JPWO2017065078A1 - Nematic liquid crystal composition and liquid crystal display device using the same - Google Patents

Abstract

The present invention provides a liquid crystal composition in which the viscosity (η) and rotational viscosity (γ1) are sufficiently small, the reaction rate of the polymerizable compound is sufficiently high, and the polymerizable compound does not remain after UV irradiation or is sufficiently suppressed. Offer things. The response speed is sufficiently fast, uniform and stable orientation control can be obtained with less energy cost, and at the same time, the VHR is good and display unevenness or image sticking does not occur, or the PSA type that is extremely suppressed This is useful because a liquid crystal display element can be produced.

Description

  The present invention relates to a nematic liquid crystal composition containing a polymerizable compound and a liquid crystal display device using the same.

A PSA (Polymer Sustained Alignment) type liquid crystal display element has a polymer structure formed in a cell in order to control the pretilt angle of liquid crystal molecules, and is practical as a liquid crystal display element having features such as high-speed response and high contrast. It has become.

  A PSA-type liquid crystal display device is a liquid crystal display device manufactured using a polymerizable compound-containing liquid crystal composition comprising a liquid crystal compound and a polymerizable compound, and polymerizes the polymerizable compound in a state where liquid crystal molecules are aligned by voltage application. And by fixing the alignment of the liquid crystal molecules. In the step of polymerizing the polymerizable compound of the PSA type liquid crystal display element, the polymerization reaction rate of the polymerizable compound is very important for productivity. It is also very important to adjust the pretilt angle that affects the response speed and contrast of the PSA type liquid crystal display element and the residual amount of the polymerizable compound that affects the reliability such as display unevenness and image sticking. Since the polymerization reaction rate of the polymerizable compound depends on the wavelength and irradiation intensity of the UV irradiation lamp, development of a polymerizable compound-containing liquid crystal composition containing the polymerizable compound adapted to the specifications of the UV irradiation lamp is required. However, sufficient response was difficult.

  Apart from the production method, as an approach to improve from the aspect of the liquid crystal composition, a composition containing a liquid crystal compound having a terphenyl ring (Patent Document 1) or a composition containing a liquid crystal compound having a naphthalene ring and a phenyl ring ( Patent Document 2) introduces a technique for reducing the polymerization reaction rate. However, when a liquid crystal compound having a terphenyl ring is used, in the manufactured liquid crystal display element, the voltage holding ratio (VHR) is reduced. The reliability of display unevenness and burn-in may be affected.

  As described above, a liquid crystal composition containing a polymerizable compound that suppresses adverse effects such as high-speed response, high contrast, display unevenness, and image sticking of the liquid crystal display element at the same time as adjusting the polymerization reaction speed adapted to the specifications of the UV irradiation lamp There has been a demand for a liquid crystal display device using the same.

US8092871B2 publication WO2014 / 148197A1 publication

  The problem to be solved by the present invention is that the viscosity (η) is sufficiently small, the rotational viscosity (γ1) is sufficiently small, the polymerizable compound reacts sufficiently fast, and there is no residue of the polymerizable compound after UV irradiation. Or a liquid crystal composition containing a sufficiently suppressed polymerizable compound, and using this, the response speed is sufficiently fast, 3D display is possible, and uniform and stable alignment control is less energy cost. And a liquid crystal display element such as a PSA type in which VHR is good and display unevenness or image sticking does not occur or is extremely suppressed.

  As a result of studying various polymerizable compounds and liquid crystal compounds, the present inventors have found that a composition composed of a polymerizable compound having a specific structure and a liquid crystal compound can solve the above-mentioned problems, and completes the present invention. It came to.

  That is, the general formula (I)

Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. To 10 alkenyloxy groups, and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms, and X ¹¹ to X ²⁰ are each independently a hydrogen atom. , Methyl group, —CF ₃ group, fluorine atom or chlorine atom, and L ¹¹ and L ¹² are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —. , —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, m ¹¹ and m ¹² each independently represent 0 or 1, and m ¹¹ + m ¹² represents 1 or 2. Compound represented by A composition containing one or more kinds of polymerizable compounds and one or more polymerizable compounds, a liquid crystal display device using the composition, and a compound represented by the general formula (I) To do.

  Since the viscosity (η) of the composition of the present invention is sufficiently low, the liquid crystal display device using the composition has a sufficiently high response speed and can display 3D, and there is no residual polymerizable compound. Since it is sufficiently suppressed, VHR is good and display unevenness or image sticking does not occur or is extremely suppressed. Further, since the polymerization reaction rate of the polymerizable compound is sufficiently high, the energy cost for production can be reduced, the production efficiency can be improved, and uniform and stable alignment control can be obtained, which is very useful.

  The composition of the present invention has the general formula (I)

1 type or 2 types or more are contained. The compound represented by the general formula (I) has a structure having a naphthalene ring, a phenyl ring, and one or more cyclohexane rings.

In the general formula (I), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or carbon. Represents an alkenyloxy group having 2 to 10 atoms, and one or more hydrogen atoms present in these groups may be substituted by a fluorine atom, but an alkyl group having 1 to 5 carbon atoms, Preferred are an alkoxyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. An alkoxyl group or an alkenyl group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms is more preferable.

X ¹¹ to X ²⁰ each independently represent a hydrogen atom, a methyl group, —CF ₃ group, a fluorine atom or a chlorine atom, preferably a hydrogen atom, a methyl group or a fluorine atom, and preferably a hydrogen atom or a fluorine atom It is more preferable that two or three of X ¹¹ to X ²⁰ are fluorine atoms, and the other is a hydrogen atom, and two of X ¹¹ to X ²⁰ are fluorine atoms. The other is particularly preferably a hydrogen atom.

L ¹¹ and L ¹² are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond. Represents —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — or a single bond, preferably —CH ₂ CH ₂ — or a single bond which does not contain an oxygen atom. Is more preferable, and a single bond is more preferable.

m ¹¹ and m ¹² each independently represent 0 or 1, and m ¹¹ + m ¹² represents 1 or 2, but m ¹¹ + m ¹² is preferably 1.

  Although the compound represented by general formula (I) contains 1 type, or 2 or more types, it is preferable to contain 1 type to 5 types, it is more preferable to contain 1 type to 3 types, and 1 type is contained. Is particularly preferred. Further, the content thereof is 0.1% to 50% by mass, preferably 0.1% to 10% by mass, and 0.3% to 8% by mass with respect to the composition. The range is more preferably 0.5% by mass to 5% by mass, 0.5% to 3% by mass, and 0.5% to 2% by mass. May be.

  More specifically, the compound represented by General Formula (I) is preferably a compound represented by General Formula (N-002) to General Formula (N-079).

Among the compounds represented by general formula (N-002) to general formula (N-079), compounds represented by general formula (N-030) to general formula (N-042), 058) to general formula (N-062), general formula (N-071) to general formula (N-074), general formula (N-077) to general formula (N- 079), and compounds represented by general formula (N-030) to general formula (N-035) are more preferable.

  The composition of the present invention contains one or more polymerizable compounds.

  The polymerizable compound preferably has a mesogenic skeleton, and specifically, the general formula (M)

The compound represented by these is mentioned.

^{Wherein, R 201 is,} P ^{201 -Sp} 201 - ^{represents, R 202 is,} P ^{202 -Sp} 202 - represents a.
P ²⁰¹ and P ²⁰² each independently represent formula (R-1) to formula (R-15)

It is preferable that they are either Formula (R-1) or Formula (R-2). P ²⁰¹ and P ²⁰² may be the same or different.

Sp ²⁰¹ and Sp ²⁰² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkylene group are not directly adjacent to each other. May be substituted with —O—, —OCO— or —COO—, but each independently represents a single bond or a carbon number in which one methylene may be substituted with —O—, —OCO— or —COO—. In the PSA mode liquid crystal display element, at least one is preferably a single bond, one is a single bond and the other is an alkylene group having 1 to 4 carbon atoms, or- O— (CH ₂ ) _s — is preferable. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4. It is also preferable that both Sp ²⁰¹ and Sp ²⁰² are single bonds.

M ²⁰¹ , M ²⁰² and M ²⁰³ are each independently a phenyl group, 1,4-phenylene group, benzene-1,2,4-triyl group, benzene-1,2,4,6-tetrayl group, 1, 4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthyl group, naphthalene-2,6-diyl group, indane-2,5-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, the group is unsubstituted or an alkyl group having 1 to 12 carbon atoms, 1 carbon atom May be substituted with ˜12 alkoxyl group, halogen, cyano group or nitro group, but each independently is unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or halogen, 4- Phenylene group, benzene-1,2,4-triyl group, benzene-1,2,4,6-tetrayl group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, or 1,3-dioxane It is preferably a -2,5-diyl group, and is a 1,4-phenylene group, a benzene-1,2,4-triyl group which is unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or a halogen, More preferred is a benzene-1,2,4,6-tetrayl group or a naphthalene-2,6-diyl group.

Z ²⁰¹ and Z ²⁰² are each independently —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, _{-OCO -, - OCOOCH 2 -,} - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH ^{= CR a -COO -, - CH} = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - COO-CR a = CH-COO -, - COO-CR a ^{= CH-OCO -, - OCO} -CR a = CH-COO -, - OCO-CR a = CH-OCO -, - (CH 2) z -C (= O) -O -, - (CH 2) z -O- (C = O) -, - O- (C = O) - (CH 2) z -, - (C = O) -O- ( CH ₂ ) z—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CF ₂ CH _2- , —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, C≡C— or a single bond (wherein, each R ^a independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, In the above formula, z represents an integer of 1 to 4, and represents —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—. , —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —C≡C— Or a single bond is preferred, -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, _{-COO-CH = CH -, -} OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -Or a single bond is more preferable.

n ²⁰¹ , n ²⁰² and n ²⁰³ each independently represents an integer of 0 to 3, and the total number of n ²⁰¹ and n ²⁰³ is 2 or more, but n ²⁰² is preferably 0, 1 or 2 0 or 1 is more preferable. n ²⁰¹ and n ²⁰³ are each independently preferably 0, 1 or 2, more preferably 1 or 2, and the total number of n ²⁰¹ and n ²⁰³ is preferably 2 or 3.

A plurality of existing P ²⁰¹ , P ²⁰² , Sp ²⁰¹ , Sp ²⁰² , Z ^201, and M ²⁰² may be the same or different.

  Although the composition of this invention contains at least 1 sort (s) of the polymeric compound represented by general formula (M), it is preferable to contain 1 type-5 types, and it is still more preferable to contain 1 type-3 types. When there is little content of the polymeric compound represented by general formula (M), in the liquid crystal display element manufactured by making a polymeric compound react, the orientation control power with respect to a liquid-crystal composition becomes weak. On the contrary, when the content of the polymerizable compound represented by the general formula (M) is too large, the energy required for the polymerization of the polymerizable compound increases, and the amount of the polymerizable compound that remains without being polymerized increases. In addition, since the remaining polymerizable compound causes display defects, the content is preferably 0.01 to 2.00% by mass, and more preferably 0.05 to 1.00% by mass. 0.10 to 0.50% by mass is particularly preferable.

More specifically, when n ²⁰¹ and n ²⁰³ are 1 in the general formula (M), the ring structure between Sp ²⁰¹ and Sp ²⁰² is the formula (XXa-1) to the formula (XXa-5). Are more preferable, the formula (XXa-1) to the formula (XXa-3) are more preferable, and the formula (XXa-1) or the formula (XXa-2) is particularly preferable. However, both ends of the equation shall be connected to Sp ²⁰¹ or Sp ²⁰² .

  The polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.

  As specific compounds of general formula (M), compounds represented by general formula (XX-1) to general formula (XX-10) are preferable, and formulas (XX-1) to (XX-4) are more preferable. .

In the formula, Sp ^xx represents an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7, and an oxygen atom is bonded to the ring. ).

The hydrogen atom in the phenyl group in the formula may be further substituted with —F, —Cl, —CF ₃ , —CH ₃ , or any one of the formulas (R-1) to (R-15). .

In the general formula (M), when n ²⁰² is 1, for example, a polymerizable compound such as the formula (M31) to the formula (M52) is preferable.

The hydrogen atom in the phenyl group and naphthalene group in the formula is further substituted with —F, —Cl, —CF ₃ , —CH ₃ , or any one of formulas (R-1) to (R-15). May be.

  The polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.

In the general formula (M), when n ²⁰¹ is 1, n ²⁰² is 1, and n ²⁰³ is 2, for example, a polymerizable compound such as formula (M301) to formula (M320) is preferable.

Hydrogen atom of the phenyl group and in the naphthalene radical in the formula, further, -F, _-Cl, -CF 3, may be substituted by -CH _3.

  The polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.

  The composition of the present invention further has a general formula (N-1)

(Wherein R ^N11 and R ^N12 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms) represents 10 alkenyloxy ^{group, R N11} and ^{R N12} in present in one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O- and / or -S And one or two or more hydrogen atoms present in R ^N11 and R ^N12 may each independently be substituted with a fluorine atom or a chlorine atom, and A ^N11 is 1 , 4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced by —O—) or 1,4- Phenylene group (in this group . Present one -CH = or nonadjacent two or more -CH = can which may be replaced by -N =) ^{represents, n N11} represents 1 or ^{2, Z N11} is - OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, and a plurality of existing ^AN11 are the same. Or may be different.) It is preferable to contain a compound represented by:

  In this case, the compound represented by the general formula (N-1) contains one or more compounds, preferably 1 to 10 compounds, more preferably 1 to 6 compounds, The content is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 50% by mass with respect to the composition.

In the formula (N-1), R ^N11 and R ^N12 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or an alkenyl having 2 to 5 carbon atoms. Or an alkenyloxy group having 2 to 5 carbon atoms, R ^N11 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^N12 is 1 carbon atom. And more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms.

A ^N11 is preferably a 1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^N11 _{is, -CH 2 O -, - CH} 2 CH 2 - or preferably a single bond, more preferably _-CH 2 O-or a single bond.

  Specifically, the compound represented by General Formula (N-1) is represented by General Formula (N-1-1) to General Formula (N-1-4), General Formula (N-1-10), or General Formula (N-1-11)

^{(Wherein, R N111} and ^{R N112} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)

(In the formula, R ^N121 and R ^N122 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N-1).)

(In the formula, R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)

(In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N-1).)

( ^Wherein , R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N-1)) are preferable.

  Of the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-1) can be used alone, or two or more compounds may be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15 %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
Although the compound represented by general formula (N-1-1) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15 %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

  Specifically, the compound represented by the general formula (N-1-1) is selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14). The compounds represented by the formulas (N-4-1.1) to (N-1-1.4) are preferred, and the compounds represented by the formulas (N-1-1.1) and A compound represented by the formula (N-1-1.3) is preferable.

  The compounds represented by formulas (N-1-1.1) to (N-1-1.14) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, 20%, 23% 25% 27% 30% 33% 35% The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

  Among the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-2) can be used alone, or two or more compounds may be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T _NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by General Formula (N-1-2) with respect to the total amount of the composition of the present invention is 5%, 7%, 10%, 13 %, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37 %, 40%, and 42%. The upper limit of the preferable content is 50%, 48%, 45%, 43%, 40%, 38%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% %, 8%, 7%, 6%, 5%.

Furthermore, the compound represented by the general formula (N-1-2) is specifically a compound group represented by the formula (N-1-2.1) to the formula (N-1-2.13). It is preferable that it is a compound chosen from Formula (N-1-2.3) to Formula (N-1-2.7), Formula (N-1-2.10), Formula (N-1-2). .11) and a compound represented by the formula (N-1-2.13), and when importance is placed on the improvement of Δε, the formula (N-1-2.3) to the formula (N-1 is preferably a compound represented by _-2.7), formula (N-1-2.10 in the case of emphasizing improvements in _{T NI),} the formula (N-1-2.11) and formula (N-1 It is preferable that it is a compound represented by -2.13).

  The compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount of is 5%, 10%, 13%, 15%, 17%, 20%, 23 %, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.

  Among the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-3) can be used alone, or two or more compounds may be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by General Formula (N-1-3) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15 %, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

  Furthermore, the compound represented by general formula (N-1-3) is specifically a compound group represented by formula (N-1-3.1) to formula (N-1-3.11). It is preferable that it is a compound chosen from these, It is preferable that it is a compound represented by Formula (N-1-3.1)-(N-1-3.7), and a formula (N-1-3.1) ), Formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compound represented by formula (N-1-3.6) Is preferred.

  The compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is also possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred. The lower limit of the preferred content of these compounds alone or with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15%, 17%, 20% %. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

  Among the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-4) can be used alone, or two or more compounds may be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the general formula (N-1-4) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 10% %, 13%, 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.

  Specifically, the compound represented by General Formula (N-1-4) is selected from the group of compounds represented by Formula (N-1-4.1) to Formula (N-1-4.14). The compounds represented by the formulas (N-1-4.1) to (N-1-4.4) are preferred, and the compounds represented by the formulas (N-1-4.1) and A compound represented by the formula (N-1-4.2) is preferable.

  The compounds represented by the formulas (N-1-4.1) to (N-1-4.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 3%, 5%, 7%, 10%, 13%, 15%, 17% And 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.

  Among the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-10) can be used alone, or two or more compounds may be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by Formula (N-1-10) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15 %, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

  Furthermore, the compound represented by the general formula (N-1-10) is specifically a compound group represented by the formula (N-1-10.1) to the formula (N-1-10.15). It is preferable that it is a compound chosen from Formula (N-1-10.1)-(N-1-10.5), and it is preferable that it is a compound represented by Formula (N-1-10.1). ) And a compound represented by the formula (N-1-10.2) are preferable.

  The compounds represented by formula (N-1-10.1) and formula (N-1-10.2) can be used alone or in combination, but the composition of the present invention can be used. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

  Among the compounds represented by the general formula (N-1-11), the compound represented by the general formula (N-1-11) can be used alone, but two or more compounds are used in combination. You can also. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the general formula (N-1-11) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15 %, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

  Furthermore, the compound represented by the general formula (N-1-11) is specifically a compound group represented by the formula (N-1-11.1) to the formula (N-1-11.15). It is preferable that it is a compound chosen from these, It is preferable that it is a compound represented by a formula (N-1-11.1)-(N-1-11.15), and a formula (N-11.2. And a compound represented by the formula (N-1-11.4) is preferable.

  The compounds represented by the formulas (N-1-11.2 and N-1-11.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the amount is 35%, 30%, 28%, 25%, 23%, 20%, 18% with respect to the total amount of the composition of the present invention. Yes, 15%, 13%.

  The composition of the present invention has a general formula (L-1) to a general formula (L-6) as a compound having a dielectric anisotropy (Δε) of substantially zero.

(In the formula, R ^{L11 to} R ^L62 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ^L61 and X ^L62 each independently represent a hydrogen atom or fluorine. It is preferable to contain a compound selected from the group consisting of compounds represented by the formula:

  1 type or 2 or more types of compounds chosen from the compound group represented by general formula (L-1)-general formula (L-6) are contained, but 1 to 10 types are preferable, and 1 to 6 types are included. More preferably, the content is 10 to 90% by mass, more preferably 20% to 70% by mass, and particularly preferably 30% to 60% by mass.

  Of the compounds selected from the group of compounds represented by formula (L-1) to formula (L-6), formulas (L-1), (L-3), (L-4) and (L The compound represented by -6) is preferable, and the compound represented by Formula (L-1) is particularly preferable.

  The composition of the present invention preferably contains compounds of general formula (I), general formula (M) and general formula (N-1) at the same time, and includes general formula (I), general formula (M) and general formula More preferably, the compound of (N-1) and the general formula (L-1) are simultaneously contained.

  The composition of the present invention includes a compound represented by general formula (I), a compound represented by general formula (M), a compound represented by general formula (N-1), and general formula (L-1) to The total amount of compounds selected from the compound group represented by formula (L-6) is preferably 85% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and 95% by mass. To 100% by mass, and more preferably 98% to 100% by mass.

  In the liquid crystal compound contained in the composition of the present invention, in order to suppress display defects such as image sticking and display unevenness, or in order not to generate at all, the compound having an alkenyl group is preferably 12% by mass or less, More preferably, it is not contained at all, and the cyclohexane ring or benzene ring in the liquid crystal compound may be substituted with a fluorine atom, but is not preferably substituted with a chlorine atom.

  The composition of the present invention has a dielectric anisotropy (Δε) at 25 ° C. of −2.0 to −8.0, preferably −2.0 to −6.0, and −2.0 to − 5.0 is more preferable, and -2.5 to -4.0 is still more preferable.

  The composition of the present invention has a refractive index anisotropy (Δn) at 20 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. preferable. More specifically, when it corresponds to a thin cell gap, it is preferably 0.10 to 0.125, and when it corresponds to a thick cell gap, it is preferably 0.08 to 0.10.

  The composition of the present invention has a viscosity (η) at 20 ° C. of 10 to 30 mPa · s, more preferably 10 to 25 mPa · s, and particularly preferably 10 to 22 mPa · s.

The composition of the present invention has a rotational viscosity (γ ₁ ) at 20 ° C. of 60 to 130 mPa · s, more preferably 60 to 110 mPa · s, and particularly preferably 60 to 100 mPa · s.

The composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C to 120 ° C, more preferably 68 ° C to 100 ° C, and particularly preferably 68 ° C to 85 ° C.

  Although the polymerization of the composition of the present invention proceeds even when no polymerization initiator is present, it may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.

  The composition of the present invention may further contain a compound represented by the general formula (Q).

In the formula, ^RQ represents a straight-chain alkyl group or a branched-chain alkyl group having 1 to 22 carbon atoms, and one or non-adjacent two or more CH ₂ groups in the group are —O—, —CH ═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ — may be substituted.

^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond.

  Specifically, the compound represented by the general formula (Q) is preferably a compound represented by the following general formula (Qa) to general formula (Qd).

In the formula, R ^Q1 is preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms.

R ^Q2 is preferably a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group.

R ^Q3 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group, a linear alkoxy group, or a branched alkoxy group.

L ^Q is preferably a linear alkylene group having 1 to 8 carbon atoms or a branched alkylene group.

  Of the compounds represented by general formula (Qa) to general formula (Qd), compounds represented by general formula (Qc) and general formula (Qd) are more preferable.

  The composition of the present invention preferably contains one or more compounds represented by the general formula (Q), preferably contains 1 to 5 types, and preferably contains 1 to 3 types. More preferably, it is more preferable to contain 1 type. Further, the content is preferably 0.001% by mass to 1% by mass, more preferably 0.001% by mass to 0.1% by mass, and further preferably 0.001% by mass to 0.05% by mass. .

  Further, a stabilizer may be added in order to improve storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done.

  The composition of the present invention may contain normal nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, polymerizable monomers and the like in addition to the above-described compounds.

  The composition of the present invention is useful for a liquid crystal display device, particularly useful for a liquid crystal display device for active matrix driving, and used for a liquid crystal display device for PSA mode, PSVA mode, VA-IPS mode or polymer stabilization mode. be able to.

  The composition of the present invention is a liquid crystal display element in which the polymerizable compound contained therein is polymerized by ultraviolet irradiation to impart liquid crystal alignment ability, and the amount of transmitted light is controlled using the birefringence of the liquid crystal composition. used. As a liquid crystal display element, it is useful for an AM-LCD (active matrix liquid crystal display element) and an IPS-LCD (in-plane switching liquid crystal display element), but is particularly useful for an AM-LCD, and a transmissive or reflective liquid crystal display. It can be used for an element.

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

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  As a method for sandwiching the composition of the present invention between two substrates, a normal vacuum injection method or an ODF method can be used.

  As a method for polymerizing a polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when polymerizing a polymerizable compound, at least the substrate on the irradiated surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the composition of the invention. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. The intensity of the irradiated ultraviolet light is preferably 0.1 mW / cm ^{2 to} 100 W / cm ^2, more preferably ² mW / cm ^{2 to} 50 W / cm ² . The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiation with ultraviolet rays is appropriately selected depending on the intensity of ultraviolet rays to be irradiated, but is preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.

  EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

The following abbreviations are used for the description of compounds in the examples.
(Side chain)
-n -C _n H _{2n + 1} linear alkyl group with n carbon atoms
n-C _n H _{2n + 1-} linear alkyl group having n carbon atoms
-On -OC _n H _{2n + 1} linear alkoxyl group with n carbon atoms
nO- C _n H _{2n + 1} O- Linear alkoxyl group with n carbon atoms
-V -CH = CH ₂
V- CH ₂ = CH-
-V1 -CH = CH-CH ₃
1V- CH ₃ -CH = CH-
-2V -CH ₂ -CH ₂ -CH = CH ₂
V2- CH ₂ = CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ -CH = CH-CH ₂ -CH ₃
(Linking group)
-n- -C _n H _2n-
-nO- -C _n H _2n -O-
-On- -OC _n H _2n -
-COO- -C (= O) -O-
-OCO- -OC (= O)-
-CF2O- -CF ₂ -O-
-OCF2- -O-CF _2-
(Ring structure)

  In the examples, the measured characteristics are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: Refractive index anisotropy at 20 ° C. Δε: Dielectric anisotropy at 20 ° C. γ ₁ : Rotational viscosity at 20 ° C. (mPa · s)
K ₃₃ : Elastic constant of bending at 20 ° C. Pre-tilt angle: Pre-tilt angle after UV irradiation by 20 J [°]
/ AUTRONIC-MELCHERS, TBA105
VHR / Initial: Voltage holding ratio before UV irradiation (1 V, 60 Hz, 60 ° C.)
/ Toyo Technica VHR-1
After VHR / UV20J: Voltage holding ratio after UV20J irradiation (1 V, 60 Hz, 60 ° C.)
/ Toyo Technica VHR-1
(Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 1)
Polymerizable compound-containing liquid crystal compositions of MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were prepared, and their physical property values. Was measured. Table 1 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.

Next, MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm ² (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. It was confirmed that these PSVA liquid crystal display elements all showed an appropriate pretilt angle of about 88 ° and a response speed correlated with a physical property value.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 2.

Example 1 MLC-A4 has a significantly higher VHR after UV irradiation compared to MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2) and MLC-A3 (Comparative Example 3). In addition, it has been found that both of the characteristics that the remaining amount of the polymerizable compound is reduced are combined. Furthermore, when a burn-in test was performed on these PSVA liquid crystal display elements, MLC-A1, MLC-A2 and MLC-A3 showed a burn-in which is considered to be caused by a low VHR and residual polymerizable compound after UV irradiation. . On the other hand, MLC-A4 did not generate any burn-in. As described above, LC-A4, which is a polymerizable compound-containing liquid crystal composition of the present invention, has excellent UV resistance, has a small amount of remaining polymerizable compound, and does not cause display defects such as image sticking. It was found to be a liquid crystal composition-containing liquid crystal composition.
(Comparative Example 4, Example 2, Example 3 and Example 4)
Polymerizable compound-containing liquid crystal compositions of MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were prepared, and their physical property values. Was measured. Table 3 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.

Next, MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm ² (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 4.

From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 5, Example 5, Example 6 and Example 7)
Polymerizable compound-containing liquid crystal compositions of MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were prepared, and their physical property values were prepared. Was measured. The composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values are shown in Table 5.

Next, MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm ² (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 6.

From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 6, Example 8, Example 9 and Example 10)
Polymerizable compound-containing liquid crystal compositions of MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were prepared, and their physical property values. Was measured. Table 7 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.

Next, MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm ² (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 8.

From the above, MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) which are the polymerizable compound-containing liquid crystal compositions of the present invention have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 7, Example 11, Example 12 and Example 13)
Polymerizable compound-containing liquid crystal compositions of MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were prepared, and their physical property values. Was measured. Table 9 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.

Next, MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm ² (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 10.

From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 8, Example 14, Example 15 and Example 16)
Polymerizable compound-containing liquid crystal compositions of MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15), and MLC-F4 (Example 16) were prepared, and their physical property values. Was measured. Table 11 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.

Next, MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm ² (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 12.

From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.

Claims (10)

Formula (I)

Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. To 10 alkenyloxy groups, and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms, and X ¹¹ to X ²⁰ are each independently a hydrogen atom. , Methyl group, —CF ₃ group, fluorine atom or chlorine atom, and L ¹¹ and L ¹² are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —. , —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, m ¹¹ and m ¹² each independently represent 0 or 1, and m ¹¹ + m ¹² represents 1 or 2. Compound represented by The composition which contains 1 type (s) or 2 or more types and contains 1 type (s) or 2 or more types of polymeric compounds. The polymerizable compound has the general formula (M)

^{(Wherein, R 201 is,} P 201 ^{-Sp 201} - ^{represents, R 202 is,} P 202 ^{-Sp 202} - ^{represents, P 201} and ^{P 202} are each independently of the formula from the formula (R-1) ( R-15)

Sp ²⁰¹ and Sp ²⁰² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is oxygen It may be substituted with —O—, —OCO— or —COO— so that the atoms are not directly adjacent, and M ²⁰¹ , M ²⁰² and M ²⁰³ are each independently a phenyl group, 1,4-phenylene group, benzene -1,2,4-triyl group, benzene-1,2,4,6-tetrayl group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthyl Group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group Represents Groups unsubstituted or substituted with an alkyl group having a carbon number of 1 to 12, alkoxyl group having 1 to 12 carbon atoms, a halogen may be substituted by a cyano group or a nitro group, Z ²⁰¹ and Z ²⁰² are, each independently, _{-O -, - S -, -} CH 2 -, - OCH 2 -, - CH 2 O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCOOCH 2 _{-, - CH 2 OCOO -,} - OCH 2 CH 2 O -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CR a -COO-, ^{-CH = CR a -OCO -, -} COO-CR a = CH -, - OCO-CR a = CH -, - COO-CR a = CH-COO -, - COO-CR a = CH-OCO -, - OCO-CR ^a = CH-COO-, -OCO-CR ^a = CH—OCO—, — (CH ₂ ) _z —C (═O) —O—, — (CH ₂ ) z—O— (C═O) —, —O— (C═O) — (CH _{2) z -, - (C} = O) -O- (CH 2) z -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF -, - CF 2 -, _{-CF 2 O -, - OCF 2} -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, C≡C- or a single bond (wherein, ^{R a} is independently Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein z represents an integer of 1 to 4, and n ²⁰¹ , n ²⁰² and n ²⁰³ are each independently Represents an integer of 0 to 3, but the total number of n ²⁰¹ and n ²⁰³ is 2 or more, and there are a plurality of P ²⁰¹ , P ²⁰² , Sp ²⁰¹ , S p ²⁰² , Z ²⁰¹ and M ²⁰² may be the same or different. The composition according to claim 1, wherein Formula (N-1)

(Wherein R ^N11 and R ^N12 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms) represents 10 alkenyloxy ^{group, R N11} and ^{R N12} in present in one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O- and / or -S And one or two or more hydrogen atoms present in R ^N11 and R ^N12 may each independently be substituted with a fluorine atom or a chlorine atom, and A ^N11 is 1 , 4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced by —O—) or 1,4- Phenylene group (in this group . Present one -CH = or nonadjacent two or more -CH = can which may be replaced by -N =) ^{represents, n N11} represents 1 or ^{2, Z N11} is - OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, and a plurality of existing ^AN11 are the same. The composition of Claim 1 or 2 which contains 1 type, or 2 or more types of compounds represented by this. General formula (L-1) to general formula (L-6)

(In the formula, R ^{L11 to} R ^L62 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X ^L61 and X ^L62 each independently represent a hydrogen atom. Or a fluorine atom, at least one of which represents a hydrogen atom.) The composition according to claim 1 or 2, comprising one or more compounds selected from the group consisting of compounds represented by: The general formula (N-1) is a general formula (N-1-1) to a general formula (N-1-4), a general formula (N-1-10), or a general formula (N-1-11).

(In the formula, R ^N111 and R ^N112 each independently represent the same meaning as R ^N41 and R ^N42 in General Formula (N-1).)

(In the formula, R ^N121 and R ^N122 each independently represent the same meaning as R ^N41 and R ^N42 in General Formula (N-1).)

(In the formula, R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)

(In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N41 and R ^N42 in General Formula (N-1).)

(In the formula, R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N41 and R ^N42 in General Formula (N-1).)
The composition according to claim 3. The composition according to claim 1 or 2, wherein the content of the compound represented by the general formula (I) is from 0.1% by mass to 10.0% by mass. The dielectric anisotropy (Δε) at 25 ° C. is in the range of −2.0 to −8.0, the refractive index anisotropy (Δn) at 20 ° C. is in the range of 0.08 to 0.14, The viscosity (η) at 20 ° C. is in the range of 10 to 30 mPa · s, the rotational viscosity at 20 ° C. (γ ₁ ) is in the range of 60 to 130 mPa · s, and the nematic phase-isotropic liquid phase transition temperature (T The composition according to claim 1 or 2, wherein _ni ) is in the range of 60 ° C to 120 ° C. Formula (I)

Wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. To 10 alkenyloxy groups, and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms, and X ¹¹ to X ²⁰ are each independently a hydrogen atom. , Methyl group, —CF ₃ group, fluorine atom or chlorine atom, and L ¹¹ and L ¹² are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —. , -CH ₂ CH _2- , -CF ₂ CF ₂ -or a single bond, and m ¹¹ and m ¹² each independently represents 0 or 1. The liquid crystal display element using the composition of any one of Claim 1 to 8. The liquid crystal display element for PSA mode, PSVA mode, or VA-IPS mode using the composition of any one of Claim 1 to 8.