JP6787478B2 - Polymerizable compounds and liquid crystal display devices - Google Patents

Description

The present invention relates to a polymerizable compound, a polymerizable composition containing the polymerizable compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, and a liquid crystal display element.

The liquid crystal display element utilizes the optical anisotropy, dielectric anisotropy, and the like of the liquid crystal molecules in the liquid crystal composition. Classification based on the operation mode of liquid crystal molecules is PC (phase change) mode, TN (twisted nematic) mode, STN (super twisted nematic) mode, BTN (bistable twisted nematic) mode, ECB (electrically controlled birefringence) mode, OCB. (Optically compensated bend) mode, IPS (in-plane switching) mode, FFS (fringe field switching) mode, VA (vertical alignment) mode and the like.

In these liquid crystal display elements, the initial orientation is generally achieved by a polyimide alignment film. On the other hand, in the liquid crystal display element having no alignment film, a liquid crystal composition containing a polar compound and a polymer or a polymerizable polar compound is used. First, a composition containing a small amount of polar compound and a small amount of polymerizable compound or a small amount of polymerizable polar compound is injected into the device. Here, the liquid crystal molecules may be oriented by the action of the polar compound. Next, by irradiating this composition with ultraviolet rays, the polymerizable compound or the polymerizable polar compound is polymerized. As a result, the liquid crystal molecules are oriented and this orientation state is stabilized, or the orientation after injection is stabilized. In this composition, the orientation of the liquid crystal molecules can be controlled by the polar compound and the polymer or the polymerizable polar compound, so that the response time of the device is shortened and the image printing is improved. Further, the element having no alignment film does not require a step of forming the alignment film, and since there is no alignment film, there is an advantage that the electric resistance of the element is not lowered due to the interaction between the alignment film and the composition. Such advantages due to the combination of polar compounds and polymers can be expected for devices with modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.

The method of combining a polymer with a liquid crystal composition can be applied to a liquid crystal display element having various operation modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, and PSA-OCB. Polymerizable compounds used in devices in such modes are required to have properties such as excellent ability to orient liquid crystal molecules, appropriate polymerization reactivity, high conversion and high solubility in liquid crystal compositions. .. Although various polymerizable compounds have been developed so far, it is desired to develop a compound having the above-mentioned properties further improved.

Japanese Unexamined Patent Publication No. 2003-307720 Japanese Unexamined Patent Publication No. 2004-131704 Japanese Unexamined Patent Publication No. 2006-133619 Special Table 2010-537256 Japanese Unexamined Patent Publication No. 10-186330 European Patent Application Publication No. 1889894 Chinese Patent Application Publication No. 101671252 International Publication No. 2013/77343 International Publication No. 2014/6962

A first object of the present invention is to obtain a polymerizable compound having at least one of excellent ability to orient liquid crystal molecules, appropriate polymerization reactivity, high conversion rate, high voltage retention and high solubility in liquid crystal compositions. Is to provide. The second issue is the high upper limit temperature of the nematic phase, the lower lower limit temperature of the nematic phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy, appropriate elastic constant, large specific resistance, appropriate pretilt, etc. It is to provide a liquid crystal complex that satisfies at least one of the physical properties of. The challenge is to provide a liquid crystal complex that has an appropriate balance with respect to at least two physical properties. A third challenge is to provide a liquid crystal display device having at least one of a wide temperature range in which the device can be used, a short response time, a low threshold voltage, a large contrast ratio, and a long life.

Item 1. A polymerizable compound represented by the following formula (1).
In equation (1)
R ¹ is a hydrogen, halogen, -SP ^1- P ¹ or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- may be replaced by -O- or -S-. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen or −SP ¹ −P ¹ . May be replaced;
MES is a mesogen group with at least one ring and N atoms;
SP ¹ is a single bond or an alkylene with 1 to 10 carbon atoms, in which at least one −CH ₂ − is −O−, −CO−, −COO−, −OCO−, or −OCOO−. It may be replaced, at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, and at least one hydrogen in these groups is replaced by a halogen. Well;
P ¹ is a polymerizable group;
a is 0, 1, 2, 3, or 4;
c is 0, 1, 2, 3, or 4.

Item 2. Item 2. The polymerizable compound according to Item 1, which is represented by the following formula (1-1).
In equation (1-1)
R ⁵ , R ⁶ and R ⁷ are independently hydrogen, halogen, -SP ^1- P ¹ , -SP ^2- P ² or alkyl with 1 to 15 carbon atoms, in which at least one -CH ₂ − may be replaced by −O− or −S−, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, among these. At least one hydrogen in the group may be replaced with a halogen, -SP ^1- P ¹ or -SP ^2- P ² .
a1 and a2 are independently 0, 1, 2, 3, or 4, and the sum of a1 and a2 is 1-8;
Rings A ¹ and A ² are independently derived from alicyclic hydrocarbons with 3 to 18 carbon atoms, aromatic hydrocarbons with 6 to 18 carbon atoms, or heteroaromatic hydrocarbons with 3 to 18 carbon atoms. At least one hydrogen in these divalent groups is a halogen, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 1 to 12 carbon atoms, or 1 carbon number. From 12 alkenyloxys may be replaced, and at least one hydrogen in these monovalent hydrocarbon groups may be replaced with halogens;
Z ¹ and Z ² are independently single-bonded or alkylenes having 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or-. may be replaced by OCO-, at least one - _{(CH 2) 2} - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, - C ( CH ₃ ) = C (CH ₃ )-or may be replaced by -CH≡CH-, and at least one hydrogen in these divalent groups may be replaced by a halogen;
b1 and b2 are independently 0, 1, 2, or 3;
SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, at least one in these groups. Hydrogen may be replaced by halogen;
P ¹ and P ² are independently represented by the following formulas (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one-(CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with a halogen.

Item 3. Item 2. The polymerizable compound according to Item 1, which is represented by any one of the following formulas (1-1-1) to (1-1-3).
In equations (1-1-1) to (1-1-3),
R ⁷ is a hydrogen, halogen, -SP ^1- P ¹ , -SP ^2- P ² or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or -S. It may be replaced by −, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen in these groups is a halogen. May be replaced by −SP ¹ −P ¹ or −SP ² −P ² ;
Rings A ¹ , ring A ² , rings A ³ and ring A ⁴ are independently alicyclic hydrocarbons with 3 to 18 carbon atoms, aromatic hydrocarbons with 6 to 18 carbon atoms, or 3 to 18 carbon atoms. Divalent groups derived from heteroaromatic hydrocarbons of, at least one hydrogen in these divalent groups is halogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, from 1 carbon atom. It may be replaced with 12 alkenyl, or alkenyloxy with 1 to 12 carbon atoms, and at least one hydrogen in these monovalent hydrocarbon groups may be replaced with halogen;
Z ¹ , Z ² , Z ³ and Z ⁴ are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, or -OCO- may be replaced by at least one - _{(CH 2) 2} - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3 )-, -C (CH ₃ ) = C (CH ₃ )-, or -CH≡CH-, and at least one hydrogen in these divalent groups may be replaced with a halogen;
SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, at least one in these groups. Hydrogen may be replaced by halogen;
P ¹ and P ² are independently represented by the following formulas (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one-(CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with a halogen.

Item 4. Item 2. The polymerizable compound according to Item 1, which is represented by any one of the following formulas (1-1-4) to (1-1-6).
In equations (1-1-4) to (1-1-6),
R ⁷ is a hydrogen, halogen, -SP ^1- P ¹ , -SP ^2- P ² or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or -S. It may be replaced by −, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen in these groups is a halogen. May be replaced by −SP ¹ −P ¹ or −SP ² −P ² ;
Rings A ¹ , ring A ² , rings A ³ and ring A ⁴ are independently alicyclic hydrocarbons with 3 to 18 carbon atoms, aromatic hydrocarbons with 6 to 18 carbon atoms, or 3 to 18 carbon atoms. Divalent groups derived from heteroaromatic hydrocarbons of, at least one hydrogen in these divalent groups is halogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, from 1 carbon atom. It may be replaced with 12 alkenyl, or alkenyloxy with 1 to 12 carbon atoms, and at least one hydrogen in these monovalent hydrocarbon groups may be replaced with halogen;
SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, at least one in these groups. Hydrogen may be replaced by halogen;
P ¹ and P ² are independently represented by the following formulas (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one-(CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with a halogen.

Item 5. Item 2. The polymerizable compound according to Item 1, which is represented by any one of the formulas (1-1-4) to (1-1-6).
In equations (1-1-4) to (1-1-6),
R ⁷ is a hydrogen, halogen, -SP ^1- P ¹ , -SP ^2- P ² or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or -S. It may be replaced by −, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen in these groups is a halogen. May be replaced by −SP ¹ −P ¹ or −SP ² −P ² ;
Rings A ¹ and A ² are independently 1,4-phenylene, and at least one hydrogen on these rings may be replaced with a halogen;
Ring ^{A 3} and ring ^{A 4} are independently 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, and at least one hydrogen on the rings replaced by halogen May be;
SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, at least one in these groups. Hydrogen may be replaced by halogen;
P ¹ and P ² are independently represented by the following formulas (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one-(CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with a halogen.

Item 6. Item 2. The polymerizable compound according to Item 1, which is represented by the following formula (1-1-7).
In equation (1-1-7)
Rings A ¹ and A ² are independently 1,4-phenylene, and at least one hydrogen on these rings may be replaced with a halogen;
SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, at least one in these groups. Hydrogen may be replaced by halogen;
P ¹ and P ² are independently represented by the following formulas (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one-(CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with a halogen.

Item 7. A polymerizable composition containing at least one polymerizable compound according to any one of Items 1 to 6.

Item 8. Item 2. The polymerizable composition according to Item 7, further comprising at least one compound selected from the compounds represented by any of the following formulas (2) to (4).
In equations (2) to (4),
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − is replaced by -O-. Also, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ independently form 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-. 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are independently single-bonded, −CH ₂ CH _2- , −CH = CH−, −C≡C−, or −COO−.

Item 9. Item 8. The polymerizable composition according to Item 7 or 8, further comprising at least one compound selected from the compounds represented by any of the following formulas (5) to (7).
In equations (5) to (7),
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − and at least one hydrogen is. May be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl. , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, - _CH 2 O-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine.

Item 10. Item 8. The polymerizable composition according to any one of Items 7 to 9, further containing at least one compound selected from the group of compounds represented by the following formula (8).
In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced with −O− and at least one hydrogen. May be replaced with fluorine;
X ¹² is -C≡N or -C≡C-C≡N;
Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl. , Or pyrimidine-2,5-dioxane;
Z ¹⁷ is a single _{bond, - (CH 2) 2 -} , - C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4.

Item 11. A liquid crystal composite produced by polymerization of the polymerizable composition according to any one of Items 7 to 10.

Item 12. An optically anisotropic substance produced by polymerization of the polymerizable composition according to any one of Items 7 to 10.

Item 13. A liquid crystal display device containing the polymerizable composition according to any one of Items 7 to 10 or the liquid crystal composite according to Item 11.

Item 14. At least one selected from the group consisting of the compound according to any one of Items 1 to 6, the polymerizable composition according to any one of Items 7 to 10, and the liquid crystal complex according to Item 11. , Used in liquid crystal display elements.

The first advantage of the present invention is a polymerizable compound having at least one of excellent ability to orient liquid crystal molecules, suitable polymerization reactivity, high conversion rate, high voltage retention, and high solubility in liquid crystal compositions. Is to provide. The second advantage is that the liquid crystal composite has a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a suitable elastic constant, and a large specific resistance. , At least one of the physical properties such as appropriate pretilt is satisfied. The advantage of this is that the liquid crystal complex has an appropriate balance with respect to at least two physical properties. A third advantage is that the liquid crystal display element has at least one of a wide temperature range in which the element can be used, a short response time, a low threshold voltage, a large contrast ratio, and a long lifetime.

The usage of terms in this specification is as follows. The liquid crystal compounds are non-polymerizable compounds having a liquid crystal phase such as a nematic phase and a smectic phase, and physical properties of a liquid crystal composition having no liquid crystal phase but having an upper limit temperature, a lower limit temperature, viscosity, and dielectric anisotropy. It is a general term for non-polymerizable compounds that are mixed for the purpose of adjusting. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The liquid crystal composition is a mixture of liquid crystal compounds. The polymerizable compound is a compound added to the composition for the purpose of producing a polymer. The polymerizable composition is a mixture of a polymerizable compound, a liquid crystal composition, an additive and the like. The liquid crystal composite is a composite produced by the polymerization of this polymerizable composition. The liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is the phase transition temperature of the nematic phase-isotropic phase in the liquid crystal composition, the polymerizable composition, or the liquid crystal composite, and may be abbreviated as the upper limit temperature. The lower limit temperature of the nematic phase may be abbreviated as the lower limit temperature. Polymerization reactivity refers to the degree of ease with which a reactant can be polymerized. The conversion rate is the weight ratio of the reactant consumed by the chemical reaction to the reactant.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition. Additives such as optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, defoamers, polymerizable compounds, polymerization initiators, and polymerization inhibitors are added to this composition as needed. Will be done. The ratio of the additive (addition amount) is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Parts per million (ppm) by weight may also be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The compound represented by the formula (1) may be abbreviated as the compound (1). At least one compound selected from the group of compounds represented by the formula (1) may be abbreviated as "Compound (1)". "Compound (1)" means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. In the compound (1-1) ring ^{A 1} and ring ^{A 2,} the line across the circle, meaning ^{that -SP} 1 -P ¹ group can be arbitrarily selected binding position on the ring, such as a six-membered ring, fused ring To do. This rule also applies to symbols such as -SP ^2- P ^two . In equations (2) to (8), symbols such as B ¹ , C ¹ , and D ¹ surrounded by hexagons correspond to rings such as ring B ¹ , ring C ¹ , and ring D ¹ . The symbol R ¹¹ is used in a plurality of equations such as equation (2) and equation (3). In these compounds, two terminal groups represented by any two R ¹¹ may be the same or different. In the formula (8), when i is 2, two ^{D 1} are present in a single expression. In this compound, two rings in which two D ¹ represents may be the same or different. This rule also applies to D ¹ when i is greater than 2. This rule also applies to other symbols such as ^one -SP ^1- P.

The expression "at least one" A "may be replaced by" B "" means that when the number of "A" is 1, the position of "A" is arbitrary and the number of "A" is 2. When more than one, it means that their positions can be freely selected without any restrictions. The expression "at least one A may be replaced by B, C or D" is expressed when at least one A is replaced by B, when at least one A is replaced by C, and at least one. When one A is replaced by D, it means that a plurality of A's are replaced by at least two of B, C and D. For example, alkyl, alkenyl, alkoxy, alkoxyalkyl, etc., where at least one −CH ₂ − (or − (CH ₂ ) ₂ −) may be replaced by −O− (or −CH = CH−). Alkoxyalkenyl and alkenyloxyalkyl are included. It is not preferable that two consecutive −CH ₂₋ are replaced with −O− to become −O−O−. Alkyl such as in, -CH ₂ methyl moiety _(-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups derived by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.

Halogen means fluorine, chlorine, bromine, and iodine. The preferred halogen is fluorine or chlorine, and the more preferred halogen is fluorine.

The present invention also includes the following items.
(A) The above-mentioned polymerization, which further contains at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a defoamer, a polymerization initiator, and a polymerization inhibitor. Sex composition.
(B) The above-mentioned polymerizable composition further containing at least one polymerization initiator.
(C) The above-mentioned polymerizable composition further containing a polymerizable compound not represented by the formula (1).
(D) Use of the compound represented by the formula (1) in a polymerizable composition suitable for a liquid crystal display device having a PSA mode.
(E) Use of the compound represented by the formula (1) in a liquid crystal display device having a PSA mode.
(F) In a liquid crystal display element having a PSA mode, a compound represented by any of the formulas (1), (1-1) and (1-1-1) to (1-1-7). Use of at least one compound selected from the group.
(G) Use of a polymerizable composition containing at least one of the above compounds in a liquid crystal display device having a PSA mode.
(H) Use of a liquid crystal composite produced by polymerization of the above-mentioned polymerizable composition in a liquid crystal display device having a PSA mode.
(I) In a liquid crystal display device having a mode of PS-TN, PS-IPS, PS-FFS, PSA-VA, or PSA-OCB, the above compound, the above polymerizable composition, or the above liquid crystal composite. use.

The present invention also includes the following items.
(J) In a liquid crystal display element having a PSA mode, it is selected from a group of a compound represented by the formula (1) and a compound represented by any of the formulas (2), (3) and (4). Use of compositions containing at least one compound.
(K) In a liquid crystal display element having a PSA mode, it is selected from a group of a compound represented by the formula (1) and a compound represented by any of the formulas (5), (6) and (7). Use of a composition containing at least one compound.
(L) Use of a composition containing a compound represented by the formula (1) and at least one compound selected from the group of compounds represented by the formula (8) in a liquid crystal display device having a PSA mode. ..

Hereinafter, the polymerizable compound of the present invention will be described first, followed by a synthetic method, a polymerizable composition, a liquid crystal composite, and a liquid crystal display device in this order.

1. 1. Polymerizable compound A compound represented by the following formula (1).
In equation (1)
R ¹ is a hydrogen, halogen, -SP ^1- P ¹ or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- may be replaced by -O- or -S-. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen or −SP ¹ −P ¹ . May be replaced;
MES is a mesogen group with at least one ring and N atoms;
SP ¹ is a single bond or an alkylene with 1 to 10 carbon atoms, in which at least one −CH ₂ − is −O−, −CO−, −COO−, −OCO−, or −OCOO−. It may be replaced, at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, and at least one hydrogen in these groups is replaced by a halogen. Well;
P ¹ is a polymerizable group;
a is 0, 1, 2, 3, or 4;
c is 0, 1, 2, 3, or 4.

First, since the compound (1) has a rod-shaped molecular structure similar to that of a liquid crystal compound, its solubility in a liquid crystal composition is high. Therefore, compound (1) is suitable as a polymerizable compound required for a device having a PSA mode. Secondly, compound (1) has appropriate polymerizable properties. Therefore, compound (1) can be stably stored. At the time of polymerization, the speed of the photoreaction can be easily controlled, and the polymerization can be carried out by appropriately irradiating with ultraviolet rays. Also, it does not require excessive UV light.

The preferred structure of the compound (1) is formula (1-1), and preferred examples of the polymerizable group P, the linking group SP, the ring A, the alkyl R, and the bonding group Z in the formula (1-1) are , Is as follows. This example also applies to compounds subordinate to compound (1). The physical properties of compound (1) can be arbitrarily adjusted by appropriately combining the types of these groups. Because large difference is not in the physical properties of the compound, the compound (1) is, ^{2 H} (deuterium), an isotope such as ^{13 C} may contain more than the amount of natural abundance.

In formula (1-1), P ¹ and P ² are independently polymerizable groups. Examples of polymerizable groups are acryloyloxy, methacryloyloxy, acrylamide, methacrylamide, vinyloxy, vinylcarbonyl, oxylanyl, oxetanyl, 3,4-epoxycyclohexyl, maleimide or itaconic acid ester. In these groups, at least one hydrogen may be replaced with fluorine, methyl, or trifluoromethyl. Preferred examples of the polymerizable group are acryloyloxy (formula (1a) below), oxylanyl (formula (1b) below), vinyloxy (formula (1c) below), maleimide (formula (1d) below) or itaconic acid ester (formula (1d) below). Equation (1e)).
Here, in the equations (1a) to (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyls with 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, in these groups. At least one hydrogen may be replaced with a halogen.

In formula (1-1), SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO. It may be replaced by −, −COO− or −OCO−, and at least one −CH ₂ −CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and these divalents. In the group, at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 3 carbon atoms.

Preferred examples of SP ¹ or SP ² is a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - (CH 2) 2 -, - CH = CH- , -C≡C-, -CH ₂ CH ₂ O-, -OCH ₂ CH _2- , -CH = CH-O-, -O-CH = CH-, -C ≡ C-O-, -O-C ≡ C-,-(CH ₂ ) ₃ -,-(CH ₂ ) _3- O-, -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₄ O-, or -O _{(CH 2) 4} - a. More preferred examples include a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - CH = CH -, - C≡C -, - CH 2 CH 2 O -, -OCH ₂ CH _2- , -CH = CH-O-, or -O-CH = CH-. Particularly preferred examples are single bond, -CH _2- , -CH = CH-, -CH = CH-O-, -O-CH = CH-, -CH ₂ CH ₂ O-, or -OCH ₂ CH _2- Is. The most preferred example is a single bond. The configuration of the −CH = CH− double bond may be cis-type or trans-type. The trans type is preferable to the cis type.

In formula (1-1), R ⁵ , R ⁶ and R ⁷ are independently hydrogen, halogen, -S ^1- P ¹ , -S ^2- P ² , or alkyl having 1 to 15 carbon atoms. In this alkyl, at least one −CH ₂ − may be replaced by −O− or −S−, and at least one − (CH ₂ ) ₂₋ is replaced by −CH = CH− or −C≡C−. In these groups, at least one hydrogen may be replaced with a halogen, -SP ^1- P ¹ or -SP ^2- P ² .

In formula (1-1), a1 and a2 are independently 0, 1, 2, 3, or 4. -SP ^1- P ¹ or -SP ^2- P ² is a monovalent group involved in polymerization. The total number of −SP ¹ −P ¹ and −SP ² −P ² (that is, a1 + a2) is 1 to 8. Preferred examples are 1 to 6, and more preferable examples are 1 to 3. The most preferred example is 1 or 2.

In formula (1-1), rings A ¹ and A ² are independently alicyclic hydrocarbons with 3 to 18 carbon atoms, aromatic hydrocarbons with 6 to 18 carbon atoms, or 3 to 18 carbon atoms. It is a divalent group derived by removing two hydrogens from a heteroaromatic hydrocarbon. In these divalent groups, at least one hydrogen is replaced with a halogen, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 1 to 12 carbon atoms, or an alkenyloxy having 1 to 12 carbon atoms. In these monovalent hydrocarbon groups, at least one hydrogen may be replaced with a halogen. Further, in ring A1, a ¹ hydrogen is replaced by -SP ^1- P ¹ , and in ring A ^2, a 2 hydrogen is replaced by -SP ^2- P ² .

Examples of alicyclic hydrocarbons are cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane and the like, represented by C _n H _2n . Other examples include decahydronaphthalene. Examples of aromatic hydrocarbons are benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, tetrahydronaphthalene and the like. Examples of heteroaromatic hydrocarbons are pyridine, pyrimidine, furan, pyran, thiophene, benzofuran and the like. These hydrocarbons may be substituted with monovalent groups such as fluorine, chlorine and alkyl. Preferred examples of ring A ¹ or ring A ² are benzene, fluorobenzene, naphthalene, fluorene, or phenanthrene. A more preferred example is benzene or cyclohexane.

In formula (1-1), Z ¹ and Z ² are independently single-bonded or alkylenes having 1 to 10 carbon atoms, in which at least one −CH ₂ − is −O−, −. CO -, - COO- or -OCO- may be replaced by at least one - _{(CH 2) 2} - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C ( It may be replaced by CH ₃ )-, -C (CH ₃ ) = C (CH ₃ )-, or -CH≡CH-, in which at least one hydrogen is replaced by a halogen in these divalent groups. May be good.

Preferred examples of Z ¹ and Z ² are single bonds, alkylene with 1 to 4 carbon atoms, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, -C (CH ₃ ) = CH-COO-, -OCO-CH = C (CH ₃ )-, -CH = C (CH ₃ ) -COO-, -OCO- (CH ₃ ) C = CH-, -C (CH ₃ ) = C (CH ₃ ) -COO-, -OCO-C (CH ₃ ) = C (CH ₃ ) )-, -CO-CH = CH-, -CH = CH-CO-, -C (CH ₃ ) = C (CH ₃ )-, -CH = CH-CH ₂ O-, -OCH ₂ -CH = CH -, -CH = CH-OCH _2- , -CH ₂ O-CH = CH-, or -CH≡CH-. More preferred examples are single bond, ethylene, -COO-, -OCO-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, or -CH≡CH-. The most preferred example is a single bond.

In formula (1-1), b1 and b2 are independently 0, 1, 2, or 3. When b2 is 0, the compound rings to b1 or perforated for ring A ^1. In this case, the preferred ring A ¹ is a divalent group derived by removing two hydrogens from fused rings such as naphthalene, anthracene, phenanthrene and benzene. When b1 and b2 are 1, the compound has ring A ¹ and ring A ² . In this case, preferred ring A ¹ or ring A ² is a divalent group derived from benzene substituted with a substituent such as benzene, fluorine, or methyl. When b1 is 1 and b2 is 2, the compound has three rings, ring A ¹ , ring A ² and ring A ² . Preferred ring A ¹ or ring A ² is a divalent group derived from benzene substituted with a substituent such as benzene, fluorine.

2. Synthesis method A method for synthesizing compound (1) or compound (1-1) will be described. Compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry. Houben-Wyle, Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons, Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. Has been done.

2-1. Production of Binding Group Z An example of the method for producing the binding group Z in the compound (1-1) is as shown in the scheme below. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ²⁾ may be the same or different. Compounds (1A) to (1I) correspond to compound (1). In the production of esters, a method for synthesizing a compound having -COO- was shown. Compounds having −OCO− can also be synthesized by this synthetic method. The same is true for other asymmetric binding groups.

(1) Single bond formation The arylboric acid (21) and the compound (22) synthesized by a known method are reacted in an aqueous carbonate solution in the presence of a catalyst such as tetrakis (triphenylphosphine) palladium. Compound (1A) is synthesized. This compound (1A) is prepared by reacting compound (23) synthesized by a known method with n-butyllithium and then zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium, compound (22). ) Is also reacted.

(2) -COO- product compound (23) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (24). Compound (24) and phenol (25) synthesized by a known method are dehydrated and condensed in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (N, N-dimethyl-4-aminopyridine). Compound (1B) is synthesized.

(3) -CF ₂ O- product compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (26). Compound (26) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) (see M. Kuroboshi et al., Chem. Lett., 1992, 827.). Compound (1C) is also synthesized by fluorinating compound (26) with (diethylamino) sulfatrifluoride (DAST) (see WH Bunnelle et al., J. Org. Chem. 1990, 55, 768.). It is also possible to generate this linking group by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(4) -CH = CH-forming compound (22) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain aldehyde (28). The phosphonium salt (27) synthesized by a known method is treated with a base such as potassium tert-butoxide to generate phosphorus iride, which is reacted with an aldehyde (28) to synthesize a compound (1D). Since a cis form is produced depending on the reaction conditions, the cis form is isomerized to a trans form by a known method if necessary.

(5) -CH ₂ O- product compound (28) is reduced with a reducing agent such as sodium borohydride to obtain compound (29). This is halogenated with hydrobromic acid or the like to obtain compound (31). Compound (1E) is synthesized by reacting compound (31) with compound (30) in the presence of potassium carbonate or the like.

(6) Production of -CH = CH-COO- A base such as sodium hydride is allowed to act on ethyl diethylphosphonoacetate to prepare phosphorus iris, and this phosphorus irid is reacted with aldehyde (32) to obtain an ester (33). .. The ester (33) is hydrolyzed in the presence of a base such as sodium hydroxide to give the carboxylic acid (34). This compound and compound (25) are dehydrated and condensed to synthesize compound (1F).

(7) -C (CH ₃ ) = CH-COO-formation A base such as sodium hydride is allowed to act on ethyl diethylphosphonoacetate to prepare phosphorus iris, and this phosphorus irid is reacted with methyl ketone (35) to ester (35). 36) is obtained. Next, the ester (36) is hydrolyzed in the presence of a base such as sodium hydroxide to obtain a carboxylic acid (37), and then the compound (1G) is synthesized by dehydration condensation with the compound (25).

(8) Formation of −CH = C (CH ₃ ) −COO− N, N-dicyclohexylmethylamine (Cy) is a compound (38) synthesized by a known method and a compound (39) synthesized by a known method. Compound (1H) is synthesized by reacting in the presence of a base such as ₂ NMe) and a catalyst such as bis (tri-tert-butylphosphine) palladium.

(9) -C (CH ₃ ) = C (CH ₃ ) -COO- product compound (25) is dehydrated and condensed with pyruvic acid to obtain compound (40). Compound (1I) is synthesized by reacting compound (40) with compound (35) in the presence of zinc and titanium tetrachloride.

2-2. Generation of Linkage Group SP and Polymerizable Group P Preferred examples of the polymerizable group P are acryloyloxy (1a), oxylanyl (1b), vinyloxy (1c) maleimide (1d) or itaconic acid ester (1e).
An example of a method for synthesizing a compound in which this polymerizable group is bonded to a ring at a linking group SP is as follows. First, an example in which the linking group SP is a single bond will be shown.

(1) Generation of single bond The method of generating a single bond is as follows. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compound (1S) to compound (1Z) correspond to compound (1).

The method for synthesizing a compound in which the linking group SP is a single bond has been described above. Other methods for producing the linking group can be synthesized with reference to the method for synthesizing the linking group Z.

2-3. MES Producing Compound (1) MES is a mesogen group having at least one ring and N atoms. A preferred example is the following (1J). Compound (1J) corresponds to compound (1). When both Ring A ¹ and Ring A ² are aromatic hydrocarbons, they can be synthesized, for example, by the following scheme.

2-4. As generated ring ^{A 1} and ring ^{A 2} of the ring ^{A 1} and ring ^{A 2,} 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-Methyl-1,4-Phenanthrene, 2-Ethyl-1,4-Phenanthrene, Naphthalene-2,6-Diyl, Decahydronaphthalene-2,6-Diyl, 1,2,3,4-Tetrahydropyranphthalene-2 , 6-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidin-2,5-Diyl, Pyridine-2,5-Diyl, Perhydrocyclopenta [a] Phenanthrene -3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl For rings such as, the starting material is commercially available, or the synthetic method is well known.

Compound (1) has appropriate polymerization reactivity, high conversion rate and high solubility in liquid crystal compositions as compared with similar compounds. Compound (1) has an appropriate balance with respect to at least two of these physical properties. Therefore, compound (1) can be added to the liquid crystal composition for PSA mode.

3. 3. Polymerizable Composition The polymerizable composition contains at least one of the compound (1) as a first component. The component of this composition may be only the first component. This composition may contain other components such as a second component and a third component. The type of the second component and the like depends on the intended use of the polymer. This polymerizable composition may further contain other polymerizable compounds different from the compound (1) as the second component. Preferred examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), and vinyl ketones. More preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. More preferred examples also include compounds having both acryloyloxy and methacryloyloxy.

Additional examples of other polymerizable compounds are compound (M-1) to compound (M-12). From compound (M-1) to compound (M-12), R ²⁵ , R ²⁶ and R ²⁷ are independently hydrogen or methyl; u, x and y are independently 0 or 1; v and w is independently an integer from 1 to 10; L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , and L ²⁶ are independently hydrogen or fluorine.

When the second component of the polymerizable composition is a polymerizable compound having a liquid crystal phase, an optically anisotropic substance is produced by polymerizing while controlling the orientation of the liquid crystal molecules. This optical variant can be used for a retardation film, a polarizing element, a circular polarizing element, an elliptical polarizing element, an antireflection film, a selective reflection film, a color compensation film, a viewing angle compensation film, and the like. Additives such as a polymerization initiator may be added to the polymerizable composition for the purpose of adjusting the physical properties of the optically anisotropic substance.

The polymerizable composition may contain a liquid crystal composition as a second component. When the purpose is a liquid crystal display element for modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, PSA-OCB, the polymerizable composition contains compound (1) as component A, and the following It is preferable to further contain a compound selected from the components B, C and D shown in. Component B is compound (2) to compound (4). Component C is compound (5) to compound (7). Component D is compound (8). When preparing such a polymerizable composition, it is preferable to select components B, C and D in consideration of positive or negative dielectric anisotropy, magnitude of dielectric anisotropy and the like. A polymerizable composition with properly selected components has a high upper limit temperature, a lower lower limit temperature, a small viscosity, a suitable optical anisotropy (ie, a large optical anisotropy or a small optical anisotropy), and a large positive or negative. It has a modulus anisotropy and a suitable elastic constant (ie, a large or small elastic constant).

The polymerizable composition is prepared by adding compound (1) to the liquid crystal composition. Additives may be added to this composition as needed. In such a composition, the amount of the compound (1), that is, the component A added is in the range of 0.01% by weight to 20% by weight based on the weight of the liquid crystal composition. A more preferable addition amount is in the range of 0.0133% by weight to 10% by weight. The most preferable addition amount is in the range of 0.05% by weight to 5% by weight. At least one of other polymerizable compounds different from compound (1) may be further added. In this case, the total addition amount of the compound (1) and the other polymerizable compound is preferably within the above range. By appropriately selecting other polymerizable compounds, the physical properties of the produced polymer can be adjusted. Examples of other polymerizable compounds are acrylates, methacrylates and the like, as described above. This example also includes compounds (M-1) to compound (M-12).

Component B is a compound having two terminal groups such as alkyl. Preferred examples of component B include compound (2-1) to compound (2-11), compound (3-1) to compound (3-19), or compound (4-1) to compound (4-7). Can be mentioned. In the compound of component B, R ¹¹ and R ¹² are independently an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, and in this alkyl or alkenyl, at least one -CH _2- is -O. It may be replaced with −, and at least one hydrogen may be replaced with fluorine.

Component B is a compound close to neutral because the absolute value of dielectric anisotropy is small. Compound (2) is mainly effective in adjusting viscosity or optical anisotropy. The compound (3) and the compound (4) are effective in widening the temperature range of the nematic phase by increasing the upper limit temperature, or in adjusting the optical anisotropy.

As the content of component B is increased, the dielectric anisotropy of the composition decreases, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably large. Therefore, when preparing a composition for a mode such as PS-IPS, PSA-VA, the content of component B is preferably 30% by weight or more, more preferably 40, based on the weight of the liquid crystal composition. Weight% or more.

Component C is a compound having a halogen or fluorine-containing group at the right end. Preferred examples of component C include compound (5-1) to compound (5-16), compound (6-1) to compound (6-113), or compound (7-1) to compound (7-57). Can be mentioned. In the compound of component C, R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-. , At least one hydrogen may be replaced with fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or. -OCF ₂ CHFCF ₃ .

Component C has a positive dielectric anisotropy and is extremely stable against heat, light, etc., so a composition for modes such as PS-IPS, PS-FFS, and PSA-OCB is prepared. Used in cases. The content of the component C is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. It is in the range of%. When the component C is added to a composition having a negative dielectric anisotropy, the content of the component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component C, the elastic constant of the composition can be adjusted and the voltage-transmittance curve of the device can be adjusted.

Component D is compound (8) whose right terminal group is -C≡N or -C≡C-C≡N. Preferred examples of the component D include compounds (8-1) to compounds (8-64). In the compound of component D, R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-. , At least one hydrogen may be replaced by fluorine; X ¹² is -C ≡ N or -C ≡ C-C ≡ N.

Component D has a positive dielectric anisotropy and a large value, and is therefore mainly used when preparing a composition for a mode such as PS-TN. By adding this component D, the dielectric anisotropy of the composition can be increased. The component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.

When preparing a composition for a mode such as PS-TN, the content of component D is preferably in the range of 1% by weight to 99% by weight, preferably 10% by weight, based on the weight of the liquid crystal composition. It is in the range of% to 97% by weight, more preferably in the range of 40% by weight to 95% by weight. When the component D is added to a composition having a negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

The polymerizable composition is prepared by a method such as dissolving the necessary components at a temperature higher than room temperature. Additives may be added to this composition depending on the application. Examples of additives are optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, defoamers, polymerization initiators, polymerization inhibitors and the like. Such additives are well known to those of skill in the art and are described in the literature.

The optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule to give a necessary twist angle. The spiral pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the spiral pitch. Preferred examples of the optically active compound include compounds (Op-18) from the following compounds (Op-1). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is an alkyl having 1 to 10 carbon atoms.

Antioxidants are effective in maintaining a large voltage retention. Preferred examples of antioxidants include the following compounds (AO-1) and compounds (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF). Can be mentioned. The ultraviolet absorber is effective for preventing a decrease in the upper limit temperature. Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples include the following compounds (AO-3) and compounds (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (trade name: BASF). ); And 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.

Light stabilizers such as amines with steric hindrance are preferred for maintaining high voltage retention. Preferred examples of the light stabilizer include the following compounds (AO-5) and compounds (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferable example thereof is IRGAFOS 168 (trade name: BASF). Defoamers are effective in preventing foaming. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil and the like.

In compound (AO-1), R ²⁹ is an alkyl having 1 to 20 carbons, an alkoxy having 1 to 20 carbons, -COOR ³² , or -CH ₂ CH ₂ COOR ³² , where R ³² has 1 carbon. To 20 alkyl. In compound (AO-2) and compound (AO-5), R ³⁰ is an alkyl having 1 to 20 carbon atoms. In compound (AO-5), R ³¹ is hydrogen, methyl or O ^· (oxygen radical), rings K and L are 1,4-cyclohexylene or 1,4-phenylene, x is 0, 1 or 2.

4. The liquid crystal complex compound (1) has appropriate polymerization reactivity, high conversion rate and high solubility in the liquid crystal composition. A liquid crystal composite is formed by polymerizing a polymerizable composition containing the compound (1) and the liquid crystal composition. Compound (1) produces a polymer in the liquid crystal composition by polymerization. This polymer has the effect of stabilizing the initial orientation of the liquid crystal molecules. Further, when polymerization is carried out while applying an electric field, pretil can be generated. Polymerization occurs by heat, light, and the like. The preferred reaction is photopolymerization. Polymerization may be carried out in a state where an electric field or a magnetic field is applied.

The polymerization reactivity and conversion rate of compound (1) can be adjusted. Compound (1) is suitable for radical polymerization. Compound (1) can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of residual compound (1) can be reduced. Examples of photoradical polymerization initiators are TPO, 1173 and 4265 from BASF's DaroCure series and 184,369,500,651,784,819,907,1300,1700,1800,1850 from the Irgacure series. And 2959.

Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-Phenylaclysine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture Is.

After adding a photoradical polymerization initiator to the polymerizable composition, polymerization can be carried out by irradiating with ultraviolet rays in a state where an electric field is applied. However, unreacted polymerization initiators or degradation products of the polymerization initiators may cause display defects such as image burn-in on the device. In order to avoid this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the emitted light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range of 250 nm to 450 nm, and most preferred wavelengths are in the range of 300 nm to 400 nm.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

5. Liquid crystal display element The effect of the polymer on the liquid crystal display element is interpreted as follows. The polymerizable composition is a mixture of a liquid crystal compound, a polymerizable compound and the like. When this composition is injected into a liquid crystal cell, it exhibits various initial orientations depending on the characteristics of the cell used and the composition. In this state, the composition is irradiated with ultraviolet rays to polymerize the polymerizable compound. At this time, an electric field may be applied to the cell. As a result, a network of polymers is formed in the polymerizable composition. Due to the effect of this network, the liquid crystal molecules are stabilized in the state before irradiation with ultraviolet rays. Further, although the initial orientation is a random orientation, it is also possible to form an ordered orientation such as a homogeneous orientation or a homeotropic orientation by irradiating with ultraviolet rays. By polymerizing the polymerizable composition by irradiation with ultraviolet rays in this way, it is possible to obtain a liquid crystal display device stabilized in various orientation states.

The polymerization of the polymerizable composition is preferably carried out in the display element. An example is as follows. A display element having two glass substrates having a transparent electrode on at least one of them is prepared. A polymerizable composition containing the compound (1), a liquid crystal composition, an additive and the like as components is prepared. This composition is injected into the display element. The display element is irradiated with ultraviolet rays to polymerize the compound (1). A liquid crystal composite is formed by this polymerization. By this method, a liquid crystal display element having a liquid crystal composite can be easily manufactured. In this method, the rubbing treatment of the alignment film may be omitted, or the alignment film may not be present.

When the amount of the polymerizable compound added is in the range of 0.1% by weight to 2% by weight based on the weight of the liquid crystal composition, a liquid crystal display element in PSA mode is produced. The PSA mode element can be driven by a drive system such as AM (active matrix) or PM (passive matrix). Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type. By increasing the amount of the polymerizable compound added, a device in the polymer dispersed mode can also be manufactured.

The present invention will be described in more detail by way of examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of the Examples. The synthesized compound was identified by a method such as NMR analysis. The physical properties of the compound, composition and device were measured by the methods described below.

For the NMR analysis measurement, DRX-500 manufactured by Bruker Biospin Co., Ltd. was used. ^{1 In the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was carried out at room temperature under the conditions of 500 MHz and 16 times of integration. Tetramethylsilane was used as an internal standard. ^{19 In the} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, and br is broad.

Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for HPLC analysis and measurement. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. The eluate used was an appropriate mixture of acetonitrile and water. As the detector, a UV detector, an RI detector, a CORONA detector and the like were appropriately used. When a UV detector was used, the detection wavelength was 254 nm. The sample was prepared to dissolve in acetonitrile to form a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

For the ultraviolet-visible spectroscopic analysis, a PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was 190 nm to 700 nm. The sample was prepared by dissolving it in acetonitrile to form a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length 1 cm) for measurement.

Measurement sample When measuring the phase structure and transition temperature (transparency point, melting point, polymerization start temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, and dielectric anisotropy of the liquid crystal compound, a mixture of this compound and the mother liquid crystal was used as a sample. When measuring the physical properties of the liquid crystal composition, the composition itself was used as a sample.

As the mother liquid crystal, the following mother liquid crystal (A) or mother liquid crystal (B) or the like was used. The ratio of the components of the mother liquid crystals (A) and (B) is shown in% by weight.

Measurement method The physical properties were measured by the following method. Many of these are methods described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method. there were. A thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Phase structure A sample was placed on a hot plate (FP-52 type hot stage manufactured by Mettler) of a melting point measuring device equipped with a polarizing microscope. While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.

(2) Transition temperature (° C)
A scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SSI Nanotechnology, X-DSC7000 was used for the measurement. The sample was raised and lowered at a rate of 3 ° C./min. The transition temperature was determined by extrapolating the starting point of the endothermic peak or exothermic peak associated with the phase change of the sample. The melting point of the compound and the polymerization initiation temperature were also measured using this device. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from the liquid crystal phase to a liquid may be abbreviated as "transparency point".

The crystal was represented as C. When the types of crystals can be distinguished, they are represented as C ₁ and C ₂ , respectively. The smectic phase was represented as S and the nematic phase was represented as N. Among the smectic phase, a smectic A phase, a smectic B phase, if can be distinguished in the smectic C phase, or a smectic F phase, respectively _{S A,} S B, expressed as _{S C} or _{S F,.} The liquid (isotropic) was represented as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C. and the transition temperature from the nematic phase to the liquid is 100.0 ° C.

(3) Upper limit temperature of nematic phase (T _NI or NI; ° C)
The sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature when a part of the sample changed from the nematic phase to the isotropic liquid was measured. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature". When the sample was a mixture of a liquid crystal compound and a mother liquid crystal, it was indicated by the _TNI symbol. When the sample is a mixture of a liquid crystal compound and a compound such as components B, C and D, it is indicated by the symbol of NI.

(4) Minimum Temperature of a Nematic Phase _{(T C;} ° C.)
A sample having a nematic phase was stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase was observed. For example, _TC was described as ≤-20 ° _C when the sample remained in the nematic phase at -20 ° C and changed to a crystalline or smectic phase at -30 ° C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(5) Viscosity (bulk viscosity; η; measured at 20 ° C; mPa · s)
The viscosity was measured using an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd.

(6) Optical anisotropy (refractive index anisotropy; measured at 25 ° C; Δn)
The measurement was performed using light having a wavelength of 589 nm with an Abbe refractometer in which a polarizing plate was attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index (n‖) was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation Δn = n‖−n⊥.

(7) Specific resistance (ρ; measured at 25 ° C; Ωcm)
1.0 mL of sample was injected into a container equipped with electrodes. A DC voltage (10 V) was applied to this container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following formula. (Specific resistance) = {(voltage) x (capacitance of container)} / {(DC current) x (vacuum permittivity)}.

(8) Voltage retention rate (VHR-1; measured at 25 ° C;%)
The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. This element was sealed with an adhesive that cures with UV light after the sample was placed. This device was irradiated with ultraviolet rays for 400 seconds. An EXCURE 4000-D type mercury xenon lamp manufactured by HOYA CANDEO OPTRONICS Co., Ltd. was used for irradiation with ultraviolet rays. A pulse voltage (60 microseconds at 5 V) was applied to this device to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(9) Voltage retention rate (VHR-2; measured at 80 ° C;%)
The voltage holding ratio was measured by the above method except that the measurement was performed at 80 ° C. instead of 25 ° C. The results are indicated by the symbol VHR-2.

(10) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s)
The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degrees and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The values of rotational viscosity were obtained from these measured values and the paper by M. Imai et al., Calculation formula (8) on page 40. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using the device whose rotational viscosity was measured.

(11) Dielectric constant anisotropy (Δε; measured at 25 ° C)
The sample was placed in a TN device in which the distance (cell gap) between the two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε ‖) of the liquid crystal molecule in the long axis direction was measured. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured. The value of permittivity anisotropy was calculated from the equation Δε ＝ ε‖−ε⊥.

(12) Elastic constant (K; measured at 25 ° C; pN)
An HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to this device, and the capacitance and applied voltage were measured. Use the measured capacitance (C) and applied voltage (V) values in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), equations (2.98) and 2.101 on page 75. The fitting was performed, and the values of K ₁₁ and K ₃₃ were obtained from the formula (2.99). Next, K ₂₂ was calculated using the values of K ₁₁ and K ₃₃ obtained earlier in the formula (3.18) on page 171. The elastic constant K is represented by the average value of K ₁₁ , K _22, and K ₃₃ thus obtained.

(13) Threshold voltage (Vth; measured at 25 ° C; V)
An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V. 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 was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(14) Response time (τ; measured at 25 ° C; ms)
An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 5.0 μm and the twist angle was 80 degrees. A square wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required for the transmittance to change from 10% to 90%. The response time was expressed as the sum of the rise time and the fall time obtained in this way.

(15) Prepare a sample in which the mother liquid crystal and the compound are mixed so that the ratio of the room-temperature compatible compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Then, after leaving it at room temperature for 1 day, it was observed whether crystals or smectic phases were precipitated.

1. 1. Example of compound (1) [Synthesis example 1] Synthesis of compound (No. 1)

Take compound (50) (3.94 g, 19.58 mmol), triethylamine (4.36 g, 43.1 mmol), and dichloromethane (100 ml) in a container and add methacrylic acid chloride (4.09 g, 39.16 mmol) with stirring. Dropped. After stirring at room temperature for 1 hour, the mixture was filtered and concentrated. The obtained residue was purified by silica gel chromatography (toluene) to obtain Compound (No. 1) (2.2 g).
Compound (50) is known and can be easily obtained by those skilled in the art.

^{1 1} H-NMR (CDCl ₃ ; δppm): 7.03 (d, 8H), 6.33 (s, 2H), 5.74 (s, 2H), 5.69 (s, 1H), 2.06 (S, 6H).

The physical properties of compound (No. 1) were as follows.
Transition temperature: C 91.0 C 99.2 I
Room temperature compatibility: 5% by weight
Voltage retention rate: 95%
As the composition used for measuring the voltage holding ratio, a composition in which 0.4% of the compound (No. 1) was added to the mother liquid crystal (B) was used.

By the same method as that described in Synthesis Example 1, the compound No. 1 shown below was used. 2 to No. 54 can be synthesized.

[Comparative Experiment 1]
As a result of measuring the room temperature compatibility of the comparative compound (R-1) disclosed in JP-A-2004-131704 (Patent Document 2), crystals were precipitated in 1% by weight with respect to the mother liquid crystal (A). .. Moreover, as a result of measuring the voltage holding ratio by the same method as in Example 1, it was 80%. Since the compound (No. 1) has a room temperature compatibility of 5% by weight, crystals are precipitated, and the voltage retention rate is 95%, it can be said that the compound (No. 1) has higher solubility in the liquid crystal composition and higher voltage retention rate.

2. Examples of polymerizable compositions The compounds in this example are represented by symbols based on the definitions in the table below. In the table, the configuration for 1,4-cyclohexylene is trans. In this embodiment, the numbers in parentheses after the symbol correspond to the compound numbers. The symbol (-) means other liquid crystal compounds. The content (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the physical property values of the composition are summarized. The physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

[Usage example 1]
2-HB-C (8-1) 6%
3-HB-C (8-1) 12%
3-HB-O2 (2-5) 15%
2-BTB-1 (2-10) 5%
3-HHB-F (6-1) 4%
3-HHB-1 (3-1) 7%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 12%
3-HHEB-F (6-10) 3%
5-HHEB-F (6-10) 6%
2-HHB (F) -F (6-2) 6%
3-HHB (F) -F (6-2) 6%
5-HHB (F) -F (6-2) 6%
3-HHB (F, F) -F (6-3) 7%
Compound (No. 1) was added to the above composition at a ratio of 0.05% by weight.
NI = 97.3 ° C; η = 18.3 mPa · s; Δn = 0.103; Δε = 4.7

[Usage example 2]
3-HB-CL (5-2) 13%
3-HH-4 (2-1) 15%
3-HB-O2 (2-5) 8%
3-HHB (F, F) -F (6-3) 6%
3-HBB (F, F) -F (6-24) 24%
5-HBB (F, F) -F (6-24) 22%
5-HBB (F) B-2 (4-5) 6%
5-HBB (F) B-3 (4-5) 6%
Compound (No. 2) was added to the above composition at a ratio of 0.3% by weight.
NI = 75.1 ° C.; η = 17.6 mPa · s; Δn = 0.115; Δε = 4.9

[Usage example 3]
7-HB (F, F) -F (5-4) 6%
3-HB-O2 (2-5) 7%
2-HHB (F) -F (6-2) 10%
3-HHB (F) -F (6-2) 8%
5-HHB (F) -F (6-2) 10%
2-HBB (F) -F (6-23) 9%
3-HBB (F) -F (6-23) 10%
5-HBB (F) -F (6-23) 14%
2-HBB-F (6-22) 4%
3-HBB-F (6-22) 5%
5-HBB-F (6-22) 5%
3-HBB (F, F) -F (6-24) 4%
5-HBB (F, F) -F (6-24) 8%
Compound (No. 8) was added to the above composition at a ratio of 1% by weight.
NI = 82.1 ° C; η = 24.0 mPa · s; Δn = 0.113; Δε = 5.2

[Usage example 4]
5-HB-CL (5-2) 13%
3-HH-4 (2-1) 15%
3-HH-5 (2-1) 4%
3-HHB-F (6-1) 5%
3-HHB-CL (6-1) 3%
4-HHB-CL (6-1) 4%
3-HHB (F) -F (6-2) 9%
4-HHB (F) -F (6-2) 9%
5-HHB (F) -F (6-2) 8%
7-HHB (F) -F (6-2) 8%
5-HBB (F) -F (6-23) 5%
1O1-HBBH-5 (4-1) 3%
3-HHBB (F, F) -F (7-6) 3%
4-HHBB (F, F) -F (7-6) 3%
5-HHBB (F, F) -F (7-6) 2%
3-HH2BB (F, F) -F (7-15) 3%
4-HH2BB (F, F) -F (7-15) 3%
Compound (No. 1) was added to the above composition at a ratio of 3% by weight.
NI = 118.1 ° C; η = 19.6 mPa · s; Δn = 0.091; Δε = 3.6

[Usage example 5]
3-HHB (F, F) -F (6-3) 11%
3-H2HB (F, F) -F (6-15) 8%
4-H2HB (F, F) -F (6-15) 7%
5-H2HB (F, F) -F (6-15) 7%
3-HBB (F, F) -F (6-24) 20%
5-HBB (F, F) -F (6-24) 20%
3-H2BB (F, F) -F (6-27) 13%
5-HHBB (F, F) -F (7-6) 3%
5-HHEBB-F (7-17) 2%
3-HH2BB (F, F) -F (7-15) 3%
1O1-HBBH-4 (4-1) 3%
1O1-HBBH-5 (4-1) 3%
Compound (No. 1) was added to the above composition at a ratio of 5% by weight.
NI = 93.9 ° C; η = 34.3 mPa · s; Δn = 0.115; Δε = 9.2

[Usage example 6]
5-HB-F (5-2) 15%
6-HB-F (5-2) 7%
7-HB-F (5-2) 7%
2-HHB-OCF3 (6-1) 6%
3-HHB-OCF3 (6-1) 7%
4-HHB-OCF3 (6-1) 6%
5-HHB-OCF3 (6-1) 5%
3-HH2B-OCF3 (6-4) 6%
5-HH2B-OCF3 (6-4) 4%
3-HHB (F, F) -OCF2H (6-3) 4%
3-HHB (F, F) -OCF3 (6-3) 5%
3-HH2B (F) -F (6-5) 3%
3-HBB (F) -F (6-23) 8%
5-HBB (F) -F (6-23) 10%
5-HBBH-3 (4-1) 4%
3-HB (F) BH-3 (4-2) 3%
Compound (No. 8) was added to the above composition at a ratio of 0.1% by weight.
NI = 87.5 ° C; η = 14.9 mPa · s; Δn = 0.092; Δε = 4.4

[Usage example 7]
5-HB-CL (5-2) 15%
3-HH-4 (2-1) 5%
3-HHB-1 (3-1) 5%
3-HHB (F, F) -F (6-3) 5%
3-HBB (F, F) -F (6-24) 20%
5-HBB (F, F) -F (6-24) 15%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F) -F (6-12) 3%
5-HHEB (F, F) -F (6-12) 5%
2-HBEB (F, F) -F (6-39) 3%
3-HBEB (F, F) -F (6-39) 5%
5-HBEB (F, F) -F (6-39) 5%
3-HHBB (F, F) -F (7-6) 4%
Compound (No. 2) was added to the above composition at a ratio of 0.5% by weight.
NI = 75.8 ° C; η = 22.3 mPa · s; Δn = 0.103; Δε = 9.0

[Usage example 8]
3-HB-CL (5-2) 4%
5-HB-CL (5-2) 4%
3-HHB-OCF3 (6-1) 5%
3-H2HB-OCF3 (6-13) 5%
5-H4HB-OCF3 (6-19) 15%
V-HHB (F) -F (6-2) 6%
3-HHB (F) -F (6-2) 5%
5-HHB (F) -F (6-2) 5%
3-H4HB (F, F) -CF3 (6-21) 8%
5-H4HB (F, F) -CF3 (6-21) 10%
5-H2HB (F, F) -F (6-15) 4%
5-H4HB (F, F) -F (6-21) 7%
2-H2BB (F) -F (6-26) 5%
3-H2BB (F) -F (6-26) 11%
3-HBEB (F, F) -F (6-39) 6%
Compound (No. 1) was added to the above composition at a ratio of 2% by weight.
NI = 71.9 ° C; η = 26.3 mPa · s; Δn = 0.098; Δε = 8.5

[Usage example 9]
5-HB-CL (5-2) 14%
7-HB (F, F) -F (5-4) 4%
3-HH-4 (2-1) 10%
3-HH-5 (2-1) 4%
3-HB-O2 (2-5) 14%
3-HHB-1 (3-1) 8%
3-HHB-O1 (3-1) 5%
2-HHB (F) -F (6-2) 8%
3-HHB (F) -F (6-2) 8%
5-HHB (F) -F (6-2) 8%
3-HHB (F, F) -F (6-3) 6%
3-H2HB (F, F) -F (6-15) 6%
4-H2HB (F, F) -F (6-15) 5%
Compound (No. 1) was added to the above composition at a ratio of 1.5% by weight.
NI = 72.9 ° C; η = 15.1 mPa · s; Δn = 0.074; Δε = 3.0

[Usage example 10]
5-HB-CL (5-2) 6%
7-HB (F) -F (5-3) 6%
3-HH-4 (2-1) 7%
3-HH-5 (2-1) 10%
3-HB-O2 (2-5) 11%
3-HHEB-F (6-10) 8%
5-HHEB-F (6-10) 10%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F) -F (6-12) 5%
3-GHB (F, F) -F (6-109) 6%
4-GHB (F, F) -F (6-109) 5%
5-GHB (F, F) -F (6-109) 5%
2-HHB (F, F) -F (6-3) 7%
3-HHB (F, F) -F (6-3) 4%
Compound (No. 8) was added to the above composition at a ratio of 0.5% by weight.
NI = 72.6 ° C; η = 19.1 mPa · s; Δn = 0.069; Δε = 5.9

[Usage example 11]
1V2-BEB (F, F) -C (8-15) 10%
3-HB-C (8-1) 13%
2-BTB-1 (2-10) 8%
5-HH-VFF (2-1) 30%
3-HHB-1 (3-1) 5%
VFF-HHB-1 (3-1) 8%
VFF2-HHB-1 (3-1) 11%
3-H2BTB-2 (3-17) 5%
3-H2BTB-3 (3-17) 5%
3-H2BTB-4 (3-17) 5%
Compound (No. 2) was added to the above composition at a ratio of 1% by weight.
NI = 84.1 ° C; η = 13.9 mPa · s; Δn = 0.131; Δε = 8.8

[Usage example 12]
5-HB (F) B (F, F) XB (F, F) -F (7-41) 6%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 8%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
3-HH-V (2-1) 38%
3-HH-V1 (2-1) 5%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 5%
V-HHB-1 (3-1) 4%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (5-1) 3%
3-BB (F, F) XB (F, F) -F (6-97) 10%
3-HHBB (F, F) -F (7-6) 3%
Compound (No. 1) was added to the above composition at a ratio of 3% by weight.
NI = 84.7 ° C; η = 17.0 mPa · s; Δn = 0.113; Δε = 8.0

[Usage example 13]
3-GB (F) B (F, F) XB (F, F) -F (7-57) 6%
5-HB (F) B (F, F) XB (F, F) -F (7-41) 3%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 4%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 4%
3-HH-V (2-1) 35%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 3%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (5-1) 3%
3-BB (F, F) XB (F, F) -F (6-97) 7%
3-GB (F, F) XB (F, F) -F (6-113) 6%
3-HHBB (F, F) -F (7-6) 4%
Compound (No. 1) was added to the above composition at a ratio of 0.05% by weight.
NI = 82.5 ° C; η = 18.3 mPa · s; Δn = 0.109; Δε = 9.4

A liquid crystal display device having a mode such as PSA can be produced by polymerizing a polymerizable composition containing the polymerizable compound (1) and the liquid crystal composition. In the most preferred embodiment, the device has a wide temperature range in which the device can be used, a short response time, a high voltage retention, a low threshold voltage, a large contrast ratio, and a long lifetime. Therefore, compound (1) can be used in liquid crystal projectors, liquid crystal televisions, and the like. Compound (1) can also be used as a raw material for an optically anisotropic substance.

Claims (7)

A polymerizable compound represented by any one of the following formulas (1-1-4) to (1-1-6) and a compound represented by any one of the following formulas (2) to (8). A polymerizable composition containing at least one compound selected from the above.
In equations (1-1-4) to (1-1-6),
R ⁷ is a hydrogen, halogen, -SP ^1- P ¹ , -SP ^2- P ² or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or -S. It may be replaced by −, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen in these groups is a halogen. May be replaced by −SP ¹ −P ¹ or −SP ² −P ² ;
Rings A ¹ , ring A ² , rings A ³ and ring A ⁴ are independently alicyclic hydrocarbons with 3 to 18 carbon atoms, aromatic hydrocarbons with 6 to 18 carbon atoms, or 3 to 18 carbon atoms. Divalent groups derived from heteroaromatic hydrocarbons of, at least one hydrogen in these divalent groups is halogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, from 1 carbon atom. It may be replaced with 12 alkenyl, or alkenyloxy with 1 to 12 carbon atoms, and at least one hydrogen in these monovalent hydrocarbon groups may be replaced with halogen;
SP ¹ and SP ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be substituted, and at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, at least one in these groups. Hydrogen may be replaced by halogen;
P ¹ and P ² are independently represented by the following formulas (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e),
M ¹ and M ² are independently hydrogen, halogen or alkyl having 1 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O- or -S-. , At least one − (CH ₂ ) ₂ − may be replaced by −CH = CH − or −C≡C−, where at least one hydrogen in these groups is a halogen, −SP ¹ −P ¹ or It may be replaced by -SP ² -P ^2;
R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − , -O- or -S-, and at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with a halogen.
In equations (2) to (4),
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − is replaced by -O-. Also, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ independently form 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-. 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are independently single-bonded, −CH ₂ CH _2- , −CH = CH−, −C≡C−, or −COO−.
In equations (5) to (7),
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − and at least one hydrogen is. May be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl. , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, - _CH 2 O-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine.
In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced with −O− and at least one hydrogen. May be replaced with fluorine;
X ¹² is -C≡N or -C≡C-C≡N;
Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl. , Or pyrimidine-2,5-dioxane;
Z ¹⁷ is a single _{bond, - (CH 2) 2 -} , - C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4. In equations (1-1-4) to (1-1-6),
Rings A ¹ and A ² are independently 1,4-phenylene, and at least one hydrogen on these rings may be replaced with a halogen .
Ring ^{A 3} and ring ^{A 4} are independently 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, and at least one hydrogen on the rings replaced by halogen May be
The polymerizable composition according to claim 1. In equation (1-1-4)
R ⁷ is hydrogen
Rings A ¹ and A ² are independently 1,4-phenylene, and at least one hydrogen on these rings may be replaced with a halogen .
The polymerizable composition according to claim 1. A liquid crystal composite produced by polymerization of the polymerizable composition according to any one of claims 1 to 3 . An optically anisotropic substance produced by the polymerization of the polymerizable composition according to any one of claims 1 to 3 . A liquid crystal display device containing the polymerizable composition according to any one of claims 1 to 3 or the liquid crystal composite according to claim 4 . Use in a liquid crystal display device at least one selected from the group consisting of the polymerizable composition according to any one of claims 1 to 3 and the liquid crystal composite according to claim 4 .