Cy-Ph-Ph5-O4 7 4-Cy-Ph-Ph5-O3 8 total 100 Tni[℃] 73.8 Δn 0.111 Y1[mPa s] 125 Δε -3.2 K33[pN] 12.5 y1/K33 10.0

(Comparative Examples 1 to 3, Examples 1 to 7)

To 99.7 parts by mass of liquid crystal composition LC-001, 0.3 parts by mass of a polymerizable compound represented by the following formula (RM-A) was added, and the obtained polymerizable compound-containing liquid crystal composition was referred to as Comparative Example 1.

With respect to 94.7 parts by mass of the liquid crystal composition LC-001, 5 parts by mass of the compound represented by the following formula (REF-A) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A) were added, The obtained polymerizable compound-containing liquid crystal composition was referred to as Comparative Example 2.

With respect to 94.7 parts by mass of the liquid crystal composition LC-001, 5 parts by mass of the compound represented by the following formula (REF-B) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A) were added, The obtained polymerizable compound-containing liquid crystal composition was referred to as Comparative Example 3.

With respect to 94.7 parts by mass of liquid crystal composition LC-001, 5 parts by mass of the compound represented by the following formula (A) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A) were added, and the obtained The polymerizable compound-containing liquid crystal composition was taken as Example 1.

With respect to 96.7 parts by mass of liquid crystal composition LC-001, 3 parts by mass of the compound represented by the following formula (A) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A) were added, and the obtained The polymerizable compound-containing liquid crystal composition was taken as Example 2.

With respect to 94.7 parts by mass of liquid crystal composition LC-001, 5 parts by mass of the compound represented by the following formula (B) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A) were added, and the obtained The polymerizable compound-containing liquid crystal composition was taken as Example 3.

With respect to 94.7 parts by mass of the liquid crystal composition LC-001, 5 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-B) were added, and the resulting polymerizable compound was added. The liquid crystal composition of the compound was taken as Example 4.

With respect to 96.7 parts by mass of the liquid crystal composition LC-001, 3 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-C) were added, and the resulting polymerizable compound was added. The liquid crystal composition of the compound was taken as Example 5.

With respect to 96.7 parts by mass of the liquid crystal composition LC-001, 3 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-D) were added, and the resulting polymerizable compound was added. The liquid crystal composition of the compound was taken as Example 6.

With respect to 96.7 parts by mass of the liquid crystal composition LC-001, 3 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-E) were added, and the resulting polymerizable compound was added. The liquid crystal composition of the compound was taken as Example 7.

[Chemical 44]

Regarding the polymerizable compound-containing liquid crystal compositions of Comparative Examples 1 to 3 and Examples 1 to 7, the amount of change in the pretilt angle by ultraviolet irradiation and the content of the polymerizable compound are shown in Table 2 below.

[Table 2]

The polymerizable compound-containing liquid crystal compositions of Comparative Examples 1 and 3 had a small amount of change in the pretilt angle and a large residual amount of the polymerizable compound. In Comparative Example 2, the residual amount of the polymerizable compound was small, and the amount of change in the pretilt angle was larger than those in Comparative Examples 1 and 3, but it was not a sufficient amount of change in the pretilt angle.

On the other hand, it can be seen that in Examples 1 to 7, which are the polymerizable compound-containing liquid crystal compositions of the present invention, the amount of change in the pretilt angle shows sufficiently large values as compared with Comparative Examples 1 to 3, and the residual polymerizable compound is The amount is small, and the polymerization speed is sufficiently fast. From the above, it was confirmed that the polymerizable compound-containing liquid crystal composition of the present invention can form a pretilt angle with short or small UV light and reduce the residual amount of the polymerizable compound.

In addition, comparing Example 1 and Example 4, it can be seen that Example 1 using the polymerizable compound represented by the formula (RM-A) and Example 4 using the polymerizable compound represented by the formula (RM-B) are similar to each other. than the pretilt angle, the amount of change in the pretilt angle is larger, and the residual amount of the polymerizable compound is smaller.

The liquid crystal cells into which the polymerizable compound-containing liquid crystal compositions of Examples 1 to 7 were injected were irradiated with ultraviolet rays for 60 minutes under the above-mentioned irradiation conditions, and then irradiated with a backlight for 3 hours while applying a voltage of 30 V at a frequency of 100 Hz using OPTIPRO manufactured by Shintec. Evaluation of poor display (screen burn-in) caused by changes in pretilt angle. As a result, the change in the pretilt angle is extremely small, and high pretilt stability is exhibited.

(Examples 8 to 9)

In Example 1, 0.005 parts by mass of an antioxidant represented by the formula (H-2-1) was further added, and the obtained polymerizable compound-containing liquid crystal composition was referred to as Example 8.

In Example 1, 0.005 parts by mass of an antioxidant represented by formula (H-4-1) was further added, and the obtained polymerizable compound-containing liquid crystal composition was referred to as Example 9.

[Chemical 45]

The same evaluations as in Example 1 were also performed for the polymerizable compound-containing liquid crystal compositions of Examples 8 to 9. As a result, in Examples 8 to 9, the amount of change in the pretilt angle was the same as that in Example 1, and the amount of change in the pretilt angle showed a sufficiently large value. In addition, in Examples 8 to 9, the residual amount of the polymerizable compound was the same as that of Example 1, the residual amount of the polymerizable compound was small, and the polymerization rate was sufficiently high. From this, it was confirmed that the polymerizable compound-containing liquid crystal compositions of Examples 8 to 9 also solved the problem of the present invention.

Claims (7)

1. A polymerizable compound-containing liquid crystal composition comprising one or more compounds represented by the general formula (i) and one or more polymerizable compounds, [hua 1]

In the formula, X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group or a trifluoromethoxy group, Y ⁱ¹ and Y ⁱ² each independently represent -O-, -CF ₂ -, -CO- or -CX ⁱ³ X ⁱ⁴ -, any one or more of Y ⁱ¹ and Y ⁱ² represents -O-, and X ⁱ³ and X ⁱ⁴ respectively independently represents the same meaning as X ⁱ¹ , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or a general the group represented by the formula (L ⁱ -1), [hua 2]

In the formula, R ⁱ¹ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms , A ⁱ¹ represents a group selected from the group consisting of, (a) 1,4-cyclohexylene, one -CH ₂ - or two or more non-adjacent -CH ₂ - present in the group may be substituted by -O- or -S-, (b) 1,4-phenylene, 1 -CH= present in the group or 2 or more non-adjacent -CH= may be substituted by -N=, 1 hydrogen present in the group Atoms can be replaced by fluorine atoms, (c) 1,4-cyclohexenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl groups, the hydrogen atoms present in these groups may be replaced by fluorine atoms, and one of the naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups -CH= or two or more non-adjacent -CH= may be substituted by -N=, Z ⁱ¹ represents -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH= CH-, -CF=CF-, -C≡C- or single bond, n ⁱ¹ means 1 or 2, when n ⁱ¹ means 2 and there are multiple A ⁱ¹ and Z ⁱ¹ , they can be the same or different, W ⁱ¹ represents a group represented by the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3), [hua 3]

In the formula, the black dot is · represents the connection point with ^{Li2 or Y i2 ,} * represents the connection point with the carbon atom adjacent to the carbon atom connected with ^{Li5, and L i6 ,} L ⁱ⁷ and L ⁱ⁸ respectively independently represent the connection with the carbon atom. The same meaning of L ⁱ¹ , W ⁱ² represents a single bond or -CL ⁱ⁹ L ⁱ¹⁰ -, L ⁱ⁹ and L ⁱ¹⁰ independently represent the same meaning as L ⁱ¹ , One -CH ₂ - or two or more non-adjacent -CH ₂ - present in L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ may be Substituted by -C≡C-, -O-, -COO-, -OCO- or -CO-, in addition, the hydrogen atom present in the alkyl or alkenyl group may be replaced by a fluorine atom. 2 . The liquid crystal composition according to claim 1 , comprising, as the polymerizable compound, one or more compounds represented by the general formula (P), 2 . [hua 4]

In the above general formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or -Sp ^p2 -P ^p2 , one or two non-adjacent ones of the alkyl groups The above -CH ₂ - may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, one or more of the alkyl groups Hydrogen atoms may be independently substituted by cyano, fluorine or chlorine atoms, P ^p1 and P ^p2 each independently represent any one of the general formulae (P ^p1 -1) to (P ^p1 -9), [hua 5]

In the formula, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and W ^p11 represents a single bond, -O-, -COO-, carbon An alkylene group having 1 to 5 atoms, t ^p11 represents 0, 1 or 2, when there are multiple R ^p11 , R ^p12 , W ^p11 and/or t ^p11 in the molecule, they may be the same or different, Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer, respectively, Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO- , -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CO-NR ^ZP1 -, -NR ^ZP1 -CO-, -SCH ₂ -, -CH ₂ S-, - CH=CR ^ZP1 -COO-,-CH=CR ^ZP1 -OCO-,-COO-CR ^ZP1 =CH-,-OCO-CR ^ZP1 =CH-,-COO-CR ^ZP1 =CH-COO-,-COO-CR ^ZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) _z -COO-, -(CH ₂ ) _z -OCO-, - OCO-(CH ₂ ) _z -, -(C=O)-O-(CH ₂ ) _z -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, - CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - or -C≡C-, where z independently represents each An integer of 1 to 4, R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, when there are multiple R ^ZP1 in the molecule, they may be the same or different, wherein, * in the formula represents the The junction of Sp ^p1 or Sp ^p2 , A ^p1 and A ^p2 each independently represent a group selected from the group consisting of, (a ^p ) 1,4-cyclohexylene group, one -CH ₂ - or two or more non-adjacent -CH ₂ - present in the group may be substituted by -O-, (b ^p ) 1,4-phenylene, 1 -CH= present in the group or 2 or more -CH= that are not adjacent to each other may be substituted by -N=, and (c ^p ) naphthalenediyl, 1,2,3,4-tetrahydronaphthalenediyl, decahydronaphthalenediyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, of which Existing 1 -CH= or non-adjacent 2 or more -CH= may be replaced by -N=, A ^p3 represents a group selected from the group consisting of the above-mentioned group (a ^p ), group (b ^p ) and group (c ^p ) and a single bond, In the above-mentioned group ( ^ap ), group ( ^bp ) and group ( ^cp ), the hydrogen atom present in the group can be independently replaced by a cyano group, a halogen atom, a group having 1 to 8 carbon atoms. Alkyl, alkoxy with 1 to 8 carbon atoms, alkenyl with 1 to 8 carbon atoms, or -Sp ^p2 -P ^p2 substituted, m ^p1 represents 0, 1, 2 or 3, and when there are multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they may be the same or different, When m ^p1 is 0 and A ^p1 is a group other than naphthalenediyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, A ^p3 represents a group other than a single bond. 3. The polymerizable compound-containing liquid crystal composition according to claim 1 or 2, further comprising one or more compounds selected from the group consisting of compounds represented by general formula (NU-01) to general formula (NU-08). 2 or more compounds, [hua 6]

where R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU81 and R ^NU82 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. One or non-adjacent two or more -CH ₂ - may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-. 4. The polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 3, further comprising a compound selected from the group consisting of general formula (N-01), general formula (N-02), general formula (N- 03), one or more compounds in the compound group represented by general formula (N-04) and general formula (N-05), [hua 7]

In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Alkenyloxy, one or two or more non-adjacent -CH ₂ - in this group may be independently represented by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, Z ¹ independently represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH -, -CF=CF- or -C≡C-, m independently represents 1 or 2, respectively. 5 . A liquid crystal display element using the polymerizable compound-containing liquid crystal composition according to claim 1 . 6 . A liquid crystal display element for active matrix driving using the polymerizable compound-containing liquid crystal composition according to claim 1 . 7 . A liquid crystal display element for a PSA mode, a PSVA mode, a PS-IPS mode, or a PS-FFS mode, using the polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 4 .