WO2013077343A1

WO2013077343A1 - Polymerizable compound

Info

Publication number: WO2013077343A1
Application number: PCT/JP2012/080130
Authority: WO
Inventors: 泰行後藤; 真依子松隈
Original assignee: Jnc株式会社; Jnc石油化学株式会社
Priority date: 2011-11-24
Filing date: 2012-11-21
Publication date: 2013-05-30
Also published as: JPWO2013077343A1; JP6136932B2

Abstract

Provided is a compound having two polymerizable groups, one bonding directly to a ring, the other having a spacer between a ring and the polymerizable group, as a compound having high solubility in a liquid crystal composition without lowering the polymerization reactivity. A compound represented by formula (1). In formula (1), for example, A¹ and A² are 1,4-phenylene in which at least one hydrogen has been substituted by fluorine; Z¹ is an alkylene having from 1 to 12 carbon atoms; Z² is an alkylene having from 1 to 12 carbon atoms; X¹ is hydrogen, fluorine, methyl, or trifluoromethyl; P¹ is a polymerizable group; and a is an integer of from 0 to 3.

Description

Polymerizable compound

The present invention includes a polymerizable compound having two polymerizable groups, one directly bonded to a ring and the other having a spacer (bonding group) between the ring and the polymerizable group, The present invention relates to a composition having a polymerizable compound, a polymer obtained from the composition, and uses thereof.

A liquid crystal display element typified by a liquid crystal display panel, a liquid crystal display module, etc. utilizes the optical anisotropy, dielectric anisotropy, etc. of the liquid crystal compound. , PC (phase changed) mode, TN (twisted nematic) mode, STN (super twisted nematic) mode, BTN (bistably twisted nematic) mode, ECB (electrically controlled birefringed birefringent) -Plane switching) mode, FFS (ringe field switching) mode, A (vertical alignment) mode, and the like.

In addition, a liquid crystal display element in which a polymerizable compound is added to a liquid crystal composition is known. For example, in a PSA (Polymer Sustained Alignment) mode liquid crystal display element, a small amount (for example, about 0.3 wt% to about 1 wt%) of a polymerizable compound is added to the liquid crystal composition, introduced into the liquid crystal display cell, and then between the electrodes. In the state where a voltage is applied to the polymerizable compound, the polymerizable compound is polymerized usually under UV irradiation to form a polymer structure in the cell. By this method, the degree of image sticking is improved, and a liquid crystal display element with a shorter response time is obtained.

This method is applied to various liquid crystal display elements, and modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, and PSA-OCB are known. The polymerizable compound added to the liquid crystal composition used in these mode elements has a rigid skeleton. This compound is generally considered to have a high ability to align liquid crystal molecules. On the other hand, the solubility in the liquid crystal composition is poor, and a large amount of the polymerizable compound cannot be added (Patent Document 1 to Patent Document 5).

JP 2003-307720 A JP 2004-131704 A JP 2006-133619 A European Patent Application Publication No. 1898894 Special table 2010-537256

One object of the present invention is to provide a polymerizable compound having high solubility in a liquid crystal composition without reducing polymerization reactivity. Another object is a liquid crystal composition containing this compound and a liquid crystal display device containing such a composition. Another object is to provide a polymer obtained from a composition containing the compound, an optical element produced from the polymer, and the like.

The present inventor has studied the skeletal structure of a polymerizable compound used in a liquid crystal display device such as a PSA mode, and found that the compound (1) increases the solubility in the liquid crystal composition without decreasing the polymerization reactivity. It was. Compound (1) has two polymerizable groups, one is directly bonded to the ring, and the other has a bonding group between the ring and the polymerizable group. The compound (1) showed sufficient polymerization reactivity by having a polymerizable group directly bonded to the ring. Compound (1) exhibited high solubility in the liquid crystal composition by having a linking group such as ester or alkylene between the ring and the polymerizable group.

A compound represented by formula (1).

In equation (1),
A ¹ is independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or At least one hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by halogen;
A ² is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or carbon in which at least one hydrogen is replaced by halogen. May be substituted with an alkyl of the number 1 to 12;
Z ¹ is alkylene having 1 to 12 carbons, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, or — May be replaced by C≡C-;
Z ² is independently a single bond or alkylene having 1 to 12 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, — May be replaced by CH═CH—, or —C≡C—;
When all A ¹ and A ² are groups in which no hydrogen is replaced, at least one of Z ¹ and Z ² has an unsaturated bond;
X ¹ is hydrogen, fluorine, methyl, or trifluoromethyl;
P ¹ is a polymerizable group;
a is an integer of 0 to 3.

Compound (1) satisfies many advantages such as high solubility in the liquid crystal composition without lowering the polymerization reactivity. By using a liquid crystal composition containing compound (1) as a raw material, a liquid crystal display device having a short response time and an improved degree of image sticking can be produced.

Terms used in this specification are as follows. “Liquid crystal compound” is a general term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The “non-polymerizable liquid crystal composition” is a liquid crystal composition composed of a liquid crystal compound having no polymerizable group. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be referred to as a compound, a composition, and an element, respectively. The compound represented by formula (1) may be referred to as compound (1) or compound of formula (1). Other formulas may be abbreviated as well. “Compound (1)” means one compound or two or more compounds represented by formula (1). The same applies to compounds represented by other formulas. The group represented by the formula (P-1) may be abbreviated as “group (P-1)”. The same applies to groups represented by other formulas. In the formulas (2) to (7), symbols such as B ¹¹ and C ¹¹ surrounded by hexagons correspond to the rings B ¹¹ and C ¹¹ , respectively. Multiple R ¹¹ were described in the same or different formula. In these compounds, two groups represented by any two R ¹¹ may be the same or different. This rule also applies to symbols such as rings A ¹ and Z ² . The ratio of the additive mixed with the composition means a weight percentage (% by weight) based on the total weight of the liquid crystal composition. When at least one —CH ₂ — may be replaced with —O—, the adjacent —CH ₂ — may be replaced with —O— and —CH ₂ — next to —O— may be replaced with —O—. It is not included to be replaced with-. “Monofunctional” means that there is one polymerizable group, and “polyfunctional” means that there are two or more polymerizable groups.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the formula (1) and the like, fluorine may be leftward or rightward. This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl.

The present invention includes the following items.
1. A compound represented by formula (1).

2. In the formula (1) described in item 1,
A ¹ is 1,4-cyclohexylene, 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 4 carbons, or At least one hydrogen may be replaced by alkyl of 1 to 4 carbons replaced by halogen;
A ² is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 4 carbons, or at least one hydrogen is replaced by halogen Optionally substituted with 1 to 4 carbon alkyls;
Z ¹ is alkylene having 1 to 12 carbons, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, or — May be replaced by C≡C-;
Z ² is a single bond or alkylene having 1 to 12 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH May be replaced by-, or -C≡C-;
At least one of Z ¹ and Z ² is a carbon number in which at least one —CH ₂ — is replaced by —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. 1 to 12 alkylene;
X ¹ is hydrogen or methyl;
P ¹ is a group selected from the groups represented by formula (P-1) to formula (P-3);

Item 2. The compound according to Item 1, wherein a is 1.

3. In the formula (1) described in item 1,
A ¹ is 1,4-cyclohexylene, 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 4 carbons, or At least one hydrogen may be replaced by alkyl of 1 to 4 carbons replaced by fluorine;
A ² is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 4 carbons, or at least one hydrogen is replaced by fluorine Optionally substituted with 1 to 4 carbon alkyls;
Z ¹ is alkylene having 1 to 7 carbons, in which at least one —CH ₂ — may be replaced by —O— or —CH═CH—;
Z ² is a single bond or alkylene having 1 to 7 carbon atoms, in which at least one —CH ₂ — may be replaced by —O— or —CH═CH—;
At least one of Z ¹ and Z ² is an alkylene of 1 to 7 carbons in which at least one —CH ₂ — is replaced by —CH═CH—;
X ¹ is hydrogen or methyl;
P ¹ is a group selected from the groups represented by formula (P-1) to formula (P-3);

Item 2. The compound according to Item 1, wherein a is 1.

4). Item 2. The compound according to item 1, represented by formula (1-1):

In formula (1-1),
Z ³ is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C May be replaced by ≡C-;
Y ¹ to Y ⁸ are independently hydrogen, fluorine, methyl, or trifluoromethyl;
When Y ¹ to Y ⁸ are all hydrogen, Z ³ is replaced by at least one —CH ₂ — with —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. 1 to 7 carbon atoms produced;
X ¹ is hydrogen, fluorine, methyl, or trifluoromethyl;
P ¹ is a polymerizable group.

5. In Formula (1-1) according to Item 4, Z ³ is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH ₂ — is —COO—, —OCO—, —OCOO— , —CH═CH—, or —C≡C—, and at least one —CH ₂ — may be replaced with —O—; Y ¹ to Y ⁸ are independently hydrogen Item 5. The compound according to Item 4, which is fluorine, methyl, or trifluoromethyl.

6). In formula (1-1) according to item 4, Z ³ is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH ₂ — may be replaced by —O—; Y Item 5. The compound according to Item 4, wherein ¹ to Y ⁸ is independently hydrogen, fluorine, methyl, or trifluoromethyl; and at least one of Y ¹ to Y ⁸ is fluorine, methyl, or trifluoromethyl.

7). Item 6. The compound according to Item 5, wherein in Formula (1-1) according to Item 4, X ¹ is hydrogen or methyl; Y ¹ to Y ⁸ are all hydrogen.

8). Item 4. The formula (1-1) according to item 4, wherein P ¹ is a group selected from the groups represented by formula (P-1) and formula (P-2) according to item 3. Compound.

9. Item 6. The compound according to Item 5, wherein in Formula (1-1) according to Item 4, P ¹ is a group represented by Formula (P-3) according to Item 3.

10. Item 2. The compound according to item 1, represented by formula (1-2):

In formula (1-2),
Z ³ is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C May be replaced by ≡C-;
L ¹ to L ¹² are independently hydrogen, fluorine, methyl, or trifluoromethyl;
When L ¹ to L ¹² are all hydrogen, Z ³ is replaced by at least one —CH ₂ — with —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. 1 to 7 carbon atoms produced;
X ¹ is hydrogen, fluorine, methyl, or trifluoromethyl;
P ¹ is a polymerizable group.

11. In Formula (1-2) according to Item 10, Z ³ is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH ₂ — is —COO—, —OCO—, —OCOO— , —CH═CH—, or —C≡C—, and at least one —CH ₂ — may be replaced with —O—; L ¹ to L ¹² are independently hydrogen Item 11. The compound according to Item 10, which is fluorine, methyl, or trifluoromethyl.

12 In formula (1-2) according to item 10, Z ³ is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH ₂ — may be replaced by —O—; L Item 11. The compound according to Item 10, wherein ¹ to L ¹² are independently hydrogen, fluorine, methyl, or trifluoromethyl; and at least one of L ¹ to L ¹² is fluorine, methyl, or trifluoromethyl.

13. Item ^12. The compound according to Item 11, wherein in Formula (1-2) according to Item 10, X ¹ is hydrogen or methyl; and L ¹ to L ¹² are all hydrogen.

14 In Formula (1-2) according to Item 10, in which P ¹ is a group selected from the groups represented by Formula (P-1) and Formula (P-2) according to Claim 3, The described compound.

15. Item 12. The compound according to Item 11, wherein in Formula (1-2) according to Item 10, P ¹ is a group represented by Formula (P-3) according to Item 3.

16. A composition comprising the compound according to any one of items 1 to 15.

17. Item 16. The composition according to item 16, wherein the compound according to any one of items 1 to 15 is added to a non-polymerizable liquid crystal composition.

18. Item 18. The composition according to item 16 or 17, further comprising at least one compound selected from the group of compounds represented by formula (2) to formula (4).

In Formula (2) to Formula (4),
R ¹¹ is independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ -May be replaced by -O-;
Ring B ¹¹ , Ring B ¹² , and Ring B ¹³ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or at least one hydrogen Is 1,4-phenylene which may be replaced by fluorine;
Z ¹¹ and Z ¹² are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —C≡. C—, —CH ₂ O—, or a single bond;
Y ¹¹ is independently fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Y ¹² and Y ¹³ are independently hydrogen or fluorine.

19. Item 19. The composition according to item 16, 17 or 18, further comprising at least one compound selected from the group of compounds represented by formula (5) to formula (7).

In the equations (5) to (7),
R ¹² and R ¹³ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — may be replaced by —O—;
Ring C ¹¹ , Ring C ¹² , and Ring C ¹³ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene;
Z ¹³ and Z ¹⁴ are independently — (CH ₂ ) ₂ —, —COO—, —CH═CH—, —C≡C—, or a single bond.

20. A polymer obtained by polymerizing the compound according to any one of items 1 to 15.

21. Item 20. A polymer obtained by polymerizing the composition according to any one of items 16 to 19.

22. Item 20. The compound according to any one of items 1 to 15, the composition according to any one of items 16 to 19, and at least one selected from the group of polymers according to item 20 or 21. Liquid crystal display element.

23. Item 20. The compound according to any one of items 1 to 15, the composition according to any one of items 16 to 19, and at least one liquid crystal display selected from the group of the polymers according to item 20 or 21. Use in devices.

The present invention includes the following items. 1) The above-described composition further containing an optically active compound, 2) the above-mentioned composition further containing additives such as an antioxidant, an ultraviolet absorber, and an antifoaming agent. 3) an AM device containing the above composition, 4) a device containing the above composition and having a TN, ECB, OCB, IPS, FFS, VA, or PSA mode, 5) the above composition A transmissive element containing 6) Use of the above composition as a composition having a nematic phase, 7) Use of the composition as an optically active composition by adding an optically active compound to the above composition.

The compound of the present invention will be described. The compound of the present invention is represented by the formula (1).

In formula (1), A ¹ is independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, carbon number 1 May be substituted with 1 to 12 alkyls or alkyls of 1 to 12 carbons in which at least one hydrogen is replaced with a halogen. When a is 2 or 3, the two groups represented by any two A ¹ may be the same or different.

Preferred A ¹ is 1,4-cyclohexylene, 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, C 1-4 Alkyl, or alkyl having 1 to 4 carbon atoms in which at least one hydrogen is replaced by fluorine, may be substituted. More preferable A ¹ is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1 , 4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene or naphthalene-2,6-diyl. Further preferred A ¹ is 1,4-phenylene or 2-fluoro-1,4-phenylene, and particularly preferred A ¹ is 1,4-phenylene.

A ² is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or carbon in which at least one hydrogen is replaced by halogen. It may be substituted with an alkyl of the formula 1 to 12.

Preferred A ² is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 4 carbons, or at least one hydrogen is halogen. It may be replaced with substituted alkyl having 1 to 4 carbon atoms. More preferable A ² is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl- 1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene or naphthalene-2,6-diyl. Further preferred A ² is 1,4-phenylene or 2-fluoro-1,4-phenylene, and particularly preferred A ² is 1,4-phenylene.

Z ¹ is alkylene having 1 to 12 carbons, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, or — C≡C— may be substituted.

Preferred Z ¹ is alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, Or it may be replaced by -C≡C-. More preferred Z ¹ is —COO—, —OCO—, —OCOO—, —CH═CH—, —CH═CH—O— or —C≡C—. Further preferred Z ¹ is —OCOO—, —CH═CH—, or —CH═CH—O—, and particularly preferred Z ¹ is —CH═CH—O—.

Z ² is independently a single bond or alkylene having 1 to 12 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, It may be replaced by —CH═CH— or —C≡C—. When all A ¹ and A ² are groups in which one hydrogen is not replaced, at least one of Z ¹ and Z ² has an unsaturated bond. An unsaturated bond means a group containing —CH═CH—, —C≡C—, or> C═O. When a is 2 or 3, two groups represented by any two Z ² may be the same or different.

Preferred Z ² is a single bond, —COO—, —OCO—, —CH═CH—, or —C≡C—. More preferred Z ² is a single bond, —COO— or —CH═CH—, and particularly preferred Z ² is a single bond.

When the linking group Z ¹ or Z ² is a group having a double bond such as —CH═CH—, the steric configuration may be a cis form or a trans form.

X ¹ is hydrogen, fluorine, methyl, or trifluoromethyl. Preferred X ¹ is hydrogen or methyl.

P ¹ is a polymerizable group. Preferred P ¹ is acryloxy group, methacryloxy group, acrylamide group, methacrylamide group, vinyl group, vinyloxy group, vinylcarbonyl group, epoxy group, oxetane group, 3,4-epoxycyclohexyl group, maleimide group, and the like. More preferred P ¹ is the group (P-1) to the group (P-3). Particularly preferred P ¹ is the group (P-1) or the group (P-2).

A is an integer from 0 to 3. Preferred a is 0 to 2, and more preferred a is 1 or 2. Particularly preferred a is 1.

Preferred examples of the compound (1) include the following compound (1-1) and compound (1-2).

In formula (1-1), Y ¹ to Y ⁸ are independently hydrogen, fluorine, methyl, or trifluoromethyl. Preferred Y ¹ to Y ⁸ are hydrogen, fluorine, or trifluoromethyl. More preferred Y ¹ to Y ⁸ are hydrogen or fluorine, and particularly preferred Y ¹ to Y ⁸ are hydrogen.

In formula (1-2), L ¹ to L ¹² are independently hydrogen, fluorine, methyl, or trifluoromethyl. Preferred L ¹ to L ¹² are hydrogen, fluorine, or trifluoromethyl. More preferred L ¹ to L ¹² are hydrogen or fluorine, and particularly preferred L ¹ to L ¹² are hydrogen.

In Formula (1-1) or Formula (1-2), Z ³ is alkylene having 1 to 7 carbons. In this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—, and Y ¹ To Y ⁸ are all hydrogen, or when L ¹ to L ¹² are all hydrogen, Z ³ is at least one —CH ₂ — is —COO—, —OCO—, —OCOO—, —CH═CH -, Or alkylene having 1 to 7 carbon atoms replaced by -C≡C-.

Preferred Z ³ is —COO—, —OCO—, —OCOO—, —CH═CH—, —CH═CH—O— or —C≡C—. More preferred Z ³ is —OCOO—, —CH═CH—, or —CH═CH—O—, and particularly preferred Z ³ is —CH═CH—O—. When Z ³ is a group having a double bond such as —CH═CH—, the configuration thereof may be a cis isomer or a trans isomer.

X ¹ is hydrogen, fluorine, methyl, or trifluoromethyl. More preferred X ¹ is hydrogen or fluorine.

More preferred examples of the compound (1) include the following compound (1-1-1) and compound (1-2-1).

In the formula (1-1-1), Y ¹ to Y ⁸ are hydrogen. One of Y ¹ to Y ⁸ may be fluorine, methyl or trifluoromethyl. In the formula (1-2-1), L ¹ to L ¹² are hydrogen. One of L ¹ to L ¹² may be fluorine, methyl or trifluoromethyl. X ¹ and X ² are independently hydrogen or methyl.

More preferred examples of compound (1) include the following compound (1-1-2) and compound (1-2-2). In formulas (1-1-2) and (1-2-2), X ¹ and X ² are independently hydrogen or methyl.

The composition of the present invention will be described. This composition contains at least one compound (1), but may contain two or more compounds (1). The composition may further contain other polymerizable compound. Preferred examples of other polymerizable compounds are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having acryloyloxy and methacryloyloxy.

Additional examples of other polymerizable compounds are compounds (M-1) to (M-12). In these compounds, R ²⁰ is hydrogen or methyl; s is 0 or 1; t and u are independently integers from 1 to 10. The symbol F in parentheses means hydrogen or fluorine.

Compound (1) may be added to the non-polymerizable liquid crystal composition. A preferable composition is a liquid crystal composition which can be used for a liquid crystal display element. The composition of the present invention needs to contain compound (1) as component A. The composition may be composed of only the component A, or the composition of the component A and other components not specifically indicated in the present specification, but the component A is selected from the following components B and C. By adding the prepared components, liquid crystal compositions having various characteristics can be provided.

As the component added to Component A, Component B consisting of at least one compound selected from the group consisting of Compound (2), Compound (3), and Compound (4) is preferable. Further, by mixing Component C consisting of at least one compound selected from the group consisting of Compound (5), Compound (6), and Compound (7), the threshold voltage, the temperature range of the liquid crystal phase, and the optical difference are mixed. The directionality, dielectric anisotropy, viscosity and the like can be adjusted.

Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance. The same applies to the component compounds added to the liquid crystal composition.

Among the components B, compounds (2-1) to (2-13) are preferred examples of compound (2), and compounds (3-1) to (3-109) are preferred examples of compound (3). Also, preferred examples of compound (4) include compounds (4-1) to (4-55).

In these compounds, the definitions of R ¹¹ and Y ¹¹ are the same as described above.

Since these compounds (2) to (4), that is, component B, have positive dielectric anisotropy and are very excellent in thermal stability and chemical stability, a liquid crystal composition for TFT is prepared. Used when The content of component B in the liquid crystal composition is suitably in the range of about 1% to about 99% by weight, preferably in the range of about 10% to about 97% by weight, based on the total weight of the liquid crystal composition. Preferably it is in the range of about 40% to about 95% by weight. Moreover, a viscosity can be adjusted by further including a compound (5) to a compound (7) (component C).

Preferred examples of compound (5), compound (6), and compound (7) (component C) include compound (5-1) to compound (5-10) and compound (6-1) to compound (6-14). ), And compound (7-1) to compound (7-6).

In these compounds, the definitions of R ¹² and R ¹³ are the same as described above.

Compound (5) to Compound (7) (Component C) are compounds having a small absolute value of dielectric anisotropy and close to neutrality. The compound (5) mainly has the effect of adjusting the viscosity or the optical anisotropy, and the compound (6) and the compound (7) have the effect of expanding the temperature range of the nematic phase by increasing the clearing point, or the like. There is an effect of adjusting optical anisotropy.

Increasing the content of component C decreases the viscosity of the liquid crystal composition, but increases the threshold voltage. Therefore, as long as the required value of the threshold voltage of the liquid crystal composition is satisfied, the content is preferably large. When preparing a liquid crystal composition for TFT, the content of component C is preferably about 30% by weight or more, more preferably about 50% by weight or more based on the total amount of the composition.

The composition of the present invention preferably contains at least one compound (1) in a proportion of about 0.05 wt% to about 20 wt%. Further, it is more preferable that at least one of the compounds (1) is contained at a ratio of about 0.1 wt% to about 10 wt%.

The composition of the present invention is generally prepared by a known method, for example, a method of dissolving necessary components at a high temperature. In addition, an additive well known to those skilled in the art may be added depending on the application, for example, to prepare a composition containing an optically active compound as described below, or a composition for GH type to which a dye is added. it can. Such additives are well known to those skilled in the art and are described in the literature.

The composition of the present invention may further contain one or more optically active compounds. As an optically active compound, a known chiral dopant can be added. This chiral dopant has the effect of inducing the helical structure of the liquid crystal to adjust the necessary twist angle and preventing reverse twist. Examples of the chiral dopant include the following compounds (Op-1) to (Op-18). In the compound (Op-18), ring E is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁴ is alkyl having 1 to 10 carbons.

The composition of the present invention can be used as a liquid crystal composition for GH type by adding dichroic dyes such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. You can also

The composition of the present invention includes NCAP produced by encapsulating nematic liquid crystal, polymer dispersed liquid crystal display device (PDLCD) produced by forming a three-dimensional network polymer in liquid crystal, for example, polymer network liquid crystal display device ( It can be used as a liquid crystal composition for birefringence control (ECB) type and DS type as well as for PNLCD.

It is possible to add additives such as a polymerization initiator, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent to the composition of the present invention.

An antioxidant is effective for maintaining a large voltage holding ratio. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); and 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 maximum temperature. Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. As specific examples, the following compounds (AO-3) and (AO-4): TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (trade name: BASF Corporation) And 1,4-diazabicyclo [2.2.2] octane (DABCO).

A light stabilizer such as an amine having steric hindrance is preferable in order to maintain a large voltage holding ratio. Preferred examples of the light stabilizer include the following compounds (AO-5) and (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A thermal stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is IRGAFOS 168 (trade name: BASF). Antifoaming agents are effective for preventing foaming. Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

In the compound (AO-1), R ²⁵ represents alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR ²⁶ , or —CH ₂ CH ₂ COOR ²⁶ ; R ²⁶ represents 1 to 20 carbons. Of alkyl. In the compounds (AO-2) and (AO-5), R ²⁷ is alkyl having 1 to 20 carbons. In the compound (AO-5), ring F and ring G is 1,4-cyclohexylene or 1,4-phenylene, v is 0, 1 or ^{2,, R 28} is hydrogen, methyl or O ^· It is.

The compound of the present invention is suitable for radical polymerization. Polymerization can be carried out more rapidly by adding a polymerization initiator or optimizing the reaction temperature, but a polymerization initiator may or may not be added.

Examples of the photo radical polymerization initiator are specific trade names, such as TPO, 1173 and 4265 from Darocur series of Ciba Specialty Chemicals Co., Ltd., 184, 369, 500, 651, 784, 819 from Irgacure series. 907, 1300, 1700, 1800, 1850, 2959, any known radical photopolymerization initiator can be used.

Other examples of radical photopolymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine A mixture but known Photoradical polymerization initiator les may also be used.

The polymer of the present invention can be produced by polymerizing the compound (1) or a composition containing them. When only one of the compounds (1) is polymerized, a homopolymer is obtained. When a composition containing a plurality of polymerizable compounds is polymerized, a copolymer is obtained. When a composition obtained by adding the compound (1) to a non-polymerizable liquid crystal composition is polymerized, a homopolymer of the compound (1) is contained in the non-polymerizable liquid crystal composition. This composition is also called a polymer.

Polymerization can be carried out by irradiating energy (electromagnetic waves). Such electromagnetic waves are ultraviolet rays, infrared rays, visible rays, X-rays, γ rays, and the like. Alternatively, high energy particles such as ions and electrons may be irradiated.

The orientation of compound (1) or this composition can be fixed by irradiation with electromagnetic waves. The wavelength range of the electromagnetic wave is preferably 150 nm to 500 nm. A more preferable range is 250 nm to 450 nm, and a particularly preferable range is 300 nm to 400 nm. The temperature at the time of irradiation is a temperature at which the compound (1) or this composition is in a liquid crystal state, but is preferably 100 ° C. or lower in order to prevent thermal polymerization.

Compound (1) is polymerized or crosslinked by polymerizing in the liquid crystal composition between the substrates of the liquid crystal display element. Polymerization may be performed in a state where a voltage or a magnetic field is applied. A preferred polymerization method is, for example, heat or photopolymerization, preferably photopolymerization. If necessary, a polymerization initiator can be added here. Polymerization conditions and suitable types of polymerization initiators are known to those skilled in the art and are described in the literature.

Compound (1) is excellent in that it reacts quickly without using a polymerization initiator. As a result, it is possible to reduce display defects due to unreacted radical photopolymerization initiator or its decomposition products and to prolong the product life. The polymerizable compound of the present invention may be used alone or in combination with other polymerizable compounds. Examples of the polymerizable compound that can be used in combination include commercially available or known monomers, for example, existing monofunctional or polyfunctional liquid crystalline monomers suitable for liquid crystal display elements described in JP-A No. 2004-123829.

The liquid crystal display element of the present invention has, for example, two substrates provided with a transparent electrode and an alignment control film for aligning liquid crystal molecules. A liquid crystal composition containing a polymerizable compound is disposed between these substrates. A device is manufactured by polymerizing the polymerizable compound in these substrates. The polymerization may be performed while applying a voltage.

The method for synthesizing the compound (1) and the component compounds contained in the composition will be described. Such compounds can be synthesized by combining organic synthetic chemistry techniques. Methods for introducing the desired end groups, rings and linking groups into the starting materials are as follows: Houben-Wyle (Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart), Organic Synthesis (Organic Syntheses, John Wily & Sons, Inc.), Organic Reactions (Johnson Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergenmon Press), and New Experimental Chemistry Course (Maruzen).

The generation of the linking group Z ¹ to the linking group Z ³ will be described in the terms (I) to (IX). 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. From compound (1A) to compound (1L) corresponds to compound (1).

(I) Generation of a single bond

Compound (1A) is synthesized by reacting arylboric acid (Q1) with compound (Q2) synthesized by a known method in an aqueous carbonate solution in the presence of a catalyst such as tetrakis (triphenylphosphine) palladium. . This compound (1A) is obtained by reacting compound (Q3) synthesized by a known method with n-butyllithium and then with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted.

(II) Formation of —CH═CH—

Compound (1B) is synthesized by reacting a phosphonium salt (Q5) synthesized by a known method with a base such as potassium t-butoxide and a phosphorus ylide generated with aldehyde (Q4).

(III) Formation of — (CH ₂ ) ₂ —

Compound (1C) is synthesized by hydrogenating compound (1B) in the presence of a catalyst such as palladium carbon.

(IV) Formation of — (CH ₂ ) ₄ —

Using phosphonium salt (Q7) instead of phosphonium salt (Q5), a compound having — (CH ₂ ) ₂ —CH═CH— is obtained according to the method of item (II). This is catalytically hydrogenated to synthesize compound (1E).

(V) Formation of —CH ₂ O— or —OCH ₂ —

Compound (Q4) is reduced with a reducing agent such as sodium borohydride to obtain compound (Q8). This is brominated with hydrobromic acid or the like to obtain compound (Q9). Compound (1F) is synthesized by reacting compound (Q9) with compound (Q10) in the presence of potassium carbonate or the like. A compound having —CH ₂ O— can also be synthesized by this method.

(VI) Formation of —COO— and —OCO—

Compound (Q3) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain carboxylic acid (Q11). Compound (1G) having —COO— is synthesized by dehydrating compound (Q11) and phenol (Q16) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine). To do. A compound having —OCO— can also be synthesized by this method.

(VII) Formation of —C≡C—

Compound (1J) is synthesized by reacting compound (Q13) with compound (Q2) in the presence of a catalyst of dichloropalladium and copper halide.

(VIII) Formation of —C≡C—COO—

After lithiation of compound (Q13) with n-butyllithium, carboxylic acid (Q14) is obtained by the action of carbon dioxide. Carboxylic acid (Q14) and phenol (Q16) are dehydrated in the presence of DCC and DMAP to synthesize compound (1K) having —C≡C—COO—. A compound having —OCO—C≡C— can also be synthesized by this method.

(IX) Formation of —C≡C—CH═CH— and —CH═CH—C≡C—

Compound (1L) having —C≡C—CH═CH— can be synthesized by cross-coupling reaction of compound (Q13) and vinyl bromide (Q15). When the cis-form compound (Q15) is used, a cis-form (1L) is produced.

The polymerizable group (P-1) or group (P-2) can be introduced by allowing an acid chloride (or acid anhydride) of acrylic acid or methacrylic acid to act on an organic group having a hydroxyl group. The polymerizable group (P-3) can be introduced by a Grignard reaction between a halogen-containing organic group and vinyl bromide. The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

The compound (a-292) is synthesized from the compound (a-1) by the above method.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by weight”.

1. Example of Compound The synthesized compound was identified by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) and the like. The melting point of the compound was determined by differential scanning calorimetry (DSC). First, each analysis method will be described.

¹ H-NMR analysis: DRX-500 (manufactured by Bruker BioSpin) was used as a measuring apparatus. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl ₃ is soluble and at room temperature under conditions of 500 MHz and 24 times of integration. In the description of the nuclear magnetic resonance spectrum, s means a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift δ value.

HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used as the measurement apparatus. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. As an eluent, acetonitrile and pure water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector, or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm.

The sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, a C-R7Aplus manufactured by Shimadzu Corporation was used. The obtained chromatogram shows the peak retention time and peak area values corresponding to the component compounds.

The peak area ratio in the chromatogram obtained from HPLC corresponds to the ratio of the component compounds. In general, the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample. However, when the above-described column is used in the present invention, the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds.

DSC measurement: Using a scanning calorimeter DSC-7 system manufactured by PerkinElmer or a Diamond DSC system, the temperature is raised and lowered at a rate of 3 ° C / min. The melting point was determined by insertion.

[Measurement sample]
When measuring the phase structure and transition temperature, the liquid crystalline 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 nematic phase, a composition prepared by mixing a compound with a mother liquid crystal was used as a sample.

When a sample in which a compound was mixed with mother liquid crystals was used, measurement was performed by the following method. A sample was prepared by mixing 15% by weight of the compound and 85% by weight of the mother liquid crystals. An extrapolated value was calculated from the measured value of this sample according to the extrapolation method represented by the following formula, and this value was described. <Extrapolated value> = (100 × <Measured value of sample> − <Weight% of mother liquid crystal> × <Measured value of mother liquid crystal>) / <Weight% of compound>

[Measuring method]
The physical properties were measured by the following methods. Many of these were the methods described in the Standard of Electronic Industries Association of Japan, EIAJ • ED-2521A, or a modified method thereof. No TFT was attached to the TN device used for measurement.

(1) Phase structure A sample (compound) is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measurement apparatus equipped with a polarizing microscope, and the phase state and its change are heated while heating at a rate of 3 ° C / min. Observation with a polarizing microscope identified the type of phase.

(2) Transition temperature (° C)
Using a scanning calorimeter DSC-7 system or a Diamond DSC system manufactured by PerkinElmer Inc., the temperature is raised and lowered at a rate of 3 ° C / min. The transition temperature was determined by insertion. 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 liquid crystal phase”. The temperature at which the compound transitions from the liquid crystal phase to the liquid may be abbreviated as “clearing point”.

The crystal was represented as C. When the types of crystals can be distinguished, they are expressed as C ₁ or C ₂ , respectively. The smectic phase is represented as S and the nematic phase is represented as N. In the smectic phase, when a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished, they are represented as S _A , S _B , S _C , or S _F , respectively. The liquid (isotropic) was designated as I. The transition temperature is expressed as “C 50.0 N 100.0 I”, for example. This indicates that the transition temperature (CN) from the crystal to the nematic phase is 50.0 ° C., and the transition temperature (clearing point) from the nematic phase to the liquid is 100.0 ° C.

(3) Low temperature compatibility Samples prepared by mixing the mother liquid crystal and the compound so that the ratio of the compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight are prepared. The sample was placed in a glass bottle. The glass bottle was stored in a freezer at −10 ° C. or −20 ° C. for a certain period, and then it was observed whether a crystal or smectic phase was precipitated.

(4) Maximum temperature of nematic phase (T _NI or NI; ° C.)
A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

(5) 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, when the sample remained in a nematic phase at −20 ° C. and changed to a crystal or smectic phase at −30 ° C., _TC was described as ≦ −20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

(6) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s)
It measured using the E-type rotational viscometer.

(7) Viscosity (Rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
The measurement followed the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular 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 value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity was measured.

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

(9) Dielectric anisotropy (Δε; measured at 25 ° C.)
A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

(10) Elastic constant (K; measured at 25 ° C .; pN)
For measurement, an HP4284A LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used. A sample was put in a horizontal alignment element in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to the cell, and the capacitance and applied voltage were measured. Using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), the values of the measured capacitance (C) and applied voltage (V) are calculated. Fitting was performed, and values of K ₁₁ and K ₃₃ were obtained from the equation (2.99). Then the equation (3.18) on page 171, to calculate the _{K 22} using the values of _{K 11} and _{K 33} was determined previously. The elastic constant is an average value of K ₁₁ , K ₂₂ , and K ₃₃ thus obtained.

(11) Threshold voltage (Vth; measured at 25 ° C .; V)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was about 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage is a voltage when the transmittance reaches 90%.

[Example 1]
Synthesis of compound (a-4)

First Step: Synthesis of Compound (S-3) In a nitrogen atmosphere, compound (S-1) (50.0 g, 0.269 mol), triethylamine (20.4 g, 0.202 mol), 2,6-di-tert Compound (S-2) (17.5 g, 0.167 mol) in dichloromethane (40 mL) was added to a mixture of butyl-p-cresol (BHT) (5.000 mg, 0.0220 mmol) and dichloromethane (500 mL) under ice-cooling. The solution was added dropwise, and then the temperature was gradually raised to room temperature. After stirring at room temperature for 16 hours, the reaction solution was poured into water, and the organic layer was washed with 1M hydrochloric acid and then with saturated brine. After drying the organic layer with anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent heptane: ethyl acetate = 5: 5 (volume ratio)) to obtain compound (S-3) as colorless crystals (18.6 g).

Second Step: Synthesis of Compound (a-4) In a nitrogen atmosphere, compound (S-3) (16.0 g, 0.0629 mol), triethylamine (3.82 g, 0.0377 mol), BHT (5.000 mg, 0 0.020 mmol) and dichloromethane (200 mL) were added dropwise a solution of compound (S-4) (4.17 g, 0.0346 mol) in dichloromethane (10 mL) under ice cooling, and then the temperature was gradually raised to room temperature. After stirring at room temperature for 16 hours, the reaction solution was poured into water, and the organic layer was washed successively with 1M hydrochloric acid, saturated brine, and 1M aqueous sodium hydroxide. After drying the organic layer with anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent toluene: ethyl acetate = 9: 1 (volume ratio)) and recrystallized from a mixed solvent of ethanol and dichloromethane to give compound (a-4) as colorless crystals (17. Obtained as 1 g).
Melting point: 67.0 ° C.
¹ H-NMR (DMSO-d; δ ppm): 7.57 (dd, 4H), 7.26 (dd, 2H), 7.20 (dd, 2H), 6.38 (s, 1H), 6 .06-5.98 (m, 1H), 5.78 (t, 1H), 5.47-5.43 (m, 1H), 5.35 (dd, 1H), 4.77-4.76 (M, 2H), 2.08 (s, 3H).

[Example 2]
Synthesis of compound (a-14)

First Step: Synthesis of Compound (S-7) Compound (S-5) (20.0 g, 0.0803 mol), tetrakis (triphenylphosphine) palladium (3.71 g, 3.21 mmol), iodine under nitrogen atmosphere To a mixture of copper chloride (1.84 g, 9.64 mmol), N, N-diisopropylethylamine (20 mL), N, N-dimethylformamide (DMF) (100 mL) was added compound (S-6) (5 .40 g, 0.0964 mol) was added dropwise and stirred for 1 hour. Next, the reaction solution was heated to 50 ° C. and stirred for 4 hours. The reaction mixture was poured into water and acidified with 2M hydrochloric acid. The aqueous layer was extracted with diethyl ether and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain compound (S-7) (15.8 g).

Second Step: Synthesis of Compound (S-8) Diethyl ether (50 mL) of sodium bis (2-methoxyethoxy) aluminum hydride (3.6 mol / L toluene solution) (24.0 mL, 0.0864 mol) under nitrogen atmosphere ) A solution of compound (S-7) (12.0 g, 0.0535 mol) in diethyl ether (60 mL) was added dropwise to the solution under ice cooling. After completion of the dropwise addition, the reaction solution was returned to room temperature and stirred for 1 hour. 1M sulfuric acid (70 mL) was added dropwise to the reaction solution, and then the organic layer was washed with water and then with saturated brine, and dried over anhydrous magnesium sulfate. The organic solvent was distilled off under reduced pressure to obtain Compound (S-8) (9.53 g).

Third Step: Synthesis of Compound (a-14) Compound (S-8) (6.00 g, 0.0265 mol), triethylamine (5.90 g, 0.0583 mol), BHT (5.000 mg, 0) under nitrogen atmosphere 0.020 mmol) and dichloromethane (100 mL) were added dropwise a solution of compound (S-2) (6.09 g, 0.0583 mol) in dichloromethane (5 mL) under ice cooling, and then the temperature was gradually raised to room temperature. After stirring at room temperature for 16 hours, the reaction solution was poured into water, and the organic layer was washed successively with 1M hydrochloric acid, saturated brine, and 1M aqueous sodium hydroxide. After drying the organic layer with anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent toluene: ethyl acetate = 9: 1 (volume ratio)) and recrystallized from a mixed solvent of ethanol and dichloromethane to give compound (a-14) as colorless crystals (6. 77 g).
Melting point: 72.0 ° C.
¹ H-NMR (DMSO-d; δ ppm): 7.61 (d, 2H), 7.55 (d, 2H), 7.47 (d, 2H), 7.20 (d, 2H), 6 .71 (d, 2H), 6.40-6.35 (m, 1H), 6.38 (s, 1H), 6.17 (s, 1H), 5.78 (t, 1H), 5. 61 (t, 1H), 4.84 (dd, 2H), 2.09 (s, 3H), 1.99 (s, 3H).

[Example 3]
Synthesis of compound (a-17)

First Step: Synthesis of Compound (S-10) A mixture of compound (S-1) (100 g, 0.537 mol) and DMF (500 mL) was heated to 40 ° C. under a nitrogen atmosphere. 60% sodium hydride (22.6 g, 0.565 mol) was added thereto, and the mixture was stirred at 70 ° C. for 1 hour. Next, compound (S-9) (52.9 g, 0.269 mol) was added dropwise to the reaction solution over 30 minutes, and the mixture was further stirred at 95 ° C. for 2 hours. The reaction solution was cooled to 60 ° C., poured into 0.6 M aqueous sodium hydroxide solution (1 L), extracted with a mixed solvent of methyl tert-butyl ether (MTBE): hexane = 1: 1 (volume ratio), Washed with 0.6M aqueous sodium hydroxide. The organic solvent was distilled off under reduced pressure to obtain compound (S-10) as a yellow liquid (47.1 g).

Second Step: Synthesis of Compound (S-12) In a nitrogen atmosphere, Compound (S-10) (47.1 g, 0.156 mol), Compound (S-11) (13.4 g, 0.156 mol), 4- A mixture of N, N′-dicyclohexylcarbodiimide (DCC) (33.7 g, 0.163 mol) in dichloromethane (100 mL) in a mixture of dimethylaminopyridine (DMAP) (1.91 g, 0.0156 mol) and dichloromethane (800 mL). The solution was added dropwise at 25 ° C. and stirred for 15 hours. After filtering the precipitate in the reaction solution, the organic layer was washed with water and dried over anhydrous magnesium sulfate. After evaporating the organic solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: dichloromethane: hexane = 1: 1 (volume ratio)) to obtain compound (S-12) as colorless crystals (46.2 g). It was.

Third Step: Synthesis of Compound (S-13) Under a nitrogen atmosphere, compound (S-12) (46.2 g, 0.125 mol) was dissolved in a mixed solvent of acetone (300 mL) and THF (600 mL), and 5 ° C. 2M hydrochloric acid was added dropwise and stirred at room temperature for 15 hours. About 200 mL of the solvent was distilled off from the reaction solution under reduced pressure, and the precipitate in the concentrated reaction solution was collected by filtration. The obtained solid was dried at 50 ° C. for 2 hours to obtain compound (S-13) as colorless crystals (31.9 g).

Fourth Step: Synthesis of Compound (a-17) Under a nitrogen atmosphere, potassium carbonate (83.8 g, 0.606 mol) was added to a mixture of compound (S-13) (31.9 g, 0.101 mol) and toluene (900 mL). Then, compound (S-14) (155 g, 1.01 mol) was added, and the mixture was heated to reflux for 40 hours. The reaction solution was allowed to cool to room temperature, and the precipitate was filtered off. The solvent of the filtrate was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent 1,2-dichloroethane: hexane = 3: 7 (volume ratio)). The obtained crystals were heated to reflux in hexane (100 mL) for 1 hour. After cooling, the precipitate was collected by filtration to obtain compound (a-17) as colorless crystals (8.31 g).
Melting point: 111.0 ° C.
¹ H-NMR (DMSO-d; δ ppm): 7.74-7.67 (m, 4H), 7.28-7.20 (m, 4H), 6.89 (d, 1H), 6. 62 (d, 1H), 6.30 (s, 1H), 6.17 (s, 1H), 5.91 (s, 1H), 5.84 (s, 1H), 2.02 (s, 3H) ), 1.94 (s, 3H).

The following compounds were synthesized from the corresponding starting materials by the synthesis methods shown in Examples 1 to 3.

[Example 4]
Compound (a-33)

Melting point: 89.4 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.55 (dd, 4H), 7.20 (d, 2H), 7.13 (d, 2H), 6.98 (d, 1H), 6. 65-6.56 (m, 2H), 6.38-6.20 (m, 3H), 6.04 (dd, 1H), 5.97 (dd, 1H).

[Example 5]
Compound (a-16)

Melting point: 80.0 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.55 (dd, 4H), 7.19 (d, 2H), 7.13 (d, 2H), 6.96 (d, 1H), 6. 63 (dd, 1H), 6.37-6.29 (m, 2H), 6.18 (d, 1H), 6.04 (d, 1H), 5.71 (t, 1H), 2.01 (S, 3H).

[Example 6]
Compound (a-68)

Melting point: 105.9 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.55 (t, 4H), 7.18 (d, 2H), 7.13 (d, 2H), 6.98 (d, 1H), 6. 58 (dd, 1H), 6.37 (s, 1H), 6.26 (dd, 1H), 6.20 (d, 1H), 5.97 (dd, 1H), 5.78 (t, 1H) ), 2.08 (s, 3H).

[Example 7]
Compound (a-31)

Melting point: 58.0 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.52 (d, 2H), 7.37-7.32 (m, 2H), 7.22 (t, 1H), 7.13 (d, 2H) ), 6.96 (d, 1H), 6.41 (s, 1H), 6.29 (s, 1H), 6.18 (d, 1H), 5.82 (s, 1H), 5.71 (S, 1H), 2.09 (s, 3H), 2.01 (s, 3H).

[Example 8]
Compound (a-25)

Melting point: 64.7 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.82 (d, 1H), 7.74 (dd, 1H), 7.54 (d, 2H), 7.36 (d, 1H), 7. 16 (d, 2H), 6.96 (d, 1H), 6.42 (s, 1H), 6.29 (s, 1H), 6.19 (d, 1H), 5.83 (s, 1H) ), 5.71 (s, 1H), 2.09 (s, 3H), 2.00 (s, 3H).

[Example 9]
Compound (a-261)

Melting point: 156.7 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.66-7.59 (m, 6H), 7.42 (dd, 1H), 7.37 (dd, 1H), 7.23-7.18 (M, 4H), 6.99 (d, 1H), 6.38 (s, 1H), 6.29 (s, 1H), 6.17 (d, 1H), 5.79 (t, 1H) , 5.72 (t, 1H), 2.09 (s, 3H), 2.01 (s, 3H).

[Example 10]
Compound (a-262)

Melting point: 91.3 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.64 (d, 2H), 7.57 (dd, 2H), 7.48 (t, 1H), 7.42 (dd, 1H), 7. 37 (dd, 1H), 7.22 (dd, 2H), 7.15 (dd, 2H), 6.97 (d, 1H), 6.38 (s, 1H), 6.29 (s, 1H ), 6.21 (d, 1H), 5.78 (t, 1H), 5.71 (t, 1H), 2.08 (s, 3H), 2.01 (s, 3H).

[Example 11]
Compound (a-199)

Melting point: 107.1 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.65 (d, 2H), 7.58 (dd, 2H), 7.48 (t, 1H), 7.40 (dd, 1H), 7. 37 (dd, 1H), 7.22 (dd, 2H), 7.15 (dd, 2H), 6.98 (d, 1H), 6.65-6.57 (m, 2H), 6.38 -6.21 (m, 3H), 6.02 (dd, 1H), 5.98 (dd, 1H).

[Example 12]
Compound (a-241)

Melting point: 113.5 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 7.63 (d, 2H), 7.57 (dd, 2H), 7.49 (t, 1H), 7.42 (dd, 1H), 7. 37 (dd, 1H), 7.22 (dd, 2H), 7.16 (dd, 2H), 6.99 (d, 1H), 6.58 (dd, 1H), 6.38 (s, 1H ), 6.26 (dd, 1H), 6.22 (d, 1H), 5.98 (dd, 1H), 5.79 (t, 1H), 2.09 (s, 3H).

2. Example of Composition The liquid crystal composition of the present invention will be described in detail by way of examples. The present invention is not limited by the following examples. The compounds in Examples were represented by symbols based on the definitions in Table 1 below. In Table 1, the configuration regarding 1,4-cyclohexylene is trans. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal composition. Finally, the physical properties 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.

[Example 13] (Use Example 1)
2-HH-3 15%
3-HH-4 5%
3-HB-O2 5%
3-HHB-1 8%
3-HHB-3 2%
3-HBB-F 20%
2-HHB (F, F) -F 14%
3-HHB (F, F) -F 4%
3-HBB (F, F) -F 2%
5-HBB (F, F) -F 6%
2-HHBB (F, F) -F 8%
3-HHBB (F, F) -F 5%
4-HHBB (F, F) -F 6%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

[Example 14] (Use Example 2)
5-HB-CL 16%
3-HH-4 12%
3-HH-5 4%
3-HHB-F 4%
3-HHB-CL 3%
4-HHB-CL 4%
3-HHB (F) -F 10%
4-HHB (F) -F 9%
5-HHB (F) -F 9%
7-HHB (F) -F 8%
5-HBB (F) -F 4%
1O1-HBBH-5 3%
3-HHBB (F, F) -F 2%
4-HHBB (F, F) -F 3%
5-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 3%
4-HH2BB (F, F) -F 3%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

NI = 113.9 ° C .; Δn = 0.090; Δε = 3.8; η = 19.2 mPa · s.

[Example 15] (Use Example 3)
3-HHB (F, F) -F 9%
3-H2HB (F, F) -F 8%
4-H2HB (F, F) -F 8%
5-H2HB (F, F) -F 8%
3-HBB (F, F) -F 21%
5-HBB (F, F) -F 20%
3-H2BB (F, F) -F 10%
5-HHBB (F, F) -F 3%
5-HHEBB-F 2%
3-HH2BB (F, F) -F 3%
1O1-HBBH-4 4%
1O1-HBBH-5 4%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

NI = 98.8 ° C .; Δn = 0.117; Δε = 9.1; η = 35.3 mPa · s.

[Example 16] (Use Example 4)
5-HB-F 12%
6-HB-F 9%
7-HB-F 7%
2-HHB-OCF3 7%
3-HHB-OCF3 7%
4-HHB-OCF3 7%
5-HHB-OCF3 5%
3-HH2B-OCF3 4%
5-HH2B-OCF3 4%
3-HHB (F, F) -OCF2H 4%
3-HHB (F, F) -OCF3 5%
3-HH2B (F) -F 3%
3-HBB (F) -F 10%
5-HBB (F) -F 10%
5-HBBH-3 3%
3-HB (F) BH-3 3%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

[Example 17] (Use Example 5)
5-HB-CL 11%
3-HH-4 8%
3-HHB-1 5%
3-HHB (F, F) -F 8%
3-HBB (F, F) -F 20%
5-HBB (F, F) -F 15%
3-HHEB (F, F) -F 10%
4-HHEB (F, F) -F 3%
5-HHEB (F, F) -F 3%
2-HBEB (F, F) -F 3%
3-HBEB (F, F) -F 5%
5-HBEB (F, F) -F 3%
3-HHBB (F, F) -F 6%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

[Example 18] (Use Example 6)
3-HB-CL 6%
5-HB-CL 4%
3-HHB-OCF3 5%
3-H2HB-OCF3 5%
5-H4HB-OCF3 15%
V-HHB (F) -F 5%
3-HHB (F) -F 5%
5-HHB (F) -F 5%
3-H4HB (F, F) -CF3 8%
5-H4HB (F, F) -CF3 10%
5-H2HB (F, F) -F 5%
5-H4HB (F, F) -F 7%
2-H2BB (F) -F 5%
3-H2BB (F) -F 10%
3-HBEB (F, F) -F 5%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

NI = 70.4 ° C .; Δn = 0.098; Δε = 8.4; η = 25.6 mPa · s.

[Example 19] (Use Example 7)
5-HB-CL 17%
7-HB (F, F) -F 3%
3-HH-4 10%
3-HH-5 5%
3-HB-O2 15%
3-HHB-1 8%
3-HHB-O1 5%
2-HHB (F) -F 7%
3-HHB (F) -F 7%
5-HHB (F) -F 7%
3-HHB (F, F) -F 6%
3-H2HB (F, F) -F 5%
4-H2HB (F, F) -F 5%
0.3 parts by weight of the following compound was added to 100 parts by weight of the composition.

NI = 71.7 ° C .; Δn = 0.074; Δε = 2.9.

[Example 20] (Use Example 8)
5-HB-CL 3%
7-HB (F) -F 7%
3-HH-4 9%
3-HH-EMe 23%
3-HHEB-F 8%
5-HHEB-F 8%
3-HHEB (F, F) -F 10%
4-HHEB (F, F) -F 5%
4-HGB (F, F) -F 5%
5-HGB (F, F) -F 6%
2-H2GB (F, F) -F 4%
3-H2GB (F, F) -F 5%
5-GHB (F, F) -F 7%
0.15 parts by weight of the following compound is added to 100 parts by weight of the composition,

Further, 0.15 parts by weight of the following compound was added.

NI = 80.1 ° C .; Δn = 0.065; Δε = 5.8; η = 20.1 mPa · s.

[Comparative Example 1]
Synthesis of compound (R-1)

Step 1 Synthesis was performed in the same manner as in Step 3 of [Example 2] except that the compound (S-8) was changed to the compound (S-1), and colorless crystals of the compound (R-1) were obtained. .
Melting point: 150.0 ° C
¹ H-NMR (DMSO-d; δ ppm): 7.24 (d, 4H), 6.96 (d, 4H), 6.41 (d, 2H), 6.26 (d, 2H), 1 .98 (s, 6H).

[Comparative Example 2]
Synthesis of compound (R-2)

First Step Under a nitrogen atmosphere, compound (S-16) (161 g, 0...) In a mixture of compound (S-15) (100 g, 0.768 mol), toluene (300 mL) and pyridine (100 mL) under ice-cooling. 845 mol) was added dropwise and stirred at room temperature for 18 hours. After adding pure water and stirring at 40 ° C. for 4 hours, the reaction solution was extracted with toluene, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The organic solvent was distilled off under reduced pressure to obtain compound (S-17) as a colorless liquid (207 g).

Second Step Under a nitrogen atmosphere, sodium hydride (55%) (16.8 g, 0.386 mol) was added to a mixture of compound (S-1) (30.0 g, 0.161 mol) and DMF (200 mL), Stir at 80 ° C. for 1 hour. BHT (5.000 mg, 0.0220 mmol) and DMF (600 mL) were added to the reaction solution, compound (S-17) (110 g, 0.387 mol) was added, and the mixture was stirred at 60 ° C. for 4 hr. Pure water was poured into the reaction solution, extracted with toluene, the organic layer was washed with water and dried over anhydrous magnesium sulfate, and then the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent toluene: ethyl acetate = 9: 1 (volume ratio)) and recrystallized from ethanol to obtain Compound (R-2) as colorless crystals (22.3 g).
Melting point: 89.0 ° C
¹ H-NMR (DMSO-d; δ ppm): 7.47 (d, 4H), 6.98 (d, 4H), 6.15 (s, 2H), 5.60 (t, 2H), 4 .52 (t, 4H), 4.26 (t, 4H), 1.96 (s, 6H).

[Comparative Example 3]
(Comparison of solubility in liquid crystal composition)
0.3% by weight of the compound (a-17) was added to the liquid crystal composition A and heated at 50 ° C. for 30 minutes. The dissolved liquid crystal composition was left at room temperature for 2 days. Thereafter, the presence or absence of crystal precipitation was visually confirmed. The same measurement was performed for compound (a-262). On the other hand, the same measurement was performed for the compound (R-1) of [Comparative Example 1] and the compound (R-2) of [Comparative Example 2]. Table 2 shows the results. In the symbols in Table 2, “◯” indicates that no crystal was observed, and “x” indicates that a crystal was observed.
The components of the liquid crystal composition A and the ratios thereof are as follows.

Table 2. Comparison of solubility in liquid crystal compositions

From Table 2, it was found that the polymerizable compound of the present invention has good solubility in the liquid crystal composition A.

[Comparative Example 4]
(Comparison of residual monomer concentration)
The liquid crystal composition A was dissolved by adding 0.3% by weight of the polymerizable compound (a-17) and irradiated with 11 mW / cm ² ultraviolet rays (EXECURE 4000-D manufactured by HOYA CANDEO OPTRONICS Co., Ltd .; mercury xenon lamp) for 273 seconds. Thereafter, the residual monomer concentration was measured by HPLC. On the other hand, the same measurement was performed for the compound (R-1) of [Comparative Example 1] and the compound (R-2) of [Comparative Example 2]. Table 3 shows the results. From this comparison, it was found that the compound of the present invention had a low residual monomer concentration.

Table 3. Comparison of polymerization reactivity

Claims

A compound represented by formula (1).

In equation (1),
A 1 is independently a single bond, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or at least One hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by halogen;
A 2 is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or carbon in which at least one hydrogen is replaced by halogen. May be substituted with an alkyl of the number 1 to 12;
Z 1 is alkylene having 1 to 12 carbons, in which at least one —CH 2 — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, or — May be replaced by C≡C-;
Z 2 is independently a single bond or alkylene having 1 to 12 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO—, —OCOO—, — May be replaced by CH═CH—, or —C≡C—;
When all A 1 and A 2 are groups in which no hydrogen is replaced, at least one of Z 1 and Z 2 has an unsaturated bond;
X 1 is hydrogen, fluorine, methyl, or trifluoromethyl;
P 1 is a polymerizable group;
a is an integer of 0 to 3.
In formula (1) according to claim 1,
A 1 is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 4 carbons, or At least one hydrogen may be replaced by alkyl of 1 to 4 carbons replaced by halogen;
A 2 is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 4 carbons, or at least one hydrogen is replaced by halogen Optionally substituted with 1 to 4 carbon alkyls;
Z 1 is alkylene having 1 to 12 carbons, in which at least one —CH 2 — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—, or — May be replaced by C≡C-;
Z 2 is a single bond or alkylene having 1 to 12 carbons, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH—. Or may be replaced by -C≡C-;
At least one of Z 1 and Z 2 is a carbon number in which at least one —CH 2 — is replaced by —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. 1 to 12 alkylene;
X 1 is hydrogen or methyl;
P 1 is a group selected from the groups represented by formula (P-1) to formula (P-3);

The compound according to claim 1, wherein a is 1.
In formula (1) according to claim 1,
A 1 is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 4 carbons, Or at least one hydrogen may be replaced by alkyl having 1 to 4 carbon atoms replaced by fluorine;
A 2 is 1,4-phenylene or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 4 carbons, or at least one hydrogen is replaced by fluorine Optionally substituted with 1 to 4 carbon alkyls;
Z 1 is alkylene having 1 to 7 carbons, in which at least one —CH 2 — may be replaced by —O— or —CH═CH—;
Z 2 is a single bond or alkylene having 1 to 7 carbon atoms, in which at least one —CH 2 — may be replaced by —O— or —CH═CH—;
At least one of Z 1 and Z 2 is an alkylene of 1 to 7 carbons in which at least one —CH 2 — is replaced by —CH═CH—;
X 1 is hydrogen or methyl;
P 1 is a group selected from the groups represented by formula (P-1) to formula (P-3);

The compound according to claim 1, wherein a is 1.
The compound according to claim 1 represented by formula (1-1).

In formula (1-1),
Z 3 is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C May be replaced by ≡C-;
Y 1 to Y 8 are independently hydrogen, fluorine, methyl, or trifluoromethyl;
When Y 1 to Y 8 are all hydrogen, Z 3 is replaced with at least one —CH 2 — with —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C—. 1 to 7 carbon atoms produced;
X 1 is hydrogen, fluorine, methyl, or trifluoromethyl;
P 1 is a polymerizable group.
In the formula (1-1) according to claim 4, Z 3 is alkylene having 1 to 7 carbon atoms, and in the alkylene, at least one —CH 2 — is —COO—, —OCO—, —OCOO. —, —CH═CH—, or —C≡C—, and at least one —CH 2 — may be replaced with —O—; Y 1 to Y 8 are independently 5. A compound according to claim 4 which is hydrogen, fluorine, methyl or trifluoromethyl.
In formula (1-1) according to claim 4, Z 3 is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—; 5. The method according to claim 4, wherein Y 1 to Y 8 are independently hydrogen, fluorine, methyl or trifluoromethyl, and at least one of Y 1 to Y 8 is fluorine, methyl or trifluoromethyl. Compound.
6. The compound according to claim 5, wherein in formula (1-1) according to claim 4, X 1 is hydrogen or methyl; and Y 1 to Y 8 are all hydrogen.
The formula (1-1) according to claim 4, wherein P 1 is a group selected from the groups represented by formula (P-1) and formula (P-2) according to claim 3. 5. The compound according to 5.
The compound according to claim 5, wherein P 1 is a group represented by the formula (P-3) according to claim 3 in the formula (1-1) according to claim 4.
The compound according to claim 1, which is represented by formula (1-2).

In formula (1-2),
Z 3 is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C May be replaced by ≡C-;
L 1 to L 12 are independently hydrogen, fluorine, methyl, or trifluoromethyl, and when L 1 to L 12 are all hydrogen, Z 3 is at least one —CH 2 — is —COO—, Alkylene having 1 to 7 carbon atoms replaced by —OCO—, —OCOO—, —CH═CH—, or —C≡C—;
X 1 is hydrogen, fluorine, methyl, or trifluoromethyl;
P 1 is a polymerizable group.
In the formula (1-2) according to claim 10, Z 3 is alkylene having 1 to 7 carbon atoms, and in the alkylene, at least one —CH 2 — is —COO—, —OCO—, —OCOO. —, —CH═CH—, or —C≡C—, and at least one —CH 2 — may be replaced with —O—; L 1 to L 12 are independently 11. A compound according to claim 10 which is hydrogen, fluorine, methyl or trifluoromethyl.
In formula (1-2) according to claim 10, Z 3 is alkylene having 1 to 7 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—; L 12 from L 1 are independently hydrogen, fluorine, methyl or trifluoromethyl; but from L 1 at least one of L 12, fluorine, according to claim 10 which is methyl or trifluoromethyl, Compound.
The compound according to claim 11, wherein in the formula (1-2) according to claim 10, X 1 is hydrogen or methyl; and L 1 to L 12 are all hydrogen.
The formula (1-2) according to claim 10, wherein P 1 is a group selected from the groups represented by formula (P-1) and formula (P-2) according to claim 3. 11. The compound according to 11.
The compound according to claim 11, wherein P 1 is a group represented by the formula (P-3) according to claim 3 in the formula (1-2) according to claim 10.
A composition comprising the compound according to any one of claims 1 to 15.
The composition according to claim 16, wherein the compound according to any one of claims 1 to 15 is added to a non-polymerizable liquid crystal composition.
The composition according to claim 16 or 17, further comprising at least one compound selected from the group of compounds represented by formula (2) to formula (4).

In Formula (2) to Formula (4),
R 11 is independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH 2 -May be replaced by -O-;
Ring B 11 , Ring B 12 , and Ring B 13 are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or at least one hydrogen Is 1,4-phenylene which may be replaced by fluorine;
Z 11 and Z 12 are independently — (CH 2 ) 2 —, — (CH 2 ) 4 —, —COO—, —CF 2 O—, —OCF 2 —, —CH═CH—, —C≡. C—, —CH 2 O—, or a single bond;
Y 11 is independently fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 ;
Y 12 and Y 13 are independently hydrogen or fluorine.
The composition according to claim 16, 17 or 18, further comprising at least one compound selected from the group of compounds represented by formula (5) to formula (7).

In the equations (5) to (7),
R 12 and R 13 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH 2 — may be replaced by —O—;
Ring C 11 , Ring C 12 , and Ring C 13 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene;
Z 13 and Z 14 are independently — (CH 2 ) 2 —, —COO—, —CH═CH—, —C≡C—, or a single bond.
A polymer obtained by polymerizing the compound according to any one of claims 1 to 15.
A polymer obtained by polymerizing the composition according to any one of claims 16 to 19.
21. At least one selected from the group of compounds according to any one of claims 1 to 15, a composition according to any one of claims 16 to 19, and a polymer according to claim 20 or 21. Liquid crystal display element including two.
21. At least one selected from the group of compounds according to any one of claims 1 to 15, a composition according to any one of claims 16 to 19, and a polymer according to claim 20 or 21. Use in two liquid crystal display elements.