JP6403037B2 - Liquid crystal display element and manufacturing method thereof - Google Patents

Description

  The present invention relates to a liquid crystal display element and a method for manufacturing the same.

  LCD TVs are widely used, but with the increase in resolution due to the increase in size, the moving speed of display objects that move on the screen is faster than that of small LCD TVs. There is a need for improvement.

  The field sequential full-color display method that does not require a color filter is characterized by the use of a backlight that is lit in order of “red → green → blue”. In a normal CRT or liquid crystal display, the frame time is 16.7 ms, but in the field sequential full color display system, the frame time is 5.6 ms, and high-speed response is required.

  As an index indicating high-speed response, the sum of τd and τr can be given. τd is the fall response time of the liquid crystal, and τr is the rise response time of the liquid crystal. In order to satisfy the high-speed response in the field sequential full color display method, it is desired that the sum of τd and τr is less than 1.5 ms.

  Currently, a liquid crystal material called a nematic liquid crystal in the market is generally used in flat panel displays such as televisions, monitors, mobile phones, smartphones, and tablet terminals. However, nematic liquid crystals have a response speed as low as about several tens of milliseconds to several milliseconds, and hence improvement is desired. Since the response speed is greatly influenced by the rotational viscosity γ1 of the liquid crystal and the elastic constant, improvement has been studied by developing new compounds and optimizing the composition, but the progress of the improvement is slow. On the other hand, a ferroelectric liquid crystal (FLC) using a smectic liquid crystal can respond at a high speed of several hundred microseconds. However, since there are only two states of light and dark, it is not easy to display halftones necessary for full color display, and a technique such as area gradation is used.

  Polymer Stabilized V-shaped-FLC (PSV-FLC) element, which is composed of a mixture of FLC and monomer, forms a fine polymer network in ferroelectric liquid crystal, and is a high-speed response characteristic of FLC. In addition to the above, halftone display is possible, and the impact resistance is improved as compared with the conventional FLC (Patent Document 1).

  In addition, in the composite material of nematic liquid crystal and polymer, when 70% by mass or more of a polymerizable compound is added to the nematic liquid crystal medium, a high-speed response with a response time of several tens of microseconds is obtained, but the driving voltage is low. Since it exceeds about 80 V and is not suitable for practical use, and the effective birefringence becomes one digit or more lower than the liquid crystal birefringence used, the transmittance of the element is lowered. On the other hand, one or more polymerizable compounds of 0.3% by mass or more and less than 1% by mass are added to the liquid crystal medium and polymerized on the glass substrate interface by UV photopolymerization with or without application of voltage. A PS (polymer-stable) or PSA (polymer-stained alignment) display that mainly induces pretilt by forming fine protrusion structures obtained by cross-linking has been proposed. (Patent Documents 2 to 6). A display such as PS or PSA mainly uses a fishbone pattern electrode in which fine slits and thin electrodes are alternately arranged in a vertical alignment mode to form a multi-domain divided into four. It is formed to realize a high viewing angle. In this case, when a voltage is applied, the liquid crystal is tilted and aligned in the linear slit direction. When the polymerizable compound is polymerized in this alignment state, a polymer thin film is formed at the substrate interface, and the liquid crystal alignment near the substrate interface is stabilized. At this time, the tilt alignment direction is induced as a pretilt, and the alignment process of the vertical alignment film is made unnecessary by the alignment division by the pattern electrode (Non-patent Document 1). It has also been reported that the response time is improved from 10 milliseconds to several milliseconds. As another polymer alignment stabilization technique, a technique of reacting a polymerizable compound in a liquid crystal is employed. By stabilizing the alignment state at the time of applying a voltage with a polymer so that the required electro-optical characteristics can be obtained, characteristics that cannot be obtained by liquid crystal alone are exhibited (Patent Documents 7 to 14).

  However, these devices also have room for improvement in terms of high-speed response. In particular, with regard to increasing the response speed of the liquid crystal display device, the liquid crystal composition has a low viscosity, a high dielectric constant, a low elastic constant, a pretilt angle, or an improved drive method such as an overdrive method. Various methods have been put into practical use, but regarding the falling rate, no effective method has been found other than lowering the viscosity of the liquid crystal composition, and improvement has been desired.

JP 2002-31821 A Special table 2013-536271 gazette Special table 2013-538249 gazette Special table 2012-527495 gazette Special table 2012-513482 gazette JP 2012-219270 A Japanese Patent No. 4175826 JP 2009-192600 A Japanese Patent No. 5020203 Japanese Patent Laid-Open No. 1999-0258758 Japanese Patent No. 5383994 US89040375 WO2011 / 055571 WO2015 / 122457

Journal of the SID 17/7, 553-559 (2009)

  The problems to be solved by the present invention include PVA (Patterned Vertical Alignment), MVA (Multi-domain Vertical Alignment) vertical alignment (VA) liquid crystal display, IPS (In-plane switching) mode, FFS (Fringe switching mode). In parallel alignment liquid crystal displays such as TN (Twisted Nematic) mode, the rise of drive voltage is suppressed, the birefringence is reduced, the transmittance is improved, and the fall time of the liquid crystal is improved. An object of the present invention is to provide a liquid crystal display element having high transmittance and excellent high-speed response, and to provide a method for producing the liquid crystal display element.

  The present inventor has developed a liquid crystal composition and a polymerizable liquid crystal composition containing a polymerizable compound to form a polymer network having a refractive anisotropy and an alignment function on the entire liquid crystal cell to achieve high-speed response, and Focusing on the content of the polymerizable compound and the conditions for forming the polymer network for the purpose of stabilizing the polymer so that the molecular orientation is aligned in the direction defined by the electrode pattern, the present invention has been completed. .

[1] A polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side is irradiated with ultraviolet rays while applying a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition to cause polymerization phase separation. A method for producing a liquid crystal display device, comprising: a step, and then a step of irradiating with ultraviolet rays by setting the voltage to less than a threshold voltage while irradiating with ultraviolet rays.
[2] In the step of polymerizing phase separation by irradiating ultraviolet rays while applying a voltage higher than the threshold voltage of the polymerizable liquid crystal composition, the liquid crystal molecules in the polymerizable liquid crystal composition are 0 ° to 30 ° with respect to the transparent substrate plane. The liquid crystal molecules are tilted from 80 degrees to 90 degrees with respect to the transparent substrate plane in the step of irradiating with ultraviolet rays by setting the voltage below the threshold voltage while being irradiated with ultraviolet rays. The method for producing a liquid crystal display element according to [1], wherein the liquid crystal display element is aligned.
[3] In the step of irradiating ultraviolet rays while applying a voltage equal to or higher than the threshold voltage of the polymerizable liquid crystal composition to cause the polymerization phase separation, the liquid crystal molecules in the polymerizable liquid crystal composition are 0 ° to 90 ° with respect to the transparent substrate plane. The liquid crystal molecules are tilted from 0 degree to 30 degrees with respect to the transparent substrate plane in the step of irradiating with ultraviolet rays by setting the voltage below the threshold voltage while being irradiated with ultraviolet rays. The method for producing a liquid crystal display element according to [1] or [2], wherein the liquid crystal display element is oriented.
[4] The liquid crystal according to any one of [1] to [3], wherein the applied voltage is an alternating current waveform, and the polymerizable liquid crystal composition has a frequency in a range exhibiting dielectric anisotropy. A method for manufacturing a display element.
[5] The above [1] to [4], wherein the voltage equal to or higher than the threshold voltage is equal to or higher than the voltage V10 that becomes 10% or higher with respect to the total change in transmittance in the voltage-transmittance characteristic voltage of the polymerizable liquid crystal composition. The manufacturing method of the liquid crystal display element as described in any one of these.
[6] The method for manufacturing a liquid crystal display element according to any one of [1] to [5], wherein the voltage less than the threshold voltage is a voltage of 0 V or more and less than 90% of the threshold voltage.
[7] As the polymerizable compound in the polymerizable liquid crystal composition, one or more compounds selected from the compounds represented by the following general formula (V) and general formula (VI) are used. [6] The method for producing a liquid crystal display element according to any one of [6].

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms. Represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other. -20 alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1-5. All 1,4-phenyle in the formula Groups, any hydrogen atom is _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.)

(In the formula, X ³ represents a hydrogen atom or a methyl group, and Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to 2). Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring.), V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms. An alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom) Or may be substituted with a cyclic substituent, and W represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups of Meaning hydrogen atoms _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.).
[8] The method for producing a liquid crystal display element according to [7], wherein one or two or more compounds represented by the general formula (V) in which Sp ¹ and Sp ² are the same is used as the polymerizable compound. .
[9] As the polymerizable compound, the compound represented by the general formula (V) in which Sp ¹ and Sp ² are the same, wherein two or more compounds having different Sp ¹ and Sp ² are used [7 ] Or the manufacturing method of the liquid crystal display element as described in [8].
[10] The method for producing a liquid crystal display element according to any one of [1] to [9], wherein a liquid crystal compound represented by the following general formula (LC) is used as the liquid crystal compound in the polymerizable liquid crystal composition: .

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms. One or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. -O-, -CH = CH-, -CO-, -OCO-, -COO- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted A ^LC1 and A ^LC2 each independently represents a group selected from the group consisting of the following groups (a), (b) and (c).
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom),
(C) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group or chroman-2,6-diyl group.

One or more hydrogen atoms contained in the group (a), group (b) or group (c) are each
It may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ .
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— is represented.
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent. ≡C—, —CF ₂ O—, —OCF ₂ — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
a represents an integer of 1 to 4. When a represents 2, 3 or 4, and there are a plurality of ^ALC1s in the general formula (LC), the plurality of ^ALC1s may be the same or different, and there are a plurality of ^ZLCs A plurality of Z ^LCs may be the same or different. )
[11] The liquid crystal display element according to any one of [1] to [10], wherein the cell structure of the liquid crystal display element is a VA mode, an IPS mode, an FFS mode, a VA-TN mode, a TN mode, or an ECB mode. Manufacturing method.
[12] A polymer or copolymer is contained in a liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side, and the content of the polymer or copolymer is the liquid crystal composition and the 0.5 mass% or more and less than 40 mass% of the total mass of the polymer or copolymer, the polymer or copolymer forms a polymer network, and the polymer network is uniaxial refractive index anisotropy Alternatively, a liquid crystal display element having an orientation easy axis and having two or more different orientation states.
[13] Two or more different alignment states of the polymer network, tilted orientation in the range of 0 to 30 degrees with respect to the transparent substrate plane, and tilted in the range of 80 to 90 degrees with respect to the transparent substrate plane The liquid crystal display element according to [12], which has an orientation.
[14] The display pixel of the liquid crystal display element has an electrode having a shape that can be divided into a plurality of domains, and two or more types having different polymer networks in one domain divided depending on the shape of the electrode As the orientation state of the transparent substrate plane, the tilt orientation is in the range of 0 to 30 degrees with respect to the transparent substrate plane and the tilt orientation direction of the tilt orientation is constant, and the transparent substrate plane is 80 degrees. The liquid crystal according to [12] or [13], wherein the liquid crystal composition has a tilted orientation in a range of 90 to 90 degrees, and the orientation of liquid crystal molecules in the liquid crystal composition when no voltage is applied has a vertical orientation or a parallel orientation. Display element.
[15] The polymer network is aligned so that the optical axis direction or the easy-alignment axis direction of the polymer network coincides with the alignment of the liquid crystal molecules in the liquid crystal composition. Having a tilted orientation in the range of 30 to 30 degrees and a tilted orientation in the range of 80 to 90 degrees with respect to the transparent substrate plane. When no voltage is applied, the liquid crystal molecules in the liquid crystal composition are transparent substrates. The liquid crystal display element according to any one of [12] to [14], which has a pretilt angle of 0 to 90 degrees with respect to a plane.
[16] The liquid crystal display element according to any one of [12] to [15], wherein a polymer network layer having a thickness of at least 0.5% of the cell thickness is formed in the cell cross-sectional direction.
[17] As the polymerizable compound in the polymerizable liquid crystal composition, one or more compounds selected from the compounds represented by the following general formula (V) and general formula (VI) are used. [16] The liquid crystal display element according to any one of [16].

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms. Represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other. -20 alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1-5. All 1,4-phenyle in the formula Groups, any hydrogen atom is _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.)

(In the formula, X ³ represents a hydrogen atom or a methyl group, and Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to 2). Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring.), V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms. An alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom) Or may be substituted with a cyclic substituent, and W represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups of Meaning hydrogen atoms _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.).
[18] The liquid crystal display device according to [17], wherein one or more compounds represented by the general formula (V) in which Sp ¹ and Sp ² are the same are used as the polymerizable compound.
[19] As the polymerizable compound, a compound represented by the general formula (V) in which Sp ¹ and Sp ² are the same, wherein two or more compounds having different Sp ¹ and Sp ² are used [17] ] Or the liquid crystal display element according to [18].
[20] The liquid crystal display element according to any one of [11] to [19], wherein a liquid crystal compound represented by the following general formula (LC) is used as the liquid crystal compound in the polymerizable liquid crystal composition.

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms. One or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. -O-, -CH = CH-, -CO-, -OCO-, -COO- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted A ^LC1 and A ^LC2 each independently represents a group selected from the group consisting of the following groups (a), (b) and (c).
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom),
(C) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group or chroman-2,6-diyl group.

One or more hydrogen atoms contained in the group (a), group (b) or group (c) are each
It may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ .
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— is represented.
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent. ≡C—, —CF ₂ O—, —OCF ₂ — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
a represents an integer of 1 to 4. When a represents 2, 3 or 4, and there are a plurality of ^ALC1s in the general formula (LC), the plurality of ^ALC1s may be the same or different, and there are a plurality of ^ZLCs A plurality of Z ^LCs may be the same or different. )
[21] The liquid crystal display element according to any one of [12] to [20], wherein the cell structure is a VA mode, an IPS mode, an FFS mode, a VA-TN mode, a TN mode, or an ECB mode.

  According to the present invention, the rise in driving voltage is suppressed, the decrease in birefringence is suppressed and the transmittance is improved, and the fall time of the liquid crystal is improved, thereby achieving high transmittance and excellent high-speed response. A liquid crystal display element can be provided.

It is a schematic diagram of the liquid crystal display element of this invention. It is the elements on larger scale of FIG. It is sectional drawing of the liquid crystal display element of this invention. It is the elements on larger scale of FIG. It is sectional drawing of the liquid crystal display element of this invention. It is a schematic diagram of the liquid crystal display element of this invention. It is the elements on larger scale of FIG. It is sectional drawing of the liquid crystal display element of this invention. 2 is a polarizing microscope photograph of Example 1. FIG. 4 is a polarizing micrograph of Comparative Example 2. It is a schematic diagram which shows the electrode structure and liquid crystal molecular arrangement | sequence of an oblique electric field system liquid crystal display device in this invention. It is a schematic diagram which shows the electrode structure of the 8-part diagonal electric field type liquid crystal display device in this invention. It is a schematic diagram of the electrode structure of the fishbone type VA liquid crystal cell in an Example.

<Liquid crystal composition>
[Liquid Crystal Compound]
The liquid crystal composition used in the present invention preferably contains a liquid crystal compound represented by the general formula (LC).

In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C, so that the oxygen atoms are not directly adjacent. ≡C— may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Alkyl group R ^LC may be respectively branched chain groups, may be straight chain groups, but is preferably a linear group.

In the general formula (LC), A ^LC1 and A ^LC2 each independently represent a group selected from the group consisting of the following group (a), group (b) and group (c).
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom),
(C) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group or chroman-2,6-diyl group.

One or two or more hydrogen atoms contained in the group (a), group (b) or group (c) may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ , respectively. Good.

In the general formula (LC), Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —. _{, -CH 2 O -, - OCF} 2 -, - CF 2 O -, - COO- or an -OCO-.

In general formula (LC), ^YLC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent. ≡C—, —CF ₂ O—, —OCF ₂ — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.

In general formula (LC), a represents an integer of 1 to 4. When a represents 2, 3 or 4, and there are a plurality of ^ALC1s in the general formula (LC), the plurality of ^ALC1s may be the same or different, and there are a plurality of ^ZLCs A plurality of Z ^LCs may be the same or different.

  The compound represented by the general formula (LC) is preferably one or more compounds selected from the group of compounds represented by the following general formula (LC1) and general formula (LC2).

In general formula (LC1) or (LC2), R ^LC11 and R ^LC21 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more CH ₂ groups in the alkyl group are One of the alkyl groups may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atoms are not directly adjacent. Alternatively, two or more hydrogen atoms may be optionally substituted with a halogen atom. As the compound represented by the general formula (LC1) or (LC2), R ^LC11 and R ^LC21 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms. An alkenyl group having 2 to 7 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, and is further linear. The alkenyl group preferably represents the following structure.

(In the formula, it shall be bonded to the ring structure at the right end.)

In general formula (LC1) or (LC2), A ^LC11 and A ^LC21 each independently represent any one of the following structures. In the structure, one or more CH ₂ groups in the cyclohexylene group may be substituted with an oxygen atom, and one or more CH groups in the 1,4-phenylene group are nitrogen atoms. And one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ .

As the compound represented by the general formula (LC1) or (LC2), ^ALC11 and ^ALC21 each independently preferably have one of the following structures.

In the general formula (LC1) or ^{(LC2), X LC11, X} LC12, X LC21 ~X LC23 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a -CF ₃ or -OCF ^{_3, Y LC11} and Y ^LC21 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, a cyano group, —CF ₃ , —OCH ₂ F, —OCHF ₂ or —OCF ₃ . As the compound represented by the general formula (LC1) or (LC2), Y ^LC11 and Y ^LC21 are each independently preferably a fluorine atom, a cyano group, —CF ₃ or —OCF ₃ , and a fluorine atom or —OCF ₃ is More preferred is a fluorine atom.

In general formula (LC1) or (LC2), Z ^LC11 and Z ^LC21 each independently represent a single bond, —CH═CH—, ^{—CF═CF—} , ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— is represented. As the compound represented by the general formula (LC1) or (LC2), Z ^LC11 and Z ^LC21 are each independently a single bond, —CH ₂ CH ₂ —, ^—COO— , ^—OCO— , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O— is preferred, and a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —OCF ₂ — or —CF ₂ O— is more preferred, and a single bond , —OCH ₂ — or —CF ₂ O— is more preferable.

In general formula (LC1) or (LC2), m ^LC11 and m ^LC21 each independently represent an integer of 1 to 4. As the compound represented by the general formula (LC1) or (LC2), ^mLC11 and ^mLC21 are preferably independently 1, 2 or 3, respectively, and when importance is attached to storage stability at low temperature and response speed. 1 or 2 is more preferable, and 2 or 3 is more preferable when improving the upper limit of the nematic phase upper limit temperature. When a plurality of A ^LC11 , A ^LC21 , Z ^LC11 and Z ^LC21 are present in the general formula (LC1) or (LC2), they may be the same or different.

  The compound represented by the general formula (LC1) is one or more compounds selected from the group consisting of compounds represented by the following general formula (LC1-a) to general formula (LC1-c). Is preferred.

In the general formula (LC1-a) ~ (LC1 -c), and R ^LC11, Y ^{LC11, X LC11} and ^{X LC12 R} LC11 is in formula each independently ^{(LC1), Y LC11, X} LC11 and ^{X LC12} Represents the same meaning. As the compounds represented by formulas (LC1-a) to (LC1-c), R ^LC11 is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, An alkenyl group having 2 to 7 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable. ^Further, preferably a hydrogen atom or a fluorine atom ^{X LC11} and ^{X LC12} each ^{independently, Y LC11} each independently a fluorine atom, -CF ₃ or -OCF ₃ are preferred.

In general formulas (LC1-a) to (LC1-c), A ^LC1a1 , ^ALC1a2 and ^ALC1b1 are trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane. Represents a -2,5-diyl group. Further, in the general formula (LC1-a) ~ (LC1 -c), X LC1b1, X LC1b2, X LC1c1 ~X LC1c4 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a -CF ₃ or -OCF ₃ Represent. As a compound represented by general formula (LC1-a) to general formula (LC1-c), ^XLC1b1 , ^XLC1b2 , and ^{XLC1c1 to XLC1c4} are each independently preferably a hydrogen atom or a fluorine atom.

  Moreover, it is also preferable that general formula (LC1) is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by the following general formula (LC1-d) to general formula (LC1-p).

In the general formula (LC1-d) ~ (LC1 -p), and R ^LC11, Y ^{LC11, X LC11} and ^{X LC12 R} LC11 is in formula each independently ^{(LC1), Y LC11, X} LC11 and ^{X LC12} Represents the same meaning. As the compounds represented by the general formulas (LC1-d) to (LC1-p), R ^LC11 is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms. An alkenyl group having 2 to 7 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable. ^{Further, X LC11} and ^{X LC12} is preferably a hydrogen atom or a fluorine atom independently. Y ^LC11 is preferably each independently a fluorine atom, —CF ₃ or —OCF ₃ .

In general formulas (LC1-d) to (LC1-p), ^ALC1d1 , ^ALC1f1 , ^ALC1g1 , ^ALC1j1 , ^ALC1k1 , ^ALC1k2 , ^{ALC1m1 to ALC1m3} are each independently a 1,4-phenylene group , Trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, or 1,3-dioxane-2,5-diyl group.

In the general formula (LC1-d) ~ (LC1 -p), X LC1d1, X LC1d2, X LC1f1, X LC1f2, X LC1g1, X LC1g2, X LC1h1, X LC1h2, X LC1i1, X LC1i2, X LC1j1 ~X LC1j4 , ^XLC1k1 , ^XLC1k2 , ^XLC1m1 and ^XLC1m2 each independently represent a hydrogen atom, a chlorine atom, a fluorine atom, —CF ₃ or —OCF ₃ . As the compounds represented by the general formulas (LC1-d) to (LC1-m), X ^{LC1d1 to} X ^LC1m2 are each independently preferably a hydrogen atom or a fluorine atom.

In the general formulas (LC1-d) to (LC1-p), Z ^LC1d1 , Z ^LC1e1 , Z ^LC1j1 , Z ^LC1k1 , Z ^LC1m1 are each independently a single bond, —CH═CH—, ^{—CF═CF—} , — C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— Represent. As the compounds represented by the general formulas (LC1-d) to (LC1-p), ^{ZLC1d1 to ZLC1m1} are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —CF ₂ O— or —OCH ₂ — is preferred.

As the compounds represented by the general formulas (LC1-d) to (LC1-p), one selected from the group consisting of compounds represented by the following general formulas (LC1-1) to (LC1-45) or Two or more compounds are preferred. In general formula (LC1-1) to general formula (LC1-45), R ^LC11 independently represents an alkyl group having 1 to 7 carbon atoms.

  The general formula (LC2) is preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (LC2-a) to general formula (LC2-g).

In the general formulas (LC2-a) to (LC2-g), R ^LC21 , Y ^LC21 , X ^{LC21 to} X ^LC23 are each independently R ^LC21 , Y ^LC21 , X ^{LC21 to} X ^LC23 in the general formula (LC2). Represents the same meaning. As the compounds represented by the general formulas (LC2-a) to (LC2-g), R ^LC21 is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or the number of carbon atoms. An alkenyl group having 2 to 7 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable. X ^{LC21 to} X ^LC23 are each independently preferably a hydrogen atom or a fluorine atom, and Y ^LC21 is independently preferably a fluorine atom, —CF ₃ or —OCF ₃ .

In general formulas (LC2-a) to (LC2-g), ^{XLC2d1 to XLC2d4} , ^{XLC2e1 to XLC2e4} , ^{XLC2f1 to XLC2f4} and ^{XLC2g1 to XLC2g4} are each independently a hydrogen atom, chlorine atom, fluorine Represents an atom, —CF ₃ or —OCF ₃ ; As the compounds represented by the general formulas (LC2-a) to (LC2-g), X ^{LC2d1 to} X ^LC2g4 are each independently preferably a hydrogen atom or a fluorine atom.

In general formulas (LC2-a) to (LC2-g), Z ^LC2a1 , Z ^LC2b1 , Z ^LC2c1 , Z ^LC2d1 , Z ^LC2e1 , Z ^LC2f1 and Z ^LC2g1 are each independently a single bond, —CH═CH—, — CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO -Or -OCO- is represented. Examples of the compound represented by the general formula (LC2-a) ~ (LC2 -g), Z LC2a1 ~Z LC2g4 each independently _-CF 2 O-or -OCH ₂ - is preferred.

  The compound represented by the general formula (LC) is also preferably one or two or more compounds selected from the group of compounds represented by the following general formula (LC3) to general formula (LC5).

^(Wherein represents ^{R LC31, R LC32, R LC41} , R LC42, alkyl groups ^{R LC51} and ^{R LC52} is 1-15 carbon atoms independently, one in the alkyl group or two or more —CH ₂ — may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atom is not directly adjacent. one or more hydrogen atoms in the group may be optionally substituted by a halogen ^{atom, a LC31, a LC32, a} LC41, a LC42, a LC51 and ^{a LC52} each independently any of the following Structure

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). indicates ^{whether, Z LC31, Z LC32, Z} LC41, Z LC42, Z LC51 and ^{Z LC51} each independently represent a single bond, -CH = CH -, - C≡C -, - CH 2 CH 2 -, - ( CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, Z ⁵ represents —CH ₂ — or an oxygen atom, and X ^LC41 represents ^Represents a hydrogen atom or a fluorine atom, m ^LC31 , m ^{L C32, m LC41, m LC42,} m LC51 and ^{m LC52} represent each independently ^{0~3, m LC31 + m LC32,} m LC41 + m LC42 and ^m LC51 ^{+ m LC52} is 1, 2 or ^{3, A LC31} ~ When a plurality of A ^LC52 and Z ^{LC31 to} Z ^LC52 are present, they may be the same or different. )
It is preferable that 1 type or 2 types or more of compounds chosen from the group which consists of a compound represented by these are included.

R ^{LC31 to} R ^LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC31 to} A ^LC52 each independently preferably have the following structure:

Z ^{LC31 to} Z ^LC51 are each independently a single bond, —CH ₂ O—, —COO—, ^—OCO— , —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or —OCH ₂ —. preferable.

  As a compound represented by General Formula (LC3), General Formula (LC4), and General Formula (LC5), General Formula (LC3-1), General Formula (LC4-1), and General Formula (LC5-1)

Wherein R ^{31 to} R ³³ are alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, or alkenyloxy groups having 2 to 8 carbon atoms. R ^{41 to} R ⁴³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. Z ^{31 to} Z ³³ are a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ —. , —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, X ⁴¹ represents a hydrogen atom or a fluorine atom, and Z ³⁴ represents —CH ₂ — or an oxygen atom. It is preferable to contain at least one compound selected from the group .

In General Formula (LC3-1) to General Formula (LC5-1), R ^{31 to} R ³³ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Represents an alkoxy group or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and an alkyl having 2 to 5 carbon atoms More preferably, it represents a group or an alkenyl group having 2 to 4 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, and an alkyl group having 3 carbon atoms. It is particularly preferred to represent.

R ^{41 to} R ⁴³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms. More preferably, it represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, and has 2 carbon atoms. It is particularly preferred to represent an alkoxy group.

Z ^{31 to} Z ³³ are a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ —, — CH ₂ O—, —OCF ₂ — or —CF ₂ O— represents a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or — It preferably represents CF ₂ O—, and more preferably represents a single bond or —CH ₂ O—.

  The liquid crystal composition contains 5% by mass to 50% by mass of a compound selected from the group of compounds represented by General Formula (LC3-1), General Formula (LC4-1), and General Formula (LC5-1). It is preferable to contain 5% to 40% by weight, more preferably 5% to 30% by weight, more preferably 8% to 27% by weight, and more preferably 10% to 25% by weight. % Content is more preferable.

  Specifically, the compound represented by the general formula (LC3-1) is preferably a compound represented by the following general formula (LC3-11) to general formula (LC3-15).

(In the formula, R ³¹ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^41a represents an alkyl group having 1 to 5 carbon atoms.)
Specifically, the compound represented by the general formula (LC4-1) is preferably a compound represented by the following general formula (LC4-11) to general formula (LC4-14).

(In the formula, R ³² represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^42a represents an alkyl group having 1 to 5 carbon atoms, and X ⁴¹ represents a hydrogen atom or Represents a fluorine atom.)
Specifically, the compound represented by the general formula (LC5-1) is preferably a compound represented by the following general formula (LC5-11) to general formula (LC5-14).

(In the formula, R ³³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^43a represents an alkyl group having 1 to 5 carbon atoms, and Z ³⁴ represents —CH _2. -Or represents an oxygen atom.)
In general formula (LC3-11), general formula (LC3-13), general formula (LC4-11), general formula (LC4-13), general formula (LC5-11), and general formula (LC5-13), R ^{31 to} R ³³ are preferably the same embodiments in general formula (LC3-1) to general formula (LC5-1). R ^{41a to} R ^41c are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

In general formula (LC3-12), general formula (LC3-14), general formula (LC4-12), general formula (LC4-14), general formula (LC5-12), and general formula (LC5-14), R ^{31 to} R ³³ are preferably the same embodiments in general formula (LC3-1) to general formula (LC5-1). R ^{41a to} R ^41c are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

  Among general formulas (LC3-11) to (LC5-14), in order to increase the absolute value of dielectric anisotropy, general formula (LC3-11), general formula (LC4-11), Formula (LC5-11), general formula (LC3-13), general formula (LC4-13) and general formula (LC5-13) are preferred, and general formula (LC3-11), general formula (LC4-11), general formula Formula (LC5-11) is more preferred.

  The liquid crystal layer in the liquid crystal display element of the present invention preferably contains one or more compounds represented by general formulas (LC3-11) to (LC5-14), and contains one or two kinds. It is more preferable to contain 1 type or 2 types of compounds represented by general formula (LC3-1).

  Moreover, as a compound represented by general formula (LC3), general formula (LC4), and general formula (LC5), general formula (LC3-2), general formula (LC4-2), and general formula (LC5-2) )

Wherein R ^{51 to} R ⁵³ are an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. R ^{61 to} R ⁶³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. B ^{1 to} B ^{3 each} represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be fluorine-substituted, Z ^{41 to} Z ⁴³ are a single bond, —CH═CH—, _{-C≡C -, - CH 2 CH 2} -, - (CH 2) 4 -, - COO -, - OCO -, - OCH 2 -, - CH 2 O -, - OCF 2 - or _-CF 2 O- the ^{stands, X 42} represents a hydrogen atom or a fluorine atom, ^{Z 4} It is -CH ₂ - represents an or an oxygen atom).
It is preferable to contain at least one compound selected from the group of compounds represented by:

In General Formula (LC3-2), General Formula (LC4-2), and General Formula (LC5-2), R ^{51 to} R ⁵³ are each an alkyl group having 1 to 8 carbon atoms, and an alkenyl having 2 to 8 carbon atoms. Group, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. More preferably, it represents an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and more preferably represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms. And particularly preferably an alkyl group having 3 carbon atoms.

R ^{61 to} R ⁶³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, It preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms. More preferably, it represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, and has 2 carbon atoms. It is particularly preferred to represent an alkoxy group.

B ^{31 to} B ³³ each represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be fluorine-substituted, but an unsubstituted 1,4-phenylene group or a trans-1,4- A cyclohexylene group is preferred, and a trans-1,4-cyclohexylene group is more preferred.

Z ^{41 to} Z ⁴³ are a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO—, —OCH ₂ —, — CH ₂ O—, —OCF ₂ — or —CF ₂ O— represents a single bond, —CH ₂ CH ₂ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or — It preferably represents CF ₂ O—, and more preferably represents a single bond or —CH ₂ O—.

  The compound represented by general formula (LC3-2), general formula (LC3-3), general formula (LC4-2), and general formula (LC5-2) is contained in an amount of 10 to 60% by mass in the liquid crystal composition. However, it is more preferable to contain 20 to 50% by mass, more preferably 25 to 45% by mass, more preferably 28 to 42% by mass, and more preferably 30 to 40% by mass. Further preferred.

  Specifically, the compound represented by the general formula (LC3-2) is preferably a compound represented by the following general formula (LC3-21) to general formula (LC3-29).

  Moreover, as a compound represented by general formula (LC3-3), the compound represented by the following general formula (LC3-31)-general formula (LC3-33) is also preferable.

(In the formula, R ⁵¹ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^61a represents an alkyl group having 1 to 5 carbon atoms. Preferred is the same embodiment as R ⁵¹ and R ⁶¹ in 2).

  Specifically, the compound represented by the general formula (LC4-2) is preferably a compound represented by the following general formula (LC4-21) to general formula (LC4-26).

(In the formula, R ⁵² represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^62a represents an alkyl group having 1 to 5 carbon atoms, and X ⁴² represents a hydrogen atom or (It represents a fluorine atom, but an embodiment similar to R ⁵² and R ⁶² in formula (LC4-2) is preferred.)
Specifically, the compound represented by the general formula (LC5-2) is preferably a compound represented by the following general formula (LC5-21) to general formula (LC5-26).

(In the formula, R ⁵³ represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^63a represents an alkyl group having 1 to 5 carbon atoms, and W ² represents —CH _2. -Represents an oxygen atom, but an embodiment similar to R ⁵³ and R ⁶³ in formula (LC5-2) is preferred.)

General formula (LC3-21), General formula (LC3-22), General formula (LC3-25), General formula (LC4-21), General formula (LC4-22), General formula (LC4-25), General formula In (LC5-21), general formula (LC5-22), and general formula (LC5-25), R ^{51 to} R ⁵³ represent general formula (LC3-2), general formula (LC4-2), and general formula ( Similar embodiments in LC5-2) are preferred. R ^{61a to} R ^63a are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms.

General formula (LC3-23), general formula (LC3-24) and general formula (LC3-26), general formula (LC4-23), general formula (LC4-24) and general formula (LC4-26), general formula In (LC5-23), general formula (LC5-24), and general formula (LC5-26), R ^{51 to} R ⁵³ represent general formula (LC3-2), general formula (LC4-2), and general formula (LC5- Similar embodiments in 2) are preferred. R ^{61a to} R ^63a are preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 3 carbon atoms, and particularly preferably an alkyl group having 3 carbon atoms.

  Among general formulas (LC3-21) to (LC5-26), in order to increase the absolute value of dielectric anisotropy, general formula (LC3-21), general formula (Lc3-22) and general formula Formula (LC3-25), Formula (LC4-21), Formula (LC4-22) and Formula (LC4-25), Formula (LC5-21), Formula (LC5-22) and Formula ( LC5-25) is preferred.

The compounds represented by the general formula (LC3-2), the general formula (Lc4-2) and the general formula (LC5-2) can be contained alone or in combination of two or more, but B ^{1 to} B ³ are 1, It is preferable to contain at least one compound each representing a 4-phenylene group and a compound in which B ^{1 to} B ³ represent a trans-1,4-cyclohexylene group.

  Other examples of the compound represented by the general formula (LC3) include the following general formula (LC3-a) and general formula (LC3-b).

(Wherein R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 each independently represent the same meaning as R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 in the general formula (LC3), and X ^{LC3b1 to} X ^LC3b6 are Represents a hydrogen atom or a fluorine atom, and at least one of X ^LC3b1 and X ^LC3b2 or X ^LC3b3 and X ^LC3b4 represents a fluorine atom, m ^LC3a1 is 1, 2 or 3, and m ^LC3b1 is 0 or 1 and when there are a plurality of A ^LC31 and Z ^LC31 , they may be the same or different.) Or one or more compounds selected from the group of compounds represented by Is preferred.

R ^LC31 and R ^LC32 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.

A ^LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group. , 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.

Z ^LC31 is a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.

  As general formula (LC3-a), it is preferable to represent the following general formula (LC3-a1).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 1 carbon atom. It is more preferable that R 7 represents an alkyl group having ^˜7 , and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.

  As general formula (LC3-b), it is preferable to represent the following general formula (LC3-b1) to general formula (LC3-b12), and general formula (LC3-b1), general formula (LC3-b6), and general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is represented. Most preferably it represents.

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R ^LC32 represents an alkyl group having 2 carbon atoms.

  The compound represented by the general formula (LC4) is preferably a compound represented by the following general formula (LC4-a) to general formula (LC4-c), and the compound represented by the general formula (LC5) is: Compounds represented by the following general formula (LC5-a) to general formula (LC5-c) are preferred.

^{(Wherein, R LC41,} R ^LC42 and ^{X LC41} each independently represent the same meaning as ^{R LC41, R LC42} and ^{X LC41} in the general formula ^{(LC4), R LC51} and ^{R LC52} is the general independently It represents the same meaning as ^{R LC51} and ^{R LC52} in formula ^{(LC5), Z LC4a1, Z} LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and ^{Z LC5c1} each independently represent a single bond, -CH = CH -, - C≡ _{C -, - CH 2 CH 2} -, - (CH 2) 4 -, - COO -, - OCH 2 -, - CH 2 O -, - OCF 2 - or an _-CF 2 O-).
^{R LC41,} R LC42, R ^LC51 and ^{R LC52} each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents -7 alkenyloxy groups.

Z ^{LC4a1 to} Z ^LC5c1 each independently preferably represents a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, and more preferably represents a single bond.

  The compound represented by the general formula (LC) is selected from the compounds represented by the following general formula (LC6) (excluding the compounds represented by the general formula (LC1) to the general formula (LC5)). It is also preferable that it is 1 type, or 2 or more types of compounds.

In General Formula (LC6), R ^LC61 and R ^LC62 each independently represent an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C, so that the oxygen atoms are not directly adjacent. ≡C— may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally halogen substituted. As the compound represented by the general formula (LC6), R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or 2 to 7 carbon atoms. The alkenyl group is preferably represented by any one of the following structures.

(In the formula, it shall be bonded to the ring structure at the right end.)

In General Formula (LC6), A ^{LC61 to} A ^LC63 each independently represent any of the following structures. In the structure, one or more CH ₂ CH ₂ groups in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —. One or two or more CH groups in the phenylene group may be substituted with a nitrogen atom.

As the compound represented by the general formula (LC6), A ^{LC61 to} A ^LC63 each independently preferably has one of the following structures.

In the general formula (LC6), Z ^LC61 and Z ^LC62 each independently represent a single bond, —CH═CH—, ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—. _{, -OCH 2 -, - CH 2} O -, - OCF 2 - or _-CF 2 O-a represents, MLC61 represents 0-3. As the compound represented by the general formula (LC6), Z ^LC61 and Z ^LC62 are each independently a single bond, —CH ₂ CH ₂ —, ^—COO— , —OCH ₂ —, —CH ₂ O—, —OCF _2. - or _-CF 2 O-are preferred.

The compound represented by the general formula (LC6) is one or more compounds selected from the group consisting of compounds represented by the following general formula (LC6-a) to general formula (LC6-v) Is preferred. In the general formulas (LC6-a1) to (LC6-p1), R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, carbon An alkenyl group having 2 to 7 atoms or an alkenyloxy group having 2 to 7 carbon atoms is represented.

[Polymerizable compound]
Examples of the polymerizable compound according to the present invention include a monofunctional polymerizable compound having one reactive group, and a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional. Can be mentioned. The polymerizable compound having a reactive group may or may not contain a mesogenic moiety.

  In the polymerizable compound having a reactive group, the reactive group is preferably a substituent having a polymerizable property by light. In particular, when the vertical alignment film is formed by thermal polymerization, the reaction of the polymerizable compound having a reactive group can be suppressed during the thermal polymerization of the vertical alignment film material. Substituents are particularly preferred.

  As the polymerizable compound according to the present invention, the following general formula (P)

(In the general formula (P), Z ^p1 represents a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, and a hydrogen atom in the halogen atom. An optionally substituted alkoxy group having 1 to 15 carbon atoms, a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom, and a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom Represents an alkenyloxy group having 1 to 15 carbon atoms or -Sp ^p2 -R ^p2 ;
R ^p1 and R ^p2 are each independently the following formulas (R-I) to (R-IX):

In the formulas (RI) to (R-IX), R ^{2 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, T is a single bond or —COO—, p, t and q are each independently 0, Represents 1 or 2,
Sp ^p1 and Sp ^p2 each represent a spacer group, and Sp ^p1 and Sp ^p2 are each independently a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is L 1 represents an integer of 1 to 11, and an oxygen atom is bonded to an aromatic ring.) L ^p1 and L ^p2 each independently represent a single bond, —O—, —S—, —CH ₂ —, _{-OCH 2 -, - CH 2 O} -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO—NR ^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 — or —C≡C— (wherein, R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein z is 1 to 4) Represents an integer.)
M ^p2 represents 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2, 5-diyl 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 -Represents a diyl group, but M ^p2 is unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a carbon atom ^May be substituted with a halogenated alkoxy group of formula 1 to 12, a halogen atom, a cyano group, a nitro group or —R ^p1 ;
M ^p1 represents the following formulas (i-11) to (ix-11):

(In the formula, it binds to Sp ^p1 with ★ and binds to L ^p1 or L ^p2 with ★★),
M ^p3 represents the following formulas (i-13) to (ix-13):

(In the formula, it binds to Z ^p1 with ★ and binds to L ^p2 with ★★),
m ^{p2 to} m ^p4 each independently represents 0, 1, 2 or 3, and m ^p1 and m ^p5 each independently represent 1, 2 or 3, but when a plurality of Z ^p1 are present, May be the same or different. When a plurality of R ^p1 are present, they may be the same or different. When a plurality of R ^p2 are present, they may be the same. They may be different, they may be the same or different when multiple Sp ^p1 are present, and they may be the same or different when multiple Sp ^p2 are present, When a plurality of L ^p1 are present, they may be the same or different, and when a plurality of M ^p2 are present, they may be the same or different. It is preferably represented by a compound represented by Moreover, it is preferable to contain the said polymeric compound 1 type (s) or 2 or more types.

In the general formula (P) according to the present invention, Z ^p1 is preferably -Sp ^p2 -R ^p2 , and R ¹¹ and R ¹² are each independently represented by the formulas (R-1) to (R-3). Either is preferable.

In the general formula (P), m ^p1 + m ^p5 is preferably 2 or more.

In the general formula (P), L ^p1 represents a single bond, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC _{2. H 4 -, - OCOC 2 H} 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) z _{-C (= O) -O -,} - (CH 2) z-O- (C = O) -, - O- (C = O) - (CH 2) z -, - CH = CH-COO-, —COO—CH═CH—, —OCOCH═CH—, — (C═O) —O— (CH ₂ ) z—, —OCF ₂ — or —C≡C—, and L ^p2 represents —OCH _{2 CH 2 O -, - COOC 2} H 4 -, - OCOC 2 H 4 -, - (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-COO -, - COO-CH = CH -, - OCOCH _{= CH -, - C 2 H} 4 OCO- or _-C 2 _H 4 is COO-, z in the above formula is preferably an integer of 1 to 4.

In addition, at least one of L ^p1 and L ^{p2 in} the general formula (P) is — (CH ₂ ) _z —C (═O) —O— or — (CH ₂ ) z—O— (C═O). - and _{-O- (C = O) - (} CH 2) z -, - (C = O) -O- (CH 2) is preferably at least one selected from the group consisting of z-.

In the general formula (P), R ^p1 and R ^p2 are each independently the following formulas (R-1) to (R-15):

Any of these is more preferable.

In the general formula (P), m ^p3 represents 0, 1, 2, or 3. When m ^p2 is 1, L ^p1 is a single bond, and when m ^p2 is 2 or 3, a plurality of L ^p1 is present. At least one is preferably a single bond.

In the general formula (P), m ^p3 represents 0, 1, 2 or 3, and when m ^p3 is 1, M ^p2 is a 1,4-phenylene group, and when m ^p3 is 2 or 3, a plurality of m ^p3 are present. ^{M p2} adjacent to ^{M p1} through at least ^{L p1} of ^{M p2} which is preferably a 1,4-phenylene group.

Further, m ^{p3 in the} general formula (P) represents 0, 1, 2, or 3, and at least one of M ^p2 is a 1,4-phenylene group substituted with one or two or more fluorines. It is preferable.

Further, m ^{p4 in the} general formula (P) represents 0, 1, 2, or 3, and at least one of M ^p3 is a 1,4-phenylene group substituted with one or two or more fluorines. It is preferable.

Further, as the general formula (P) in the spacer group ^{(Sp p1, Sp p2, Sp} p4), a single _{bond, -OCH 2 -, - (CH} 2) z O -, - CO -, - C 2 H 4 _{-, - COO -, - OCO} -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - (CH 2) z -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH ═CH—, —CF ₂ —, —CF ₂ O—, — (CH ₂ ) _z —C (═O) —O—, — (CH ₂ ) _z —O— (C═O) —, —O— (C═O) — (CH ₂ ) _z —, — (C═O) —O— (CH ₂ ) _z —, —O— (CH ₂ ) _z —O—, —OCF ₂ —, —CH═CH -COO-, -COO-CH = CH-, -OCOCH = CH- or -C≡C- is preferred, and Z is an integer of 1-10. Rukoto is preferable.

  The polymerizable compound of the general formula (P) according to the present invention is represented by the general formula (Pa), the general formula (Pb), the general formula (Pc), and the general formula (Pd). It is preferably at least one compound selected from the group consisting of compounds.

In the above general formulas (Pa) to (Pd), R ^p1 and R ^p2 are each independently the following formulas (RI) to (R-IX):

In the formulas (RI) to (R-IX), R ^{2 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. 1 to 5 halogenated alkyl groups, W is a single bond, —O— or a methylene group, T is a single bond or —COO—, p, t and q are each independently 0, Represents 1 or 2,
Ring A and Ring B are each independently 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5- Diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indane-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1, A 3-dioxane-2,5-diyl group, which is unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, or an alkoxy having 1 to 12 carbon atoms group, halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, that is substituted with a nitro group or a -R ^p1 preferably,
Ring C represents the following formulas (ci) to (c-ix):

(In the formula, it binds to Sp ^p1 with ★ and binds to L ^p5 or L ^p6 with ★★),
Sp ^p1 and Sp ^p4 each represent a spacer group, and X ^{p1 to} X ^p4 preferably each independently represent a hydrogen atom or a halogen atom,
L ^p4 , L ^p5 and L ^p6 are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC _{2. H 4 -, - OCOC 2 H} 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) z _{-C (= O) -O -,} - (CH 2) z -O- (C = O) -, - O- (C = O) - (CH 2) z -, - (C = O) -O — (CH ₂ ) _z —, —O— (CH ₂ ) _z —O—, —OCF ₂ —, —CH═CHCOO—, —COOCH═CH—, —OCOCH═CH— or —C≡C—. It is preferable that z in the formula is an integer of 1 to 4.

L ^p3 is preferably —CH═CHCOO—, —COOCH═CH—, or —OCOCH═CH—.

In the compound represented by the general formula ( ^Pa ), it is preferable that m ^p6 and m ^p7 each independently represent 0, 1, 2, or 3. Moreover, it is more preferable that it is ^mp6 + ^mp7 = 2-5.

In the compound represented by the general formula (Pd), ^mp12 and ^mp15 each independently represent 1, 2 or 3, and ^mp13 preferably represents 0, 1, 2 or 3, m ^p14 preferably represents 0 or 1. Moreover, it is more preferable that it is ^mp12 + ^mp15 = 2-5. When a plurality of R ^p1 are present, they may be the same or different. When a plurality of R ^p1 are present, they may be the same or different, and a plurality of R ^p2 are present. In some cases, they may be the same or different. When a plurality of Sp ^p1 are present, they may be the same or different. When there are a plurality of Sp ^p4 , they are the same. They may be the same or different when there are a plurality of L ^p4 and L ^p5, and they may be the same when there are a plurality of rings A to C. Or different.

  The preferable structure of the compound represented by general formula (Pa)-general formula (Pd) which concerns on this invention below is illustrated.

  Preferable examples of the compound represented by the general formula (Pa) according to the present invention include polymerizable compounds represented by the following formulas (Pa-1) to (Pa-31).

  Preferred examples of the compound represented by the general formula (Pb) according to the present invention include polymerizable compounds represented by the following formulas (Pb-1) to (Pb-34).

  Preferred examples of the compound represented by the general formula (Pc) according to the present invention include polymerizable compounds represented by the following formulas (Pc-1) to (Pc-52).

  The compound represented by the general formula (Pd) according to the present invention is preferably a compound represented by the following general formula (P-d ').

(In the compound represented by the above general formula (Pd ′), ^mp10 more preferably represents 2 or 3. The other symbols are the same as those in the above general formula (pd), and will be omitted.)
Preferred examples of the compound represented by the general formula (Pd) according to the present invention include polymerizable compounds represented by the following formulas (Pd-1) to (Pd-31).

The “alkyl group having 1 to 15 carbon atoms” according to the present invention is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the general formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 15 carbon atoms, and R ¹ and R ² are each independently 1 to 1 carbon atoms. Eight alkyl groups are preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.

  Examples of the “alkyl group having 1 to 15 carbon atoms” according to the present invention include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, t-butyl, 3-pentyl, and isopentyl. Group, neopentyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group and the like. In the present specification, examples of alkyl groups are common and are appropriately selected from the above examples depending on the number of carbon atoms of each alkyl group.

  The example of the “alkoxy group having 1 to 15 carbon atoms” according to the present invention is preferably present at a position where at least one oxygen atom in the substituent is directly bonded to the ring structure, and includes a methoxy group, ethoxy group Group, propoxy group (n-propoxy group, i-propoxy group), butoxy group, pentyloxy group, octyloxy group and decyloxy group are more preferable. In addition, in this specification, the example of an alkoxy group is common and is suitably selected from the said illustration according to the number of carbon atoms of each alkoxy group.

  Examples of the “alkenyl group having 2 to 15 carbon atoms” according to the present invention are vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl. Group, 2-pentenyl group, 3-pentenyl group, 2-hexenyl group and the like. More preferable alkenyl groups according to the present invention include the following formula (i) (vinyl group), formula (ii) (1-propenyl group), formula (iii) (3-butenyl group) and formula (iv) ) (3-pentenyl group):

(In the above formulas (i) to (iv), * represents a binding site to the ring structure.)
However, when the liquid crystal composition of the present invention contains a polymerizable monomer, structures represented by formula (ii) and formula (iv) are preferable, and a structure represented by formula (ii) is more preferable. preferable. In the present specification, examples of the alkenyl group are common and are appropriately selected from the above examples depending on the number of carbon atoms of each alkenyl group.

  Among the polymerizable compounds in the present invention, examples of the polymerizable compound having a monofunctional reactive group that is preferable for increasing the solubility with a low-molecular liquid crystal and suppressing crystallization include the following general formula (VI).

(In the formula, X ³ represents a hydrogen atom or a methyl group, and Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to 2). Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring.), V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms. An alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom) Or may be substituted with a cyclic substituent, and W represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups of Meaning hydrogen atoms -CH _3, -OCH _3, fluorine atom, or a cyano group may be substituted. The polymerizable compound represented by) are preferred.

In the general formula (VI), X ³ represents a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferred, and when importance is placed on reducing the residual amount of reaction, a methyl group is preferred. preferable.

In the general formula (VI), Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t represents an integer of 2 to 11, an oxygen atom Represents the bond to the aromatic ring), but the length of the carbon chain affects Tg, so when the polymerizable compound content is less than 10% by weight, it is preferably not too long. A bond or an alkylene group having 1 to 5 carbon atoms is preferable, and when the polymerizable compound content is less than 6% by weight, a single bond or an alkylene group having 1 to 3 carbon atoms is more preferable. When the polymerizable compound content is 10% by weight or more, an alkylene group having 5 to 10 carbon atoms is preferable. Also, Sp ³ is -O- _{(CH 2) t} - may represent a, t is preferably 1 to 5, 1 to 3 is more preferable. Furthermore, the number of carbon atoms is used a mixture of a plurality of number of carbon atoms of Sp ³ are different polymerizable compounds such that the desired pre-tilt angle as needed so affects the pretilt angle can be obtained at the substrate surface including the alignment film It is preferable.

  In the general formula (VI), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within a range where the oxygen atoms are not adjacent to each other) .) Or may be substituted with a cyclic substituent, and is preferably substituted with two or more cyclic substituents.

  More specifically, the polymerizable compound represented by the general formula (VI) is represented by the general formula (X1a).

(In the formula, A ¹ represents a hydrogen atom or a methyl group,
A ² is a single bond or an alkylene group having 1 to 8 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. May be)
A ³ and A ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group do not have oxygen atoms directly bonded to each other) And each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
A ⁴ and A ⁷ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group do not have oxygen atoms directly bonded to each other) And each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group of 1 to 9 carbon atoms)
p represents 0-10,
B ¹ , B ² and B ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are In addition, the oxygen atoms may be independently substituted with an oxygen atom, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other, and one or two or more of the alkyl groups may be substituted. A hydrogen atom may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms).

The general formula (X1a) is preferably a compound represented by the following general formula (II-b).
Formula (II-b)

  The compounds represented by the general formula (II-b) are specifically compounds represented by the following formulas (II-q) to (II-z), (II-aa) to (II-al). It is preferable.

  The compounds represented by the general formula (VI), the general formula (XaI), and the general formula (II-b) may be one kind or two or more kinds.

  Moreover, as a polymeric compound represented by general formula (VI), general formula (X1b)

(In the formula, A ⁸ represents a hydrogen atom or a methyl group, and the 6-membered rings T ¹ , T ² and T ³ are each independently

(Where q represents an integer of 1 to 4),
q represents 0 or 1,
Y ¹ and Y ² are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—. _{, -CF = CF -, - (} CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 - or _-CH 2 _CH 2 _CH = CH—
Y ³ and Y ⁴ are each independently a single bond, an alkylene group having 1 to 12 carbon atoms (one or two or more methylene groups in the alkylene group are such that oxygen atoms are not directly bonded to each other, Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkylene group are each independently a fluorine atom or a methyl group. Or may be substituted with an ethyl group).
B ⁸ represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkylene group having a terminal acryloyl group or methacryloyl group. And a compound represented by

  Illustrative compounds are shown below, but are not limited thereto.

  Furthermore, the polymerizable compound represented by the general formula (VI) specifically includes the general formula (X1c)

(Wherein R ⁷⁰ represents a hydrogen atom or a methyl group, and R ⁷¹ represents a hydrocarbon group having a condensed ring).

  Illustrative compounds are shown below, but are not limited thereto.

  Among the polymerizable compounds in the present invention, the polymerizable compound having a polyfunctional reactive group that is preferable for increasing the solubility with a low-molecular liquid crystal and suppressing crystallization is represented by the following general formula (V).

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms. Represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other. -20 alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1-5. All 1,4-phenyle in the formula Groups, any hydrogen atom is -CH _3, -OCH _3, fluorine atom, or may be substituted by a cyano group.) The polymerizable compound represented by are preferred.

In the general formula (V), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the amount of residual reaction. In this case, a methyl group is preferred.

In the general formula (V), Sp ¹ and Sp ² are each independently a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 11). In which the oxygen atom is bonded to an aromatic ring.) The pretilt angle in the liquid crystal display element of the present invention is the number of carbon atoms, the content with liquid crystal, and the alignment film used. It is affected by the type and orientation processing conditions. It is preferable to use a material that spontaneously induces a pretilt angle on the surface of the alignment film depending on the molecular structure of the polymerizable compound. Therefore, although not necessarily limited, for example, when the pretilt angle is about 5 degrees, the carbon chain is preferably not so long, a single bond or an alkylene group having 1 to 5 carbon atoms is more preferable, and a single bond Alternatively, an alkylene group having 1 to 3 carbon atoms is more preferable. Furthermore, in order to make the pretilt angle within about 2 degrees, it is preferable to use a polymerizable compound having 6 to 12 carbon atoms, and more preferably 8 to 10 carbon atoms. Also, when Sp ¹ and Sp ² represent -O- (CH ₂ ) _s- , it affects the pretilt angle, so that it is preferable to adjust the lengths of Sp ¹ and Sp ² as necessary. For the purpose of increasing the pretilt angle, s is preferably 1 to 5, and more preferably 1 to 3. For the purpose of reducing the pretilt angle, s is preferably 6 to 10. In addition, since at least one of Sp ¹ and Sp ² is a single bond, a molecular asymmetry is exhibited, which is preferable because pretilt is induced.

In addition, a compound in which Sp ¹ and Sp ² are the same in the general formula (V) is also preferable, and it is preferable to use two or more compounds in which Sp ¹ and Sp ² are the same. In this case, it is more preferable to use two or more different Sp ¹ and Sp ² from each other.

  In the general formula (V), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within a range where the oxygen atoms are not adjacent to each other) ), May be substituted with a cyclic substituent, and is preferably substituted with two or more cyclic substituents.

  In the general formula (V), U specifically preferably represents the following formulas (Va-1) to (Va-13). In order to increase the anchoring force, biphenyl having high linearity is preferable, and it is preferable to represent the formula (Va-1) to the formula (Va-6). Further, the structure representing the formula (Va-11) to the formula (Va-11) is preferable in terms of high solubility with liquid crystal, and is used in combination with the formula (Va-1) to the formula (Va-6). preferable.

(In the formula, both ends are bonded to Sp ¹ or Sp ^2. Z ^p1 and Z ^p2 are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —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—, —COO—CH ₂ —, —OCO _{-CH 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CY 1 = CY 2 -, -. C≡C- or all of the 1,4-phenylene group represents in formula single bond Any hydrogen atom is —CH ₃ , —OCH ₃ , a fluorine atom, or a cyano group In addition, one or more CH ₂ CH ₂ groups in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —. May be.)
When U has a ring structure, at least one of Sp ¹ and Sp ² is —O— (CH ₂ ) _s — (wherein s represents an integer of 1 to 7 and an oxygen atom is bonded to an aromatic ring) It is preferable that both represent —O— (CH ₂ ) _s —.

  In the general formula (V), k represents an integer of 1 to 5, but k is preferably a bifunctional compound of 1 or k is a trifunctional compound of 2, and more preferably a bifunctional compound. .

  Specifically, the compound represented by the general formula (V) is preferably a compound represented by the following general formula (Vb).

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 1 to 7 and an oxygen atom is bonded to an aromatic ring), Z ¹ represents —OCH ₂ —, —CH ₂ O—, _{-COO -, - OCO -, -} CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - 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- _{, -COO-CH 2 -, -} OCO-CH 2 -, - CH 2 -COO -, - C _{^{2 -OCO -, - CY 1 =}} CY 2 - (Y 1 and ^{Y 2} each independently represents a hydrogen atom or a fluorine atom.), - C≡C- or a single bond, C represents 1,4 A phenylene group, a trans-1,4-cyclohexylene group or a single bond is represented, and in all 1,4-phenylene groups in the formula, an arbitrary hydrogen atom may be substituted with a fluorine atom.)

In the general formula (Vb), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, both of which are diacrylate derivatives each representing a hydrogen atom, or both are dimethacrylate derivatives having a methyl group. A compound in which one represents a hydrogen atom and the other represents a methyl group is also preferable. As for the polymerization rate of these compounds, diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, and a preferred embodiment can be used depending on the application.

In the general formula (Vb), Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) s —, at least one of which is —O - _(CH 2) is preferably s-, both -O- _(CH 2) aspects representing the s- is more preferable. In this case, s is preferably 1 to 6.

In the general formula (Vb), Z ¹ represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, — CF ₂ CF ₂ —, —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 -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, -CY ¹ = CY ^2- (Y ¹ and Y ² each independently represent a hydrogen atom or a fluorine atom), -C≡C- or a single bond, -OCH _2- , -CH ₂ O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - C H ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond is preferable, —COO—, —OCO— or a single bond is more preferable, and a single bond is particularly preferable. In the general formula (Vb), C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted with a fluorine atom. -A phenylene group or a single bond is preferable. When C represents a ring structure other than a single bond, Z ¹ is preferably a linking group other than a single bond. When C is a single bond, Z ¹ is preferably a single bond.

  As described above, in the general formula (Vb), it is preferable that C represents a single bond and the ring structure is formed of two rings. Specific examples of the polymerizable compound having a ring structure include the following general formula: Compounds represented by (V-1) to (V-6) are preferred, compounds represented by general formulas (V-1) to (V-4) are particularly preferred, and represented by general formula (V-2). Most preferred are the compounds

  In the above general formula (Vb), the compounds represented by the following general formulas (V1-1) to (V1-5) are preferable for enhancing the solubility with the liquid crystal composition, and the general formula (V1-1) ) Is particularly preferred.

  In addition, the general formula (Vb) is preferably used in the case where it is formed of three ring structures, and the compounds represented by the general formulas (V1-6) to (V1-13) have solubility in the liquid crystal composition. It is preferable in terms of enhancement. Furthermore, the compounds represented by the general formulas (V-1) to (V-6) having strong anchoring force with the liquid crystal have a weak general anchoring force and good compatibility with the liquid crystal composition (V1- It is also preferred to use a mixture with the compound represented by 1) to (V1-5).

(Wherein, q1 and q2 is independently an integer of 1 to 12, ^{R 3} represents a hydrogen atom or a methyl group.)
As the compound represented by the general formula (V), specifically, a compound represented by the following general formula (Vc) is preferable in terms of increasing the reaction rate, and the pretilt angle is thermally stable. This is preferable. Furthermore, a desired pretilt angle can be obtained by adjusting the number of carbon atoms of Sp ¹ , Sp ² and Sp ³ as necessary. The relationship between pretilt and the number of carbon atoms shows the same tendency as in the case of two functional groups.

(In the formula, X ¹ , X ² and X ³ each independently represent a hydrogen atom or a methyl group, and Sp ¹ , Sp ² and Sp ³ each independently represent a single bond, having 1 to 12 carbon atoms. Represents an alkylene group or —O— (CH ₂ ) _s — (wherein s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), and Z ¹¹ represents —OCH ₂ —. , —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —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 -, -} COO-CH 2 -, - OCO-CH 2 -, - CH _2- COO—, —CH ₂ —OCO—, —CY ¹ ═CY ² —, —C≡C— or a single bond, J represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or Represents a single bond, and all 1,4-phenylene groups in the formula may have an arbitrary hydrogen atom substituted with a fluorine atom.)

  It is also preferable to use a compound having a photo-alignment function as the polymerizable compound. Among them, it is preferable to use a compound that exhibits photoisomerization.

As the polymerizable compound having a photo-alignment function, specifically, in the general formula (Vb),
X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ). _s − (wherein _s represents an integer of 1 to 7 and an oxygen atom is bonded to an aromatic ring), Z ¹ represents —N═N—, and C represents 1,4-phenylene. A compound representing a group, a trans-1,4-cyclohexylene group (any hydrogen atom may be substituted by a fluorine atom) or a single bond is preferred.

  Especially, the compound represented by the following general formula (Vn) is preferable.

(In the formula, Rn1 and Rn2 each independently represent a hydrogen atom or a methyl group, and in the formula, pn and qn each independently represents an integer of 1 to 12.)

[Polymerization initiator]
As the polymerization method of the polymerizable compound used in the present invention, radical polymerization, anionic polymerization, cationic polymerization, etc. can be used, but polymerization is preferably performed by radical polymerization, radical polymerization by photo-Fries rearrangement, and initiation of photopolymerization. Radical polymerization with an agent is more preferred.

  As the radical polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable. Specifically, the following compounds are preferable.

  Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenone series such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4′-phenoxyacetophenone, 4′-ethoxyacetophenone;

Benzoins such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Benzyl, methylphenylglyoxyesters;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4' -Benzophenone series such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone;
Thioxanthone systems such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone;
Aminobenzophenone series such as Michler's ketone and 4,4'-diethylaminobenzophenone;
10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferable. Of these, benzyldimethyl ketal is most preferred.

  It is also preferable to use a plurality of polymerization initiators in consideration of radical lifetime and reactivity.

  Furthermore, without using the above-described polymerization initiator, polymerization can be carried out by containing a polymerizable liquid crystal compound having a conjugated structure that absorbs ultraviolet rays as radical polymerization by photofleece rearrangement. For example, it is preferable to use a polymerizable liquid crystal compound having a conjugated structure represented by general formulas (X1c-1) to (X1c-4) instead of the polymerization initiator because the voltage holding ratio of the liquid crystal element is not lowered. It is also preferable to use these in combination with a polymerization initiator for the purpose of promoting polymerization.

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition used in the present invention preferably contains the liquid crystal composition exemplified above and the polymerizable compound exemplified above in an amount of 0.5% by mass or more and less than 10% by mass. The lower limit of the content of the functional compound is preferably 1% by mass or more, preferably 2% by mass or more, and the upper limit is preferably less than 9% by mass, more preferably less than 7% by mass. In addition, the polymerizable liquid crystal composition used in the present invention preferably contains the liquid crystal composition exemplified above and 10% by mass or more and less than 40% by mass polymerizable compound exemplified above. In this case, the lower limit of the content of the polymerizable compound is preferably 15% by mass or more, preferably 20% by mass or more, and the upper limit is preferably less than 30% by mass, and more preferably less than 25% by mass. Furthermore, the polymerizable liquid crystal composition used in the present invention preferably contains the liquid crystal composition exemplified above and the polymerizable compound exemplified above in an amount of 5% by mass or more and less than 15% by mass.

  The polymerizable liquid crystal composition used in the present invention contains 0.5% by mass or more and less than 40% by mass of a polymerizable compound, so that uniaxial optical anisotropy or uniaxial refractive index anisotropy or It is preferable to form a polymer network having an easy-orientation axis direction, and it is more preferable that the optical axis or the easy-orientation axis of the polymer network and the easy-orientation axis of the low-molecular liquid crystal are substantially coincident. . The polymer network includes a polymer binder in which a polymer thin film is formed by aggregating a plurality of polymer networks. The polymer binder has refractive index anisotropy indicating uniaxial orientation, low molecular liquid crystal is dispersed in the thin film, and the uniaxial optical axis of the thin film and the optical axis of the low molecular liquid crystal are in substantially the same direction. The feature is that it is complete. Therefore, unlike a polymer dispersion type liquid crystal or polymer network type liquid crystal which is a light scattering type liquid crystal, light scattering does not occur and a high contrast display can be obtained in a liquid crystal element using polarized light. It is characterized in that the response time of the liquid crystal element is improved by shortening the time. Furthermore, the polymerizable liquid crystal composition used in the present invention is a PSA (Polymer Sustained Alignment) that forms a polymer network layer on the entire liquid crystal element and induces a pretilt by forming a polymer thin film layer on the liquid crystal element substrate. ) Type liquid crystal composition.

  In any concentration, it is preferable to contain at least two kinds of polymerizable compounds having different Tg and adjust Tg as necessary. The polymerizable compound that is a precursor of a polymer having a high Tg is a polymerizable compound having a molecular structure that increases the crosslink density, and preferably has 2 or more functional groups. The precursor of the polymer having a low Tg preferably has a structure in which the number of functional groups is 1 or 2 or more, and an alkylene group or the like is provided as a spacer between the functional groups to increase the molecular length. When adjusting the Tg of the polymer network for the purpose of improving the thermal stability and impact resistance of the polymer network, it is preferable to appropriately adjust the ratio of the polyfunctional monomer to the monofunctional monomer. Tg is also related to thermal mobility at the molecular level in the main chain and side chain of the polymer network, and has an influence on electro-optical properties. For example, when the crosslink density is increased, the molecular mobility of the main chain is lowered, the anchoring force with the low molecular liquid crystal is increased, the drive voltage is increased, and the fall time is shortened. On the other hand, when the crosslinking density is lowered so that Tg is lowered, the thermal mobility of the polymer main chain is increased, so that the anchoring force with the low-molecular liquid crystal is lowered, the driving voltage is lowered, and the fall time is increased. The anchoring force at the polymer network interface is influenced by the molecular mobility of the polymer side chain in addition to the above Tg, and the polymer is obtained by using a polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group. The anchoring force of the interface is lowered. In addition, the polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group is effective in inducing a pretilt angle at the substrate interface and acts in the direction of reducing the polar anchoring force.

When the polymerizable liquid crystal composition exhibits a liquid crystal phase, the polymerizable compound in the polymerizable liquid crystal composition is polymerized to increase the molecular weight of the polymerizable compound to cause phase separation of the liquid crystal composition and the polymerizable compound. . The form of separation into two phases varies greatly depending on the type of liquid crystal compound contained and the type of polymerizable compound. A phase separation structure may be formed by binodal decomposition in which an infinite number of polymerizable compound phases are generated and grown as island-like nuclei in the liquid crystal phase, and phase separation is caused by fluctuations in concentration between the liquid crystal phase and the polymerizable compound phase. A phase separation structure may be formed by spinodal decomposition. In order to form a polymer network by binodal decomposition, it is preferable that the content of at least low-molecular liquid crystal is 85% by mass or more, and the size is smaller than the wavelength of visible light by using a compound having a high reaction rate of the polymerizable compound. Innumerable nuclei of the polymerizable compound are generated to form a nano-order phase separation structure, which is preferable. As a result, when the polymerization in the polymerizable compound phase proceeds, a polymer network having a void interval shorter than the wavelength of visible light is formed depending on the phase separation structure, whereas the voids in the polymer network are caused by phase separation of the low-molecular liquid crystal phase. However, if the size of the void is smaller than the wavelength of visible light, the liquid crystal display device has high contrast, no light scattering, high contrast, strong influence of anchoring force from the polymer network, and short fall time. Is particularly preferable. The nucleation of the polymerizable compound phase in the binodal decomposition is preferably adjusted as needed as affected by changes in compatibility depending on the type and combination of compounds, reaction rate, temperature and other parameters. The reaction rate, in the case of ultraviolet polymerization, may be adjusted as appropriate to the ultraviolet irradiation conditions so as to promote the reactivity depending on the functional group of the polymerizable compound, the type and content of the photoinitiator, and the ultraviolet irradiation intensity. An ultraviolet irradiation intensity of 20 mW / cm ² or more is preferable. When the low-molecular liquid crystal content is 85% by mass or more, it is preferable to form a polymer network with a phase separation structure by spinodal decomposition. In spinodal decomposition, a phase separation fine structure is obtained due to fluctuations in the concentration of two phases with periodicity, so that visible light can be obtained. This is preferable because a uniform gap interval smaller than the wavelength can be easily formed. It is preferable to form the polymer network. When the proportion of the polymerizable compound is less than 15% by mass, it is preferable to form a phase separation structure by binodal decomposition, and when it is 15% by mass or more, it is preferable to form a phase separation structure by spinodal decomposition. When the content of the polymerizable compound is increased, there exists a phase transition temperature at which the low-molecular liquid crystal phase and the polymerizable compound phase are separated into two phases due to the influence of temperature. An isotropic phase is exhibited at a temperature higher than the two-phase separation transition temperature, but if it is low, separation occurs and a uniform phase separation structure cannot be obtained. When two-phase separation is performed according to temperature, it is preferable to form a phase separation structure at a temperature higher than the two-phase separation temperature. In any of the above cases, a polymer network is formed while maintaining the same alignment state as that of the low-molecular liquid crystal. The formed polymer network exhibits optical anisotropy so as to follow the orientation of the low-molecular liquid crystal. As the form of the liquid crystal layer in the polymer network, a structure in which the liquid crystal composition forms a continuous layer in the three-dimensional network structure of the polymer, a structure in which droplets of the liquid crystal composition are dispersed in the polymer, or both are mixed. Further, there is a structure in which a polymer network layer exists starting from both substrate surfaces, and only a liquid crystal layer is provided in the vicinity of the center of the opposite substrate. In any structure, it is preferable that a pretilt angle of 0 to 90 ° is induced with respect to the liquid crystal element substrate interface by the action of the polymer network. The polymer network to be formed preferably has a function of aligning the coexisting low molecular liquid crystal in the alignment direction indicated by the alignment film of the liquid crystal cell, and further has a function of pretilting the low molecular liquid crystal with respect to the polymer interface direction. It is also preferable. Introducing a polymerizable compound that pretilts the low-molecular liquid crystal with respect to the polymer interface is useful and preferable for improving the transmittance and lowering the driving voltage of the liquid crystal element. Moreover, it may have refractive index anisotropy, and it is preferable to use a polymerizable compound having a mesogenic group for the function of aligning the liquid crystal in the alignment direction. Alternatively, a pretilt may be formed by forming a polymer network by applying ultraviolet rays or the like while applying a voltage.

For vertically aligned cells such as VA mode, a polymerizable compound having a polyvalent alkyl group having no mesogenic group that induces vertical alignment or a polyvalent branched alkylene group may be used, and a polymerizable compound having a mesogenic group Is also preferred in combination. When a polymer network is formed in a vertically aligned cell by phase separation polymerization using the polymerizable liquid crystal composition described above, the fibrous or columnar polymer network is in the vertical direction of the low molecular liquid crystal with respect to the liquid crystal cell substrate. It is preferable that they are formed in substantially the same direction. In addition, when a vertical alignment film that induces a pretilt angle by rubbing the liquid crystal on the cell substrate surface so as to induce a tilted alignment is used, the liquid crystal is pretilted and aligned. It is preferable that a fiber-like or columnar polymer network is inclined in the same direction as the low-molecular liquid crystal. The polymerizable compound may be selected so that the inclination of the polymer network occurs spontaneously at the substrate interface. Alternatively, a polymer network may be formed by applying a voltage to place the liquid crystal in an inclined alignment state and irradiating ultraviolet rays or the like.
Furthermore, as a method for inducing the pretilt angle while applying a voltage, polymerization may be performed while applying a voltage in a voltage range of about 0.9 V to 2 V higher than the threshold voltage of the polymerizable liquid crystal composition. Then, a voltage higher than the threshold voltage may be applied for a short time of several seconds to several tens of seconds during the polymer network formation process, and then the polymer network may be formed below the threshold voltage. More preferably, the fibrous or columnar polymer network is formed to be inclined so as to induce a pretilt angle of 90 ° to 80 ° with respect to the transparent substrate plane, and a pretilt angle of 90 ° to 85 ° is preferred. A pretilt angle of 9 to 85 degrees is preferred, a pretilt angle of 89.9 to 87 degrees is preferred, and a pretilt angle of 89,9 to 88 degrees is preferred. The fibrous or columnar polymer network formed by any method is characterized in that the two cell substrates are connected to each other. Thereby, the thermal stability of the pretilt angle is improved, and the reliability of the liquid crystal display element can be increased.

  In addition, as a method for inducing the pretilt angle of a low-molecular liquid crystal by forming a fibrous or columnar polymer network in an inclined orientation, the alkylene group between the functional group and the mesogenic group has 6 or more carbon atoms. And a bifunctional acrylate having a small pretilt angle induction angle, a functional group, and a bifunctional acrylate having a large pretilt angle induction angle in which the number of carbon atoms of the alkylene group between the mesogenic groups is 5 or more. A desired pretilt angle can be induced in the vicinity of the interface by adjusting the compounding ratio of these compounds.

  Furthermore, a method of forming a fibrous or columnar polymer network by adding a polymerizable compound having a reversible photo-alignment function in a range of at least 0.01% to 1% is mentioned. In this case, the trans form has a rod-like shape similar to that of the low-molecular liquid crystal and affects the alignment state of the low-molecular liquid crystal. The trans isomer contained in the polymerizable liquid crystal composition of the present invention is such that when ultraviolet rays are irradiated as parallel light from the upper surface of the cell, the direction of ultraviolet rays and the long axis direction of the rod-like molecules are aligned in parallel. At the same time, the liquid crystal is aligned so as to be aligned in the molecular long axis direction of the trans form. When the cell is tilted and irradiated with ultraviolet rays, the molecular long axis of the trans body is oriented in the tilt direction and the liquid crystal is oriented in the tilt direction of the ultraviolet rays. That is, a pre-tilt angle is induced and a photo-alignment function is exhibited. The pretilt angle induced by crosslinking the polymerizable compound at this stage is fixed by a fibrous or columnar polymer network formed by polymerization phase separation. Therefore, the pretilt angle that is important in the VA mode is induced by a method of separating the polymerization phase while applying a voltage, a method of adding a plurality of polymerizable compounds having different induced pretilt angles, and a reversible photo-alignment function. The liquid crystal element of the present invention can be produced using a method of aligning low-molecular liquid crystals and polymerizable liquid crystal compounds in the direction in which ultraviolet rays travel by using the photo-alignment function exhibited by the polymerizable compound, and separating the polymerization phase as necessary. .

  The polymerizable compound having a photo-alignment function is preferably a photoisomeric compound that absorbs ultraviolet rays to become a trans isomer, and further, the polymerizable compound having a photo-alignment function has a reaction rate of the polymerizable compound having the photo-alignment function. It is preferably slower than the reaction rate of the polymerizable compound other than the above. When irradiated with ultraviolet rays, the polymerizable compound having a photo-alignment function immediately becomes a trans isomer, and when aligned in the light traveling direction, the surrounding liquid crystal compound including the polymerizable property is aligned in the same direction. At this time, the pre-tilt angle in the direction in which UV light travels when the polymer phase separation proceeds and the long axis direction of the low molecular liquid crystal and the easy axis direction of the polymer network are aligned with the easy axis of the polymerizable compound having the photo-alignment function. Is induced.

  Furthermore, in parallel alignment cells such as IPS and FFS modes, the polymer liquid crystal composition is used for the alignment direction of the alignment film having a fibrous or columnar polymer network on the liquid crystal cell substrate surface by phase separation polymerization. The low-molecular liquid crystals are aligned in parallel, but they are formed in the same direction as the refractive index anisotropy or easy-orientation axis direction of the formed fibrous or columnar polymer network and the alignment direction of the low-molecular liquid crystals. Is preferred. Furthermore, it is more preferable that the fibrous or columnar polymer network is present in substantially the entire cell except for the voids in which the low-molecular liquid crystal is dispersed. For the purpose of inducing the pretilt angle with respect to the polymer interface direction, it is preferable to use a polyvalent alkyl group having no mesogenic group, or a polymerizable compound having a polyvalent alkylene group and a polymerizable compound having a mesogenic group. .

  Furthermore, although the electro-optical characteristics are affected by the surface area of the polymer network interface and the gap spacing of the polymer network, it is important not to cause light scattering, and the average gap spacing is preferably smaller than the wavelength of visible light. For example, there is a method of increasing the monomer composition content in order to increase the surface area of the interface and reduce the gap interval. As a result, the polymer phase is formed so that the surface area of the interface is increased by changing the polymerization phase separation structure and making the gap interval fine, and the drive voltage and the fall time are shortened. The polymerization phase separation structure is also affected by the polymerization temperature.

  In the present invention, it is preferable to obtain a phase separation structure having fine voids by polymerizing at a high phase separation rate. The phase separation rate is greatly influenced by the compatibility between the low-molecular liquid crystal and the polymerizable compound and the polymerization rate. Since it largely depends on the molecular structure and content of the compound, it is preferable to adjust the composition as appropriate. When the compatibility is high, it is preferable to use a polymerizable compound having a high polymerization rate. In the case of ultraviolet polymerization, it is preferable to increase the ultraviolet intensity. It is also preferable to increase the content of the polymerizable compound in the polymerizable liquid crystal composition. When the compatibility is low, the phase separation rate is sufficiently high, which is preferable for producing the liquid crystal element of the present invention. As a method for reducing the compatibility, a method of polymerizing at a low temperature can be mentioned. When the temperature is lowered, the degree of alignment order of the liquid crystal is increased and the compatibility between the liquid crystal and the monomer is decreased, so that the polymerization phase separation rate can be increased. Still another method includes a method in which the polymerizable liquid crystal composition is polymerized at a temperature showing a supercooled state. In this case, it is sufficient to make the temperature slightly lower than the melting point of the polymerizable liquid crystal composition. Therefore, it is preferable that the phase separation can be accelerated only by lowering the temperature by several degrees. As a result, the polymer phase separation structure corresponding to the case where a monomer composition content of several tens of percent is added to the liquid crystal, that is, the surface area of the polymer network interface, which is a structure that acts to shorten the fall time, has a large gap spacing. A fine polymer network structure is formed. Therefore, it is preferable that the polymerizable liquid crystal composition of the present invention is appropriately adjusted in consideration of the alignment function, the crosslinking density, the anchoring force, and the gap interval so that the fall time is shortened.

In a liquid crystal device using the polymerizable liquid crystal composition of the present invention, it is necessary to prevent light scattering in order to obtain a high contrast display. It is important to control the phase separation structure to obtain an appropriate polymer network layer structure so as to obtain switching characteristics. The polymer network layer structure will be specifically described as follows.
<Continuous structure of polymer network layer>
A structure in which a polymer network layer is formed on the entire surface of the liquid crystal display element in the liquid crystal phase and the liquid crystal phase is continuous, and the orientation axis of the polymer network and the uniaxial optical axis are substantially the same as the orientation axis of the low-molecular liquid crystal It is preferable that the polymer network is formed so as to induce a pretilt angle of the low-molecular liquid crystal, and light is obtained by reducing the average gap distance of the polymer network to be smaller than the wavelength of visible light and smaller than at least 450 nm. Since scattering does not occur, it is preferable. Furthermore, in order to make the fall time of the response shorter than the response time of the low-molecular liquid crystal alone due to the interaction effect (anchoring force) between the polymer network and the low-molecular liquid crystal, it is preferable to be in the range of 50 nm to 450 nm. In order that the influence of the cell thickness of the liquid crystal is small and the fall time is as long as the cell thickness is large, at least the average gap interval is in the range of around 200 nm and the upper limit is around 450 nm. It is preferable to enter. Increasing the drive gap increases the average gap spacing. However, in order to suppress the increase in drive voltage to 25 V or less and shorten the fall response time, it is sufficient to enter the range from about 250 nm to 450 nm. The fall response time can be improved in the range of about 5 msec to about 1 msec, which is preferable. Further, in order to suppress the drive voltage from increasing within about 5V, it is preferable that the average gap interval is in the range of about 300 nm to 450 nm. Furthermore, it is also possible to control the average gap interval of the polymer network so that the falling response time is a high-speed response of 1 msec or less. Although the drive voltage may increase to 30 V or more, the average gap interval may be set between about 50 nm and about 250 nm, and in order to reduce it to 0.5 msec or less, it is preferable to set from about 50 nm to about 200 nm. The average diameter of the polymer network is in the range of 20 nm to 700 nm, contrary to the average gap spacing. As the content of the polymerizable compound increases, the average diameter tends to increase. Increasing the polymerization phase separation rate by increasing the reactivity increases the density of the polymer network and decreases the average diameter of the polymer network. Therefore, the phase separation conditions may be adjusted as necessary. When the content of the polymerizable compound is 10% or less, the average diameter is preferably 20 nm to 160 nm, and when the average gap distance is 200 nm to 450 nm, the average diameter is 40 nm to 160 nm. preferable. When the polymerizable compound content is greater than 10%, a range of 50 nm to 700 nm is preferable, and a range of 50 nm to 400 nm is more preferable.
<Discontinuous structure of polymer network layer>
In contrast to a structure in which a polymer network layer is formed on the entire surface of a liquid crystal display element and the liquid crystal phase is continuous, if the content of the polymerizable compound is low and the amount necessary for the polymer network layer to cover the entire cell is insufficient, the polymer network Layers are formed discontinuously. When the polarity of the substrate surface such as polyimide alignment film is high, the polymerizable compound tends to gather near the liquid crystal cell substrate interface, and the polymer network layer is formed so that the polymer network grows from the substrate surface and adheres to the substrate interface. A polymer network layer, a liquid crystal layer, a polymer network layer, and a counter substrate are stacked in this order from the surface. Polymer having a laminated structure of polymer network layer / liquid crystal layer / polymer network layer and having a thickness of at least 0.5%, preferably 1%, more preferably 5% or more of the cell thickness in the cell cross-sectional direction When the network layer is formed, the effect of shortening the fall time due to the action of the anchoring force between the polymer network and the low-molecular liquid crystal is exhibited and a favorable tendency is exhibited. However, since the influence of the cell thickness increases, if the fall time becomes longer as the cell thickness is increased, the thickness of the polymer network layer may be increased as necessary. The polymer network structure in the polymer network layer is such that the low-molecular liquid crystal and the easy-orientation axis or uniaxial optical axis are aligned in substantially the same direction, and the low-molecular liquid crystal is formed so as to induce a pretilt angle. Just do it. The average gap distance is preferably in the range of 90 nm to 450 nm.

  For example, when the content of the polymerizable compound is 1% by mass to 6% by mass, it is preferable to use a bifunctional monomer having a mesogenic group having a high anchoring force, and the polymerization rate is low with a structure having a short distance between the functional groups. It is preferable to use a fast bifunctional monomer, and it is preferable to form a polymer phase separation structure at a low temperature of 0 ° C. or lower. When the content of the polymerizable compound is 6% by mass to less than 10% by mass, a combination of the bifunctional monomer and a monofunctional monomer having a low anchoring force is preferable, and a range of 25 ° C. to −20 ° C. is necessary. It is preferable to form a polymer phase separation structure. Furthermore, if the melting point is room temperature or higher, it is preferable to lower the melting point by about 5 ° C. because the same effect as low temperature polymerization can be obtained. When the content of the polymerizable compound is changed from 10% by mass to 40% by mass, the influence of the polymer binder or the polymer network greatly affects the orientation and driving voltage of the low molecular liquid crystal and increases the driving voltage. It is preferable to use a polymerizable compound having a mesogenic group having an orientation function and a relatively weak anchoring force. For example, a polymerizable compound having a weak anchoring force and having a mesogenic group is effective to increase the number of carbon atoms of an alkylene group between the functional group and the mesogenic group, and preferably has 5 to 10 carbon atoms. In addition, when the polymerizable compound exceeds 30% by mass, liquid crystal droplets may be dispersed in the polymer binder. Even in this case, the polymer binder has a refractive index anisotropy and is oriented on the substrate surface. It is preferable that the orientation direction indicated by the film is aligned with the optical axis direction of the polymer binder.

  The higher the concentration of the polymerizable compound in the polymerizable liquid crystal composition, the greater the anchoring force between the liquid crystal composition and the polymer interface, and the higher the τd. On the other hand, when the anchoring force between the liquid crystal composition and the polymer interface increases, τr decreases. In order to make the sum of τd and τr less than 1.5 ms, the concentration of the polymerizable compound in the polymerizable liquid crystal composition is 1% by mass or more and less than 40% by mass, and 2% by mass or more and 15% by mass or less. Preferably, 3 mass% or more and 8 mass% or less are more preferable.

When used in a TFT drive liquid crystal display element, it is necessary to improve the reliability such as suppression of flicker and afterimages caused by printing, and the voltage holding ratio is an important characteristic. The cause of lowering the voltage holding ratio is considered to be ionic impurities contained in the polymerizable liquid crystal composition. In particular, mobile ions strongly influence the voltage holding ratio. Therefore, it is preferable to remove the mobile ions by performing a purification treatment or the like so that at least a specific resistance of 10 ¹⁴ Ω · cm or more is obtained. In addition, when a polymer network is formed by radical polymerization, the voltage holding ratio may decrease due to ionic impurities generated from the photopolymerization initiator, etc., but the polymerization initiator generates a small amount of organic acid and low-molecular byproducts. Is preferably selected.

[Liquid crystal display element]
The liquid crystal display element of the present invention contains a polymer or copolymer in a liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side, and the content of the polymer or copolymer is the content of the polymer or copolymer. 0.5% by mass or more and less than 40% by mass of the total mass of the liquid crystal composition and the polymer or copolymer, the polymer or copolymer forms a polymer network, and the polymer network is uniaxial. It has a refractive index anisotropy or an easy orientation axis and has two or more different orientation states. The liquid crystal display element of the present invention preferably has an alignment film for aligning the liquid crystal composition on at least one transparent substrate. By applying a voltage to the alignment film provided on the substrate and the electrode provided on the substrate, the alignment of the liquid crystal molecules is controlled. The polymer network or polymer binder has a uniaxial refractive index anisotropy or an easy axis direction, and the optical axis direction or the easy axis direction of the polymer network or the polymer binder and the easy axis direction of the low molecular liquid crystal are the same direction. Preferably there is. In this respect, it differs from a light scattering polymer network liquid crystal or polymer dispersed liquid crystal that does not have a uniaxial refractive index anisotropy or an orientation easy axis direction.

  Furthermore, it is preferable that the easy orientation axis direction of the alignment film and the easy orientation direction of the polymer network or polymer binder are the same. By providing a polarizing plate, a retardation film, etc., display is performed using this orientation state. The liquid crystal display element can be applied to operation modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, π cell, OCB, and cholesteric liquid crystal. Among these, VA, IPS, FFS, VA-TN, TN, and ECB are particularly preferable. The liquid crystal display element of the present invention is a PSA (Polymer Sustained Alignment) type liquid crystal display element having a polymer or copolymer on the alignment film in that the liquid crystal composition contains a polymer or copolymer. Is different.

  The content of the polymer or copolymer in the liquid crystal composition is 0.5% by mass or more and less than 40% by mass of the total mass of the liquid crystal composition and the polymer or copolymer. Is preferably 0.7% by mass or more, preferably 0.9% by mass or more, and the upper limit is preferably less than 30% by mass, and more preferably less than 20% by mass.

  In the PSA type liquid crystal display element, the alignment process is omitted by providing a plurality of slits with a width of 3 to 5 μm in the electrode instead of the rubbing alignment process and tilting the liquid crystal in the slit direction. In mass production technology, when UV irradiation is applied while applying a voltage of several tens of volts, the alignment of the liquid crystal is stabilized so that a pretilt angle (tilt angle with respect to the substrate normal) is obtained at the substrate interface, and the polymer is stabilized. A thin film is formed. Utilizing the pretilt angle induced by the action of this polymer thin film, it has been used for the production of PSVA (polymer-stabilized vertical alignment) LCD or PSALCD. Further, for the purpose of improving the viewing angle, a pattern electrode designed so that a multi-domain can be formed is used to divide the pretilt angle direction in one pixel into a plurality of parts. When a liquid crystal having negative dielectric anisotropy is used, when a voltage higher than the saturation voltage is applied to the cell so that the liquid crystal transitions from the vertical alignment to the bend alignment and ultraviolet irradiation is performed, the monomer added in a small amount in the liquid crystal When polymerizing on the vertical alignment film, an alignment film that induces a pretilt angle by stabilizing the slightly tilted liquid crystal alignment that is the bend deformation end is polymerized. Thereby, when the ultraviolet irradiation is finished and the voltage application is stopped, a slightly tilted (pretilt) vertical alignment is obtained. However, when this method is applied to a liquid crystal display element that can improve the response relaxation time by forming a polymer network or the like in the entire cell, it is irradiated with ultraviolet rays by applying a voltage of several tens of volts above the saturation voltage. Thus, the polymer network stabilizes the liquid crystal in the parallel alignment state. This is because the refractive anisotropy or the easy alignment axis of the polymer network is formed so as to hold the liquid crystal molecules in the parallel alignment state, so that the vertical alignment cannot be obtained.

  In a vertical alignment type LCD, electro-optical characteristics such as transmittance and response time are provided by applying a pretilt angle within 2 degrees to the cell normal direction in order to align the tilt orientation of the tilt alignment in a certain direction by applying a voltage. We are trying to improve. However, in order to form a polymer network slightly tilted so as to induce a pretilt angle, it is considered to apply a voltage slightly higher than the threshold voltage of the liquid crystal so that the liquid crystal is tilted within 2 degrees. It is done. However, in a liquid crystal display device such as a PVA (Pattern Vertical Alignment) electrode that aligns the tilt alignment direction uniformly, a low voltage near the threshold voltage is applied to form the refractive anisotropy or easy alignment axis of the polymer network. The transmittance decreases because the tilt orientation direction of the liquid crystal is not determined. This is because when the voltage is applied in the vicinity of the threshold voltage, it is slightly deformed to bend alignment, and the end on the alignment film side in bend deformation is substantially vertical, and the influence of the vertical alignment film is strong. This is because the liquid crystal becomes vertical alignment, and the tilt alignment direction cannot be defined in a certain direction near the substrate interface and becomes unstable. On the other hand, when a voltage higher than the saturation voltage of the electro-optic characteristic is applied, the liquid crystal near the substrate interface is in a tilted alignment state, and since the electric field is strong, the influence of the electric field distribution by the pattern electrode is strong, and the tilted orientation direction is in a certain direction. Thus, the transmittance can be improved. However, since a polymer network with parallel alignment is formed in the entire cell, vertical alignment cannot be obtained as described above.

  Since the tilt orientation depends greatly on the type of the electrode pattern, for example, the fishbone type electrode shown in FIG. 13 has the same width as that of the fine line electrode and the line electrode alternately having a width of about 3 to 5 μm. In this pattern electrode, the liquid crystal on the line electrode is aligned so that the tilt alignment direction of the liquid crystal is substantially parallel to the slit direction. Therefore, it is necessary to provide an orientation memory in which the tilt orientation direction is constant in the slit direction as the refractive anisotropy or the easy orientation axis of the polymer network. In the case of an axially symmetrical vertical alignment pattern electrode, it has a subpixel structure comprising a point electrode and a substantially square counter electrode. The central axis is vertically aligned even when a voltage is applied, but the liquid crystal director is radially inclined and aligned with the point electrode of the central axis as a starting point. When the device is viewed from above, the liquid crystal director is continuously oriented 360 degrees radially from the central axis. When a high voltage is applied to stabilize the alignment state in a part of the polymer network, a part of the polymer network is formed so that the radial inclined alignment direction is stabilized. By making the voltage less than the threshold voltage during the ultraviolet irradiation, the liquid crystal returns to a substantially vertical alignment. The formed radial orientation orientation can be left in the polymer network as a locus, and both orientation control when voltage is applied and vertical orientation when no voltage is applied can be achieved.

  That is, in the PVA liquid crystal display element, the refractive index anisotropy or the easy axis of alignment of the polymer network coincides with the liquid crystal alignment state in order to stabilize the alignment state obtained by applying a voltage higher than the threshold voltage. In order to stabilize the alignment state obtained by applying a voltage less than the threshold voltage, the polymer network is formed so that the refractive index anisotropy or the easy axis of alignment coincides with the liquid crystal alignment state. The coexistence of a polymer network that stabilizes the alignment state of two different liquid crystals in this case makes the influence of the formed polymer network different on the liquid crystal alignment. For example, if only the polymer network that stabilizes the alignment state of the liquid crystal below the threshold voltage is formed, when the alignment of the liquid crystal is changed by voltage switching, the alignment state of the liquid crystal affected by the polymer network is changed. Since the liquid crystal display element is different from the liquid crystal alignment state originally required, the alignment after the alignment transition in the switching of the PVA cell is distorted and the desired alignment state cannot be obtained, thereby affecting the electro-optic effect. As a result, contrast, transmittance and the like are lowered. Therefore, it is easy to change the alignment between the two states by coexisting two alignment states, the alignment state obtained by applying a voltage higher than the threshold voltage to the polymer network and the alignment state obtained by applying a voltage lower than the threshold voltage. And display characteristics are improved. Therefore, in order to stabilize the alignment state of the liquid crystal above the threshold voltage and the alignment state of the liquid crystal below the threshold voltage, and to form a polymer network so that the two alignment states are mixed, the polymerizability Part of the polymerizable compound contained in the liquid crystal composition is used for the purpose of stabilizing the alignment state of the liquid crystal above the threshold voltage, and the remaining polymerizable compound is used to stabilize the liquid crystal alignment state below the threshold voltage. It is preferable to use it for the polymer network formed. If a voltage lower than the threshold voltage is applied during UV polymerization after a voltage higher than the threshold voltage is applied, a transition of liquid crystal alignment occurs, but an alignment defect may occur during this transition, and this alignment defect stabilizes the polymer. If this is done, the uniformity of the alignment state of the liquid crystal below the threshold voltage is lost, which causes a decrease in contrast and transmittance. In particular, when the voltage equal to or higher than the threshold voltage is equal to or higher than the saturation voltage, many alignment defects occur when the liquid crystal alignment transition is caused by changing to a voltage lower than the threshold voltage during ultraviolet irradiation. For this reason, it is necessary to suppress the occurrence of alignment defects (disclinations) at the time of alignment transition by applying a voltage equal to or lower than the saturation voltage, but at the same time, as described above, the tilt of the liquid crystal at the substrate interface is weakened and tilted. Since the azimuth direction becomes unstable, it is not preferable. In order to suppress alignment defects caused by alignment transitions during UV polymerization, an intermediate voltage is applied to lower the voltage above the threshold voltage during UV polymerization to a voltage below the threshold voltage, and at least the response time of the liquid crystal It is preferably a time that does not affect the formation of the polymer network, and may be a time that can suppress the occurrence of alignment defects, and may be a time that does not stabilize the alignment defects in the liquid crystal. Depending on the reactivity of the polymerizable compound, it is preferably within 5 seconds. The intermediate voltage is preferably at least the threshold voltage and not more than the saturation voltage, and is preferably an intermediate gradation voltage. The waveform is preferably a rectangular wave, and is preferably a stepped waveform in which the voltage decreases stepwise in the order of a voltage that is equal to or higher than the threshold voltage, a voltage between, and a voltage that is equal to or lower than the threshold voltage. Further, the voltage between them may be a ramp wave that continuously decreases the voltage from a voltage higher than the threshold voltage to a voltage lower than the threshold voltage. Furthermore, in order to prevent alignment defects from remaining after the polymer is stabilized by a method other than applying an intermediate voltage, the voltage above the threshold voltage is cut off during UV irradiation, but UV irradiation is synchronized with voltage application. The voltage below the threshold voltage is applied again so that the alignment of the liquid crystal becomes substantially vertical alignment. At this time, it is sufficient to irradiate ultraviolet rays again in synchronization with the voltage. That is, in the case of continuously irradiating ultraviolet rays, an intermediate voltage may be applied at the time of transition of liquid crystal alignment during irradiation. In the case of intermittently irradiating ultraviolet rays, the ultraviolet irradiation may be interrupted for a moment when the liquid crystal alignment transitions, and the ultraviolet rays may be irradiated when the transition is completed.

  Furthermore, since the polymer network having the function of stabilizing each of these two different alignment states is mixed, the liquid crystal alignment state when no voltage is applied to the element after the polymer network is formed is two different alignment states. It is influenced by the polymer network to be held, and the liquid crystal alignment state when no voltage is applied is determined by the balance of influence of each polymer network. For example, in the liquid crystal display element of the vertical alignment mode, when the influence of the polymer network that stabilizes the liquid crystal alignment state below the threshold voltage is increased, the liquid crystal display element exhibits the vertical alignment originally required and the liquid crystal display This is preferable because the contrast is increased. Conversely, if the influence of the polymer network that stabilizes the alignment of the liquid crystal above the threshold voltage is too strong, the pretilt angle of the liquid crystal increases and the contrast decreases. In order to improve the display quality by increasing the transmittance and contrast of the liquid crystal display element, it is important to adjust the balance of the influence of each of the polymer networks that stabilize two different liquid crystal alignment states. If the influence of the polymer network acting to stabilize the alignment state of the liquid crystal above the threshold voltage is too strong, the maximum transmittance is improved, but the black level is increased and the contrast is lowered. Also, if the influence of the polymer network that acts to stabilize the alignment state of the liquid crystal below the threshold voltage is too strong, a good black level can be obtained, but this is not preferable because the maximum transmittance is lowered and the contrast is lowered.

Applying a voltage that tilts the liquid crystal such as bend alignment deformation to make the orientation of the liquid crystal tilt constant improves the maximum transmittance, so the liquid crystal alignment state above the threshold voltage is stabilized so that the tilt orientation is constant. The effect of the polymer network formed so as to be reduced is minimized, and the polymer network is stabilized so as to stabilize a substantially vertical alignment state in which a good black level can be obtained by applying a voltage less than the threshold voltage during ultraviolet irradiation. When formed, the favorable black level and the orientation of the tilted orientation become constant and the maximum transmittance increases, so that high contrast can be obtained and display quality is improved, which is preferable. At this time, in order to minimize the influence of the polymer network formed so that the tilt orientation is constant, the polymer network is formed by applying a voltage higher than the threshold voltage, and the tilt orientation is completely polymerized. It is preferable that the voltage application time is such that it is not stabilized, and it is sufficient to continue the ultraviolet irradiation so that a substantially vertical alignment is obtained when a voltage equal to or lower than the threshold voltage is applied during the ultraviolet irradiation.
[Method of manufacturing liquid crystal display element and action of polymer network]
The method for producing a liquid crystal display element according to the present invention involves applying ultraviolet light to a polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side while applying a voltage higher than the threshold voltage of the polymerizable liquid crystal composition. And a process of separating the polymerization phase and thereafter, a step of irradiating with ultraviolet rays by setting the voltage to less than a threshold voltage while irradiating with ultraviolet rays. As a result, a polymer network that stabilizes the alignment state of the liquid crystal above the threshold voltage and the alignment state of the liquid crystal that is less than the threshold voltage is formed, and the polymer network that stabilizes two different liquid crystal alignment states is mixed and formed. Is the method. Further, in the case of a vertical alignment mode liquid crystal display device including a pattern electrode cell, etc., in the step of vent alignment deformation in the step of irradiating with ultraviolet rays while applying a voltage higher than the threshold voltage of the polymerizable liquid crystal composition, The liquid crystal molecules in the polymerizable liquid crystal composition are aligned in the vicinity of the transparent substrate plane with an inclination of 0 to 30 degrees with respect to the transparent substrate plane, and the voltage is set to be lower than the threshold voltage while being irradiated with ultraviolet rays. Further, in the step of further irradiating with ultraviolet rays, it is preferable that the liquid crystal molecules are aligned substantially vertically and tilted in the vicinity of the transparent substrate plane at an angle of 80 to 90 degrees with respect to the transparent substrate plane. The state in which the liquid crystal molecules are aligned at an inclination in the range of 0 to 30 degrees with respect to the transparent substrate plane indicates a state in which the birefringence of the liquid crystal is increased by voltage application, and the alignment state of the liquid crystal is on the transparent substrate plane On the other hand, when it is 0 degree, the birefringence is maximized, which is preferable. However, an orientation inclined by 30 degrees with respect to the substrate plane is also preferable. In particular, the PVA cell is preferable because the tilt direction can be made constant. In any case, it is preferable to form a polymer network in which the orientation is stabilized so that the tilt orientation direction of the liquid crystal by voltage application becomes a constant direction.

  At this time, in order to make the influence of the polymer network formed so that the tilt orientation direction becomes constant, a voltage higher than the threshold voltage is applied during the ultraviolet irradiation to cause the liquid crystal to bend and deform. The time for this state is preferably shorter than the time for applying a voltage equal to or lower than the threshold voltage, and any state may be used as long as orientation transition occurs when voltage application equal to or higher than the threshold voltage is terminated. If the influence of the polymer network formed so that the tilt orientation is constant, the pretilt angle will increase and the required black level will not be obtained. When a voltage equal to or lower than the voltage is applied, the ultraviolet irradiation may be continued so as to transition from the bent alignment deformation to the substantially vertical alignment, and it is preferable that no polymerizable compound remains in the liquid crystal. It is preferable to form a main polymer network in the step of further irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays. At this time, the pretilt angle is determined by the ratio of the time for applying the voltage higher than the threshold voltage and the time for applying the voltage lower than the threshold voltage, and the time for applying the voltage higher than the threshold voltage is determined in the liquid crystal phase separation process. From the initial state where no polymer network is formed to the time when the polymerization phase separation starts and the polymer network is partially formed, the state where it is possible to return from the bend orientation deformation to the substantially vertical orientation when the voltage application is stopped It is preferable that The time for applying a voltage equal to or higher than the threshold voltage is preferably 1 to 15 seconds. When moving from this step to the next step, it is preferable to irradiate ultraviolet rays by applying a voltage below the threshold voltage in a state where the alignment transition to a substantially vertical alignment occurs, and the polymer network is completely formed and remains in the liquid crystal. It is preferable to eliminate the polymerizable compound. The state in which the voltage below the threshold voltage is applied is a substantially vertical alignment state, but it may be a slight bend alignment deformation, and the voltage is adjusted as necessary so that the required black level and tilt alignment orientation are constant. . The time for applying the voltage below the threshold voltage may be until the formation of the polymer network is almost completed, and even if the amount of monomer remaining in the liquid crystal is very small, the electro-optical characteristics are affected even if the residual monomer is polymerized. If not, it is not necessary to apply a voltage equal to or lower than the threshold voltage.

  Further, the ultraviolet ray is irradiated between the step of irradiating the ultraviolet ray while applying a voltage higher than the threshold voltage and separating the polymerization phase, and the step of irradiating the ultraviolet ray with the voltage lower than the threshold voltage while irradiating the ultraviolet ray. Alternatively, a step of applying a grayscale voltage that is at least the threshold voltage and less than or equal to the saturation voltage may be provided. The halftone voltage is preferably less than the applied voltage in the first step and more than or equal to the threshold voltage. The halftone voltage is applied for the purpose of delaying the transition from the bent orientation deformation to the substantially vertical orientation. Since the occurrence of alignment defects is suppressed by the delay effect, it is preferably applied as necessary.

  The state in which the liquid crystal molecules are aligned at a pretilt angle of 80 to 90 degrees with respect to the transparent substrate plane indicates that the birefringence is increased when the liquid crystal is aligned at 90 degrees with respect to the transparent substrate plane when no voltage is applied. Although it is minimized and useful for increasing the contrast of the liquid crystal display element, it is preferred that the pretilt angle is tilted within 89.9 to 85 degrees with respect to the substrate plane in order to incline in a certain direction when a voltage is applied. More preferably. If the angle exceeds 80 degrees with respect to the substrate plane, the birefringence increases and the amount of transmitted light increases, which is not preferable because the display contrast decreases, and the display black level becomes good at 85 degrees or more with respect to the substrate plane. This is preferable because high contrast can be obtained. Further, in an IPS (In-plane switching) display mode, FFS (Fringe Field Switching) mode, and TN (Twisted Nematic) mode liquid crystal display element, ultraviolet rays are applied while applying a voltage higher than the threshold voltage of the polymerizable liquid crystal composition. In the step of performing the polymerization phase separation by irradiation, the liquid crystal molecules in the polymerizable liquid crystal composition are aligned with an inclination in the range of 0 to 90 degrees depending on the applied voltage with respect to the transparent substrate plane, In the step of irradiating with ultraviolet light by setting the voltage below the threshold voltage while irradiating, the liquid crystal molecules are aligned at a pretilt angle of 0 to 30 degrees with respect to the transparent substrate plane depending on the applied voltage. It is also preferable.

  The liquid crystal molecules are inclined in the range of 0 to 90 degrees with respect to the transparent substrate plane, and the alignment forms a polymer network so as to stabilize the alignment state of the liquid crystal to which a voltage is applied. However, it is a precondition that when the voltage application is stopped, the alignment state of the liquid crystal corresponding to less than the threshold voltage is obtained. In the case of the IPS mode, the tilt angle of the properties of the alignment film used in the element greatly depends on the tilt angle, and may be in the range of 1 to 2 degrees. The tilt angle of the liquid crystal molecules including the twisted orientation is 0. .5 to 3 degrees is preferable, and 0 to 2 degrees is preferable. In the step of irradiating ultraviolet rays while applying a voltage higher than the threshold voltage of the polymerizable liquid crystal composition to separate the polymerization phase, it is preferable to apply a voltage that causes a state of torsional deformation. In the step of further irradiating the ultraviolet ray with the voltage lower than the threshold voltage, it is preferable to perform polymerization under the condition that the voltage is lower than the threshold voltage and the parallel alignment becomes black display in a state in which the torsional deformation is not stabilized. In the FFS mode, when a voltage higher than the threshold voltage is applied, the alignment state of the liquid crystal depends on the electric field distribution in the device, and the splay alignment, bend alignment, and twist alignment states coexist. Indicates. It is preferable that the tilt angle in the alignment state of the liquid crystal molecules in these states falls within the range of 0 to 45 degrees, and the same range is stabilized when the alignment is stabilized by the polymer network. However, when the voltage application is stopped, it is preferable that the alignment state of the liquid crystal corresponding to less than the threshold voltage is obtained, and it is preferable to return to the parallel alignment state from these states and irradiate ultraviolet rays. In the TN mode, the tilt angle is preferably in the range of 45 degrees to 90 degrees.

  On the other hand, a polymer network is formed so as to stabilize the alignment state of the liquid crystal by applying a voltage lower than the threshold voltage. In the IPS mode, FFS mode, and TN mode, the pretilt angle is applied to the substrate interface by rubbing alignment treatment. Therefore, it is preferable to form a polymer network so as to stabilize the alignment state of the liquid crystal to which a voltage less than the threshold voltage is applied, even if the liquid crystal alignment angle is inclined within this range. The tilt angle of the liquid crystal molecules including the twist orientation is preferably 0.5 to 3 degrees using other alignment processing methods such as a photo-alignment film, and a wide viewing angle is within 0 to 2 degrees. Useful and more preferred to obtain.

  Moreover, it is preferable that the voltage to be applied is an alternating current waveform, and the polymerizable liquid crystal composition has a frequency in a range showing dielectric anisotropy. The waveform is preferably a rectangular wave that can increase the effective voltage when the peak voltage is constant. The upper limit of the frequency may be a frequency that does not attenuate the signal transmitted to the pixel by the driving circuit used for the liquid crystal display element, and it is preferable that the frequency is at least 2 kHz or less. The frequency shown by the dielectric anisotropy in the frequency dependence of the dielectric constant exhibited by the polymerizable liquid crystal composition before ultraviolet irradiation may be 10 kHz or less. The lower limit value may be a frequency at which flicker occurs when the element is driven. In this case, the frequency may be any frequency that minimizes flicker, and is preferably at least 20 Hz or more.

  The method for producing a liquid crystal display element of the present invention is characterized in that a polymer network is formed so as to maintain two liquid crystal alignment states as described above. The polymer network is formed such that the refractive index anisotropy or the easy axis of alignment of the polymer network coincides with the liquid crystal alignment direction equal to or higher than the threshold voltage or the liquid crystal alignment direction lower than the threshold voltage. This creates a state in which the polymer network that stabilizes the alignment of the liquid crystal when a voltage is applied and the polymer network that stabilizes the alignment of the liquid crystal when no voltage is applied coexist, and the liquid crystal alignment when no voltage is applied It is possible to improve display characteristics such as an improvement in contrast by suppressing orientation distortion that occurs when orientation deformation is caused by voltage application from the state. On the other hand, only the polymer network formed so as to maintain the liquid crystal alignment state when no voltage is applied is formed so as to maintain the liquid crystal alignment below the threshold voltage when changing to the liquid crystal alignment state when the voltage is applied. Since the influence of the polymer network is strong, when the liquid crystal alignment state is shifted to a threshold voltage or higher, an alignment strain is applied to cause a decrease in transmittance. By forming a polymer network that stabilizes the alignment of the liquid crystal when a voltage is applied to a part of the polymer network, distortion of the alignment change caused by switching is suppressed, and the originally required change in liquid crystal alignment can be obtained and transmitted. The rate can be improved. The polymer network formed so as to stabilize the alignment state of each liquid crystal when a voltage is applied and when no voltage is applied is the refractive index anisotropy or alignment of the polymer network along the alignment of two different liquid crystals. It is characterized by forming an easy axis.

  Furthermore, the influence of the polymer network formed to stabilize the liquid crystal state above the threshold voltage changes depending on the application time of the voltage above the threshold voltage during UV irradiation, making it possible to change the electro-optical characteristics. Become. For example, when the polymer network is formed with the alignment state of the liquid crystal at the time of voltage application as a parallel alignment including a tilted alignment of 0 to 30 degrees with respect to the substrate plane, the voltage application time equal to or higher than the threshold voltage during ultraviolet irradiation is set. When shortened, the action to maintain the parallel alignment is small, so that the liquid crystal tends to align according to the action of the polymer network to maintain the vertical alignment. Furthermore, the influence of both orientations from the polymer network holding two different orientations is balanced, and a small pre-tilt angle of less than 1 degree is induced with respect to the normal direction of the transparent substrate. As the application time of the voltage above the threshold voltage during UV irradiation is increased, the influence of the polymer network that tries to maintain the parallel orientation becomes stronger, so the pretilt is based on the balance between the force that maintains the vertical orientation and the force that maintains the parallel orientation. The angle increases and the pretilt angle increases, and it becomes possible to make it 10 degrees or more with respect to the normal direction of the transparent substrate. Moreover, since the application time of a voltage equal to or higher than the threshold voltage during ultraviolet irradiation largely depends on the reactivity of the polymerizable liquid crystal composition used, it is preferable to appropriately adjust it so as to obtain a desired pretilt angle. In particular, it is preferable to obtain a pretilt angle in the range of 80 to 90 degrees with respect to the substrate plane, more preferably 85 to 89.9 degrees, and 87 to 89.9 degrees. Is more preferable.

  The polymer network formed to maintain the alignment state of the liquid crystal obtained by applying a voltage higher than the threshold voltage is a parallel alignment state in a vertical alignment mode liquid crystal display device using negative dielectric anisotropy. Alternatively, a tilted orientation with a constant azimuth is desirable. The alignment state obtained at a voltage lower than the threshold voltage is preferably a substantially vertical alignment, and in particular, a substantially vertical alignment of 80 to 90 degrees with respect to the substrate plane is preferable, and a good black level that provides high contrast is obtained. It is preferable that it is the orientation state which shows. In an IPS (In-plane switching) display mode by a lateral electric field using negative dielectric anisotropy or positive dielectric anisotropy, a liquid crystal obtained by applying a voltage higher than the threshold voltage during ultraviolet irradiation The orientation state is preferably twisted orientation. The alignment state obtained at a voltage lower than the threshold voltage is preferably parallel alignment with a constant azimuth angle. In FFS (Fringe Field Switching) mode, the alignment state obtained by applying a voltage higher than the threshold voltage during UV irradiation is at least one of bend alignment, splay alignment, tilt alignment, or a mixed alignment state. Preferably there is. When the voltage is lower than the threshold voltage, it is preferable to have a substantially parallel orientation. After forming the polymer network to maintain the alignment state of the liquid crystal when a voltage is applied, the polymer is stabilized after the formation of the polymer network by stabilizing the alignment state of the liquid crystal below the threshold voltage. The alignment state can be easily changed to the alignment state, and both high transmittance and high-speed response can be achieved.

  The applied voltage at the time of ultraviolet irradiation is preferably adjusted as appropriate so that the display of the liquid crystal display element after the formation of the polymer network has a high contrast, and greatly depends on the characteristics of the electro-optical effect of the polymerizable liquid crystal composition before the ultraviolet irradiation. Therefore, it is necessary to match the voltage-transmittance characteristics exhibited by the polymerizable liquid crystal composition. The voltage that is equal to or higher than the threshold voltage is preferably a voltage V10 that is 10% or more of the total change in transmittance in the voltage-transmittance characteristic voltage of the polymerizable liquid crystal composition, and the total change in transmittance. Is more preferably a voltage V20 or more at which 20% or more, and more preferably a voltage V50 or more at which the total change in transmittance is 50% or more. However, the voltage is preferably not more than 6 times the threshold voltage. As the voltage that is equal to or higher than the threshold voltage applied during the ultraviolet irradiation, an alternating voltage is preferably applied, and a rectangular wave is preferably applied. The frequency is preferably a frequency that cannot be visually recognized by the flicker, and when an electronic circuit such as a TFT substrate is formed on a glass substrate, it may be a frequency at which the polymerization voltage does not attenuate, and is 30 Hz to 5 kHz. It is preferable that there is a degree.

  The voltage applied in the middle of the ultraviolet irradiation is changed from the threshold voltage to less than the threshold voltage, but the voltage less than the threshold voltage may be in a range where the orientation of the liquid crystal does not change with the voltage. The voltage is preferably less than 80%, more preferably less than 80%, and even more preferably 70% or less. In addition, the applied voltage is set to the threshold voltage or lower during the ultraviolet irradiation, but at this time, it is preferable to return to the liquid crystal alignment state at the OFF time in the liquid crystal display element. For example, in the vertical alignment mode as described above. In other words, it may be returned to the vertical alignment, and in the FFS mode or the IPS mode, the parallel alignment may be used. In order to return to the liquid crystal alignment state when the liquid crystal display element is OFF, it is preferable that the influence of the polymer network that stabilizes the liquid crystal alignment during voltage application is lowered to a voltage lower than the threshold voltage in a slight state.

  The ultraviolet rays are irradiated after applying a voltage higher than the threshold voltage. However, if the voltage application time becomes longer during the ultraviolet irradiation, the influence of the polymer network that stabilizes the orientation of the liquid crystal during voltage application during the ultraviolet irradiation increases. It becomes unpreferable because it does not return to the liquid crystal alignment state when the required liquid crystal display element is OFF. Therefore, it is preferable to manufacture the liquid crystal display element of the present invention by appropriately optimizing the optimum voltage during ultraviolet irradiation. In addition, when the voltage during UV irradiation is made lower than the threshold voltage, the voltage is gradually lowered during UV irradiation in order to adjust the response relaxation time in the liquid crystal of the polymerizable liquid crystal composition, and the applied voltage is lowered. By making the time longer than the response relaxation time in the liquid crystal during ultraviolet irradiation, the influence of backflow that occurs in the response relaxation process may be minimized, and the applied voltage drop time ranges from 10 ms to 1000 ms. Is preferably within. On the contrary, it may be lowered quickly, and is preferably at least shorter than the relaxation time indicated by the polymerizable liquid crystal composition, preferably 100 ms or less.

  A polymer network of parallel alignment components is partially formed by irradiating with ultraviolet rays in a state where a voltage higher than the threshold voltage is applied, and the liquid crystal is returned to the vertical alignment by lowering the voltage below the threshold voltage while continuing the ultraviolet irradiation. This completes the polymerization phase separation. In the fishbone type liquid crystal cell, the pretilt angle can be changed by the ratio of the above-mentioned parallel alignment component and vertical alignment component. When the voltage is turned off in the initial stage of polymer network formation, the tilt alignment direction is determined and the vertical alignment is determined. By using the residual monomer, it becomes possible to achieve both the vertical alignment and the tilt alignment orientation, which is an alignment control technique in the nanophase separation liquid crystal.

  The parallel alignment state means that a negative dielectric anisotropic liquid crystal is in a substantially parallel alignment state when a voltage is applied, and is preferably in the range of 0.1 to 30 degrees with respect to the substrate surface. It is preferable that the tilt orientation is in the range of 1 to 10 degrees. The vertical alignment when no voltage is applied means that the vertical alignment film is brought into a substantially vertical alignment state. The alignment of the liquid crystal is inclined at 80 to 89.9 degrees with respect to the substrate plane. It is preferable that the angle is inclined from 85 degrees to 89.9 degrees.

In the case of a positive dielectric anisotropic liquid crystal, a vertical alignment is obtained when a voltage is applied, but the liquid crystal is tilted and aligned in the range of 45 to 89.9 degrees with respect to the substrate plane. It is also included.
The parallel alignment when no voltage is applied means that the parallel alignment film is brought into a substantially parallel alignment state. The alignment of the liquid crystal is tilted from 0.1 to 30 degrees with respect to the substrate plane. It is included.

  Therefore, the method for producing a liquid crystal display element according to the present invention includes a light irradiation step of irradiating a polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one, and at least one of the above. Applying a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition to the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes, and starting the light irradiation step It is preferable that the voltage in the voltage application step is applied at the time of the operation. Therefore, the voltage application step and the light irradiation step may be performed simultaneously, or the light irradiation step may be started after the voltage application step. Moreover, it is preferable to start the light irradiation process at the stage where the alignment defects generated at the time of alignment transition at the time of voltage application disappear.

  For example, in the case where alignment defects hardly occur during voltage application, the voltage application process and the light irradiation process may be started (or performed) at the same time, and the voltage application process and the light irradiation process are interrupted simultaneously. Alternatively, the light irradiation process may be performed in an ON state of the liquid crystal element, and the voltage application process may be interrupted immediately before the ON state alignment is stabilized by forming a polymer network in the middle of the polymerization process. In the OFF state, only the light irradiation process is performed so that no polymerizable compound remains in the liquid crystal. Moreover, it is preferable to interrupt the ultraviolet irradiation so that a polymer network is not formed during the orientation transition from the ON state to the OFF state.

  Irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side with ultraviolet rays in a state where a voltage higher than the threshold voltage of the polymerizable liquid crystal composition is applied, the polymerizable liquid crystal There may be a period (time) during which a voltage higher than the threshold voltage of the composition is applied. In other words, the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side is irradiated with ultraviolet rays while applying a voltage higher than the threshold voltage of the polymerizable liquid crystal composition to cause polymerization phase separation. In the process, the light irradiation process may be performed during the voltage application process, and it is preferable that the period of the light irradiation process and the period of the voltage application process overlap.

  In a preferred embodiment of the method for producing a liquid crystal display element according to the present invention, in the light irradiation step of irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side with ultraviolet rays, the ultraviolet rays are irradiated. It is sufficient that the orientation transition from the ON state to the OFF state is possible, and the voltage application process is preferably 3 to 30 seconds, more preferably 5 to 10 seconds. It is preferable to provide an interruption period of ultraviolet irradiation immediately after the end. What is necessary is just to complete | finish the said light irradiation process by restarting ultraviolet irradiation in the state which the liquid crystal alignment transition process complete | finished and the alignment state balanced.

  In the method for producing a liquid crystal display device according to the present invention, two sheets having electrodes on at least one of the polymerizable liquid crystal compositions sandwiched between two transparent substrates having electrodes on at least one side are irradiated from the time for irradiating ultraviolet rays. It is preferable that the time during which a voltage higher than the threshold voltage of the polymerizable liquid crystal composition is applied to the polymerizable liquid crystal composition sandwiched between the transparent substrates is shorter.

In the method for manufacturing a liquid crystal display device according to the present invention, a voltage equal to or higher than the threshold voltage of the polymerizable liquid crystal composition is applied to the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side. The voltage application step may be provided one or more times (two times, three times or more and ten times or less). The magnitude of the applied voltage at this time may be the same or different. Preferably they are different. As a form of the voltage application step, the polymerizable liquid crystal composition is used as a primary voltage in a state where the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side is irradiated with ultraviolet rays. after the threshold voltage or more primary voltage (V ₁₎ is applied a predetermined time, applied in a state in which irradiation with ultraviolet rays, be a threshold voltage above the primary voltage (V ₁₎ following intermediates voltage (V _m) Form is preferred.

  In the method for producing a liquid crystal display device according to the present invention, the voltage application step of applying a voltage not higher than the threshold voltage of the polymerizable liquid crystal composition in the state of being irradiated with ultraviolet rays is performed once or more times (twice, 3 times or more 10 times). Or less). The magnitude of the applied voltage at this time may be the same or different. In addition, when applying a voltage lower than the threshold voltage, the applied voltage may be lowered stepwise to a voltage lower than the threshold voltage or may be lowered continuously to a voltage lower than the threshold voltage.

  In the above preferred embodiment, when a voltage lower than the threshold voltage is applied during ultraviolet polymerization after applying a voltage equal to or higher than the threshold voltage, a transition of liquid crystal alignment occurs, but an alignment defect may occur during this transition. If the defect is stabilized, the uniformity of the alignment state of the liquid crystal below the threshold voltage is lost, which causes a decrease in contrast and transmittance. In particular, when the voltage equal to or higher than the threshold voltage is equal to or higher than the saturation voltage, many alignment defects occur when the liquid crystal alignment transition is caused by changing to a voltage lower than the threshold voltage during ultraviolet irradiation. For this reason, it is necessary to suppress the occurrence of alignment defects (disclinations) at the time of alignment transition by applying a voltage equal to or lower than the saturation voltage, but at the same time, as described above, the tilt of the liquid crystal at the substrate interface is weakened and tilted. Since the azimuth direction becomes unstable, it is not preferable. In order to suppress alignment defects caused by alignment transitions during UV polymerization, an intermediate voltage is applied to lower the voltage above the threshold voltage during UV polymerization to a voltage below the threshold voltage, and at least the response time of the liquid crystal It is preferably a time that does not affect the formation of the polymer network, and may be a time that can suppress the occurrence of alignment defects, and may be a time that does not stabilize the alignment defects in the liquid crystal. Depending on the reactivity of the polymerizable compound, it is preferably within 5 seconds. The intermediate voltage is preferably at least the threshold voltage and not more than the saturation voltage, and is preferably an intermediate gradation voltage. The waveform is preferably a rectangular wave, and is preferably a stepped waveform in which the voltage decreases stepwise in the order of a voltage that is equal to or higher than the threshold voltage, a voltage between, and a voltage that is equal to or lower than the threshold voltage. Further, the voltage between them may be a ramp wave that continuously decreases the voltage from a voltage higher than the threshold voltage to a voltage lower than the threshold voltage. Furthermore, in order to prevent alignment defects from remaining after the polymer is stabilized by a method other than applying an intermediate voltage, the voltage above the threshold voltage is cut off during UV irradiation, but UV irradiation is synchronized with voltage application. The voltage below the threshold voltage is applied again so that the alignment of the liquid crystal becomes substantially vertical alignment. At this time, it is sufficient to irradiate ultraviolet rays again in synchronization with the voltage. That is, in the case of continuously irradiating ultraviolet rays, an intermediate voltage may be applied at the time of transition of liquid crystal alignment during irradiation. In the case of intermittently irradiating ultraviolet rays, the ultraviolet irradiation may be interrupted for a moment when the liquid crystal alignment transitions, and the ultraviolet rays may be irradiated when the transition is completed.

  It is preferable to form a polymer network in which the alignment is stabilized so that the tilt alignment direction of the liquid crystal by voltage application becomes a constant direction. At this time, in order to make the influence of the polymer network formed so that the tilt orientation direction becomes constant, a voltage higher than the threshold voltage is applied during the ultraviolet irradiation to cause the liquid crystal to bend and deform. The time for this state is preferably shorter than the time for applying a voltage equal to or lower than the threshold voltage, and any state may be used as long as orientation transition occurs when voltage application equal to or higher than the threshold voltage is terminated. If the influence of the polymer network formed so that the tilt orientation is constant, the pretilt angle will increase and the required black level will not be obtained. When a voltage equal to or lower than the voltage is applied, the ultraviolet irradiation may be continued so as to transition from the bent alignment deformation to the substantially vertical alignment, and it is preferable that no polymerizable compound remains in the liquid crystal. It is preferable to form a main polymer network in the step of further irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays. At this time, the pretilt angle is determined by the ratio of the time for applying the voltage higher than the threshold voltage and the time for applying the voltage lower than the threshold voltage, and the time for applying the voltage higher than the threshold voltage is determined in the liquid crystal phase separation process. From the initial state where no polymer network is formed to the time when the polymerization phase separation starts and the polymer network is partially formed, the state where it is possible to return from the bend orientation deformation to the substantially vertical orientation when the voltage application is stopped It is preferable that The time for applying a voltage equal to or higher than the threshold voltage is preferably 1 to 15 seconds. When moving from this step to the next step, it is preferable to irradiate ultraviolet rays by applying a voltage below the threshold voltage in a state where the alignment transition to a substantially vertical alignment occurs, and the polymer network is completely formed and remains in the liquid crystal. It is preferable to eliminate the polymerizable compound. The state in which the voltage below the threshold voltage is applied is a substantially vertical alignment state, but it may be a slight bend alignment deformation, and the voltage is adjusted as necessary so that the required black level and tilt alignment orientation are constant. . The time for applying the voltage below the threshold voltage may be until the formation of the polymer network is almost completed, and the amount of monomer remaining in the liquid crystal is very small, and even if the remaining monomer is polymerized, the electro-optical characteristics are not affected. In this case, it is not necessary to apply a voltage equal to or lower than the threshold voltage.

  Further, the ultraviolet ray is irradiated between the step of irradiating the ultraviolet ray while applying a voltage higher than the threshold voltage and separating the polymerization phase, and the step of irradiating the ultraviolet ray with the voltage lower than the threshold voltage while irradiating the ultraviolet ray. Alternatively, a step of applying a grayscale voltage that is at least the threshold voltage and less than or equal to the saturation voltage may be provided. The halftone voltage is preferably less than the applied voltage in the first step and more than or equal to the threshold voltage. The halftone voltage is applied for the purpose of delaying the transition from the bent orientation deformation to the substantially vertical orientation. Since the occurrence of alignment defects is suppressed by the delay effect, it is preferably applied as necessary.

  One preferred embodiment of the method for producing a liquid crystal display element according to the present invention includes a light irradiation step of irradiating a polymerizable liquid crystal composition sandwiched between two transparent substrates each having an electrode on at least one side, with an ultraviolet ray. A voltage application step of applying a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition, and the light irradiation step is started during the voltage application step, and the voltage is made lower than the threshold voltage while being irradiated with ultraviolet rays. And a step of irradiating with ultraviolet rays. Further, the polymerizable liquid crystal composition is more than the threshold voltage of the polymerizable liquid crystal composition with respect to the polymerizable liquid crystal composition from the time of irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side with ultraviolet rays. It is preferable that the time for applying the voltage is shorter.

  Thereby, it is possible to make a transition from an alignment state having a threshold voltage or more to an alignment state having a threshold voltage or less, and it is possible to irradiate ultraviolet light to the alignment state of two liquid crystals.

  A modification of the preferred embodiment described above includes a light irradiation step of irradiating a polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side, and a threshold value of the polymerizable liquid crystal composition. A first voltage application step of applying a first voltage (V1) equal to or higher than the voltage, and a second voltage (V2) equal to or higher than a threshold voltage of the polymerizable liquid crystal composition and lower than the first voltage (V1). A second voltage application step, wherein the light irradiation step is started during the first voltage application step and / or the second voltage application step, and the voltage is set to be lower than the threshold voltage while being irradiated with ultraviolet rays. And a step of irradiating with ultraviolet rays. Further, the polymerizable liquid crystal composition is more than the threshold voltage of the polymerizable liquid crystal composition with respect to the polymerizable liquid crystal composition from the time of irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side with ultraviolet rays. It is preferable that the time for applying the voltage is shorter.

  One of other preferred embodiments of the production method according to the present invention is that the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side is equal to or higher than the threshold voltage of the polymerizable liquid crystal composition. A voltage application step for applying a voltage of the light, and a light irradiation step in which the light irradiation step is started during the voltage application step, and the polymerizable liquid crystal composition is irradiated with ultraviolet rays. A process for producing a liquid crystal display element comprising: a step of interrupting ultraviolet irradiation, wherein the process includes an interruption period of ultraviolet irradiation; Further, the polymerizable liquid crystal composition is more than the threshold voltage of the polymerizable liquid crystal composition with respect to the polymerizable liquid crystal composition from the time of irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side with ultraviolet rays. It is preferable that the time for applying the voltage is shorter. As a result, a polymer network that maintains an orientation state that is equal to or higher than the threshold voltage is formed, but the influence can be made slight, and a polymer network that maintains a state that is equal to or lower than the threshold voltage is mainly formed. It is possible and preferable. Furthermore, in the manufactured liquid crystal element, it is possible to switch between two states of an alignment state having a threshold voltage or higher and an alignment state having a threshold voltage or lower. When the applied voltage time above the threshold voltage of the polymerizable liquid crystal composition is long, the alignment state above the threshold voltage is maintained, and it is impossible to return to the alignment state below the threshold voltage, and ON-OFF switching is obtained. It is not preferable because it is not possible.

  In a modification of the preferred embodiment, a voltage application step of applying a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition to the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side. And a light irradiation step in which the light irradiation step is started during the voltage application step, and the polymerizable liquid crystal composition is irradiated with ultraviolet rays, and the light irradiation step and the voltage application step. After stopping simultaneously, the said light irradiation process is restarted, a voltage is made less than a threshold voltage, and further irradiated with an ultraviolet-ray, irradiating with an ultraviolet-ray, It is a manufacturing method of the liquid crystal display element characterized by the above-mentioned. In addition, the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side is interrupted by irradiating with ultraviolet rays, but the polymerizable liquid crystal composition is applied to the polymerizable liquid crystal composition from the entire irradiation time. It is preferable that the time for applying a voltage equal to or higher than the threshold voltage of the composition is shorter. This is preferable because it is possible to prevent the alignment defect generated by the alignment transition from the threshold voltage to the threshold voltage or less from being held by the polymer network, and to obtain a high contrast and high-speed response liquid crystal element.

  One of other preferred embodiments of the production method according to the present invention is that the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side is equal to or higher than the threshold voltage of the polymerizable liquid crystal composition. A voltage applying step of applying a voltage of, a light irradiating step in which the light irradiation step is started during the voltage applying step, and irradiating the polymerizable liquid crystal composition with ultraviolet rays; To a third voltage (V3) lower than the threshold voltage, and further irradiating with ultraviolet rays, and to a fourth voltage (V4) lower than the third voltage (V3) lower than the threshold voltage while irradiating ultraviolet rays. And a step of further irradiating with ultraviolet rays. Further, the polymerizable liquid crystal composition is more than the threshold voltage of the polymerizable liquid crystal composition with respect to the polymerizable liquid crystal composition from the time of irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one side with ultraviolet rays. It is preferable that the time for applying the voltage is shorter.

  As a result, even if the orientation of the liquid crystal ON state and the orientation of the OFF state of the obtained liquid crystal element form a polymer network, it is possible to resemble the respective orientation states of the liquid crystal before polymerization, and a high-contrast and high-speed response is achieved. The liquid crystal element shown is obtained, which is preferable.

  Note that the scope of the present invention is not limited to the preferred embodiments of the present invention described above. In addition, the light irradiation step (including the first and second) and the voltage application step in the above are the same as the description of the step of polymerized phase separation according to the present invention, and thus are omitted here.

  The distance (d) between the substrates of the liquid crystal display element of the present invention is preferably in the range of 2 to 5 μm, more preferably 3.5 μm or less. In general, the birefringence is adjusted so that the product of the birefringence of the liquid crystal composition and the cell thickness is close to 0.275. In the polymerizable liquid crystal composition of the present invention, a polymer network is formed after the polymerization phase separation. Therefore, the birefringence of the liquid crystal display element when an electric field is applied is lowered due to the anchoring force action of the polymer network and the optical properties of the polymer network, so that it is included in the liquid crystal composition, the polymerization composition, or the polymerizable liquid crystal composition. The product of the birefringence (Δn) and the distance (d) between the substrates is particularly preferably in the range of 0.3 to 0.4 μm when the driving voltage is increased within about 5 V due to the formation of the polymer network. A range of 0.30 to 0.35 μm is more preferable for an increase within a range, and a range of 0.29 to 0.33 μm is particularly preferable for an increase within a drive voltage of 1 V. By making the product of the distance (d) between the substrates of the liquid crystal display element and the product of the birefringence (Δn) of the liquid crystal composition and the distance (d) between the substrates within the above ranges, the transmittance is limited to only low-molecular liquid crystals. It is possible to obtain a display that is relatively high and has a high-speed response and favorable color reproducibility. The birefringence of the liquid crystal composition used for the polymerizable liquid crystal composition may be set so that the product of the cell thickness (d) and the birefringence index (Δn) is 1 to 1.9 times with respect to 0.275. preferable.

The driving voltage of the liquid crystal display element of the present invention is not determined only by the dielectric anisotropy or elastic constant of the liquid crystal composition, but is greatly influenced by the anchoring force acting between the liquid crystal composition and the polymer interface.
For example, Japanese Patent Application Laid-Open No. 6-222320 discloses the relationship of the following formula as a description regarding the driving voltage of a polymer dispersed liquid crystal display element.

(Vth represents a threshold voltage, 1Kii and 2Kii represent elastic constants, i represents 1, 2, or 3, Δε represents dielectric anisotropy, and <r> represents a transparent polymer substance interface. (Indicates the average gap distance, A indicates the anchoring force of the transparent polymer substance to the liquid crystal composition, and d indicates the distance between the substrates having transparent electrodes.)

According to this, the driving voltage of the light-scattering liquid crystal display element is determined by the average gap spacing at the interface of the transparent polymer material, the distance between the substrates, the elastic constant / dielectric anisotropy of the liquid crystal composition, and the transparency with the liquid crystal composition. Determined by the anchoring energy between the conductive polymer materials.
Among these, parameters that can be controlled by the liquid crystal display device of the present invention are liquid crystal properties and anchoring force between polymers. Since the anchoring force largely depends on the molecular structure of the polymer and the molecular structure of the low-molecular liquid crystal, if a polymerizable compound having a strong anchoring force is selected, the response time can be shortened to 1.5 ms or less. At the same time, since the driving voltage increases to 30 V or more, it is preferable to appropriately select the liquid crystal compound and the polymerizable compound and adjust the composition so that the driving voltage is 30 V or less and the response speed is 1.5 ms or less. . It is preferable to adjust the composition so that the driving voltage and the response speed are balanced by appropriately blending a polymer precursor having a strong anchoring force and a polymer precursor having a weak anchoring force. On the other hand, as the physical properties of the liquid crystal composition required for lowering the driving voltage, it is particularly preferable that the dielectric anisotropy is 6 or more for the P-type liquid crystal and -3 or less for the N-type liquid crystal. . The birefringence is preferably 0.09 or more. Furthermore, it is more preferable to make the birefringence of the liquid crystal composition and the refractive index of the fibrous or columnar polymer network as close as possible to eliminate light scattering. However, since the retardation of the liquid crystal element is affected by the concentration of the polymer precursor, it is preferable to use the liquid crystal composition with an increased or decreased birefringence so that the necessary retardation can be obtained.

In the liquid crystal display device of the present invention, the above-mentioned liquid crystal composition is irradiated with energy rays while the temperature is set to −50 ° C. to 30 ° C., and a polymerizable compound is polymerized to have a refractive index anisotropy or an easy alignment axis. It is preferably obtained by forming a polymer network having a direction. The upper limit of the polymerization temperature is 30 ° C, preferably 20 ° C to -10 ° C. As will be described later in Examples, the present inventor has found that τd is further accelerated by low temperature polymerization and normal temperature polymerization depending on the composition of the polymerizable compound. This is because 1) the polymerization is performed in a state where the orientation degree of the liquid crystal molecules is increased at a low temperature, and 2) the phase separation is facilitated by reducing the compatibility between the polymer polymerized by the low temperature polymerization and the liquid crystal composition. The phase separation speed is increased and the gap distance of the polymer network becomes fine. 3) Even if a polymerizable compound having a relatively low anchoring force is used, the influence of the anchoring force seems to be strong because the gap gap is fine. This is thought to be due to the formation of a refractive index anisotropic polymer network.

Furthermore, in the liquid crystal display element of the present invention, the optical axis direction or the easy alignment axis direction of the polymer network or polymer binder having uniaxial refractive index anisotropy or easy alignment axis direction forms a pretilt angle with respect to the transparent substrate. It is preferable to adjust the strength of the electric field to control the orientation of the low-molecular liquid crystal, and by tilting it with respect to the substrate surface, the energy rays are applied while applying a voltage to the liquid crystal layer described above. It is preferable that the composition is obtained by polymerizing the polymerizable compound by irradiation to obtain a polymer having a refractive index anisotropy or an orientation easy axis direction in the liquid crystal composition. In the vertically oriented VA mode, a voltage is applied so that the pretilt angle is 20 degrees or less with respect to the normal direction of the substrate, and polymerization is performed, so that the portulsion currently used in the VA mode cell is used. This is particularly preferable because it not only has an effect corresponding to the fine polymer protrusions of the PSA liquid crystal, but also exhibits a high-speed response that cannot be realized by PSA. In addition, by applying an electric field direction from a plurality of directions to form a polymer, a multi-domain can be formed, and a viewing angle can be improved, which is more preferable. Furthermore, the alignment direction of the low-molecular liquid crystal is regulated by applying photo-alignment treatment or rubbing alignment treatment to the low-molecular liquid crystal to induce a pretilt angle at the substrate interface vertical alignment film interface. The occurrence of alignment defects is preferably suppressed, and it is also preferable to use a pattern electrode that is inclined in a plurality of directions or to perform the alignment treatment. The liquid crystal layer is applied with an alternating electric field in a temperature range of −50 ° C. to 30 ° C. as appropriate to a liquid crystal composition containing a polymerizable compound, and irradiated with ultraviolet rays or an electron beam, thereby providing refractive index anisotropy. Is formed in the liquid crystal so that the optical axis direction of the polymer network forms a pretilt angle with respect to the substrate surface. This pretilt angle is a liquid crystal element in which the polymer axis after polymerization is tilted with respect to the substrate surface when the polymer phase is separated in an alignment state induced by applying an electric field due to the dielectric anisotropy of the low-molecular liquid crystal It is more preferable that the polymerizable compound has a high molecular weight. Furthermore, it is also preferable to induce a pretilt angle by combining a polymer network obtained by stabilizing an alignment state to which a voltage is applied and a polymer network obtained by stabilizing an alignment state to which no voltage is applied.

  For the two substrates used in the liquid crystal display element of the present invention, a transparent material having flexibility such as glass or plastic can be used. 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 or a thin film diode 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. 1.5 to 10 μm is more preferable. When a polarizing plate is used, the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d is adjusted so that the contrast is maximized, and 1/550 nm is reduced depending on the display mode. It is preferable to make it 2 or 1/4. 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 columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. 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 polymerizable liquid crystal composition between two substrates, a normal vacuum injection method, an ODF method, or the like can be used. In the ODF liquid crystal display device manufacturing process, a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed. A liquid crystal display element can be produced by bonding a front plane and a back plane after dropping a predetermined amount of the polymerizable liquid crystal composition under air. The polymerizable liquid crystal composition used in the present invention can be suitably used because the liquid crystal / monomer composite material can be stably dropped in the ODF process.

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, ultraviolet rays or electron beams, which are active energy rays, 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. In addition, when polymerization is performed in a state where the polymerizable liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. . Moreover, for the liquid crystal composition containing a polymerizable compound,
While applying an alternating electric field to the polymerizable liquid crystal composition in a temperature range of −50 ° C. to 20 ° C., it is preferable to irradiate ultraviolet rays or electron beams. 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 100 Hz to 5 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 a horizontal electric field type 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.

As for the temperature at the time of irradiation, the polymerizable liquid crystal composition preferably has a temperature range of -50 ° C to 30 ° 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 be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and it is preferable to cut and use ultraviolet rays of less than 365 nm as necessary. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. 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 irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays.

(Horizontal electric field type)
First, a liquid crystal display element according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the liquid crystal display element of the present invention. A liquid crystal display element 10 according to an embodiment of the present invention includes a first substrate 2 having an alignment layer 4 formed on the surface thereof, a space away from the first substrate, and a photo-alignment layer formed on the surface. And a liquid crystal layer 5 filled between the first substrate 2 and the second substrate 7 and in contact with the pair of alignment layers, the alignment layer 4 (4a, 4b). ) And the first substrate 2 have an electrode layer 3 including a thin film transistor, a common electrode 22 and a pixel electrode as an active element.

  FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element. In FIG. 1, for convenience of explanation, each component is illustrated separately. As shown in FIG. 1, the configuration of the liquid crystal display element 10 according to the embodiment of the present invention is sandwiched between a first transparent insulating substrate 2 and a second transparent insulating substrate 7 that are arranged to face each other. A liquid crystal display element of a lateral electric field type (an FFS mode as one form of IPS as an example in the figure) having the polymerizable liquid crystal composition (or liquid crystal layer 5). The first transparent insulating substrate 2 has an electrode layer 3 formed on the surface on the liquid crystal layer 5 side. In addition, a pair that directly contacts the polymerizable liquid crystal composition constituting the liquid crystal layer 5 between the liquid crystal layer 5 and the first transparent insulating substrate 2 and the second transparent insulating substrate 7 to induce homogeneous alignment. The liquid crystal molecules in the polymerizable liquid crystal composition are aligned so as to be substantially parallel to the substrates 2 and 7 when no voltage is applied. As shown in FIGS. 1 and 3, the second substrate 7 and the first substrate 2 may be sandwiched between a pair of polarizing plates 1 and 8. Further, in FIG. 1, a color filter 6 is provided between the second substrate 7 and the alignment film 4. The liquid crystal display element according to the present invention may be a so-called color filter on array (COA), or a color filter may be provided between an electrode layer including a thin film transistor and a liquid crystal layer, or the thin film transistor. A color filter may be provided between the electrode layer containing and the second substrate.

  That is, the liquid crystal display element 10 of one embodiment of the present invention includes the first polarizing plate 1, the first substrate 2, the electrode layer 3 including a thin film transistor, the alignment film 4, and the polymerizable liquid crystal composition. The liquid crystal layer 5, the alignment film 4, the color filter 6, the second substrate 7, and the second polarizing plate 8 are sequentially stacked.

  The first substrate 2 and the second substrate 7 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. The two substrates 2 and 7 are bonded together by a sealing material and a sealing material such as an epoxy thermosetting composition disposed in the peripheral region, and in order to maintain the distance between the substrates, for example, Spacer columns made of resin formed by granular spacers such as glass particles, plastic particles, alumina particles, or the photolithography method may be arranged.

  FIG. 2 is an enlarged plan view of a region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 3 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 taken along the line III-III in FIG. As shown in FIG. 2, the electrode layer 3 including a thin film transistor formed on the surface of the first substrate 2 includes a plurality of gate lines 24 for supplying scanning signals and a plurality of data for supplying display signals. The wirings 25 are arranged in a matrix so as to cross each other. In FIG. 2, only a pair of gate lines 24 and a pair of data lines 25 are shown.

  A unit pixel of the liquid crystal display device is formed by a region surrounded by the plurality of gate lines 24 and the plurality of data lines 25, and the pixel electrode 21 and the common electrode 22 are formed in the unit pixel. A thin film transistor including a source electrode 27, a drain electrode 26, and a gate electrode 28 is provided in the vicinity of the intersection where the gate wiring 24 and the data wiring 25 intersect each other. The thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21. A common line (not shown) is provided in parallel with the gate wiring 24. The common line is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.

  A preferred embodiment of the structure of the thin film transistor is provided, for example, as shown in FIG. 3 so as to cover the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 and cover the substantially entire surface of the substrate 2. A gate insulating layer 12, a semiconductor layer 13 formed on the surface of the gate insulating layer 12 so as to face the gate electrode 11, and a protective layer provided to cover a part of the surface of the semiconductor layer 13 14, a drain electrode 16 provided so as to cover one side end of the protective layer 14 and the semiconductor layer 13 and to be in contact with the gate insulating layer 12 formed on the surface of the substrate 2, and the protection A source electrode 17 which covers the other side edge of the layer 14 and the semiconductor layer 13 and is in contact with the gate insulating layer 12 formed on the surface of the substrate 2; And 16 and the source electrode 17 insulating protective layer 18 provided to cover the, the it has. An anodic oxide film (not shown) may be formed on the surface of the gate electrode 11 for reasons such as eliminating a step with the gate electrode.

  Amorphous silicon, polycrystalline polysilicon, or the like can be used for the semiconductor layer 13, but when a transparent semiconductor film such as ZnO, IGZO (In—Ga—Zn—O), or ITO is used, it is caused by light absorption. It is also preferable from the viewpoint of suppressing the adverse effect of the optical carrier and increasing the aperture ratio of the element.

  Furthermore, an ohmic contact layer 15 may be provided between the semiconductor layer 13 and the drain electrode 16 or the source electrode 17 in order to reduce the width and height of the Schottky barrier. For the ohmic contact layer, a material in which an impurity such as phosphorus such as n-type amorphous silicon or n-type polycrystalline polysilicon is added at a high concentration can be used.

  The gate wiring 26, the data wiring 25, and the common line 29 are preferably metal films, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or an alloy thereof, and Al or an alloy thereof. It is particularly preferable to use this wiring. The insulating protective layer 18 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, silicon oxynitride film, or the like.

  In the embodiment shown in FIGS. 2 and 3, the common electrode 22 is a flat electrode formed on almost the entire surface of the gate insulating layer 12, while the pixel electrode 21 is an insulating protective layer 18 covering the common electrode 22. It is a comb-shaped electrode formed on the top. That is, the common electrode 22 is disposed at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are disposed so as to overlap each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or IZTO (Indium Zinc Tin Oxide). Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened by the unit pixel area increases, and the aperture ratio and transmittance increase.

  In addition, the pixel electrode 21 and the common electrode 22 have an interelectrode distance (also referred to as a minimum separation distance): R between the pixel electrode 21 and the common electrode 22 in order to form a fringe electric field between the electrodes. The distance between the first substrate 2 and the second substrate 7 is smaller than G. Here, the distance between electrodes: R represents the distance in the horizontal direction on the substrate between the electrodes. FIG. 3 shows an example in which the plate-shaped common electrode 22 and the comb-shaped pixel electrode 21 overlap each other, and therefore an example in which the inter-electrode distance: R = 0 is shown, and the minimum separation distance: R is the first substrate 2. The distance between the first substrate 7 and the second substrate 7 (ie, the cell gap) is smaller than G, so that a fringe electric field E is formed. Therefore, the FFS type liquid crystal display element can use a horizontal electric field formed in a direction perpendicular to a line forming the comb shape of the pixel electrode 21 and a parabolic electric field. The electrode width of the comb-shaped portion of the pixel electrode 21: l and the width of the gap of the comb-shaped portion of the pixel electrode 21: m are such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable to form. Further, the minimum separation distance R between the pixel electrode and the common electrode can be adjusted as the (average) film thickness of the gate insulating layer 12. In addition, unlike the liquid crystal display element according to the present invention, an inter-electrode distance (also referred to as a minimum separation distance) between the pixel electrode 21 and the common electrode 22: R is different from that of the first substrate 2 and the second substrate. The distance from the substrate 7 may be larger than G (IPS method). In this case, for example, a configuration in which comb-like pixel electrodes and comb-like common electrodes are provided alternately in substantially the same plane can be cited.

  A preferred form of the liquid crystal display element according to the present invention is preferably an FFS mode liquid crystal display element using a fringe electric field, and the shortest separation distance d between the common electrode 22 and the pixel electrode 21 is set to be the alignment film 4. When the distance is shorter than the shortest distance D between the substrates (distance between substrates), a fringe electric field is formed between the common electrode and the pixel electrode, and the horizontal and vertical alignments of the liquid crystal molecules can be used efficiently. In the case of the FFS mode liquid crystal display element of the present invention, when a voltage is applied to the liquid crystal molecules arranged so that the long axis direction is parallel to the alignment direction of the alignment layer, the pixel electrode 21 and the common electrode 22 are interposed. Parabolic electric field equipotential lines are formed up to the top of the pixel electrode 21 and the common electrode 22 and are arranged along the electric field in which the long axes of the liquid crystal molecules in the liquid crystal layer 5 are formed. Therefore, liquid crystal molecules can be driven even with a low dielectric anisotropy.

  In the color filter 6 according to the present invention, it is preferable to form a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 23 from the viewpoint of preventing light leakage. The color filter 6 is usually composed of one dot of video or image from three filter pixels of R (red), G (green), and B (blue). For example, these three filters are arranged in the extending direction of the gate wiring. Yes. The color filter 6 can be produced 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 onto 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 manufactured. In addition, a so-called color filter-on-array in which pixel electrodes provided with active elements such as TFTs and thin film diodes are provided on the substrate may be used.

  On the electrode layer 3 and the color filter 6, a pair of alignment films 4 that are in direct contact with the polymerizable liquid crystal composition constituting the liquid crystal layer 5 and induce homogeneous alignment are provided.

  In addition, the polarizing plate 1 and the polarizing plate 8 can be adjusted so that the viewing angle and the contrast are good by adjusting the polarization axis of each polarizing plate, so that their transmission axes operate in a normally black mode. In addition, it is preferable to have transmission axes perpendicular to each other. In particular, any one of the polarizing plate 1 and the polarizing plate 8 is preferably arranged so as to have a transmission axis parallel to the alignment direction of the liquid crystal molecules. Further, 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. Furthermore, a retardation film for widening the viewing angle can also be used.

  As another embodiment of the liquid crystal display element, in the case of the IPS system, the shortest separation distance d between the adjacent common electrode and the pixel electrode is longer than the shortest separation distance G between the liquid crystal alignment films. The electrode and the pixel electrode are formed on the same substrate, and the common electrode and the pixel electrode are alternately arranged, and the shortest separation distance d between the adjacent common electrode and the pixel electrode is the liquid crystal alignment Examples include a structure longer than the shortest separation distance G between the films.

  In the method for manufacturing a liquid crystal display device according to the present invention, after a film is formed on the substrate having the electrode layer and / or the substrate surface, the pair of substrates are separated and faced so that the film is inside, and then the liquid crystal It is preferred to fill the composition between the substrates. In that case, it is preferable to adjust the space | interval of a board | substrate through a spacer.

  It is preferable to adjust the distance between the substrates (the average thickness of the obtained liquid crystal layer, which is also referred to as a separation distance between the coatings) to be 1 to 100 μm. The average separation distance between the films is more preferably 1.5 to 10 μm.

  In the present invention, examples of the spacer used for adjusting the distance between the substrates include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.

  The FFS type liquid crystal display element described with reference to FIGS. 1 to 3 is an example, and can be implemented in various other forms without departing from the technical idea of the present invention.

Another embodiment of the liquid crystal display element according to the present invention will be described below with reference to FIGS.
For example, FIG. 4 is another embodiment of the plan view in which the region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 1 is enlarged. As shown in FIG. 4, the pixel electrode 21 may have a slit. Further, the slit pattern may be formed so as to have an inclination angle with respect to the gate wiring 24 or the data wiring 25.

  The pixel electrode 21 shown in FIG. 4 has a shape in which a substantially rectangular flat plate electrode is cut out by a substantially rectangular frame-shaped notch. Further, a comb-like common electrode 22 is formed on one surface of the back surface of the pixel electrode 21 via an insulating protective layer 18 (not shown). When the shortest separation distance R between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the FFS method is used. The surface of the pixel electrode is preferably covered with a protective insulating film and an alignment film layer. Similarly to the above, a storage capacitor 23 for storing a display signal supplied via the data line 25 may be provided in an area surrounded by the plurality of gate lines 24 and the plurality of data lines 25. The shape of the notch is not particularly limited, and is not limited to the substantially rectangular shape shown in FIG. 4, and a notch having a known shape such as an ellipse, a circle, a rectangle, a rhombus, a triangle, or a parallelogram. Can be used. When the shortest separation distance R between the adjacent common electrode and the pixel electrode is longer than the shortest separation distance G between the alignment layers, an IPS display device is obtained.

  FIG. 5 is another embodiment different from FIG. 3, and is another example of a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut along the line III-III in FIG. The first substrate 2 having the alignment layer 4 and the electrode layer 3 including the thin film transistor 20 formed on the surface thereof and the second substrate 8 having the alignment layer 4 formed on the surface thereof face each other at a predetermined distance D. The liquid crystal layer 5 containing the liquid crystal composition is filled in this space. A gate insulating layer 12, a common electrode 22, an insulating protective layer 18, a pixel electrode 21, and an alignment layer 4 are stacked in this order on part of the surface of the first substrate 2. As shown in FIG. 4, the pixel electrode 21 has a shape in which the center and both ends of the flat plate are cut out by a triangular cutout, and the remaining region is cut out by a rectangular cutout. In addition, the common electrode 22 has a structure in which a comb-like common electrode is disposed on the first substrate side from the pixel electrode substantially in parallel with the substantially elliptical cutout portion of the pixel electrode 21.

  In the example shown in FIG. 5, the common electrode 22 having a comb shape or a slit is used, and the interelectrode distance between the pixel electrode 21 and the common electrode 22 is R = α (in FIG. 5, for convenience, the interelectrode distance is horizontal. Ingredients are listed as R). Further, FIG. 3 shows an example in which the common electrode 22 is formed on the gate insulating layer 12, but as shown in FIG. 5, the common electrode 22 is formed on the first substrate 2, The pixel electrode 21 may be provided through the gate insulating layer 12. The electrode width of the pixel electrode 21: l, the electrode width of the common electrode 22: n, and the interelectrode distance: R are appropriately adjusted to such a width that all liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable. When the shortest separation distance R between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the FFS method is used, and when it is longer, the IPS method is used. Further, in FIG. 5, the positions in the thickness direction of the pixel electrode 21 and the common electrode 22 are different.

(Vertical electric field type)
Another preferred embodiment of the present invention is a vertical electric field type liquid crystal display device using a liquid crystal composition. FIG. 6 is a diagram schematically showing a configuration of a vertical electric field type liquid crystal display element. Moreover, in FIG. 7, for convenience of explanation, each component is illustrated separately. FIG. 7 is an enlarged plan view of a region surrounded by a line VII of an electrode layer 300 including a thin film transistor (or also referred to as a thin film transistor layer 300) formed on the substrate in FIG. 8 is a cross-sectional view of the liquid crystal display element shown in FIG. 6 taken along the line VIII-VIII in FIG. Hereinafter, a vertical electric field type liquid crystal display device according to the present invention will be described with reference to FIGS.

The liquid crystal display element 1000 according to the present invention includes a second substrate 800 provided with a transparent electrode (layer) 600 (also referred to as a common electrode 600) made of a transparent conductive material, as shown in FIG. A first substrate 200 including a thin film transistor layer 300 on which a pixel electrode made of a transparent conductive material and a thin film transistor for controlling the pixel electrode included in each pixel are formed; and the first substrate 200 and the second substrate 800 The polymerizable liquid crystal composition (or the liquid crystal layer 500) is sandwiched between the liquid crystal molecules in the polymerizable liquid crystal composition, and the alignment when no voltage is applied is substantially perpendicular to the substrates 200 and 800. This is a liquid crystal display element. As shown in FIGS. 6 and 8, the second substrate 800 and the first substrate 200 may be sandwiched between a pair of polarizing plates 100 and 900. Further, in FIG. 6, a color filter 700 is provided between the first substrate 200 and the common electrode 600. Furthermore, a pair of alignment films 400 are formed on the surfaces of the transparent electrodes (layers) 600 and 1400 so as to be adjacent to the liquid crystal layer 500 according to the present invention and in direct contact with the polymerizable liquid crystal composition constituting the liquid crystal layer 500. Yes.
That is, the liquid crystal display element 1000 according to the present invention includes a first polarizing plate 100, a first substrate 200, an electrode layer (also referred to as a thin film transistor layer) 300 including a thin film transistor, a photo-alignment film 400, and a liquid crystal composition. A layer 500 containing an object, an alignment film 400, a common electrode 600, a color filter 700, a second substrate 800, and a second polarizing plate 900 are sequentially stacked. The alignment film 400 is preferably a photo-alignment film.

  The alignment film is a liquid crystal cell manufactured using alignment treatment (mask rubbing or photo-alignment), and is slightly inclined from the normal direction of the glass substrate on the inner side (liquid crystal layer side) of the transparent electrode of the liquid crystal cell ( 0.1 to 5.0 °) a vertical alignment film is formed.

In response to the alignment regulating force of the vertical alignment film, the polymerizable monomers are arranged in the vertical direction, and the polymerizable monomer is polymerized and fixed by irradiation with ultraviolet light to form a polymer network. The polymer network formed in this manner is (1) a polymer network that extends over the upper and lower substrates, (2) a polymer network that is formed from the upper (lower) substrate toward the liquid crystal direction, but halfway, ( 3) A polymer network is formed only near the surface of the alignment film. (Mainly in the case of a monofunctional monomer), (4) It is presumed to have approximately four types of structures in which polymer networks are bonded (not floating) in the liquid crystal layer. In any of these forms, the refractive index anisotropy or easy orientation axis of the polymer network is formed to stabilize the alignment state above the threshold voltage, and stabilize the alignment state below the threshold voltage. The polymer network which stabilizes two different orientation states formed so as to be mixed is mixed.
The polymer polymer network having anisotropy formed in this manner is almost completely separated from the liquid crystal layer, and the liquid crystal molecules are considered to be aligned between these polymer networks. The molecular alignment structure of the so-called polymer network type liquid crystal, in which liquid crystal molecules and polymer networks coexist and cause light scattering when no voltage is applied, is clearly different from that of the alignment maintaining layer that is unevenly distributed in the vicinity of the alignment film used in PSA etc. It has a completely different structure.
As an example, a polymer network and a liquid crystal molecular arrangement structure by a method using an alignment film are shown. On the other hand, in the so-called MVA method having structures such as ribs and slits, PVA, and the like, the polymer network near the substrate interface and the pretilt of liquid crystal molecules are somewhat affected by the oblique electric field strength applied through the structures and slits. It is only different, and is essentially assumed to have the structure shown in the above figure.
In the VA type liquid crystal display device having such a polymer network and liquid crystal molecule alignment by liquid crystal molecules, the anchoring force for the liquid crystal molecules when no voltage is applied is due to the synergistic action of the anchoring force of the liquid crystal alignment film and the polymer network. As a result, the response speed when the voltage is OFF can be increased.

(Horizontal / diagonal electric field type)
As a new display technology that can divide and align the liquid crystal display area by a simple method that only devise the electrode structure without performing complicated processes such as mask rubbing and mask irradiation on the alignment film, oblique and horizontal electric fields are liquid crystal. A method of acting on the layer has been proposed.

FIG. 11 is a plan view schematically showing a minimum unit structure in one pixel PX of a TFT liquid crystal display element using the above technique. The structure and operation of the horizontal / diagonal electric field mode liquid crystal display device will be briefly described below.
The pixel electrode PE has a main pixel electrode PA and a sub-pixel electrode PB. The main pixel electrode PA and the sub-pixel electrode PB are electrically connected to each other, and both the main pixel electrode PA and the sub-pixel electrode PB are provided on the array substrate AR. The main pixel electrode PA extends along the second direction Y, and the subpixel electrode PB extends along the first direction X different from the second direction Y. In the illustrated example, the pixel electrode PE is formed in a substantially cross shape. The sub-pixel electrode PB is coupled to a substantially central portion of the main pixel electrode PA, and extends from the main pixel electrode PA toward both sides thereof, that is, the left side and the right side of the pixel PX. The main pixel electrode PA and the sub-pixel electrode PB are substantially orthogonal to each other. The pixel electrode PE is electrically connected to a switching element (not shown) in the pixel electrode PB.

  The common electrode CE has a main common electrode CA and a sub-common electrode CB, and the main common electrode CA and the sub-common electrode CB are electrically connected to each other. The common electrode CE is electrically insulated from the pixel electrode PE. In the common electrode CE, at least a part of the main common electrode CA and the sub-common electrode CB is provided on the counter substrate CT. The main common electrode CA extends along the second direction Y. The main common electrode CA is disposed on both sides of the main pixel electrode PA. At this time, none of the main common electrodes CA overlaps with the main pixel electrode PA in the XY plane, and a substantially equal interval is formed between each of the main common electrodes CA and the main pixel electrode PA. Yes. That is, the main pixel electrode PA is located approximately in the middle of the adjacent main common electrode CA. The sub-common electrode CB extends along the first direction X. The sub-common electrode CB is disposed on both sides of the sub-pixel electrode PB. At this time, none of the sub-common electrodes CB overlaps the sub-pixel electrode PB in the XY plane, and a substantially equal interval is formed between each of the sub-common electrodes CB and the sub-pixel electrode PB. Yes. That is, the sub-pixel electrode PB is located approximately in the middle of the adjacent sub-common electrode CB.

  In the illustrated example, the main common electrode CA is formed in a strip shape extending linearly along the second direction Y. The sub-common electrode CB is formed in a strip shape extending linearly along the first direction X. Note that the two main common electrodes CA are arranged in parallel at intervals along the first direction X. In the following, in order to distinguish these, the main common electrode on the left side in the drawing is referred to as CAL. The right main common electrode is called CAR. Further, the two sub-common electrodes CB are arranged in parallel along the second direction Y at intervals, and in the following, in order to distinguish these, the upper main common electrode in the drawing is referred to as CBU. The lower main common electrode is called CBB. The main common electrode CAL and the main common electrode CAR are at the same potential as the sub-common electrode CBU and the sub-common electrode CBB. In the illustrated example, the main common electrode CAL and the main common electrode CAR are connected to the sub-common electrode CBU and the sub-common electrode CBB, respectively.

  The main common electrode CAL and the main common electrode CAR are respectively disposed between the pixel PX and pixels adjacent to the left and right. That is, the main common electrode CAL is disposed across the boundary between the illustrated pixel PX and the left pixel (not shown), and the main common electrode CAR is the illustrated pixel PX and the right pixel (not shown). ). The sub-common electrode CBU and the main common electrode CBB are disposed between pixels adjacent to the pixel PX in the vertical direction. That is, the sub-common electrode CBU is disposed across the boundary between the illustrated pixel PX and the upper pixel (not illustrated), and the sub-common electrode CBB is illustrated with the illustrated pixel PX and the lower pixel (not illustrated). Z)).

  In the illustrated example, in one pixel PX, four regions partitioned by the pixel electrode PE and the common electrode CE are mainly formed as openings or transmission portions that contribute to display. In this example, the initial alignment direction of the liquid crystal molecules LM is a direction substantially parallel to the second direction Y. The first alignment film AL1 is disposed on the surface of the array substrate AR that faces the counter substrate CT, and extends over substantially the entire active area ACT. The first alignment film AL1 covers the pixel electrode PE and is also disposed on the second interlayer insulating film 13. Such a first alignment film AL1 is formed of a material exhibiting horizontal alignment. The array substrate AR may further include a first main common electrode and a first sub-common electrode as part of the common electrode.

  FIG. 12 is a schematic diagram of an electrode structure of an eight-division oblique electric field mode liquid crystal cell. In this way, a wider viewing angle can be realized by dividing one pixel into eight.

  Next, the operation of the liquid crystal display panel having the above configuration will be described. When no voltage is applied to the liquid crystal layer, that is, when there is no electric field (OFF) when no electric field is formed between the pixel electrode PE and the common electrode CE, as shown by the broken line in FIG. The liquid crystal molecules LM of LQ are aligned such that the major axis thereof faces the first alignment processing direction PD1 of the first alignment film AL1 and the second alignment processing direction PD2 of the second alignment film AL2. Such OFF time corresponds to the initial alignment state, and the alignment direction of the liquid crystal molecules LM at the OFF time corresponds to the initial alignment direction. Strictly speaking, the liquid crystal molecules LM are not always aligned parallel to the XY plane, and are often pretilted. For this reason, the strict initial alignment direction of the liquid crystal molecules LM is a direction obtained by orthogonally projecting the alignment direction of the liquid crystal molecules LM in the OFF state on the XY plane.

  Both the first alignment treatment direction PD1 and the second alignment treatment direction PD2 are substantially parallel to the second direction Y. At the OFF time, the liquid crystal molecules LM are initially aligned so that the major axis thereof is oriented in a direction substantially parallel to the second direction Y, as indicated by a broken line in FIG. That is, the initial alignment direction of the liquid crystal molecules LM is parallel to the second direction Y (or 0 ° with respect to the second direction Y).

  As in the illustrated example, when the first alignment treatment direction PD1 and the second alignment treatment direction PD2 are parallel and in the same direction, the liquid crystal molecules LM in the cross section of the liquid crystal layer LQ are substantially horizontal in the vicinity of the intermediate portion of the liquid crystal layer LQ. Alignment is performed with a pretilt angle of approximately zero, and alignment is performed with a pretilt angle that is symmetrical in the vicinity of the first alignment film AL1 and the vicinity of the second alignment film AL2 (spray alignment). Thus, in the state in which the liquid crystal molecules LM are splay aligned, the liquid crystal molecules LM in the vicinity of the first alignment film AL1 and the liquid crystal molecules LM in the vicinity of the second alignment film AL2 in the direction inclined from the normal direction of the substrate Is optically compensated. Therefore, when the first alignment processing direction PD1 and the second alignment processing direction PD2 are parallel to each other and in the same direction, light leakage is small in the case of black display, and a high contrast ratio can be realized. It becomes possible to improve the quality. When the first alignment treatment direction PD1 and the second alignment treatment direction PD2 are parallel and opposite to each other, the liquid crystal molecules LM are in the vicinity of the first alignment film AL1, in the second alignment film AL2 in the cross section of the liquid crystal layer LQ. And in the middle part of the liquid crystal layer LQ with a substantially uniform pretilt angle (homogeneous alignment). Part of the backlight light from the backlight 4 passes through the first polarizing plate PL1 and enters the liquid crystal display panel LPN. The light incident on the liquid crystal display panel LPN is linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1. Such a polarization state of linearly polarized light hardly changes when it passes through the liquid crystal display panel LPN in the OFF state. Therefore, the linearly polarized light transmitted through the liquid crystal display panel LPN is absorbed by the second polarizing plate PL2 having a crossed Nicol positional relationship with the first polarizing plate PL1 (black display).

  On the other hand, in a state where a voltage is applied to the liquid crystal layer LQ, that is, in a state where a potential difference is formed between the pixel electrode PE and the common electrode CE (when ON), the substrate is interposed between the pixel electrode PE and the common electrode CE. A horizontal electric field (or an oblique electric field) substantially parallel to the line is formed. The liquid crystal molecules LM are affected by the electric field and rotate in a plane whose major axis is substantially parallel to the XY plane as indicated by the solid line in the figure.

  In the example shown in FIG. 11, the liquid crystal molecules LM in the lower half of the region between the pixel electrode PE and the main common electrode CAL rotate clockwise with respect to the second direction Y in the drawing. The liquid crystal molecules LM in the upper half region rotate counterclockwise with respect to the second direction Y and are oriented so as to face the upper left in the figure. Of the region between the pixel electrode PE and the main common electrode CAR, the liquid crystal molecules LM in the lower half region rotate counterclockwise with respect to the second direction Y and face the lower right in the drawing. The liquid crystal molecules LM in the upper half region are aligned so as to rotate clockwise with respect to the second direction Y and to face the upper right in the drawing. Thus, in each pixel PX, in a state where an electric field is formed between the pixel electrode PE and the common electrode CE, the alignment direction of the liquid crystal molecules LM is divided into a plurality of directions with the position overlapping the pixel electrode PE as a boundary. , A domain is formed in each orientation direction. That is, a plurality of domains are formed in one pixel PX.

At such ON time, linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1 is incident on the liquid crystal display panel LPN, and the polarization state is the alignment of the liquid crystal molecules LM when passing through the liquid crystal layer LQ. It changes according to the state. At such ON time, at least part of the light that has passed through the liquid crystal layer LQ is transmitted through the second polarizing plate PL2 (white display). According to such a structure, since four domains can be formed in one pixel, viewing angles in the four directions can be optically compensated, and a wide viewing angle can be achieved. Therefore, it is possible to provide a liquid crystal display device with high display quality, which can realize display with high transmittance without gradation inversion. Further, by setting the area of the opening portion to be substantially the same for each of the four regions partitioned by the pixel electrode PE and the common electrode CE within one pixel, the transmittance of each region becomes substantially equal, The light transmitted through the part optically compensates for each other, and a uniform display can be realized over a wide viewing angle range.
(Fishbone electrode)
14 shows a fishbone type electrode structure shown in FIG. A liquid crystal layer is sealed between two glass substrates bonded to each other with a predetermined cell gap. Transparent electrodes made of ITO are formed on the opposing surfaces of the two opposing substrates. A glass substrate having a thickness of about 0.7 mm is used, and a common electrode is used as the counter substrate. The transparent electrode is provided with a slit portion 512c from which a part of the electrode material (ITO) is removed. A slit portion 512c having a cross shape connecting the midpoints of the opposing sides of the rectangular cell and having a width of about 3 to 5 μm functions as an alignment regulating structure, and extends in a 45 ° oblique direction from the slit portion 512c and has a width of 5 μm. A plurality of 512c are formed with a pitch of 8 μm, and these function as an auxiliary orientation control factor that suppresses disturbance in the azimuth direction during tilting. The width of the display pixel electrode is 3 μm. The pixel trunk electrode 512a and the pixel branch electrode 512b have a structure in which branch electrodes are extended in four different directions by 90 degrees with the center of the pixel as the center of symmetry while having an angle of 45 degrees. The liquid crystal molecules are tilted when a voltage is applied, but tilted so that the orientation of the tilted alignment coincides with these four directions. Therefore, a four-divided domain is formed in one pixel to increase the display viewing angle. Make it wide.

  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”.

[Example 1]
A composition (Δn0.103, viscosity η16.5, Δε-3.1) represented by the following (LCN-1) was prepared as an N-type liquid crystal composition. The N-type liquid crystal composition (LCN-1) was heated to 60 ° C., and the solid polymerizable compound (V1-1-1) and the polymerizable compound (V1-1-2) were mixed and dissolved. It was confirmed with a polarizing microscope that the polymerizable compounds (V1-1-1) and (V1-1-2) were uniformly dissolved at room temperature to show a nematic liquid crystal phase. The polymerization photoinitiator Irgacure 651 was mixed with this solution to prepare a polymerizable liquid crystal composition. Table 1 shows a composition table of the adjusted polymerizable liquid crystal composition.

  A polymerizable liquid crystal composition obtained by using a fishbone pattern electrode vertical alignment (PVA) cell coated with a polyimide vertical alignment film having a cell gap of 3.6 μm so as to obtain uniaxial alignment (homogeneous alignment) of liquid crystal. Was injected into the cell by vacuum injection. The cell is provided with a large number of slits so that the liquid crystal is tilted and oriented in the slit direction by applying a voltage. Both the line electrode width and the slit width of the fishbone pattern electrode were 3.5 μm, and the length of the line electrode was 100 μm.

After the injection, the injection port was sealed with a sealing agent 3026E (manufactured by Three Bond). While applying a rectangular wave voltage of 2.45 V at a frequency of 1 kHz, using an ultraviolet LED light source with a wavelength of 365 nm, irradiating with an ultraviolet ray having an irradiation intensity of 15 mW / cm ² for 12 seconds, The voltage was returned to 0V to return to vertical alignment, and when the voltage was returned to 0V, ultraviolet rays were applied for 68 seconds to produce a fishbone type PVA cell. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed. The ultraviolet irradiation time was set to 80 seconds as a whole.

  After completing the UV irradiation, apply a voltage to the cell and place the slit direction at 45 degrees with respect to one of the two polarization axes of the crossed Nicol polarizing plate so that the bright field is the brightest. The liquid crystal alignment state was observed. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In this cell, in order to confirm the tilt alignment direction of the liquid crystal, the slit direction is set to the two polarization axes of the crossed Nicol polarizing plate so that the transmittance is minimized in the tilted alignment state by applying a voltage of 7.5V. It adjusted so that it might become parallel with either. As shown in the polarizing micrograph of FIG. 9, when the tilt orientation is aligned in the slit direction, a black line is observed to match the slit and the line electrode, but when the polarization direction and the slit direction are matched, the slit and the line electrode match. Innumerable black lines were observed, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction. From this, it can be seen that when the voltage is applied to the liquid crystal and the liquid crystal is tilted and oriented, the transmittance is improved because the liquid crystal is tilted in the slit direction.

  When voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 was 65%, which was close to the transmittance of 69% exhibited by the liquid crystal alone.

[Comparative Example 1]
In the same manner as in Example 1, the composition of Comparative Example 1 in Table 1 was injected into the cell. Before performing ultraviolet irradiation, a voltage of 15 V was applied and waited for several minutes until alignment defects disappeared. Thereafter, the voltage was set to 0V. Then, after confirming that the liquid crystal was uniformly aligned in the slit direction with a polarizing microscope, ultraviolet rays were irradiated for 80 seconds. After the irradiation, a voltage of 9V is applied to the cell in which the polymer network is formed, and the liquid crystal is tilted and aligned. When the polarization direction and the slit direction are aligned by observation with a polarizing microscope, a number of black lines are observed, and the orientation of the tilt alignment is It was observed that the portion aligned in the slit direction and the bright portion where the tilt orientation direction deviated from the slit direction were mixed, and the entire slit did not become a black line, and the tilt orientation direction was not uniform. When the transmittance was measured by gradually increasing the voltage, the maximum transmittance T100 was as low as 36.1%.
[Comparative Example 2-3]
In the same manner as in Example 1, the compositions of Comparative Examples 2 and 3 in Table 1 were injected into the cell. Before performing ultraviolet irradiation, a voltage of 15 V was applied to the cell and waited for several minutes until the alignment defect disappeared. Then, the voltage of Table 2 was applied to each cell, and it confirmed that the liquid crystal inclined-aligned uniformly to the slit direction with the polarizing microscope, and irradiated the ultraviolet-ray for 80 second, applying a voltage. In order to observe the orientation of the liquid crystal using a polarizing microscope, a voltage of 9 V is applied to the cell after the irradiation is completed, the liquid crystal is tilted and aligned, and the polarization direction and the slit direction are aligned, and innumerable black lines are partially observed. A portion where the orientation of the tilted alignment is aligned in the slit direction and a bright portion where the tilted orientation is out of the slit direction are mixed so that the entire slit does not become a black line, and the tilted orientation is not uniform. It was observed as in a polarizing micrograph of Comparative Example 2 shown in FIG. When the transmittance was measured by gradually increasing the voltage, the maximum transmittance T100 was 40.3% in Comparative Example 2 and 36.1% in Comparative Example 3, which was improved compared to Comparative Example 1, but the liquid crystal of the liquid crystal. The tilt orientation directions were all low in the slit direction.
[Comparative Example 4]
In the same manner as in Example 1, the composition of Comparative Example 4 in Table 1 was injected into the cell. Before performing ultraviolet irradiation, a voltage of 15 V was applied to the cell and waited for several minutes until the alignment defect disappeared. Thereafter, the voltage shown in Table 2 was applied to the cell, and it was confirmed that the liquid crystal was tilted and aligned uniformly in the slit direction with a polarizing microscope, and ultraviolet light was irradiated for 80 seconds while the voltage was applied. When the alignment of the liquid crystal is observed using a polarizing microscope, it shows a bright field when no voltage is applied, and when the minimum transmittance T0 is measured, the polymer network maintains an alignment state equal to or higher than the threshold voltage at 39.6%. The liquid crystal alignment state which is formed in a substantially parallel manner is stabilized, and black in the dark field cannot be obtained. When the voltage was applied and the maximum transmittance T100 was measured, it was 60.3%.
[Examples 2 to 5]
In the same manner as in Example 1, the compositions of Examples 2 to 5 in Table 1 were injected into the cell.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). The ultraviolet irradiation intensity of 15 mW / cm ² using a UV LED light source wavelength 365 nm, and irradiated for 80 seconds at 25 ° C.. After applying a rectangular wave of 2.39 V to 7.5 V at a frequency of 1 kHz as a voltage, adjusting the time appropriately for 5 to 15 seconds from the start of ultraviolet irradiation, the polymerization voltage is set to 0 V in a state where ultraviolet irradiation is performed, and the voltage is vertical. It returned to orientation and the fishbone type PVA cell was produced. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed.

  After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by arranging the slit direction at an angle of 45 degrees with respect to any of the crossed Nicols polarizing plates. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In order to confirm the tilt orientation, the slit direction was adjusted to the polarizing plate direction so that the transmittance was minimized by applying a voltage of 7.5 V to the tilt orientation state. Black lines were observed so as to coincide with the slits and the line electrodes when the tilt orientations were aligned in the slit direction. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction.

When voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 was 60% or more, which was close to the transmittance of 69% exhibited by the liquid crystal alone.
[Example 6]
In the same manner as in Example 1, the composition of Example 6 in Table 1 was injected into the cell.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). The ultraviolet irradiation intensity of 15 mW / cm ² using a UV LED light source wavelength 365 nm, and irradiated for 80 seconds at 25 ° C.. A rectangular wave of 2.45 V at a frequency of 1 kHz was applied as a voltage for 12 seconds from the start of ultraviolet irradiation, and then the voltage was changed to 0 V in the ultraviolet irradiation state to return to a vertical orientation to produce a fishbone type PVA cell. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed.

  After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by arranging the slit direction at an angle of 45 degrees with respect to any of the crossed Nicols polarizing plates. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In order to confirm the tilt orientation, the slit direction was adjusted to the polarizing plate direction so that the transmittance was minimized by applying a voltage of 7.5 V to the tilt orientation state. Even if the polymerizable compound and the liquid crystal composition were changed, a black line was observed so as to coincide with the slit and the line electrode when the tilted orientation was aligned in the slit direction. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction.

When voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 was 60% or more, which was close to the transmittance of 69% exhibited by the liquid crystal alone.
[Example 7]
In the same manner as in Example 1, the composition of Example 7 in Table 1 was injected into the cell.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). The ultraviolet irradiation intensity of 15 mW / cm ² using a UV LED light source wavelength 365 nm, and irradiated for 80 seconds at 25 ° C.. A rectangular wave of 2.45 V at a frequency of 1 kHz was applied as a voltage for 8 seconds from the start of ultraviolet irradiation, and then the voltage was changed to 0 V in the ultraviolet irradiation state to return to a vertical orientation to produce a fishbone type PVA cell. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed. After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by placing the slit so that the linear direction of the slit was 45 degrees oblique to any of the crossed Nicols polarizing plates. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In order to confirm the tilt orientation, the slit direction was adjusted to the polarizing plate direction so that the transmittance was minimized by applying a voltage of 7.5 V to the tilt orientation state. Even if the polymerizable compound and the liquid crystal composition were changed, a black line was observed so as to coincide with the slit and the line electrode when the tilted orientation was aligned in the slit direction. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction.

When voltage-transmittance characteristics were measured by applying a rectangular wave of 60 Hz, the maximum transmittance T100 was 65.4% or more, which was close to the transmittance of 69% exhibited by the liquid crystal alone.
[Example 8]
In the same manner as in Example 1, the composition of Example 8 in Table 1 was injected into the cell.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). Using an ultraviolet LED light source having a wavelength of 365 nm, ultraviolet rays having an irradiation intensity of 15 mW / cm ² were irradiated at 25 ° C. for 1200 seconds. After applying a rectangular wave of 3.4 V at a frequency of 1 kHz as a voltage for 100 seconds from the start of ultraviolet irradiation, the voltage was changed to 0 V in the state of ultraviolet irradiation, and the fishbone type PVA cell was fabricated. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed.

  In order to confirm the tilt orientation in the same manner as in Example 7, a voltage of 7.5 V was applied to enter the tilt orientation state, and the slit direction was aligned with the polarizing plate direction so that the transmittance was minimized. Even if the polymerizable compound and the liquid crystal composition were changed, a black line was observed so as to coincide with the slit and the line electrode when the tilted orientation was aligned in the slit direction. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction.

When voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 was 64.3%, which was close to the transmittance of 69% exhibited by the liquid crystal alone.
[Example 9]
In the same manner as in Example 1, the composition of Example 9 in Table 1 was prepared.

Parallel rubbing with ITO by applying a rubbing alignment process so that the pretilt angle is about 1 ° with respect to the normal direction of the substrate surface after applying a polyimide alignment film so that vertical alignment (homeotropic alignment) of the liquid crystal is obtained. Using the oriented cell, the obtained polymerizable liquid crystal composition was injected into the cell by a vacuum injection method. After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). Ultraviolet rays having an irradiation intensity of 15 mW / cm ² were irradiated at 25 ° C. for 80 seconds. After applying a rectangular wave of 12 V at a frequency of 1 kHz and changing the time from 2 to 10 seconds from the start of UV irradiation, the voltage is set to 0 V in the UV irradiation state to return to a vertical orientation, and the fishbone PVA cell is Produced. As a result, two differently oriented polymer networks were formed: a polymer network of parallel alignment components and a polymer network of vertical alignment components. After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by arranging the rubbing alignment axis direction parallel to any of the crossed Nicols polarizing plates.

  Cell numbers 1 and 2 are dark fields, and even if the cells are rotated in the azimuth direction, the black level of the dark field does not change and homeotropic alignment is achieved. The polymer network optical axis direction and the liquid crystal alignment easy axis direction are the cell planes. It was confirmed that it was formed to go straight to. Cell numbers 3 to 4 indicate that there are azimuths in which a dark field similar to cell numbers 1 and 2 is obtained even if the cells are rotated in the azimuth direction, and there are azimuths in which the dark field is slightly brightened. In cell number 5, unlike the other cells, even if the cell was rotated in the azimuth direction, there was no azimuth indicating a dark field, which was a little brighter than the dark fields of cell numbers 1 to 4. It was confirmed that the fall time is shortened by the effect of the anchoring force of the polymer network formed so that the polymer network optical axis direction and the liquid crystal alignment easy axis coincide. Cell numbers 1 to 5 were arranged at an angle of 45 degrees with respect to any of the crossed Nicols polarizing plates, and the liquid crystal alignment state of the cells was observed with a polarizing microscope. When no voltage was applied, a dark field (excluding cell number 5) was shown, and when the voltage was gradually increased, it changed to a bright field. The electro-optical characteristics were measured in this cell arrangement state, and the results are summarized in Table 3.

  When the voltage application time during ultraviolet irradiation was changed from 2 seconds to 10 seconds, the pretilt angle increased from 1.9 ° to 22.4 °. As the pretilt angle increased, Toff (relaxation time) increased from 3.8 ms to 7.7 ms, and minimum transmittance T0 increased from 0.01% to 5.26%. In particular, when the voltage application time was 10 seconds, T0 increased rapidly. On the other hand, the drive voltage V90 decreased from 8.1V to 5.5V. At the start of UV irradiation, a voltage of 12V indicating parallel alignment is applied to leave a trajectory of the polymer network that stabilizes the parallel alignment. When the voltage is set to 0 V during UV irradiation, a polymer network that stabilizes the vertical alignment is formed. However, the influence of (a) is increased as the voltage application time becomes longer as (a) a component that stabilizes parallel alignment and (b) a polymer network indicating a component that stabilizes vertical alignment is mixed. Increases and the pretilt angle increases. The results explain that the pretilt angle is determined by the balance between the anchoring force of the polymer network that is going to be parallel and the anchoring force of the polymer network that is going to be vertical. When the voltage application time is 10 seconds or more, the influence of (a) increases, and the contrast decreases in the direction of parallel orientation when T0 is 0.1% or more. When the polymerization voltage application time is 7 seconds or less, the influence of (a) is small, so that T0 is 0.1% or less and shows a good value and high contrast is obtained.

[Example 10]
The polymerizable liquid crystal composition of Example 6 was used, and the production of the cell was the same as in Example 7. As shown in Table 4, after stopping the ultraviolet irradiation after the voltage application time and measuring the voltage-transmittance characteristics during the ultraviolet irradiation, the remaining time was irradiated with the ultraviolet rays so that the total irradiation time was 80 seconds. Then, the voltage-transmittance characteristics after completion of ultraviolet irradiation were measured. By measuring the voltage-transmittance during UV irradiation, the influence of the polymer network showing (a) a component that stabilizes parallel alignment and (b) a component that stabilizes vertical alignment was investigated. Table 4 shows the voltage-transmittance characteristics and response time after voltage application in the same cell, and the voltage-transmittance characteristics and response time after UV irradiation for the remaining time with the polymerization voltage set to 0V. Comparing the voltage-transmittance characteristics (V90, T0, T100) after the voltage application of cell numbers 1 to 5 shows almost the same characteristics. Further, the voltage-transmittance characteristics (V90, T0, T100) after completion of ultraviolet irradiation are substantially the same. However, in cell number 6, T0 and the pretilt angle after voltage application are rapidly increased as compared with cell numbers 1-5. This is due to the increase in the parallel alignment stabilizing component of (a). Therefore, in order to obtain a dark field showing a good black level, it is necessary to appropriately adjust the polymerization voltage application time so that T0 does not increase. In Example 10, it is preferable that the polymerization application time is within 10 seconds. Comparing the voltage-transmittance characteristics after completion of ultraviolet irradiation of cell numbers 1 to 5, a good T0 of 0.1% or less was obtained, but cell number 6 was higher than T0 after the polymerization voltage application was completed. Further increasing, the influence of (a) is increasing. As a result, since the pretilt angle is large, the response time becomes long and it is not suitable for a display device. That is, in the case of a vertically aligned cell, by adjusting the polymerization voltage application time so that the black level is not sacrificed (0.1% or less), Toff becomes 4 ms or less and the maximum transmittance T100 is high. Transmittance characteristics are obtained.

[Example 11]
The polymerizable liquid crystal composition of Example 1 was used, and the production of the cell was performed in the same manner as in Example 1.

After the injection, the injection port was sealed with a sealing agent 3026E (manufactured by Three Bond). While applying a rectangular wave voltage of 2.45 V at a frequency of 1 kHz, using an ultraviolet LED light source with a wavelength of 365 nm, irradiating with an ultraviolet ray having an irradiation intensity of 15 mW / cm ² for 12 seconds, A voltage was set to 0.9 V to return to vertical alignment, and when the voltage was returned to 0.9 V, ultraviolet rays were applied for 68 seconds to produce a fishbone type PVA cell. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed.

  After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by arranging the slit direction at an angle of 45 degrees with respect to any of the crossed Nicols polarizing plates. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In order to confirm the tilt orientation, the slit direction was adjusted to the polarizing plate direction so that the transmittance was minimized by applying a voltage of 7.5 V to the tilt orientation state. Black lines were observed so as to coincide with the slits and the line electrodes when the tilt orientations were aligned in the slit direction. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction.

When voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 was 63% or more, which was close to the transmittance of 69% exhibited by the liquid crystal alone.
[Example 12-15]
In the same manner as in Example 1, the composition of Example 6 in Table 1 was injected into the cell.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). As the ultraviolet irradiation conditions, ultraviolet light having an irradiation intensity of 15 mW / cm ² was irradiated at 25 ° C. for 80 seconds using a light source of an ultraviolet LED having a wavelength of 365 nm. On the other hand, the voltage application condition is that, under the ultraviolet irradiation condition, a rectangular wave voltage is applied as a primary voltage described in Table 5 at a frequency of 1 kHz, applied for 6 seconds from the start of ultraviolet irradiation, and then irradiated with ultraviolet light. After applying the primary voltage shown in Table 5 for 1 second instead of the intermediate voltage shown in Table 5, the intermediate voltage shown in Table 5 is applied to the secondary voltage described in Table 5 below the liquid crystal threshold voltage while irradiating ultraviolet rays. A fishbone type PVA cell was prepared in a state where the vertical orientation was restored instead. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed.

After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by arranging the slit direction at an angle of 45 degrees with respect to any of the crossed Nicols polarizing plates. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In order to confirm the tilt orientation, the slit direction was adjusted to the polarizing plate direction so that the transmittance was minimized by applying a voltage of 7.5 V to the tilt orientation state. When the tilt alignment direction is aligned in the slit direction, a black line is observed so as to coincide with the slit and the line electrode, and it was confirmed that the alignment defects that sometimes occur when the voltage is turned off are not stabilized in the polymer. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction. When the voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 showed a value close to the transmittance of 69% exhibited by the liquid crystal alone as described in Table 5 Element Characteristics.
[Examples 16-18]
In the same manner as in Example 1, the composition of Example 6 in Table 1 was injected into the cell.

After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). The ultraviolet irradiation conditions were as follows: ultraviolet light having an irradiation intensity of 15 mW / cm ² was irradiated for 80 seconds at 25 ° C. using a light source of an ultraviolet LED having a wavelength of 365 nm, and an ultraviolet irradiation interruption period was provided as described later (in addition, ultraviolet irradiation) Is not included in 80 seconds). On the other hand, the voltage application condition is that, under the ultraviolet irradiation condition, a rectangular wave voltage is applied as a primary voltage described in Table 5 with a frequency of 1 kHz, applied for 10 seconds from the start of ultraviolet irradiation, and then the voltage and the ultraviolet light are simultaneously applied. The intermediate voltage shown in Table 5 was not applied, and the ultraviolet irradiation was interrupted for 1 second, and then only the ultraviolet rays were irradiated in a state of returning to the vertical alignment to produce a fishbone type PVA cell. As a result, a polymer network of parallel alignment components and a polymer network of vertical alignment components were formed.

After completion of the ultraviolet irradiation, the liquid crystal alignment state of the cell was observed with a polarizing microscope by arranging the slit direction at an angle of 45 degrees with respect to any of the crossed Nicols polarizing plates. It was confirmed that the state in which no voltage was applied was a completely vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased and applied, the slit portion changed from vertical alignment to inclined alignment and the brightness increased. In order to confirm the tilt orientation, the slit direction was adjusted to the polarizing plate direction so that the transmittance was minimized by applying a voltage of 7.5 V to the tilt orientation state. When the tilt alignment direction is aligned in the slit direction, a black line is observed so as to coincide with the slit and the line electrode, and it was confirmed that the alignment defects that sometimes occur when the voltage is turned off are not stabilized in the polymer. When the polarization direction and the slit direction were matched, innumerable black lines were observed so as to coincide with the slit and the line electrode, and it was confirmed that the orientation of the tilted alignment was aligned in the slit direction. When voltage-transmittance characteristics were measured by applying a 60 Hz rectangular wave, the maximum transmittance T100 showed a value close to the transmittance of 69% exhibited by a single liquid crystal as shown in Table 5.
(Table 5 Production conditions)

(Table 6 Device characteristics)

  In the present specification and examples, the abbreviation “Gap” in the table of the examples is cell gap (μm), “V90” is drive voltage (V)), Ton (turn-on time in milliseconds), Toff (turn-off) Time in milliseconds). This application uses all the contents of Japanese Patent Application No. 2006-075809 filed in Japan on April 5, 2016, which is the basic application.

  DESCRIPTION OF SYMBOLS 1 ... Polarizing plate, 2 ... 1st transparent insulating substrate, 3 ... Electrode layer, 4 ... Orientation film, 4a ... Orientation direction, 5 liquid crystal layer, 5a ... Liquid crystal molecule at the time of no voltage application, 5b ... Liquid crystal at the time of voltage application Molecule, 6 ... color filter, 7 ... second transparent insulating substrate, 8 ... polarizing plate, 9 ... continuous or discontinuous polymer network, 10 ... liquid crystal display element, 11 ... gate electrode, 12 ... gate insulating layer, 13 ... Semiconductor layer, 14 ... protective layer, 15 ... ohmic contact layer, 16 ... drain electrode, 17 ... source electrode, 18 ... insulating protective layer, 21 ... pixel electrode, 22 ... common electrode, 23 ... storage capacitor, 24 ... gate wiring, 25 ... data wiring, 26 ... drain electrode, 27 ... source electrode, 28 ... gate electrode, 29 ... common line, 100 ... polarizing plate, 110 ... gate electrode, 120 ... gate insulating layer, 130 ... semiconductor layer, 140 ... Protective layer, 160 ... drain electrode, 190b ... organic insulating film, 200 ... first substrate, 210 ... pixel electrode, 220 ... storage capacitor, 230 ... drain electrode, 240 ... data wiring, 250 ... gate wiring, 260 ... source electrode 270 ... Gate electrode, 300 ... Thin film transistor layer, 400 ... Alignment film, 500 ... Liquid crystal layer, 510 ... Liquid crystal display device, 512 ... Pixel electrode, 512a ... Pixel trunk electrode, 512b ... Pixel branch electrode, 512c ... Pixel slit, 516 ... Scanning wiring, 517 ... Signal wiring, 600 ... Common electrode, 700 ... Color filter, 800 ... Second substrate, 900 ... Polarizing plate, 1000 ... Liquid crystal display element, 1400 ... Transparent electrode (layer), PX ... Pixel, PE ... pixel electrode, PA ... main pixel electrode, PB ... sub-pixel electrode, CE ... common electrode, CA ... main common electrode, CAL ... Side main common electrode, CAR ... right main common electrode, CB ... sub-common electrode, CBU ... upper sub common electrode, CBB ... lower sub-common electrode

Claims (20)

Irradiating the polymerizable liquid crystal composition sandwiched between two transparent substrates having electrodes on at least one with ultraviolet rays while applying a voltage equal to or higher than the threshold voltage of the polymerizable liquid crystal composition, and separating the polymerization phase; Thereafter, a step of irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays, and further containing a polymer or copolymer in the obtained liquid crystal composition, the polymer or copolymer The content of the liquid crystal composition and the polymer or copolymer is 0.5% by mass or more and less than 40% by mass, and the polymer or copolymer forms a polymer network, and the polymer A method for producing a liquid crystal display element, wherein the network has a uniaxial refractive index anisotropy or an easy alignment axis, and the polymer network has two or more different alignment states.   In the step of irradiating ultraviolet rays while applying a voltage equal to or higher than the threshold voltage of the polymerizable liquid crystal composition to separate the polymerization phase, the liquid crystal molecules in the polymerizable liquid crystal composition are in the range of 0 to 30 degrees with respect to the transparent substrate plane. In the step of irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays, the liquid crystal molecules are inclined at 80 to 90 degrees with respect to the transparent substrate plane. The manufacturing method of the liquid crystal display element of Claim 1.   In the step of irradiating ultraviolet rays while applying a voltage equal to or higher than the threshold voltage of the polymerizable liquid crystal composition to separate the polymerization phase, the liquid crystal molecules in the polymerizable liquid crystal composition are in the range of 0 to 90 degrees with respect to the transparent substrate plane. In the step of irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays, the liquid crystal molecules are inclined at 0 to 30 degrees with respect to the transparent substrate plane. The manufacturing method of the liquid crystal display element of Claim 1 or 2.   The method for producing a liquid crystal display element according to any one of claims 1 to 3, wherein the voltage to be applied is an alternating current waveform, and the polymerizable liquid crystal composition has a frequency in a range in which dielectric anisotropy is exhibited.   The voltage equal to or higher than the threshold voltage is a voltage V10 or higher that becomes 10% or higher with respect to the total change amount of the transmittance in the voltage-transmittance characteristic voltage of the polymerizable liquid crystal composition. The manufacturing method of the liquid crystal display element of description.   The method for manufacturing a liquid crystal display element according to claim 1, wherein the voltage less than the threshold voltage is a voltage of 0 V or more and less than 90% of the threshold voltage. The polymerizable compound in the polymerizable liquid crystal composition uses one or more compounds selected from compounds represented by the following general formula (V) and general formula (VI): The manufacturing method of the liquid crystal display element of one term.

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms. Represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other. -20 alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1-5. All 1,4-phenyle in the formula Groups, any hydrogen atom is _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.)

(In the formula, X ³ represents a hydrogen atom or a methyl group, and Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to 2). Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring.), V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms. An alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom) Or may be substituted with a cyclic substituent, and W represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups of Meaning hydrogen atoms _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.). Wherein the polymerizable compound, a method of manufacturing a liquid crystal display device according to claim 7 to use one or more compounds represented by the general formula Sp ¹ and Sp ² are identical (V). The compound represented by the general formula (V) in which Sp ¹ and Sp ² are the same as the polymerizable compound, wherein two or more compounds having different Sp ¹ and Sp ² are used. The manufacturing method of the liquid crystal display element of description. The method for producing a liquid crystal display element according to any one of claims 1 to 9, wherein a liquid crystal compound represented by the following general formula (LC) is used as the liquid crystal compound in the polymerizable liquid crystal composition.

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms. One or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. -O-, -CH = CH-, -CO-, -OCO-, -COO- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted A ^LC1 and A ^LC2 each independently represents a group selected from the group consisting of the following groups (a), (b) and (c).
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom),
(C) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group or chroman-2,6-diyl group.
One or more hydrogen atoms contained in the group (a), group (b) or group (c) are each
It may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ .
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— is represented.
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent. ≡C—, —CF ₂ O—, —OCF ₂ — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
a represents an integer of 1 to 4. When a represents 2, 3 or 4, and there are a plurality of ^ALC1s in the general formula (LC), the plurality of ^ALC1s may be the same or different, and there are a plurality of ^ZLCs A plurality of Z ^LCs may be the same or different. )   The method for manufacturing a liquid crystal display element according to claim 1, wherein the cell structure of the liquid crystal display element is a VA mode, an IPS mode, an FFS mode, a VA-TN mode, a TN mode, or an ECB mode.   A polymer or copolymer is contained in a liquid crystal composition sandwiched between two transparent substrates each having an electrode on at least one side, and the content of the polymer or copolymer is the liquid crystal composition and the polymer or 0.5 mass% or more and less than 40 mass% of the total mass of the copolymer, the polymer or copolymer forms a polymer network, and the polymer network is uniaxial refractive index anisotropy or easy to align An axis having two or more different orientation states, and the two or more different orientation states of the polymer network are inclined in the range of 0 to 30 degrees with respect to the transparent substrate plane. A liquid crystal display element characterized by having an orientation and a tilted orientation in a range of 80 to 90 degrees with respect to a transparent substrate plane.   The display pixel of the liquid crystal display element has an electrode with a shape that can be divided into a plurality of domains, and two or more alignment states with different polymer networks in one domain divided depending on the shape of the electrode The tilt orientation in the range of 0 to 30 degrees with respect to the transparent substrate plane and the tilt orientation direction of the tilt orientation is constant, and 80 to 90 with respect to the transparent substrate plane. The liquid crystal display element according to claim 12, wherein the liquid crystal display element has a tilted orientation in a range of degrees and the orientation of liquid crystal molecules in the liquid crystal composition when no voltage is applied has a vertical orientation or a parallel orientation.   The polymer network is aligned such that the optical axis direction or the easy axis direction of the polymer network coincides with the alignment of the liquid crystal molecules in the liquid crystal composition. As two or more different alignment states, 0 to 30 degrees with respect to the transparent substrate plane. The liquid crystal molecules in the liquid crystal composition with respect to the transparent substrate plane when no voltage is applied. The liquid crystal display element according to claim 12, which has a pretilt angle of 0 to 90 degrees.   The liquid crystal display element according to claim 12, wherein a polymer network layer having a thickness of at least 0.5% of the cell thickness with respect to the cell cross-sectional direction is formed. The polymerizable compound in the polymerizable liquid crystal composition uses any one or two or more compounds selected from the compounds represented by the following general formula (V) and general formula (VI). The liquid crystal display element according to one item.

(In the formula, X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms. Represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other. -20 alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1-5. All 1,4-phenyle in the formula Groups, any hydrogen atom is _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.)

(In the formula, X ³ represents a hydrogen atom or a methyl group, and Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to 2). Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring.), V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms. An alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom) Or may be substituted with a cyclic substituent, and W represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups of Meaning hydrogen atoms _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.). The liquid crystal display element according to claim 16, wherein one or two or more compounds represented by the general formula (V) in which Sp ¹ and Sp ² are the same are used as the polymerizable compound. The compound represented by the general formula (V) in which Sp ¹ and Sp ² are the same as the polymerizable compound, wherein two or more compounds having different Sp ¹ and Sp ² are used. The liquid crystal display element as described. The liquid crystal display element according to claim 12, wherein a liquid crystal compound represented by the following general formula (LC) is used as the liquid crystal compound in the polymerizable liquid crystal composition.

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms. One or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. -O-, -CH = CH-, -CO-, -OCO-, -COO- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted A ^LC1 and A ^LC2 each independently represents a group selected from the group consisting of the following groups (a), (b) and (c).
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other may be substituted with an oxygen atom or a sulfur atom) ),
(B) 1,4-phenylene group (one CH group present in this group or two or more non-adjacent CH groups may be substituted with a nitrogen atom),
(C) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group or chroman-2,6-diyl group.
One or more hydrogen atoms contained in the group (a), group (b) or group (c) are each
It may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ .
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or —OCO— is represented.
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, and an alkyl group having 1 to 15 carbon atoms. One or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C, so that the oxygen atom is not directly adjacent. ≡C—, —CF ₂ O—, —OCF ₂ — may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.
a represents an integer of 1 to 4. When a represents 2, 3 or 4, and there are a plurality of ^ALC1s in the general formula (LC), the plurality of ^ALC1s may be the same or different, and there are a plurality of ^ZLCs A plurality of Z ^LCs may be the same or different. )   The liquid crystal display element according to any one of claims 12 to 19, wherein the cell structure is a VA mode, an IPS mode, an FFS mode, a VA-TN mode, a TN mode, or an ECB mode.

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