CN108603120B

CN108603120B - Liquid crystal composition and liquid crystal display element

Info

Publication number: CN108603120B
Application number: CN201680079899.8A
Authority: CN
Inventors: 斋藤将之
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2016-01-29
Filing date: 2016-12-02
Publication date: 2022-01-18
Anticipated expiration: 2036-12-02
Also published as: KR20180103856A; JPWO2017130566A1; CN108603120A; WO2017130566A1; TWI713651B; TW201739906A; JP6747456B2

Abstract

The invention provides a liquid crystal composition which can achieve vertical orientation of liquid crystal molecules through the action of a polar compound and a polymer, and a liquid crystal display element containing the composition. The present invention is a nematic liquid crystal composition which contains a polar compound as a first additive and a polymerizable compound having at least three polymerizable groups as a second additive and has negative dielectric anisotropy, and which may also contain a specific liquid crystal compound having negative large dielectric anisotropy as a first component and a specific liquid crystal compound having a high upper limit temperature or a small viscosity as a second component, and a liquid crystal display element containing the composition.

Description

Liquid crystal composition and liquid crystal display element

Technical Field

The present invention relates to a liquid crystal composition having negative dielectric anisotropy, a liquid crystal display element containing the same, and the like. In particular, the present invention relates to a liquid crystal composition containing a polar compound and a polymerizable compound (or a polymer thereof) and capable of achieving vertical alignment of liquid crystal molecules by the action of these compounds, and a liquid crystal display device.

Background

In a liquid crystal display device, the operation modes based on liquid crystal molecules are classified into Phase Change (PC), Twisted Nematic (TN), Super Twisted Nematic (STN), Electrically Controlled Birefringence (ECB), Optically Compensated Bend (OCB), in-plane switching (IPS), Vertical Alignment (VA), Fringe Field Switching (FFS), field-induced photo-reactive alignment (FPA), and the like. The driving methods of the elements are classified into Passive Matrix (PM) and Active Matrix (AM). The PM is classified into a static type (static) and a multiplexing type (multiplex), etc., and the AM is classified into a Thin Film Transistor (TFT), a Metal Insulator Metal (MIM), etc. TFTs are classified into amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing steps. The light source is classified into a reflection type using natural light, a transmission type using a backlight, and a semi-transmission type using both natural light and backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has suitable properties. By improving the characteristics of the composition, an AM element having good characteristics can be obtained. The correlation between the properties of both is summarized in the following Table 1. The properties of the composition are further illustrated based on commercially available AM elements. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The upper limit temperature of the nematic phase is preferably about 70 ℃ or higher, and the lower limit temperature of the nematic phase is preferably about-10 ℃ or lower. The viscosity of the composition correlates to the response time of the element. In order to display a moving image as an element, the response time is preferably short. Ideally shorter than 1 millisecond of response time. Therefore, it is preferable that the viscosity in the composition is small. Further, it is preferable that the viscosity at low temperature is low.

TABLE 1 Properties of the compositions and AM elements

The optical anisotropy of the composition correlates with the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δ n × d) of the optical anisotropy (Δ n) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of operation mode. The value is in the range of about 0.30 μm to about 0.40 μm in a VA mode element, and in the range of about 0.20 μm to about 0.30 μm in an IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the element. Therefore, a large dielectric anisotropy is preferable. The large specific resistance of the composition contributes to a large voltage holding ratio and a large contrast ratio of the element. Therefore, a composition having a large specific resistance at room temperature in the initial stage, but also at a temperature close to the upper limit temperature of the nematic phase is preferable. The composition is preferably a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to ultraviolet light or heat is correlated to the lifetime of the element. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

In a general-purpose liquid crystal display device, the vertical alignment of liquid crystal molecules can be achieved by using a specific polyimide alignment film. In a Polymer Stabilized Alignment (PSA) type liquid crystal display element, the effect of the polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into an element. Then, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network structure of the polymer in the composition. In the composition, the orientation of liquid crystal molecules can be controlled by the polymer, so that the response time of the element is shortened, and the afterimage of the image is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

On the other hand, a liquid crystal composition containing a polymer and a polar compound is used for a liquid crystal display element having no alignment film. First, a composition to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into an element. Here, the polar compound is adsorbed to the substrate surface and aligned. The liquid crystal molecules are aligned according to the alignment. Then, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. In the composition, the orientation of liquid crystal molecules can be controlled by the polymer and the polar compound, so that the response time of the element is shortened, and the afterimage of the image is improved. Further, the element having no alignment film does not require a step of forming an alignment film. Since the alignment film is not present, the resistance of the element is not lowered by the interaction between the alignment film and the composition. Such an effect of using a combination of a polymer and a polar compound can be expected in an element having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having positive dielectric anisotropy is used for an AM element having a TN mode. A composition having negative dielectric anisotropy is used for an AM element having a VA mode. A composition having positive or negative dielectric anisotropy is used for an AM element having an IPS mode or an FFS mode. A composition having positive or negative dielectric anisotropy is used for a polymer stable alignment type AM device. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in patent documents 1 to 6 below. In the present invention, a polar compound is combined with a polymerizable compound (or a polymer thereof) and a liquid crystalline compound, and the composition is used for a liquid crystal display element having no alignment film.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/090362 specification

Patent document 2: international publication No. 2014/094959 specification

Patent document 3: international publication No. 2013/004372 specification

Patent document 4: international publication No. 2012/104008 specification

Patent document 5: international publication No. 2012/038026 specification

Patent document 6: japanese patent laid-open No. Sho 50-35076

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is a liquid crystal composition containing a polar compound and a polymerizable compound (or the polymer), where the polar compound and the polymerizable compound have high compatibility with the liquid crystal compound. Another object is a liquid crystal composition in which the vertical alignment of liquid crystal molecules can be achieved by the action of the polymer. Another object is to provide a liquid crystal composition which satisfies at least one of the characteristics of a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, and the like. Another object is a liquid crystal composition having a proper balance between at least two characteristics. Another object is a liquid crystal display element comprising the composition. Still another object is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life.

Means for solving the problems

The present invention relates to a liquid crystal composition containing a polar compound as a first additive and a polymerizable compound having at least three polymerizable groups as a second additive and having negative dielectric anisotropy, and a liquid crystal display element containing the same.

ADVANTAGEOUS EFFECTS OF INVENTION

An advantage of the present invention is a liquid crystal composition containing a polar compound and a polymerizable compound (or the polymer), where the polar compound and the polymerizable compound have high compatibility with the liquid crystal compound. Another advantage is a liquid crystal composition in which vertical alignment of liquid crystal molecules can be achieved by the action of the polymer. Another advantage is a liquid crystal composition that satisfies at least one of the characteristics of a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, and the like. Another advantage is a liquid crystal composition having a suitable balance between at least two properties. Another advantage is a liquid crystal display element containing the composition. Still another advantage is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

Detailed Description

The usage of the terms in the specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. The term "liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The "liquid crystalline compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds which are not yet having a liquid crystal phase and are mixed in the composition for the purpose of adjusting the characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The compound has a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystalline compound having an alkenyl group is not polymerizable in its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are optionally added to the liquid crystal composition. The liquid crystalline compound or the additive is mixed in the order mentioned. Even in the case where an additive is added, the proportion (content) of the liquid crystalline compound is represented by a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive. The proportion (addition amount) of the additive is represented by a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive. Parts per million (ppm) by weight are sometimes used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as "lower limit temperature". The "large specific resistance" means that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and also has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. The "large voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and also has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. In the composition or the device, the characteristics may be examined before and after a time-dependent change test (including an accelerated deterioration test). The expression "increase in dielectric anisotropy" means that the value increases positively in a composition having positive dielectric anisotropy, and increases negatively in a composition having negative dielectric anisotropy.

The compound represented by the formula (1) may be simply referred to as "compound (1)". At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as "compound (1)". The "compound (1)" means one compound, a mixture of two compounds or a mixture of three or more compounds represented by the formula (1). The same applies to the compounds represented by the other formulae. The expression "at least one 'a'" means that the number of 'a's is arbitrary. The expression "at least one 'a' may be substituted with 'B' means that the position of 'a' is arbitrary when the number of 'a' is one, and the position thereof may be selected without limitation when the number of 'a' is two or more. The rules also apply to the expression "at least one 'a' is substituted with 'B'.

"at least one-CH₂The expression "may be substituted by-O-is used in the description. In said case, -CH₂-CH₂-CH₂Can pass through non-contiguous-CH₂-conversion to-O-CH by-O-substitution₂-O-. However, adjacent-CH₂-is not substituted by-O-. This is because-O-CH is formed in the substitution₂- (peroxides). That is, the expression means "one-CH₂-may be substituted by-O-with at least two non-adjacent-CH ₂-may be substituted by-O- ". The rule applies not only to the case of substitution to-O-, but also to the case of substitution to a divalent group such as-CH ═ CH-or-COO-. In the alkyl group, at least one-CH is sometimes present₂-by cycloalkylene having 3 to 8 carbon atoms. The carbon number of the alkyl group is increased by the substitution. In this case, the maximum number of carbon atoms is 30. The rules apply not only to monovalent radicals such as alkyl groups, but also to divalent radicals such as alkylene groups.

In the chemical formula of the component compound, the end group R¹The notation of (a) is used for a variety of compounds. In these compounds, any two R¹The two radicals indicated may be identical or else different. For example, R of the compound (1-1)¹Is ethyl, and R of the compound (1-2)¹In the case of ethyl. Also, there are R of the compound (1-1)¹R of the compound (1-2) is ethyl¹In the case of propyl. The rules apply to other tokens. In the formula (1), when a is 2, two rings A are present. In the compounds, the two rings represented by the two rings a may be the same or may be different. The rule also applies to any two of a greater than 2A ring A. The rules apply to other tokens. The rules also apply to the two-Sp of compounds (5-7) ¹⁰-P⁵And so on.

The hexagonally surrounded symbols A, B, C, D and the like correspond to rings such as ring a, ring B, ring C, ring D and the like, respectively, and represent rings such as a six-membered ring, a condensed ring and the like. In the formula (5), the oblique lines intersecting the hexagons indicate that any hydrogen on the ring can be replaced by-Sp¹⁰-P⁵And the like. The 'v' et al subscripts indicate the number of substituted groups. When subscript 'v' is 0, there is no such substitution. When the subscript 'v' is 2 or more, a plurality of-Sp is present on the ring U¹⁰-P⁵。-Sp¹⁰-P⁵The various groups represented may be the same or different. In the expression "ring a and ring C are independently X, Y or Z", the subject is plural, and thus "independently" is used. When the subject is "ring a," independent "is not used since the subject is singular. When "ring a" is used in a plurality of formulae, the rule "may be the same or may be different" applies to "ring a". The same applies to other groups.

2-fluoro-1, 4-phenylene refers to the following two divalent radicals. In the formula, fluorine may be oriented to the left (L), or may be oriented to the right (R). The rules apply to unsymmetrical divalent radicals such as tetrahydropyran-2, 5-diyl, which are generated by removing two hydrogens from the ring. The rules also apply to divalent bonding groups such as carbonyloxy (-COO-or-OCO-).

The alkyl group of the liquid crystalline compound is linear or branched and does not include a cyclic alkyl group. Straight chain alkyls are preferred over branched alkyls. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups. In order to increase the upper limit temperature, the steric configuration associated with the 1, 4-cyclohexylene group is a trans configuration rather than a cis configuration.

The present invention is as follows.

The liquid crystal composition according to item 1, which contains a polar compound as a first additive and a polymerizable compound having at least three polymerizable groups as a second additive, and has negative dielectric anisotropy.

Item 2 the liquid crystal composition according to item 1, which contains at least one compound selected from the group of compounds represented by formula (1) as a first component,

in the formula (1), R¹And R²Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms; ring a and ring C are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane (chroman) -2, 6-diyl, or chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring B is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, or 7, 8-difluorochroman-2, 6-diyl; z ¹And Z²Independently a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-; a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

Item 3. the liquid crystal composition according to item 1 or item 2, which contains at least one compound selected from the group of compounds represented by formulae (1-1) to (1-22) as a first component,

in the formulae (1-1) to (1-22), R¹And R²Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms.

Item 4. the liquid crystal composition according to any one of item 1 to item 3, wherein the proportion of the first component is in a range of 10 to 90% by weight based on the weight of the liquid crystal composition.

Item 5. the liquid crystal composition according to any one of item 1 to item 4, which contains at least one compound selected from the group of compounds represented by formula (2) as a second component,

in the formula (2), R³And R⁴Independently an alkyl group of carbon number 1 to 12, an alkoxy group of carbon number 1 to 12, an alkenyl group of carbon number 2 to 12, an alkyl group of carbon number 1 to 12 in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group of carbon number 2 to 12 in which at least one hydrogen is substituted with fluorine or chlorine; ring D and ring E are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene; z ³Is a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-; c is 1, 2 or 3.

Item 6. the liquid crystal composition according to any one of item 1 to item 5, which contains at least one compound selected from the group of compounds represented by formulae (2-1) to (2-13) as a second component,

in the formulae (2-1) to (2-13), R³And R⁴Independently an alkyl group of carbon number 1 to 12, an alkoxy group of carbon number 1 to 12, an alkenyl group of carbon number 2 to 12, an alkyl group of carbon number 1 to 12 in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group of carbon number 2 to 12 in which at least one hydrogen is substituted with fluorine or chlorine.

Item 7. the liquid crystal composition of item 5 or item 6, wherein the proportion of the second component is in a range of 10 to 70 wt% based on the weight of the liquid crystal composition.

Item 8. the liquid crystal composition according to any one of item 1 to item 7, which contains a polar compound containing a polar group having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus, as the first additive.

Item 9. the liquid crystal composition according to any one of items 1 to 8, which contains at least one compound selected from the group of polar compounds represented by formula (3) and formula (4) as a first additive,

MES-R⁶ (3)

(R⁵)_x-R⁶ (4)

in the formula (3), MES is a mesogen having at least one ring; in the formula (4), R ⁵Is an alkyl group having 4 to 20 carbon atoms, in which at least one-CH group₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or cycloalkylene of carbon number 3 to 8, in which groups at least one hydrogen may be substituted by fluorine or chlorine; in the formulae (3) and (4), R⁶A polar group having at least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, and a nitrogen atom having a primary, secondary or tertiary amino structure; x is 1 or 2.

Item 10 the liquid crystal composition according to any one of item 1 to item 9, which contains at least one compound selected from the group of polar compounds represented by formula (3-1) as a first additive,

in the formula (3-1), R⁷Is hydrogen, fluorine, chlorine or alkyl with carbon number of 1 to 25, at least one-CH in the alkyl₂Can be through-NR⁰-, -O-, -S-, -CO-O-, -O-CO-O-or a cycloalkylene group of carbon number 3 to 8, and at least one tertiary carbon (C-) - (C-)>CH-) may be through nitrogen (C: (A)>N-) and of these, at least one hydrogen may be fluorinatedOr chloro, where R is⁰Hydrogen or alkyl having 1 to 12 carbon atoms; r⁸Is an alkyl group having 1 to 25 carbon atoms, in which at least one-CH group₂Can be through-NR⁰-, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-or cycloalkylene of carbon number 3 to 8, at least one tertiary carbon (C: (C)) >CH-) may be through nitrogen (C: (A)>N-) and of these radicals, at least one hydrogen may be substituted by fluorine or chlorine, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, wherein R⁸At least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, or a nitrogen atom having a primary, secondary or tertiary ammonia structure; ring F and ring G are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms or a heteroalicyclic group having 4 to 25 carbon atoms, which may be a condensed ring, wherein at least one hydrogen of these groups may be substituted by a group T, wherein the group T is-OH, - (CH) or₂)_i-OH, fluorine, chlorine, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R⁰)₂、-C(＝O)R⁰、-N(R⁰)₂、-(CH₂)_i-N(R⁰)₂Aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms or alkoxycarbonyloxy group having 2 to 25 carbon atoms, wherein at least one hydrogen may be substituted by fluorine or chlorine, wherein R is⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and i is 1, 2, 3 or 4; z⁴is-O-, -S-, -CO-O-, -OCO-, -O-CO-O-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_i-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_i-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-、-OCO-CH＝CH-、-C(R⁰)₂-or a single bond, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and i is 1, 2, 3 or 4; d is 0, 1, 2, 3, 4 or 5.

Item 11 the liquid crystal composition according to any one of item 1 to item 10, which contains at least one compound selected from the group of polar compounds represented by formula (4-1) as a first additive,

R⁹-R¹⁰ (4-1)

in the formula (4-1), R⁹Is an alkyl group having 4 to 20 carbon atoms, in which at least one-CH group₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or cycloalkylene of carbon number 3 to 8, in which groups at least one hydrogen may be substituted by fluorine or chlorine; r¹⁰Is an alkyl group having 1 to 25 carbon atoms, in which at least one-CH group₂Can be through-NR⁰-, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-or cycloalkylene of carbon number 3 to 8, at least one tertiary carbon (C: (C))>CH-) may be through nitrogen (C: (A)>N-) and of these radicals, at least one hydrogen may be substituted by fluorine or chlorine, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, wherein R¹⁰Has at least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, and a nitrogen atom having a primary, secondary or tertiary amino structure.

Item 12 the liquid crystal composition according to item 9, wherein in the formulae (3) and (4) according to item 9, R⁶Is a group selected from the group of polar groups represented by the formulae (A1) to (A4),

sp in formulae (A1) to (A4)⁴、Sp⁶And Sp⁷Independently a single bond or a group (-Sp "-X" -), where Sp "is an alkylene group having 1 to 20 carbon atoms in which at least one-CH group is present ₂May be substituted by-O-, -S-, -NH-, -N (R)⁰)-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-S-CO-、-CO-S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰) -, -CH-or-C.ident.C-in which at least one hydrogen may be substituted by fluorine, chlorine or-CN and X 'is-O-, -S-, -CO-O-, -O-CO-O-, -CO-N (R')⁰)-、-N(R⁰)-CO-、-N(R⁰)-CO-N(R⁰)-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR⁰-、-CY²＝CY³-, -C.ident.C-, -CH-CO-O-, -O-CO-CH-or a single bond, where R is⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and Y²And Y³Independently hydrogen, fluorine, chlorine or-CN; sp⁵Is composed of>CH-、>CR^a1-、>N-or>C<；X¹is-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂、-SH、-SR^a1、

Here, R⁰Hydrogen or alkyl having 1 to 12 carbon atoms; x²is-O-, -CO-, -NH-, -NR^a1-, -S-or a single bond; z⁹Is C1-15 alkylene, C5 OR C6 alicyclic group, OR their combination, wherein at least one hydrogen can pass through-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂Fluoro or chloro; here, R^a1Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-C ≡ C-, -CH ═ CH-, -COO-, -OCO-, -CO-, or-O-, where at least one hydrogen may be substituted by fluorine or chlorine; ring P is an aromatic group having 6 to 25 carbon atoms or an alicyclic group having 3 to 25 carbon atoms, which may be a condensed ring, wherein one to three hydrogen atoms may pass through R^LSubstituted, here, R^Lis-OH, - (CH)₂)_r-OH, fluorine, chlorine, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R⁰)₂、-C(＝O)R⁰、-N(R⁰)₂、-(CH₂)_r-N(R⁰)₂、-SH、-SR⁰Aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms or alkoxycarbonyloxy group having 2 to 25 carbon atoms, wherein at least one hydrogen may be substituted by fluorine or chlorine, wherein R is ⁰Is hydrogen or alkyl of 1 to 12 carbon atoms and r is 1, 2,3 or 4; p is 0, 1, 2 or 3; q is 2,3, 4 or 5.

Item 13 the liquid crystal composition of item 9 or item 10, wherein the first additive is at least one compound selected from the group of polar compounds represented by formulae (3-1-1) to (3-1-4),

in the formulae (3-1-1) to (3-1-4), R¹⁵Is alkyl with 1 to 8 carbon atoms or fluorine; ring Q and ring R are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 3-phenylene, 2-ethyl-1, 4-phenylene, 2, 6-diethyl-1, 4-phenylene, 2-trifluoromethyl-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene or 2,3,5, 6-tetrafluoro-1, 4-phenylene; ring S is cyclohexyl or phenyl; z¹⁰Is a single bond, -CH₂CH₂-, -COO-or-OCO-; z¹¹Is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 OR 6 carbon atoms OR a combination thereof, wherein at least one hydrogen atom may be replaced by-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂Fluorine or chlorine, where R^a1Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-C ≡ C-, -CH ═ CH-, -COO-, -OCO-, -CO-, or-O-, where at least one hydrogen may be substituted by fluorine or chlorine; sp ⁴Is a single bond, -CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂O-or-OCH₂-；Sp⁷Is a single bond or an alkylene group having 1 to 5 carbon atoms, wherein-CH is present in the alkylene group₂-may be substituted by-O-or-NH-; s is 0, 1,2, 3, 4 or 5; x³is-OH, -COOH, -SH, -OCH₃or-NH₂；X⁴Is a single bond or-O-.

Item 14. the liquid crystal composition according to item 9 or item 11, wherein the first additive is at least one compound selected from the group of polar compounds represented by formulae (4-1-1) to (4-1-29),

R⁹-OH (4-1-1)

R⁹-COOH (4-1-9)

R⁹-NH₂ (4-1-11)

in the formulae (4-1-1) to (4-1-29), R⁹Is an alkyl group having 4 to 20 carbon atoms, in which at least one-CH group₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or cycloalkylene of 3 to 8 carbon atoms, in which at least one hydrogen may be substituted by fluorine or chlorine.

Item 15 the liquid crystal composition of any one of items 1 to 14, wherein a proportion of the first additive ranges from 0.05 wt% to 10 wt% based on the weight of the liquid crystal composition.

Item 16. the liquid crystal composition according to any one of item 1 to item 15, which contains at least one compound selected from the group of polymerizable compounds represented by formula (5) as a second additive,

in formula (5), ring T and ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted with a fluorine or chlorine-substituted alkyl group having 1 to 12 carbon atoms; the ring U is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, Or at least one hydrogen is substituted by a fluorine or chlorine substituted alkyl group of carbon number 1 to 12; z ¹²And Z¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -CO-, -COO-or-OCO-, and at least one-CH₂CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine; p⁴、P⁵And P⁶Is a polymerizable group; sp⁹、Sp¹⁰And Sp¹¹Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -COO-, -OCO-or-OCOO-, and at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine; t is 0, 1 or 2; u, v and w are independently 0, 1, 2, 3 or 4, and the sum of u, v and w is 3 or more.

Item 17 the liquid crystal composition of item 16, wherein in the formula (5) according to item 16, P⁴、P⁵And P⁶Independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-5),

in the formulae (P-1) to (P-5), M¹、M²And M³Independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 18. the liquid crystal composition according to any one of item 1 to item 17, which contains at least one compound selected from the group of polymerizable compounds represented by formulae (5-1) to (5-7) as a second additive,

In formulae (5-1) to (5-7), P⁴、P⁵And P⁶Independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3),

here, M¹、M²And M³Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine or chlorine; sp⁹、Sp¹⁰And Sp¹¹Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -COO-, -OCO-or-OCOO-, and at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

Item 19. the liquid crystal composition of any one of items 16 to 18, wherein a proportion of the second additive ranges from 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition.

Item 20. a liquid crystal display element containing the liquid crystal composition according to any one of items 1 to 19.

Item 21 is the liquid crystal display device of item 20, wherein the liquid crystal display device operates in an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the liquid crystal display device is driven in an active matrix mode.

Item 22. a polymer stable alignment type liquid crystal display element, which contains the liquid crystal composition according to any one of items 1 to 19, and in which a polymerizable compound is polymerized.

Item 23. a liquid crystal display element having no alignment film, which contains the liquid crystal composition according to any one of items 1 to 19, and in which a polymerizable compound is polymerized.

Item 24. use of the liquid crystal composition according to any one of items 1 to 19 in a liquid crystal display element.

Item 25. use of the liquid crystal composition of any one of items 1 to 19 in a polymer-stabilized alignment type liquid crystal display element.

Item 26. use of the liquid crystal composition according to any one of items 1 to 19 in a liquid crystal display element having no alignment film.

The present invention also includes the following items. (a) A method for manufacturing a liquid crystal display element, comprising disposing the liquid crystal composition between two substrates, and irradiating the composition with light in a state where a voltage is applied to the composition to polymerize a polymerizable compound contained in the composition. (b) The liquid crystal composition has an upper limit temperature of a nematic phase of 70 ℃ or higher, an optical anisotropy at a wavelength of 589nm (measured at 25 ℃) of 0.08 or higher, and a dielectric anisotropy at a frequency of 1kHz (measured at 25 ℃) of-2 or lower.

The present invention also includes the following items. (c) The above-mentioned composition contains at least one compound selected from the group consisting of compounds (5) to (7) described in Japanese patent laid-open No. 2006-199941, which are liquid-crystalline compounds having positive dielectric anisotropy. (d) The above composition containing at least two of the above polar compounds. (e) And the composition further contains a polar compound different from the polar compound. (f) The above composition contains additives such as one, two or at least three kinds of optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. (g) An AM element comprising the above composition. (h) An element having a TN mode, ECB mode, OCB mode, IPS mode, FFS mode, VA mode, or FPA mode, which contains the above-mentioned composition. (i) A transmission element comprising the composition. (j) The above composition is used as a composition having a nematic phase. (k) The use of the composition as an optically active composition by adding an optically active compound to the composition.

The composition of the present invention is illustrated in the following order. First, the composition is explained. Secondly, the main characteristics of the component compounds and the main effects of the compounds on the composition will be described. Third, the combination of the components in the composition, the preferred proportions of the components, and their basis are described. Fourth, preferred embodiments of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compound will be explained. Finally, the use of the composition is illustrated.

First, the composition is explained. The compositions of the present invention are classified as composition a and composition B. The composition a may contain other liquid crystalline compounds, additives, and the like in addition to the liquid crystalline compound selected from the compounds (1) and (2). The "other liquid crystalline compound" is a liquid crystalline compound different from the compound (1) and the compound (2). Such compounds are mixed in the composition for the purpose of further adjusting the properties. The additive is an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound, or the like.

The composition B substantially contains only a liquid crystalline compound selected from the compound (1) and the compound (2). "substantially" means that the composition may contain additives but does not contain other liquid crystalline compounds. The amount of ingredients of composition B is low compared to composition a. From the viewpoint of cost reduction, composition B is superior to composition a. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystalline compounds, the composition a is superior to the composition B.

Secondly, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be described. The main properties of the component compounds based on the effects of the present invention are summarized in Table 2. In the notation of Table 2, L means large or high, M means medium, and S means small or low. The notation L, M, S is a classification based on qualitative comparisons between component compounds, with notation 0 meaning a value of zero, or close to zero.

TABLE 2 Properties of liquid crystalline Compounds

Characteristics of	Compound (1)	Compound (2)
			Upper limit temperature	S～L	S～L
Viscosity of the oil	M～L	S～M
			Optical anisotropy	M～L	S～L
Dielectric anisotropy	M～L¹⁾	0
			Specific resistance	L	L

1) Negative dielectric anisotropy

When the component compounds are mixed in the composition, the main effects of the component compounds on the properties of the composition are as follows. The compound (1) improves dielectric anisotropy. The compound (2) raises the upper limit temperature, or lowers the viscosity. The compound (3) or the compound (4) is adsorbed on the substrate surface by the action of the polar group, and controls the orientation of the liquid crystal molecules. In order to obtain the desired effect, these compounds must have high compatibility with the liquid crystalline compound. The compound (5) forms a polymer by polymerization. The polymer stabilizes the orientation of liquid crystal molecules, thereby shortening the response time of the element and improving the afterimage of the image.

Third, the combination of the components in the composition, the preferred proportions of the components, and their basis are described. A preferred combination of ingredients in the composition is compound (1) + compound (2). The vertical alignment of liquid crystal molecules can be achieved by combining a polar compound and a polymerizable compound (or a polymer thereof) in the composition. When the amount of the "other liquid crystalline compound" is small, the same effect can be obtained even when the compound is added to the composition.

The preferable proportion of the compound (1) is about 10% by weight or more for improving the dielectric anisotropy, and about 90% by weight or less for reducing the viscosity. Even more preferably, the ratio is in the range of about 15 wt% to about 80 wt%. A particularly preferred ratio is in the range of about 20% to about 70% by weight.

The preferable proportion of the compound (2) is about 10% by weight or more in order to increase the upper limit temperature or to decrease the viscosity, and the preferable proportion of the compound (2) is about 70% by weight or less in order to increase the dielectric anisotropy. Even more preferably, the ratio is in the range of about 10 wt% to about 65 wt%. A particularly preferred ratio is in the range of about 15% to about 60% by weight.

The compound (3) and the compound (4) are added to the composition for the purpose of controlling the alignment of liquid crystal molecules. The preferable ratio of the compound (3) or the compound (4) is about 0.05% by weight or more for aligning liquid crystal molecules, and the preferable ratio of the compound (3) or the compound (4) is about 10% by weight or less for preventing display defects of the device. Even more preferably, the ratio is in the range of about 0.1 wt% to about 7 wt%. A particularly preferred ratio is in the range of about 0.5 wt% to about 5 wt%.

The compound (5) is added to the composition for the purpose of being suitable for a polymer stable alignment type element. The preferable proportion of the compound (5) is about 0.03% by weight or more in order to improve the long-term reliability of the device, and the preferable proportion of the compound (5) is about 10% by weight or less in order to prevent display failure of the device. Even more preferably, the ratio is in the range of about 0.1 wt% to about 2 wt%. A particularly preferred ratio is in the range of about 0.2 wt% to about 1.0 wt%.

Fourth, preferred embodiments of the component compounds will be described. In the formulae (1) and (2), R¹And R²Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms. Preferred R is for improving stability to ultraviolet light or heat¹Or R²Is an alkyl group having 1 to 12 carbon atoms, and R is preferably selected to improve dielectric anisotropy¹Or R²Is alkoxy with 1 to 12 carbon atoms.

R³And R⁴Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, at least one hydrogen atomA fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms, or a fluorine or chlorine substituted alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted. Preferred R is for improving stability to ultraviolet light or heat ³Or R⁴Is an alkyl group having 1 to 12 carbon atoms, and R is preferably selected for lowering the lower limit temperature or for lowering the viscosity³Or R⁴Is an alkenyl group having 2 to 12 carbon atoms.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. Further preferred alkyl groups for reducing the viscosity are ethyl, propyl, butyl, pentyl or heptyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy. Further preferred alkoxy groups for reducing the viscosity are methoxy or ethoxy.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. Further preferred alkenyl groups for reducing the viscosity are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred steric configuration of-CH ═ CH-in these alkenyl groups depends on the position of the double bond. For reasons of viscosity reduction and the like, the trans configuration is preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. Among alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. Further preferred alkenyloxy groups are allyloxy or 3-butenyloxy groups in order to reduce the viscosity.

Preferred examples of alkyl groups in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl or 8-fluorooctyl. Further preferable examples of the compound include 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl and 5-fluoropentyl for improving the dielectric anisotropy.

Preferred examples of alkenyl groups in which at least one hydrogen is substituted by fluorine or chlorine are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl or 6, 6-difluoro-5-hexenyl. Further preferable examples for lowering the viscosity are 2, 2-difluorovinyl group and 4, 4-difluoro-3-butenyl group.

Ring A and ring C are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine. Preferred rings A or C are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl or 7, 8-difluorochroman-2, 6-diyl. Further preferred as ring A or ring C is 1, 4-cyclohexylene or 1, 4-phenylene. Among these rings, the ring A or the ring C is preferably a 1, 4-cyclohexylene group for lowering the viscosity, the ring A or the ring C is preferably a tetrahydropyran-2, 5-diyl group for improving the dielectric anisotropy, and the ring A or the ring C is preferably a 1, 4-phenylene group for improving the optical anisotropy. Tetrahydropyran-2, 5-diyl as

Or

Preferably, it is

Ring B is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, or 7, 8-difluorochromane-2, 6-diyl. Preferred ring B is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene or 7, 8-difluorochroman-2, 6-diyl. Further preferred ring B is 2, 3-difluoro-1, 4-phenylene or 2-chloro-3-fluoro-1, 4-phenylene. A particularly preferred ring B is 2, 3-difluoro-1, 4-phenylene. Among these rings, the preferred ring B is 2, 3-difluoro-1, 4-phenylene for lowering the viscosity, 2-chloro-3-fluoro-1, 4-phenylene for lowering the optical anisotropy, and 7, 8-difluorochroman-2, 6-diyl for increasing the dielectric anisotropy.

Ring D and ring E are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene. For lowering the viscosity, or for raising the upper temperature limit, the preferred ring D or E is 1, 4-cyclohexylene, and for lowering the lower temperature limit, the preferred ring D or E is 1, 4-phenylene.

Z¹And Z²Independently a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-. For reducing the viscosity, preferred is Z¹Or Z²Is a single bond, and Z is preferably Z for lowering the lower limit temperature ¹Or Z²is-CH₂CH₂-, preferred Z for the purpose of enhancing dielectric anisotropy¹Or Z²is-CH₂O-or-OCH₂-。Z³Is a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-. For reducing the viscosity, preferred is Z³Is a single bond, and Z is preferably Z for lowering the lower limit temperature³is-CH₂CH₂To raise the upper limit temperature, Z is preferred³is-COO-or-OCO-.

a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. For lowering the viscosity, a is preferably 1, and for raising the upper limit temperature, a is preferably 2 or 3. For lowering the viscosity, b is preferably 0, and for lowering the lower limit temperature, b is preferably 1. c is 1, 2 or 3. For lowering the viscosity, c is preferably 1, and for raising the upper limit temperature, c is preferably 2 or 3.

In the formula (3), MES is a mesogen having at least one ring. Mesogenic groups are well known to those skilled in the art. The mesogen refers to a portion (moiey) that contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (mesophase). A preferable example of the compound (3) is the compound (3-1).

In the formula (4), R⁵Is an alkyl group having 4 to 20 carbon atoms, in which at least one-CH group₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or cycloalkylene of 3 to 8 carbon atoms, in which at least one hydrogen may be substituted by fluorine or chlorine. x is 1 or 2, preferably 1.

Preferred R⁵Is an alkyl group having 4 to 20 carbon atoms. Further preferred is R⁵Is an alkyl group having 6 to 18 carbon atoms. At least one-CH₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or-O-, and at least one hydrogen may be substituted by fluorine or chlorine.

In the formulae (3) and (4), R⁶Is a polar group. The compound (3) and the compound (4) are preferably stable to ultraviolet light or heat because they are added to the composition. When the compound (3) and the compound (4) are added to the composition, the compound preferably does not lower the voltage holding ratio of the device. The compound (3) and the compound (4) preferably have low volatility. The preferred molar mass is 130g/mol or more. Further, the preferred molar mass is in the range of 150g/mol to 500 g/mol.

The polar group has a non-covalently bonded interaction with the surface of the glass substrate or the metal oxide film. Preferred polar groups have heteroatoms selected from the group of nitrogen, oxygen, sulfur and phosphorus. Preferred polar groups have at least one or at least two of these heteroatoms. Further preferred polar groups are monovalent groups derived by removing hydrogen from a compound selected from the group of alcohols, primary, secondary and tertiary amines, ketones, carboxylic acids, thiols, esters, ethers, thioethers and combinations of these. The structure of these groups may be linear, branched, cyclic, or a combination thereof. Particularly preferred polar groups have at least one of an oxygen atom of an OH structure or a nitrogen atom of a primary, secondary or tertiary amino structure. The most preferred polar group is a hydroxyl group (carbon-OH).

Polar group R⁶Examples of (A) are the groups represented by the formulae (A1) to (A4).

Sp in formulae (A1) to (A4)⁴、Sp⁶And Sp⁷Independently a single bond or a group (-Sp ' -X ' -), and X ' is bonded to the ring P. Sp' is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 12 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -S-, -NH-, -N (R)⁰)-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-S-CO-、-CO-S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰) -, -CH-or-C.ident.C-in which at least one hydrogen may be substituted by fluorine, chlorine or-CN, and X 'is-O-, -S-, -CO-O-, -O-CO-O-, -CO-N (R')⁰)-、-N(R⁰)-CO-、-N(R⁰)-CO-N(R⁰)-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR⁰-、-CY²＝CY³-, -C.ident.C-, -CH-CO-O-, -O-CO-CH-or a single bond, where R is⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, Y²And Y³Independently hydrogen, fluorine, chlorine or-CN. Preferred X' is-O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR-⁰-、-NR⁰-CO-、-NR⁰-CO-NR⁰-or a single bond. Sp⁵Is composed of>CH-、>CR^a1-、>N-or>C<. Namely Sp in the formula (A2)⁵Is composed of>CH-、>CR^a1-or>N-, Sp in the formula (A3)⁵Means that>C<。

Preferably Sp "is- (CH)₂)_p1-、-(CH₂CH₂O)_q1-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂-or-CH₂CH₂-NHCH₂CH₂Here, p1 is an integer of 1 to 12, and q1 is an integer of 1 to 3. Preferred radicals (-Sp '-X') "-) is- (CH₂)_p1-、-(CH₂)_p1-O-、-(CH₂)_p1-O-CO-、-(CH₂)_p1-O-CO-O-, where p1 and q1 have the meanings indicated above. Further preferred radicals Sp "are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

X¹is-NH₂、-NHR^a1、-N(R^a1)₂、-OR^a1、-OH、-COOH、-SH、-SR^a1、

Here, R^a1Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-C.ident.C-, -CH ═ CH-, -COO-, -OCO-, -CO-or-O-, of which groups at least one hydrogen may be substituted by fluorine or chlorine, R⁰Hydrogen or an alkyl group having 1 to 12 carbon atoms.

X²is-O-, -CO-, -NH-, -NR^a1-, -S-or a single bond, Z⁹Represents an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 to 6 carbon atoms OR a combination of at least one ring and an alkylene group, wherein at least one hydrogen in these groups may be replaced by-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂Fluorine or chlorine, where R^a1Have the meaning indicated above. p is 0, 1, 2 or 3. q is 2, 3, 4 or 5.

Ring P is an aromatic group having 6 to 25 carbon atoms or an alicyclic group having 3 to 25 carbon atoms, which may be a condensed ring, wherein one to three hydrogen atoms may pass through R^LAnd (4) substitution. R^Lis-OH, - (CH)₂)_r-OH, fluorine, chlorine, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R⁰)₂、-C(＝O)R⁰、-N(R⁰)₂、-(CH₂)_r-N(R⁰)₂、-SH、-SR⁰Aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms or alkoxycarbonyloxy group having 2 to 25 carbon atoms, wherein at least one hydrogen may be substituted by fluorine or chlorine, wherein R is⁰Hydrogen or an alkyl group having 1 to 12 carbon atoms.

Particularly preferred nitrogen-containing radicals R⁶is-NH₂、-NH-(CH₂)_n3H、-(CH₂)_n-NH₂、-(CH₂)_n-NH-(CH₂)_n3H、-NH-(CH₂)_n-NH₂、-NH-(CH₂)_n-NH-(CH₂)_n3H、-(CH₂)_n1-NH-(CH₂)_n2-NH₂、-(CH₂)_n1-NH-(CH₂)_n2-NH-(CH₂)_n3H、-O-(CH₂)_n-NH₂、-(CH₂)_n1-O-(CH₂)_n-NH₂、-(CH₂)_n1-NH-(CH₂)_n2-OH、-O-(CH₂)_n1-NH-(CH₂)_n2-NH₂、-O-(CH₂)_n1-NH-(CH₂)_n2-OH or- (CH)₂)_n1-NH-(CH₂)_n2-NH-(CH₂)_n3H, where n, n1, n2, and n3 are independently integers of 1 to 12, preferably 1, 2, 3, or 4.

Particularly preferred non-nitrogen-containing radicals R⁶is-OH, - (CH)₂)_n-OH、-O-(CH₂)_n-OH、-[O-(CH₂)_n1-]_n2-OH、-COOH、-(CH₂)_n-COOH、-O-(CH₂)_n-COOH or- [ O- (CH)₂)_n1-]_n2-COOH, where n, n1 and n2 are independently integers from 1 to 12, preferably 1, 2, 3 or 4.

In situ liquid crystal compositionIn view of high solubility in (A), R⁶Particularly preferred is-OH or-NH₂. OH is superior to O-, -CO-or COO-because it has a high anchoring force. Particularly preferred is a group having a plurality of hetero atoms (nitrogen, oxygen). Compounds having such polar groups are effective even at low concentrations.

In the formula (3-1), R⁷Is hydrogen, fluorine, chlorine, alkyl with carbon number of 1-25, at least one-CH in the alkyl₂Can be through-NR⁰-, -O-, -S-, -CO-O-, -O-CO-O-or a cycloalkylene group of carbon number 3 to 8, and at least one tertiary carbon (C-) - (C-)>CH-) may be through nitrogen (C: (A)>N-) and of these radicals, at least one hydrogen may be substituted by fluorine or chlorine, where R⁰Hydrogen or an alkyl group having 1 to 12 carbon atoms.

R⁸Is an alkyl group having 1 to 25 carbon atoms, in which at least one-CH group₂Can be through-NR⁰-, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-or a C3 to C8 cycloalkylene group, where R ⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, at least one tertiary carbon (C:)>CH-) may be through nitrogen (C: (A)>N-) and at least one hydrogen may be substituted by fluorine or chlorine, wherein R⁸Has at least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, or a nitrogen atom having a primary, secondary or tertiary ammonia structure.

Ring F and ring G are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms or a heteroalicyclic group having 4 to 25 carbon atoms, which may be a condensed ring, wherein at least one hydrogen of these groups may be substituted by a group T, wherein the group T is-OH, - (CH) or₂)_i-OH, fluorine, chlorine, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R⁰)₂、-C(＝O)R⁰、-N(R⁰)₂、-(CH₂)_i-N(R⁰)₂Aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms or alkoxycarbonyloxy group having 2 to 25 carbon atoms, wherein at least one hydrogen may be fluorine orChloro, here, R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and i is 1, 2, 3 or 4.

Z⁴is-O-, -S-, -CO-O-, -OCO-, -O-CO-O-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_i-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_i-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-、-OCO-CH＝CH-、-C(R⁰)₂-or a single bond, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and i is 1, 2, 3 or 4.

d is 0, 1, 2,3, 4 or 5.

In the formula (4-1), R⁹Is an alkyl group having 4 to 20 carbon atoms, in which at least one-CH group₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or cycloalkylene of 3 to 8 carbon atoms, in which at least one hydrogen may be substituted by fluorine or chlorine.

R¹⁰Is an alkyl group having 1 to 25 carbon atoms, in which at least one-CH group₂Can be through-NR⁰-, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-or a C3 to C8 cycloalkylene group, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, at least one tertiary carbon (C:)>CH-) may be through nitrogen (C: (A)>N-) and at least one hydrogen may be substituted by fluorine or chlorine, wherein R¹⁰Has at least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, and a nitrogen atom having a primary, secondary or tertiary amino structure.

In the formulae (3-1-1) to (3-1-4), R¹⁵Is alkyl with carbon number of 1 to 8 or fluorine. The ring Q and the ring R are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 3-phenylene, 2-ethyl-1, 4-phenylene, 2, 6-diethyl-1, 4-phenylene, 2-trifluoromethyl-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene or 2,3,5, 6-tetrafluoro-1, 4-phenylene. Ring S is cyclohexyl or phenyl.

Z¹⁰Is a single bond, -CH₂CH₂-, -COO-or-OCO-. Z¹¹Is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 OR 6 carbon atoms, OR a combination thereof, wherein at least one hydrogen atom in these groups may be replaced by-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂Fluorine or chlorine, where R^a1Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-C ≡ C-, -CH ═ CH-, -COO-, -OCO-, -CO-, or-O-, at least one of which groups may be substituted by fluorine or chlorine.

Sp⁴Is a single bond, -CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂O-or-OCH₂-。Sp⁷Is a single bond or an alkylene group having 1 to 5 carbon atoms, wherein-CH is present in the alkylene group₂-may be substituted by-O-or-NH-. X³is-OH, -COOH, -SH, -OCH₃or-NH₂。X⁴Is a single bond or-O-. s is 0, 1, 2, 3, 4 or 5.

Aromatic refers to aryl or substituted aryl. Heteroaryl refers to an aromatic group having at least one heteroatom. The aryl and heteroaryl groups may be either monocyclic or polycyclic. That is, these groups have at least one ring, which may be condensed (e.g., naphthyl), two rings may be linked by a covalent bond (e.g., biphenyl), or a combination of condensed and linked rings. Preferred heteroaryl groups have at least one heteroatom selected from the group of nitrogen, oxygen, sulfur and phosphorus.

Preferred aryl or heteroaryl groups have a carbon number of 6 to 25 and may also be five-, six-or seven-membered rings. Preferred aryl or heteroaryl groups may be monocyclic, but also bicyclic or tricyclic. These radicals may be condensed rings or may be substituted.

Preferred aryl groups are those obtained by reacting a phenyl group selected from benzene, biphenyl, terphenyl, [1, 1': 3',1"]Terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene (pyrene), dihydropyrene (dihydropyrene),

(chrysene), perylene (perylene), tetracene (tetracene), pentacene (pentac)ene), benzopyrene, fluorene (fluorene), indene (indene), indenofluorene (indenofluorene), spirobifluorene (spirobifluorene) from which one hydrogen is removed.

Preferred heteroaryl groups are those obtained by reacting a substituted or unsubstituted heteroaryl group with a five-membered ring compound selected from pyrrole, pyrazole, imidazole, 1,2, 3-triazole, 1,2, 4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, or pyridine, pyridazine, pyrimidine, pyrazine, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, a monovalent group derived from a six-membered ring compound such as 5-tetrazine by removing one hydrogen atom.

Preferred heteroaryl groups are also those prepared by reacting a heteroaryl group selected from indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthoimidazole, phenanthroimidazole, pyridoimidazole (pyrimidazole), pyrazinoimidazole, quinoxaloimidazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, bipyridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, benzisoquinoline, acridine, phenothiazine, phenoxazine, benzopyrazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocaine, phenanthridine, phenanthroline, thieno [2,3b ] thiophene, thieno [3,2b ] thiophene, dithienothiophene, isobenzothiophene, benzothiophene, purine, naphthoxazole, naphtho, phenanthroline, thieno [2,3b ] thiophene, thieno [3,2b ] thiophene, A monovalent group derived from a condensed ring compound such as dibenzothiophene or benzothiadiazolethiophene by removing one hydrogen atom. Preferred heteroaryl groups are also monovalent radicals derived by removing one hydrogen from a ring formed by combining two radicals selected from these five-membered rings, six-membered rings, condensed rings. These heteroaryl groups may be substituted with alkyl, alkoxy, thioalkyl, fluoro, fluoroalkyl, aryl or heteroaryl groups.

The alicyclic group may be saturated or may be unsaturated. That is, these groups may have only single bonds, or may have a combination of single bonds and multiple bonds. Saturated rings are preferred over unsaturated rings.

Alicyclic groupMay be one ring or may be a plurality of rings. Preferred examples of these groups are monocyclic, bicyclic or tricyclic rings having 3 to 25 carbon atoms, and these groups may be condensed rings or may be substituted. Preferred examples of these radicals are five-, six-, seven-or eight-membered rings in which at least one carbon may be substituted by silicon and at least one may be substituted by silicon>CH-can be through>N-substituted and at least one-CH₂-may be substituted by-O-or-S-.

Preferred alicyclic groups are divalent groups derived by removing two hydrogens from a five-membered ring such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, and pyrrolidine, a six-membered ring such as cyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1, 3-dioxane, 1, 3-dithiane, and piperidine, a seven-membered ring such as cycloheptane, a condensed ring such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo [1.1.1] pentane, bicyclo [2.2.2] octane, spiro [3.3] heptane, and octahydro-4, 7-methyleneindane.

In the formula (5), P⁴、P⁵And P⁶Independently a polymerizable group. Preferred P⁴、P⁵Or P ⁶Is a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-5). Further preferred is P⁴、P⁵Or P⁶Is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P⁴、P⁵Or P⁶Is a group represented by the formula (P-1) or (P-2). Most preferred P⁴、P⁵Or P⁶Is a group represented by the formula (P-1). A preferred group represented by formula (P-1) is-OCO-CH ═ CH₂or-OCO-C (CH)₃)＝CH₂. The wavy lines of the formulae (P-1) to (P-5) represent the sites of bonding.

In the formulae (P-1) to (P-5), M¹、M²And M³Independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. For the purpose of enhancing reactivity, M is preferred¹、M²Or M³Is hydrogen or methyl. Further preferred isM of (A)¹Is hydrogen or methyl, and further preferred M²Or M³Is hydrogen.

Sp⁹、Sp¹⁰And Sp¹¹Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -COO-, -OCO-or-OCOO-, and at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine. Preferred is Sp⁹、Sp¹⁰Or Sp¹¹Is a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-, -OCO-, -CO-CH-or-CH-CO-. Further preferred is Sp⁹、S_p ¹⁰Or S_p ¹¹Is a single bond.

Ring T and ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferably ring T or ring V is phenyl. The ring U is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, Or at least one hydrogen is substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms. Preferred rings U are 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

Z¹²And Z¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -CO-, -COO-or-OCO-, and at least one-CH₂CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z¹²Or Z¹³Is a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-. Further preferred is Z¹²Or Z¹³Is a single bond.

t is 0, 1 or 2. Preferably t is 0 or 1. u, v and w are independently 0, 1, 2, 3 or 4, and the sum of u, v and w is 3 or more. Preferably u, v or w is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to the compound (1-22) described in the item 3. Of these compounds, it is preferable that at least one of the first components is the compound (1-1), the compound (1-3), the compound (1-4), the compound (1-6), the compound (1-8) or the compound (1-10). Preferably, at least two of the first components are a combination of the compound (1-1) and the compound (1-6), the compound (1-1) and the compound (1-10), the compound (1-3) and the compound (1-6), the compound (1-3) and the compound (1-10), the compound (1-4) and the compound (1-6), or the compound (1-4) and the compound (1-8).

Preferred compound (2) is the compound (2-1) to the compound (2-13) described in the item 6. Of these compounds, it is preferable that at least one of the second components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-8) or compound (2-9). Preferably, at least two of the second components are compound (2-1) and compound (2-3), compound (2-1) and compound (2-5), or a combination of compound (2-1) and compound (2-6).

Preferred compounds (3) are the compounds (3-1-1) to (3-1-4) described in the item 13. Of these compounds, it is preferable that at least one of the first additives is the compound (3-1-1). Preferably, at least two of the first additives are a combination of the compound (3-1-1) and the compound (3-1-2).

Preferred compounds (4) are the compounds (4-1-1) to (4-1-29) described in the item 14. In general, compound (3) is superior to compound (4).

Particularly preferred compound (3-1) is selected from the following compounds.

In the formulae (3-1-1-1) to (3-1-4-4), R¹⁵Is alkyl with carbon number of 1 to 8 or fluorine.

Particularly preferred compound (4-1) is selected from the following compounds (4-1-1-1) to (4-1-29-1).

Preferred compound (5) is compound (5-1) to compound (5-7) described in item 18. Of these compounds, it is preferable that at least one of the second additives is the compound (5-2), the compound (5-5) or the compound (5-7). Preferably, at least two of the second additives are the compound (5-1) and the compound (5-2), the compound (5-2) and the compound (5-5), or a combination of the compound (5-2) and the compound (5-7).

Sixth, additives that can be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to impart a twist angle (torsion angle). Examples of such compounds are compound (6-1) to compound (6-5). The preferable proportion of the optically active compound is about 5% by weight or less. Even more preferably, the ratio is in the range of about 0.01 wt% to about 2 wt%.

An antioxidant is added to the composition in order to prevent a decrease in specific resistance caused by heating in the atmosphere or to maintain a large voltage holding ratio at room temperature and at a temperature close to the upper limit temperature even after the device is used for a long time. Preferable examples of the antioxidant include a compound (7) wherein n is an integer of 1 to 9, and the like.

In the compound (7), n is preferably 1, 3, 5, 7 or 9. Further, n is preferably 7. Since the compound (7) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. In order to obtain the above effects, the preferable proportion of the antioxidant is about 50ppm or more, and the preferable proportion of the antioxidant is about 600ppm or less so as not to lower the upper limit temperature or not to raise the lower limit temperature. Even more preferably in the range of about 100ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Further, light stabilizers such as hindered ammonia are also preferable. In order to obtain the above-mentioned effects, the preferable proportion of these absorbents or stabilizers is about 50ppm or more, and in order not to lower the upper limit temperature or to raise the lower limit temperature, the preferable proportion of these absorbents or stabilizers is about 10000ppm or less. Even more preferably the ratio is in the range of about 100ppm to about 10000 ppm.

In order to be suitable for a guest-host (GH) mode element, a dichroic dye (dichromatic dye) such as an azo dye or an anthraquinone dye is added to the composition. The preferred proportion of pigment ranges from about 0.01% to about 10% by weight. In order to prevent foaming, an antifoaming agent such as dimethylsilicone oil or methylphenylsilicone oil is added to the composition. The preferable ratio of the defoaming agent is about 1ppm or more in order to obtain the above effects, and about 1000ppm or less in order to prevent display failure. Even more preferably in the range of about 1ppm to about 500 ppm.

Polymerizable compounds are used to adapt to polymer-stabilized alignment (PSA) type devices. The compound (5) is suitable for the purpose. The compound (5) and a polymerizable compound different from the compound (5) may be added to the composition. Preferable examples of such polymerizable compounds are compounds such as acrylic acid esters, methacrylic acid esters, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane ) and vinyl ketones. Further preferred is an acrylate or methacrylate. The preferable proportion of the compound (5) is about 10% by weight or more based on the total weight of the polymerizable compound. More preferably, the content is about 50% by weight or more. Particularly preferred is a ratio of about 80% by weight or more. Particularly preferred proportions are also 100% by weight. The reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules can be adjusted by changing the kind of the compound (5) or by combining another polymerizable compound with the compound (5) at an appropriate ratio. By optimizing the pretilt angle, a short response time of the element can be achieved. The alignment of the liquid crystal molecules is stabilized, and thus a large contrast ratio or a long lifetime can be achieved.

The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of an appropriate initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, brilliant good solid (Irgacure)651 (registered trademark; BASF), brilliant good solid (Irgacure)184 (registered trademark; BASF), or Darocur (Darocur)1173 (registered trademark; BASF) as a photopolymerization initiator is suitable for radical polymerization. The preferable proportion of the photopolymerization initiator ranges from about 0.1% by weight to about 5% by weight, based on the total weight of the polymerizable compound. Even more preferably, the ratio is in the range of about 1 wt% to about 3 wt%.

When the polymerizable compound is stored, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-t-butyl catechol, 4-methoxyphenol, phenothiazine and the like.

The polar compound is an organic compound having polarity. Here, no compound having an ionic bond is contained. Atoms such as oxygen, sulfur and nitrogen are negatively charged and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity arises because part of the charge is distributed unequally among the atoms of different species in the compound. For example, the polar compound has-OH, -COOH, -SH, -NH ₂、>NH、>N-, or the like.

Seventh, a method for synthesizing the component compound will be explained. These compounds can be synthesized using known methods. A synthesis method is exemplified. The compound (1-1) is synthesized by the method described in Japanese patent laid-open No. Hei 2-503441. The compound (2-1) is synthesized by the method described in Japanese patent laid-open publication No. 59-176221. The compound (3-1) was synthesized by the method described in International publication No. 2012-038026. A part of compound (4) is commercially available. The compound (5-1) was synthesized by the method described in International publication No. 2013-161576. A part of compound (7) is commercially available. The compound of formula (7) wherein n is 1 can be obtained from Sigma Aldrich Corporation. The compound (7) wherein n is 7, etc. is synthesized by the method described in the specification of U.S. Pat. No. 3660505.

Compounds not described in the synthesis method can be synthesized by the method described in the following protocol: organic Synthesis (Organic Syntheses, John Wiley & Sons, Inc.), "Organic Reactions (Organic Reactions, John Wiley father publishing corporation)," Comprehensive Organic Synthesis (Comprehensive Organic Syntheses, pegman publishing (Pergamon Press)), "new experimental chemistry lecture (pill), etc. The composition is prepared from the compound obtained in the above-described manner using a known method. For example, the component compounds are mixed and then dissolved in each other by heating.

Finally, the use of the composition is illustrated. Most compositions have a lower temperature of about-10 ℃ or less, an upper temperature of about 70 ℃ or more, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds, or by mixing other liquid crystalline compounds. Further, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 may also be prepared by trial and error. The device containing the composition has a large voltage holding ratio. The composition is suitable for AM elements. The composition is particularly suitable for transmissive AM elements. The composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

The compositions are useful in AM elements. And further can be used for PM elements. The composition can be used for AM elements and PM elements with modes of PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and the like. Particularly, it is preferable to use the AM device having TN, OCB, IPS, FFS or other modes. In an AM element having an IPS mode or an FFS mode, the alignment of liquid crystal molecules may be parallel to a glass substrate or may be perpendicular to the glass substrate when no voltage is applied. These elements may be reflective, transmissive or transflective. Preferably for use in transmissive devices. But also for amorphous silicon-TFT elements or polysilicon-TFT elements. The composition may be used for a device of a Nematic Curvilinear Aligned Phase (NCAP) type prepared by microencapsulation (microencapsulation) or a device of a Polymer Dispersed (PD) type in which a three-dimensional network polymer is formed in the composition.

An example of a conventional method for producing a polymer stabilized alignment type device is as follows. An element including two substrates, referred to as an array substrate and a color filter substrate, is assembled. The substrate has an alignment film. At least one of the substrates has an electrode layer. The liquid crystal composition is prepared by mixing liquid crystalline compounds. A polymerizable compound is added to the composition. Further additives may be added as required. Injecting the composition into an element. Light irradiation is performed in a state where a voltage is applied to the element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. A composition containing a polymer is produced by the polymerization. The polymer stable alignment type element is manufactured in the order as described above.

In the above procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. Depending on the orientation, the molecules of the polymerizable compound are also oriented. Since the polymerizable compound is polymerized by ultraviolet rays in the above state, a polymer maintaining the above orientation is produced. By the effect of the polymer, the response time of the element is shortened. Since the afterimage of the image is a poor operation of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. Further, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between substrates of the liquid crystal display element.

An example of a method for producing an element having no alignment film is as follows. A mixture of a liquid crystalline compound, a polymerizable compound, and a polar compound is injected into an element having no alignment film. Light irradiation is performed in a state where a voltage is applied to the element. The polymerizable compound is polymerized by light irradiation. By the polymerization, a layer of a composition containing a polymer and a polar compound is formed on a substrate.

In the order, the polar compound is arranged on the substrate due to the interaction of the polar group with the surface of the substrate. The polar compound aligns liquid crystal molecules. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted, and the polymerizable compound is also aligned depending on the alignment. Since the polymerizable compound is polymerized by ultraviolet rays in the above state, a polymer maintaining the above orientation is produced. The polymer has an effect of additionally stabilizing the orientation of liquid crystal molecules, thereby shortening the response time of the device. Since the afterimage of the image is a poor operation of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer.

[ examples ]

The present invention will be further described in detail by way of examples. The present invention is not limited by these examples. The present invention comprises mixtures of composition (M1) and composition (M2). The invention also includes mixtures of at least two of the compositions of the examples. The synthesized compound is identified by Nuclear Magnetic Resonance (NMR) analysis or the like. The properties of the compounds, compositions and devices were measured by the following methods.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement.¹In the measurement of H-NMR, a sample was dissolved in CDCl₃The number of measurements was measured at room temperature under conditions of 500MHz and 16 cumulative times in a deuterated solvent. Tetramethylsilane was used as an internal standard.¹⁹In the measurement of F-NMR, CFCl was used₃As an internal standard, the number of times is accumulated to 24 times. In the description of the NMR spectrum, s is a singlet (singleton), d is a doublet (doublet), t is a triplet (triplet), and q is a quartetPeak (quartz), quin refers to quintet (quintet), sex refers to sextuple (sextet), m refers to multiplet (multiplet), br refers to broad (broad).

Gas chromatographic analysis: for measurement, a GC-14B gas chromatograph manufactured by Shimadzu corporation was used. The carrier gas was helium (2 mL/min). The sample vaporizer was set at 280 ℃ and the detector (flame ionization detector, FID) was set at 300 ℃. The separation of the component compounds was carried out by using a capillary column DB-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; non-polar) manufactured by Agilent Technologies Inc. After the column was held at 200 ℃ for 2 minutes, the temperature was raised to 280 ℃ at a rate of 5 ℃/min. After preparing the sample into an acetone solution (0.1 wt%), 1. mu.L thereof was injected into the sample vaporization chamber. The record is a chromatograph module (Chromatopac) model C-R5A manufactured by Shimadzu corporation or an equivalent thereof. The obtained gas chromatogram showed the retention time of the peak and the area of the peak corresponding to the component compound.

Chloroform, hexane, and the like can be used as a solvent for diluting the sample. To separate the constituent compounds, the following capillary column may be used. HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Agilent technologies, Inc., Rtx-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Restek Corporation, and BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Australian SGE International Pty.Ltd. For the purpose of preventing overlapping of compound peaks, capillary columns manufactured by Shimadzu corporation CBP1-M50-025 (length 50M, inner diameter 0.25mm, film thickness 0.25 μ M) were used.

The ratio of the liquid crystalline compound contained in the composition can be calculated by the following method. The mixture of liquid crystalline compounds was analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio of the liquid crystalline compound. When the capillary column described above is used, the correction coefficient of each liquid crystalline compound can be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the area ratio of the peak.

Measurement of the sample: when the characteristics of the composition and the element were measured, the composition was used as a sample as it is. In order to measure the characteristics of the compound, a sample for measurement was prepared by mixing the compound (15 wt%) in a mother liquid crystal (85 wt%). From the values obtained by the measurement, the characteristic values of the compounds were calculated by an extrapolation method (extrapolation method). (extrapolated value) { (measured value of sample) — 0.85 × (measured value of mother liquid crystal) }/0.15. When a smectic phase (or crystal) precipitates at 25 ℃ at the stated ratio, the ratio of the compound to the mother liquid crystal is set at 10% by weight: 90 wt%, 5 wt%: 95% by weight, 1% by weight: the order of 99 wt.% was changed. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy relating to the compound were obtained by the extrapolation method.

The following mother liquid crystal was used. The proportions of the component compounds are expressed in% by weight.

The determination method comprises the following steps: the characteristics were measured by the following methods. These methods are mostly described in the JEITA specification (JEITA. ED-2521B) specified by the examination of Japan Electronics and Information Technology Industries Association (JEITA) or modified methods thereof. The TN element used for the measurement was not provided with a Thin Film Transistor (TFT).

(1) Upper limit temperature of nematic phase (NI;. degree. C.): the sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 ℃/min. The temperature at which a portion of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature".

(2) Lower limit temperature of nematic phase (TC;): the nematic phase was observed after the sample was placed in a glass bottle and kept in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days. For example, when the sample is kept nematic at-20 ℃Phase state, and changing into crystalline or smectic phase at-30 deg.C_CIs reported as < -20 ℃. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(3) Viscosity (. eta.; measured at 20 ℃ C.; mPas): for the measurement, an E-type rotational viscometer manufactured by tokyo counter gmbh was used.

(4) Viscosity (rotational viscosity; γ 1; measured at 25 ℃; mPas): the measurement was carried out according to the method described in "Molecular Crystals and Liquid Crystals" (Molecular Crystals and Liquid Crystals) volume 259, page 37 (1995) of M.Current well (M.Imai) et al. A VA device having a gap (cell gap) of 20 μm between two glass substrates was used as a sample. The element was applied with a voltage in a range of 39 volts to 50 volts, in 1 volt unit, in a stepwise manner. After 0.2 seconds of no voltage application, voltage application was repeated with only 1 square wave (square pulse; 0.2 seconds) and no voltage application (2 seconds). The peak current (peak current) and peak time (peak time) at which the transient current (transient current) is generated by the application are determined. Values for rotational viscosity were obtained from these measurements and the calculation of equation (8) on page 40 of the paper by m.imai et al. The dielectric anisotropy required for the calculation was measured by the method described in measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δ n; measured at 25 ℃): the measurement was performed using a light having a wavelength of 589nm by an Abbe refractometer having a polarizing plate attached to an eyepiece lens. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n/is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index n ″) is measured when the direction of the polarized light is perpendicular to the direction of the friction. The value of the optical anisotropy is calculated from the formula Δ n ═ n/n ″.

(6) Dielectric anisotropy (. DELTA.. di-elect cons.; measured at 25 ℃): the value of the dielectric anisotropy is calculated from the formula Δ ∈/∈ ≠ or. The dielectric constants (. epsilon./. and. epsilon. mu.were measured as follows).

1) Measurement of dielectric constant (. epsilon. /): a solution of octadecyl triethoxy silane (0.16mL) in ethanol (20mL) was coated on the well-cleaned glass substrate. The glass substrate was rotated by a rotator and then heated at 150 ℃ for 1 hour. A VA cell having a gap (cell gap) of 4 μm between two glass substrates was loaded with a sample, and the cell was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds.

2) Measurement of dielectric constant (. epsilon. DELTA. -): the polyimide solution was coated on the well-cleaned glass substrate. After the glass substrate is fired, the obtained alignment film is subjected to rubbing treatment. The sample was injected into a TN cell having a cell gap of 9 μm between two glass substrates and a twist angle of 80 degrees. Sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (∈ ∈ in the short-axis direction of the liquid crystal molecules was measured after 2 seconds.

(7) Threshold voltage (Vth; measured at 25 ℃; V): for measurement, a luminance meter model LCD5100 manufactured by tsukamur electronics gmbh was used. The light source is a halogen lamp. A VA element in a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 4 μm and the rubbing directions were antiparallel was loaded with a sample, and the element was sealed using an adhesive cured with ultraviolet rays. The voltage applied to the element (60Hz, rectangular wave) was increased stepwise from 0V to 20V in units of 0.02V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve is prepared in which the transmittance is 100% when the light amount reaches the maximum and the transmittance is 0% when the light amount is the minimum. The threshold voltage is represented by a voltage at which the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25;%): the TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) between the two glass substrates was 5 μm. After the sample is injected, the element is sealed with an adhesive cured with ultraviolet rays. The TN cell was charged by applying a pulse voltage (5V, 60 μ sec). The decayed voltage was measured by a high-speed voltmeter over a period of 16.7 milliseconds, and the area a between the voltage curve per unit cycle and the horizontal axis was determined. The area B is the area where the voltage is not attenuated. The voltage holding ratio is expressed by a percentage of the area a to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80;%): the voltage holding ratio was measured in the same manner as described above except that the measurement was performed at 80 ℃ instead of 25 ℃. The resulting value is represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25;%): after the irradiation with ultraviolet light, the voltage holding ratio was measured to evaluate the stability to ultraviolet light. The TN cells used for the measurement had a polyimide alignment film and a cell gap of 5 μm. The sample was injected into the cell and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio motor), and the spacing between the elements and the light source was 20 cm. In the measurement of VHR-3, the voltage decayed was measured during 16.7 milliseconds. Compositions with large VHR-3 have a large stability to UV light. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25;%): after the TN cells impregnated with the samples were heated in a thermostatic bath at 80 ℃ for 500 hours, the voltage holding ratio was measured, and the stability to heat was evaluated. In the measurement of VHR-4, the voltage decayed was measured during 16.7 milliseconds. Compositions with large VHR-4 have a large stability to heat.

(12) Response time (. tau.; measured at 25 ℃ C.; ms): for measurement, a luminance meter model LCD5100 manufactured by tsukamur electronics gmbh was used. The light source is a halogen lamp. The Low-pass filter (Low-pass filter) is set to 5 kHz. The sample was placed in a VA device having a spacing (cell gap) of 3.5 μm between two glass substrates and no alignment film. The element is sealed with an adhesive hardened with ultraviolet rays. The element was irradiated with 78mW/cm while applying a voltage of 30V²UV 449 seconds (35J) (405 nm). For the irradiation of ultraviolet rays, a multi-metal lamp for ultraviolet curing M04-L41 manufactured by Kawasaki (EYE GRAPHICS) Co., Ltd was used. A rectangular wave (120Hz) is applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. Looking when said quantity of light reaches a maximumThe transmittance was 100%, and the transmittance was 0% when the light amount was the minimum. The maximum voltage of the rectangular wave is set so that the transmittance becomes 90%. The lowest voltage of the rectangular wave is 2.5V set to have a transmittance of 0%. The response time is represented by the time (rise time; millisecond) required for the transmittance to change from 10% to 90%.

(13) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ℃ C.; pN): for the measurement, an elastic constant measuring instrument model EC-1 manufactured by TOYO Corporation, Toyang technology Corporation was used. The sample was injected into a vertical alignment device having a gap (cell gap) of 20 μm between two glass substrates. A charge of 20 to 0 volts was applied to the element, and the electrostatic capacitance and the applied voltage were measured. The values of the measured electrostatic capacitance (C) and applied voltage (V) were fitted (fitting) using the equations (2.98) and (2.101) on page 75 of the handbook of liquid crystal devices (journal of the industry), and the value of the elastic constant was obtained from the equation (2.100).

(14) Specific resistance (. rho.; measured at 25 ℃ C.;. omega. cm): 1.0mL of the sample was placed in a container equipped with an electrode. A DC voltage (10V) was applied to the vessel, and a DC current after 10 seconds was measured. The specific resistance is calculated by the following equation.

(specific resistance) { (voltage) × (capacitance of container) }/{ (direct current) × (dielectric constant of vacuum) }.

(15) Pretilt angle (degrees): an spectroscopic ellipsometer M-2000U (manufactured by j.a. woollam co., Inc.) was used for measurement of the pretilt angle.

(16) Alignment stability (liquid crystal alignment axis stability): the change in the liquid crystal alignment axis on the electrode side of the liquid crystal display element was evaluated. The liquid crystal alignment angle phi (before) on the electrode side before the stress was applied was measured, and after applying a square wave of 4.5V and 60Hz to the element for 20 minutes, the liquid crystal was buffered for 1 second, and after 1 second and 5 minutes, the liquid crystal alignment angle phi (after) on the electrode side was measured again. From these values, the change Δ Φ (deg.) of the liquid crystal alignment angle after 1 second and 5 minutes was calculated using the following formula.

Δ Φ (deg.) Φ (after) - Φ (before) (equation 2)

These measurements were carried out with reference to J.Hilbert, B.Jansen, C.Hexingg, J.F.Elman, E.Montbahh, D.Blainet and P.J.Bos (J.Hilfiker, B.Johs, C.Herzinger, J.F.Elman, E.Montbach, D.Bryant, and P.J.Bos), Solid Films (Thin Solid Films), 455-plus 456, (2004) 596-plus 600. It can be said that the smaller the Δ Φ, the smaller the rate of change of the liquid crystal alignment axis, the better the stability of the liquid crystal alignment axis.

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in table 3 below. In Table 3, the configuration of the 1, 4-cyclohexylene group-related solid is trans configuration. The numbers in parentheses following the marked compounds indicate the chemical formula to which the compound belongs. The symbol (-) indicates other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition are summarized.

TABLE 3 expression of Compounds Using symbols

R-(A₁)-Z₁-·····-Z_n-(A_n)-R′

Embodiments of the elements

1. Raw materials

The composition to which the polar compound is added is injected into the element having no alignment film. After irradiation with ultraviolet rays, the vertical alignment of the liquid crystal molecules in the cell was investigated. First, the raw materials will be described. The raw materials are suitably selected from the group consisting of compositions (M1) to (M18), polar compounds (PC-1) to (PC-33), and polymerizable compounds (RM-1) to (RM-7). The composition is as follows.

[ composition (M1) ]

NI＝73.2℃；Tc<-20℃；Δn＝0.113；Δε＝-4.0；Vth＝2.18V；η＝22.6mPa·s.

[ composition (M2) ]

NI＝82.8℃；Tc<-30℃；Δn＝0.118；Δε＝-4.4；Vth＝2.13V；η＝22.5mPa·s.

[ composition (M3) ]

NI＝78.1℃；Tc<-30℃；Δn＝0.107；Δε＝-3.2；Vth＝2.02V；η＝15.9mPa·s.

[ composition (M4) ]

NI＝88.5℃；Tc<-30℃；Δn＝0.108；Δε＝-3.8；Vth＝2.25V；η＝24.6mPa·s；VHR-1＝99.1％；VHR-2＝98.2％；VHR-3＝97.8％.

[ composition (M5) ]

NI＝81.1℃；Tc<-30℃；Δn＝0.119；Δε＝-4.5；Vth＝1.69V；η＝31.4mPa·s.

[ composition (M6) ]

NI＝98.8℃；Tc<-30℃；Δn＝0.111；Δε＝-3.2；Vth＝2.47V；η＝23.9mPa·s.

[ composition (M7) ]

NI＝77.5℃；Tc<-30℃；Δn＝0.084；Δε＝-2.6；Vth＝2.43V；η＝22.8mPa·s.

[ composition (M8) ]

NI＝70.6℃；Tc<-20℃；Δn＝0.129；Δε＝-4.3；Vth＝1.69V；η＝27.0mPa·s.

[ composition (M9) ]

NI＝93.0℃；Tc<-30℃；Δn＝0.123；Δε＝-4.0；Vth＝2.27V；η＝29.6mPa·s.

[ composition (M10) ]

NI＝87.6℃；Tc<-30℃；Δn＝0.126；Δε＝-4.5；Vth＝2.21V；η＝25.3mPa·s.

[ composition (M11) ]

NI＝93.0℃；Tc<-20℃；Δn＝0.124；Δε＝-4.5；Vth＝2.22V；η＝25.0mPa·s.

[ composition (M12) ]

NI＝76.4℃；Tc<-30℃；Δn＝0.104；Δε＝-3.2；Vth＝2.06V；η＝15.6mPa·s.

[ composition (M13) ]

NI＝78.3℃；Tc<-20℃；Δn＝0.103；Δε＝-3.2；Vth＝2.17V；η＝17.7mPa·s.

[ composition (M14) ]

NI＝81.2℃；Tc<-20℃；Δn＝0.107；Δε＝-3.2；Vth＝2.11V；η＝15.5mPa·s.

[ composition (M15) ]

NI＝88.7℃；Tc<-30℃；Δn＝0.115；Δε＝-1.9；Vth＝2.82V；η＝17.3mPa·s.

[ composition (M16) ]

NI＝89.9℃；Tc<-20℃；Δn＝0.122；Δε＝-4.2；Vth＝2.16V；η＝23.4mPa·s.

[ composition (M17) ]

NI＝77.1℃；Tc<-20℃；Δn＝0.101；Δε＝-3.0；Vth＝2.04V；η＝13.9mPa·s.

[ composition (M18) ]

NI＝75.9℃；Tc<-20℃；Δn＝0.114；Δε＝-3.9；Vth＝2.20V；η＝24.7mPa·s.

The first additive is a polar compound (PC-1) to a polar compound (PC-33).

The second additive is a polymerizable compound (RM-1) to a polymerizable compound (RM-7).

2. Vertical alignment of liquid crystal molecules

Example 1

The polar compound (PC-1) was added in a proportion of 5% by weight and the polymerizable compound (RM-1) was added in a proportion of 0.5% by weight to the composition (M1). The mixture was injected on a thermal stage at 100 ℃ into an element having a gap (cell gap) of 4.0 μm between two glass substrates and no alignment film. The element was irradiated with ultraviolet rays (28J) using an ultra-high pressure mercury lamp USH-250-BY (manufactured BY Ushio motor), thereby polymerizing the polymerizable compound. The element is arranged in a polarizing microscope in which a polarizing element and an analyzer are arranged orthogonally, and light is irradiated from below onto the element to observe whether or not light leakage occurs. When the liquid crystal molecules were sufficiently aligned and light did not pass through the element, the vertical alignment was judged to be "good". When light transmitted through the element was observed, it was indicated as "defective".

Examples 2 to 33 and comparative example 1

An element having no alignment film is produced using a mixture of the composition, the polar compound, and the polymerizable compound. The presence or absence of light leakage was observed in the same manner as in example 1. The results are summarized in Table 4. In comparative example 1, for comparison, no polymerizable compound was added.

TABLE 4 vertical alignment of liquid Crystal molecules

As is clear from table 4, in examples 1 to 33, although the composition, the polar compound or the polymerizable compound was changed in type, no light leakage was observed. The results show that the vertical alignment was good and the liquid crystal molecules were stably aligned even without an alignment film in the device. On the other hand, light leakage was observed in comparative example 1. The results indicate that the homeotropic orientation is not good. Therefore, it is known that a polymer formed from a polymerizable compound plays an important role in the vertical alignment of liquid crystal molecules.

Industrial applicability

The liquid crystal composition of the present invention can be used for liquid crystal projectors, liquid crystal televisions, and the like.

Claims

1. A liquid crystal composition which contains a polar compound as a first additive and at least one compound selected from the group consisting of polymerizable compounds represented by the formulae (5-1) to (5-7) as a second additive and has negative dielectric anisotropy,

2. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group of compounds represented by formula (1) as a first component,

in the formula (1), R¹And R²Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms; ring A and ring C are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring B is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, or 7, 8-difluorochroman-2, 6-diyl; z ¹And Z²Independently a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-; a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

3. The liquid crystal composition according to claim 2, which contains at least one compound selected from the group of compounds represented by formulae (1-1) to (1-22) as a first component,

4. The liquid crystal composition of claim 2, wherein the proportion of the first component ranges from 10 wt% to 90 wt% based on the weight of the liquid crystal composition.

5. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group of compounds represented by formula (2) as a second component,

6. The liquid crystal composition according to claim 5, which contains at least one compound selected from the group of compounds represented by formulae (2-1) to (2-13) as a second component,

in the formulae (2-1) to (2-13), R³And R⁴Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atomsAn alkenyl group having 2 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

7. The liquid crystal composition of claim 5, wherein the proportion of the second component is in the range of 10 to 70% by weight based on the weight of the liquid crystal composition.

8. The liquid crystal composition according to claim 1, which contains a polar compound as a first additive, the polar compound containing a polar group having a hetero atom selected from nitrogen, oxygen, sulfur and phosphorus.

9. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group of polar compounds represented by formula (3) and formula (4) as a first additive,

MES-R⁶ (3)

(R⁵)_x-R⁶ (4)

10. The liquid crystal composition according to claim 9, which contains at least one compound selected from the group of polar compounds represented by formula (3-1) as a first additive,

in the formula (3-1), R⁷Is hydrogen, fluorine, chlorine or alkyl with carbon number of 1 to 25, at least one-CH in the alkyl₂Can be through-NR⁰-, -O-, -S-, -CO-O-, -O-CO-O-or a cycloalkylene group of 3 to 8 carbon atoms, and at least one tertiary carbon (> CH-) may be substituted by nitrogen (> N-), of which groups at least one hydrogen may be substituted by fluorine or chlorine, where R⁰Hydrogen or alkyl having 1 to 12 carbon atoms; r⁸Is an alkyl group having 1 to 25 carbon atoms, in which at least one-CH group₂Can be through-NR⁰-, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-or cycloalkylene radicals of 3 to 8 carbon atoms, at least one tertiary carbon (> CH-) being substituted by nitrogen (> N-), at least one hydrogen of these radicals being substituted by fluorine or chlorine, where R ⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, wherein R⁸At least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, or a nitrogen atom having a primary, secondary or tertiary ammonia structure; ring F and ring G are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms or a heteroalicyclic group having 4 to 25 carbon atoms, which may be a condensed ring, wherein at least one hydrogen of these groups may be substituted by a group T, wherein the group T is-OH, - (CH) or₂)_i-OH, fluorine, chlorine, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R⁰)₂、-C(＝O)R⁰、-N(R⁰)₂、-(CH₂)_i-N(R⁰)₂Aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms or alkoxycarbonyloxy group having 2 to 25 carbon atoms, wherein at least one hydrogen may be substituted by fluorine or chlorine, wherein R is⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and i is 1, 2, 3 or 4; z⁴is-O-, -S-, -CO-O-, -OCO-, -O-CO-O-, -OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_i-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_i-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-、-OCO-CH＝CH-、-C(R⁰)₂-or a single bond, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and i is 1, 2, 3 or 4; d is 0, 1, 2, 3, 4 or 5.

11. The liquid crystal composition according to claim 9, which contains at least one compound selected from the group of polar compounds represented by the formula (4-1) as a first additive,

R⁹-R¹⁰ (4-1)

In the formula (4-1), R⁹Is an alkyl group having 4 to 20 carbon atoms, in which at least one-CH group₂-may be substituted by-CH ═ CH-, -CF ═ CH-, -CH ═ CF-, -C ≡ C-, or cycloalkylene of carbon number 3 to 8, in which groups at least one hydrogen may be substituted by fluorine or chlorine; r¹⁰Is an alkyl group having 1 to 25 carbon atoms, in which at least one-CH group₂Can be through-NR⁰-, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-or cycloalkylene radicals of 3 to 8 carbon atoms, at least one tertiary carbon (> CH-) being substituted by nitrogen (> N-), at least one hydrogen of these radicals being substituted by fluorine or chlorine, where R⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, wherein R¹⁰Has at least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, and a nitrogen atom having a primary, secondary or tertiary amino structure.

12. The liquid crystal composition according to claim 9, wherein in the formulae (3) and (4) according to claim 9, R6 is a group selected from the group of polar groups represented by the formulae (A1) to (A4),

sp in formulae (A1) to (A4)⁴、Sp⁶And Sp⁷Independently a single bond or a group (-Sp '-X' -), where Sp"is an alkylene group having 1 to 20 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -S-, -NH-, -N (R)⁰)-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-S-CO-、-CO-S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰) -, -CH-or-C.ident.C-in which at least one hydrogen may be substituted by fluorine, chlorine or-CN and X 'is-O-, -S-, -CO-O-, -O-CO-O-, -CO-N (R') ⁰)-、-N(R⁰)-CO-、-N(R⁰)-CO-N(R⁰)-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR⁰-、-Cy²＝Cy³-, -C.ident.C-, -CH-CO-O-, -O-CO-CH-or a single bond, where R is⁰Is hydrogen or alkyl of 1 to 12 carbon atoms, and Y²And Y³Independently hydrogen, fluorine, chlorine or-CN; sp⁵Is > CH-, > CR^a1-, > N-or > C <; x¹is-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂、-SH、-SR^a1、

Here, R⁰Hydrogen or alkyl having 1 to 12 carbon atoms; x²is-O-, -CO-, -NH-, -NR^a1-, -S-or a single bond; z⁹Is C1-15 alkylene, C5 OR C6 alicyclic group, OR their combination, wherein at least one hydrogen can pass through-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂Fluoro or chloro; here, R^a1Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-C ≡ C-, -CH ═ CH-, -COO-, -OCO-, -CO-, or-O-, where at least one hydrogen may be substituted by fluorine or chlorine; ring P having 6 to 25 carbon atomsAromatic group or alicyclic group having 3 to 25 carbon atoms, which may be a condensed ring, wherein one to three hydrogens may pass through R^LSubstituted, here, R^Lis-OH, - (CH)₂)_r-OH, fluorine, chlorine, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R⁰)₂、-C(＝O)R⁰、-N(R⁰)₂、-(CH₂)_r-N(R⁰)₂、-SH、-SR⁰Aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms or alkoxycarbonyloxy group having 2 to 25 carbon atoms, wherein at least one hydrogen may be substituted by fluorine or chlorine, wherein R is ⁰Is hydrogen or alkyl of 1 to 12 carbon atoms and r is 1, 2, 3 or 4; p is 0, 1, 2 or 3; q is 2, 3, 4 or 5.

13. The liquid crystal composition according to claim 9, wherein the first additive is at least one compound selected from the group of polar compounds represented by formulae (3-1-1) to (3-1-4),

in the formulae (3-1-1) to (3-1-4), R¹⁵Is alkyl with 1 to 8 carbon atoms or fluorine; ring Q and ring R are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 3-phenylene, 2-ethyl-1, 4-phenylene, 2, 6-diethyl-1, 4-phenylene, 2-trifluoromethyl-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene or 2, 3, 5, 6-tetrafluoro-1, 4-phenylene; ring S is cyclohexyl or phenyl; z¹⁰Is a single bond, -CH₂CH₂-, -COO-or-OCO-; z¹¹Is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 OR 6 carbon atoms OR a combination thereof, wherein at least one hydrogen atom may be replaced by-OH, -OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂Fluorine or chlorine, where R^a1Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-C ≡ C-, -CH ═ CH-, -COO-, -OCO-, -CO-, or-O-, where at least one hydrogen may be substituted by fluorine or chlorine; sp ⁴Is a single bond, -CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂O-or-OCH₂-；Sp⁷Is a single bond or an alkylene group having 1 to 5 carbon atoms, wherein-CH is present in the alkylene group₂-may be substituted by-O-or-NH-; s is 0, 1, 2, 3, 4 or 5; x³is-OH, -COOH, -SH, -OCH₃or-NH₂；X⁴Is a single bond or-O-.

14. The liquid crystal composition according to claim 9, wherein the first additive is at least one compound selected from the group of polar compounds represented by formulae (4-1-1) to (4-1-29),

R⁹-OH (4-1-1)

R⁹-COOH (4-1-9)

R⁹-NH₂ (4-1-11)

15. The liquid crystal composition of claim 1, wherein the proportion of the first additive is in the range of 0.05 wt% to 10 wt% based on the weight of the liquid crystal composition.

16. The liquid crystal composition of claim 1, wherein the proportion of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition.

17. A liquid crystal display element comprising the liquid crystal composition according to claim 1.