TW201803973A - Liquid crystal display element and method for manufacturing same - Google Patents

Abstract

The present invention provides a liquid crystal display element which has high transmittance and excellent high-speed response in vertically aligned liquid crystal displays, such as PVA or MVA, and parallel aligned liquid crystal displays, such as IPS, FFS, or TN mode displays, by suppressing an increase in driving voltage, suppressing a decrease in birefringence, improving transmittance, and improving fall time in a liquid crystal. The present invention also provides a method for manufacturing said liquid crystal display element. Provided is a liquid crystal display element, wherein a liquid crystal composition sandwiched between two transparent substrates at least one of which has an electrode contains a polymer or a copolymer, the content of the polymer or the copolymer is at least 0.5 mass% and less than 40 mass% of the combined mass of the liquid crystal composition and the polymer or copolymer, the polymer or the copolymer forms a polymer network, and the polymer network has uniaxial refractive index anisotropy or an easy-alignment axis, and two or more different alignment states.

Description

Liquid crystal display element and manufacturing method thereof

The invention relates to a liquid crystal display element and a manufacturing method thereof.

Although LCD TVs have been widely used, with the increase in image quality brought by the large size, the moving speed of smaller LCD TVs is faster. Therefore, the response speed of LCDs needs to be accelerated to improve the quality of moving images. .

The field sequential full-color display method that does not require a color filter is characterized by using a backlight source that lights up in the order of "red → green → blue". In the usual CRT or LCD display, the frame time is 16.7ms, while in the field sequential full-color display mode, high-speed responsiveness with a frame time of 5.6ms is required.

As an index indicating high-speed responsiveness, the sum of τ d and τ r may be mentioned. τ d is the falling response time of the liquid crystal, and τ r is the rising response time of the liquid crystal. In order to satisfy the high-speed responsiveness of the field-sequential full-color display mode, the sum of τ d and τ r is expected to be less than 1.5 ms.

Liquid crystal materials currently known as nematic liquid crystals in the market are generally used in flat displays such as televisions, monitors, mobile phones, smart phones, and tablet terminals. However, since the response speed of the nematic liquid crystal is about ten to several milliseconds to several milliseconds, improvement is desired. The response speed is greatly affected by the rotational viscosity γ 1 and elastic constant of the liquid crystal. Therefore, research and improvement are carried out through the development of novel compounds or optimization of composition, but the progress of improvement is slow. In contrast, a ferroelectric liquid crystal (FLC) using a smectic liquid crystal can achieve a high-speed response of hundreds of microseconds. however, Because it is only light and dark, it is not easy to achieve the intermediate gradient display required for full-color display, and methods such as area gradient are used.

Among the FLCs, the Polymer Stabilized V shaped-FLC (PSV-FLC) element composed of a mixture of FLC and monomers forms a fine polymer network in the ferroelectric liquid crystal. In addition to the high-speed response of FLC, Intermediate gradation display is also possible, and the impact resistance is also improved compared to the conventional FLC (Patent Document 1).

In addition, in a nematic liquid crystal and polymer composite, if a polymerizable compound of 70% by mass or more is added to the nematic liquid crystal medium, a high-speed response with a response time of tens of microseconds can be obtained, but the driving voltage However, it will exceed about 80V, which is not practical, and the effective birefringence will be reduced by more than one digit compared to the birefringence of the liquid crystal used, so the transmittance of the device will be reduced. On the other hand, the following PS (polymer-stabilised) or PSA (polymer-sustained alignment) displays have been proposed: 0.3% by mass or more and less than 1% by mass of one or more A polymerizable compound is added to a liquid crystal medium, and UV light polymerization is applied to form a fine protrusion structure obtained by polymerization or cross-linking at the interface of a glass substrate by UV light polymerization, which mainly induces pretilt (Patent Document 2 ~ 6). Displays such as PS or PSA mainly use a fishbone pattern electrode that is configured with linear slits of fine width and linear electrodes of fine width in a vertical alignment mode to form a multi-domain divided into four. Achieve high viewing angle. In this case, if a voltage is applied, the liquid crystal will be tilted and aligned in the direction of the linear slit. 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, a tilted orientation orientation is induced in a pre-tilted form, and division by an orientation formed by a pattern electrode does not require a complicated alignment processing step of a vertical alignment film (Non-Patent Document 1). Also, the response time may be mentioned Improved from 10 milliseconds to several milliseconds. Other polymer alignment stabilization techniques employ a method of reacting a polymerizable compound in a liquid crystal. A polymer stabilizes the alignment state when a voltage is applied to obtain desired electro-optical characteristics, and can display characteristics that cannot be obtained only with a liquid crystal simple substance (Patent Documents 7 to 14).

However, even these components have room for improvement from the viewpoint of high-speed responsiveness. In particular, high-speed response of the rising speed of liquid crystal display devices, low viscosity of liquid crystal compositions, high dielectric constant, low elastic constant, pretilt angle, or improvement of driving methods such as overdrive method, etc. Various methods have been put into practical use, but the current state of decline is that no effective method has been found other than lowering the viscosity of the liquid crystal composition, and improvement is expected.

[Patent Document 1] Japanese Patent Laid-Open No. 2002-31821

[Patent Document 2] Japanese Patent Publication No. 2013-536271

[Patent Document 3] Japanese Patent Publication No. 2013-538249

[Patent Document 4] Japanese Patent Publication No. 2012-527495

[Patent Document 5] Japanese Patent Publication No. 2012-513482

[Patent Document 6] Japanese Patent Laid-Open No. 2012-219270

[Patent Document 7] Japanese Patent No. 4175826

[Patent Document 8] Japanese Patent Laid-Open No. 2009-192600

[Patent Document 9] Japanese Patent No. 5020203

[Patent Document 10] Japanese Patent Laid-Open No. 1999-0258758

[Patent Document 11] Japanese Patent No. 5839994

[Patent Document 12] US8940375

[Patent Document 13] WO2011 / 055571

[Patent Document 14] WO2015 / 122457

[Non-Patent Document 1] Journal of the SID17 / 7, 553-559 (2009)

The problems to be solved by the present invention are PVA (Patterned vertical alignment), MVA (Multi-domain Vertical Alignment) liquid crystal display (VA), IPS (In-plane switching) mode, FFS (Fringe Field switching) mode TN (Twisted Nematic) mode and other parallel alignment liquid crystal displays, suppress the increase of driving voltage, suppress the decrease of birefringence, improve the transmittance, and at the same time improve the fall time of the liquid crystal, thereby providing a high transmittance and excellent high-speed response The display element also provides a method for manufacturing the liquid crystal display element.

The purpose of the present inventors is to form a polymer network having refractive anisotropy and an alignment function in the entire liquid crystal cell in the liquid crystal composition and the polymerizable liquid crystal composition containing a polymerizable compound. The polymer stabilizes the oblique alignment direction of the liquid crystal molecules toward the direction prescribed by the electrode pattern, and focuses on the content rate of the polymerizable compound and the conditions for forming the polymer network to complete the present invention.

[1] A method for manufacturing a liquid crystal display device, comprising the steps of applying a polymerizable liquid crystal composition having a threshold voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes. A step of irradiating ultraviolet rays to simultaneously polymerize the polymer phases, and a step of irradiating ultraviolet rays so that the voltage does not reach a critical voltage and further radiating ultraviolet rays.

[2] The method for producing a liquid crystal display device according to the above [1], wherein the method is for applying a polymerizable liquid crystal group In the step of separating the polymerized phase with a voltage higher than the critical voltage of the product and simultaneously irradiating ultraviolet rays, the liquid crystal molecules in the polymerizable liquid crystal composition are aligned at an angle of 0 to 30 degrees with respect to the plane of the transparent substrate, and the ultraviolet rays are irradiated In the step of reducing the voltage to a threshold voltage and further irradiating ultraviolet rays, the liquid crystal molecules are aligned at an angle of 80 to 90 degrees with respect to the plane of the transparent substrate.

[3] The method for producing a liquid crystal display device according to the above [1] or [2], in the step of applying a voltage equal to or higher than a critical voltage of the polymerizable liquid crystal composition and simultaneously irradiating ultraviolet rays to separate the polymerized phases, the polymerizable liquid crystal The liquid crystal molecules in the composition are aligned at an angle of 0 to 90 degrees with respect to the plane of the transparent substrate, and in the step of irradiating ultraviolet rays so that the voltage does not reach a critical voltage and further radiating ultraviolet rays, the liquid crystal molecules are relative to the plane of the transparent substrate Tilt from 0 degrees to 30 degrees.

[4] The method for manufacturing a liquid crystal display element according to any one of the above [1] to [3], wherein the applied voltage is an AC waveform and the polymerizable liquid crystal composition exhibits a range of dielectric properties. frequency.

[5] The method for manufacturing a liquid crystal display device according to any one of the above [1] to [4], wherein the voltage equal to or higher than the critical voltage is a transmission in a voltage-transmittance characteristic voltage relative to the polymerizable liquid crystal composition The total change of the rate will be above the voltage V10 of more than 10%.

[6] The method for manufacturing a liquid crystal display device according to any one of the above [1] to [5], wherein the voltage that does not reach the critical voltage is 0 V or more and that the voltage does not reach 90% of the critical voltage.

[7] The method for producing a liquid crystal display element according to any one of the above [1] to [6], wherein one or more compounds selected from the compounds represented by the following general formula (V) and general formula (VI) are used Two or more compounds are used as polymerizable compounds in the polymerizable liquid crystal composition.

(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- (where s represents an integer from 1 to 11, and an oxygen atom is bonded to an aromatic ring.), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or 5 carbon atoms Polyvalent cyclic substituents of ~ 30, the alkylenes in polyvalent alkylenes may be replaced by oxygen atoms in the range where the oxygen atoms are not adjacent, or by alkyl groups with 5-20 carbon atoms (the alkylene in the group) The group may be substituted by an oxygen atom in a range where the oxygen atoms are not adjacent.) Or a cyclic substituent, k represents an integer of 1 to 5. In all 1,4-phenylene groups, any hydrogen atom may be substituted as -CH ₃ , -OCH ₃ , a fluorine atom, or 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 represents an integer from 2 to 11) The oxygen atom is bonded to the aromatic ring.), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms. The alkylene group may be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent, or may be substituted with an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be replaced with an oxygen atom in a range where the oxygen atoms are not adjacent. ) Or a cyclic substituent, W represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups in the formula may be substituted with any hydrogen atom -CH ₃ , -OCH ₃ , a fluorine atom or a cyano group.).

[8] The method for producing a liquid crystal display device according to the above [7], wherein one or two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² are used as the polymerizable compound.

[9] The method for producing a liquid crystal display element according to the above [7] or [8], wherein two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² are used as the polymerizable compound, wherein the two or more kinds of compounds each other Sp ¹ and Sp ² are different.

[10] The method for producing a liquid crystal display element according to any one of the above [1] to [9], which uses a liquid crystal compound represented by the following general formula (LC) 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 more CH ₂ groups in the alkyl group may be -O-,- CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- substitution, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. A ^LC1 and A ^LC2 each independently represents a group selected from the group consisting of the following groups (a), (b), and (c).

唍-2,6-二基。 (a) trans-1,4-cyclohexyl (one CH ₂ group present in this group or two or more adjacent CH ₂ groups may be substituted by an oxygen atom or a sulfur atom.), (b) 1,4-phenylene (one CH group present in this group or two or more non-adjacent CH groups may be substituted by a nitrogen atom.), (C) 1,4-bicyclic (2.2.2) phenylene Octyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or

唍 -2,6-diyl.

Each of the one or more hydrogen atoms contained in the aforementioned group (a), group (b) or group (c) may be substituted with a fluorine atom, a chlorine atom, -CF ₃ or -OCF ₃ .

Z ^LC represents 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-.

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≡C in a manner that the oxygen atoms are not directly adjacent. -, -CF ₂ O-, -OCF ₂ -are substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.

a represents an integer from 1 to 4. When a represents 2, 3, or 4 and there is a plurality of A ^LC1 in the general formula (LC), the plurality of A ^LC1s may be the same or different, and when there are a plurality of Z ^LCs , the plurality The Z ^{LCs present} may be the same or different. )

[11] The method for manufacturing a liquid crystal display element according to any one of the above [1] to [10], wherein the unit structure of the liquid crystal display element is VA mode, IPS mode, FFS mode, VA-TN mode, TN mode Or ECB mode.

[12] A liquid crystal display element comprising a polymer or a copolymer in a liquid crystal composition sandwiched between at least one transparent substrate having two electrodes, and the content of the polymer or copolymer is the liquid crystal composition and the The total mass of the polymer or copolymer is more than 0.5% by mass and less than 40% by mass. The polymer or copolymer forms a polymer network, and the polymer network has uniaxial refractive index anisotropy or easy alignment. Axis, and has two or more different orientation states.

[13] The liquid crystal display element according to the above [12], which has the following oblique alignment as two or more different alignment states of the polymer network: in the range of 0 to 30 degrees with respect to the plane of the transparent substrate Tilt alignment, and tilt alignment in the range of 80 degrees to 90 degrees relative to the plane of the transparent substrate.

[14] The liquid crystal display element according to the above [12] or [13], which has an electrode having a shape capable of dividing a display pixel of the liquid crystal display element into a plurality of regions, and the electrode is divided into one region depending on the shape of the electrode. , Has the following tilt alignment as two or more different alignment states of the polymer network: relative to the plane of the transparent substrate, the tilt alignment in the range of 0 to 30 degrees, and the tilt alignment of the tilt alignment is fixed in the azimuth direction And the inclined alignment in the range of 80 degrees to 90 degrees with respect to the plane of the transparent substrate, the liquid crystal molecule alignment in the liquid crystal composition when no voltage is applied has vertical alignment or parallel alignment.

[15] The liquid crystal display device according to any one of the above [12] to [14], wherein the optical axis direction or easy alignment axis direction of the polymer network is consistent with the alignment of the liquid crystal molecules in the liquid crystal composition, and has The following tilt alignments are two or more different alignment states: tilt alignment in the range of 0 to 30 degrees with respect to the plane of the transparent substrate, and tilt alignment in the range of 80 to 90 degrees with respect to the plane of the transparent substrate, When no voltage is applied, the liquid crystal molecules in the liquid crystal composition have a pretilt angle of 0 to 90 degrees relative to the plane of the transparent substrate.

[16] The liquid crystal display element according to any one of the above [12] to [15], wherein a polymer network layer having a thickness of at least 0.5% or more of the cell thickness is formed in the cell cross-sectional direction.

[17] The liquid crystal display element according to any one of the above [12] to [16], which uses one or two or more selected from the compounds represented by the following general formula (V) and general formula (VI) The compound is used as a polymerizable compound in the polymerizable liquid crystal composition.

(Wherein 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 -(In the formula, s represents an integer of 1 to 11, and an oxygen atom is bonded to an aromatic ring.), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or 5 to 30 carbon atoms Valent cyclic substituents, the alkylene group in the polyvalent alkylene group may be replaced by an oxygen atom in the range where the oxygen atoms are not adjacent, or the alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be an oxygen group The range where the atoms are not adjacent is substituted by an oxygen atom.) Or a cyclic substituent, k represents an integer of 1 to 5. All 1,4-phenylene groups in the formula may be substituted with any hydrogen atom -CH ₃ , -OCH ₃ , a fluorine atom, or 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 represents an integer from 2 to 11) The oxygen atom is bonded to the aromatic ring.), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms. The alkylene group may be replaced by an oxygen atom in a range where the oxygen atoms are not adjacent, or an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be replaced by an oxygen atom in a range where the oxygen atoms are not adjacent.) Or Substituted by cyclic substituents, W represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups in the formula may be substituted with any of the hydrogen atoms -CH ₃ and -OCH ₃ , fluorine atom or cyano.).

[18] The liquid crystal display device according to the above [17], wherein one or two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² are used as the polymerizable compound.

[19] The liquid crystal display device according to the above [17] or [18], wherein two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² are used as the polymerizable compound, of which the two The above compounds differ from each other in Sp ¹ and Sp ² .

[20] The liquid crystal display element according to any one of the above [11] to [19], which uses a liquid crystal compound represented by the following general formula (LC) as a liquid crystal compound in a polymerizable liquid crystal composition.

(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≡C- substitution, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. A ^LC1 and A ^LC2 each independently represents a group selected from the group consisting of the following groups (a), (b), and (c).

唍-2,6-二基。 (a) trans-1,4-cyclohexyl (one CH ₂ group present in this group or two or more adjacent CH ₂ groups may be substituted by an oxygen atom or a sulfur atom.), (b) 1,4-phenylene (one CH group present in this group or two or more non-adjacent CH groups may be substituted by a nitrogen atom.), (C) 1,4-bicyclic (2.2.2) phenylene Octyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or

唍 -2,6-diyl.

Each of the one or more hydrogen atoms contained in the aforementioned group (a), group (b) or group (c) may be substituted with a fluorine atom, a chlorine atom, -CF ₃ or -OCF ₃ .

Z ^LC represents 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-.

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≡C in a manner that the oxygen atoms are not directly adjacent. -, -CF ₂ O-, -OCF ₂ -are substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom.

a represents an integer from 1 to 4. When a represents 2, 3, or 4 and there is a plurality of A ^LC1 in the general formula (LC), the plurality of A ^LC1s may be the same or different, and when there are a plurality of Z ^LCs , the plurality The Z ^{LCs present} 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, it is possible to suppress a rise in driving voltage, suppress a decrease in birefringence, improve transmittance, and at the same time improve a fall time of a liquid crystal, thereby providing a liquid crystal display element having high transmittance and excellent high-speed response.

1‧‧‧ polarizing plate

2‧‧‧ the first transparent insulating substrate

3‧‧‧ electrode layer

4‧‧‧alignment film

4a‧‧‧Alignment direction

5‧‧‧LCD layer

5a‧‧‧ Liquid crystal molecules when no voltage is applied

5b‧‧‧ Liquid crystal molecules when voltage is applied

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 insulation

13‧‧‧Semiconductor layer

14‧‧‧ protective layer

15‧‧‧ohm contact layer

16‧‧‧ Drain electrode

17‧‧‧Source electrode

18‧‧‧Insulation 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‧‧‧ shared line

100‧‧‧ polarizing plate

110‧‧‧Gate electrode

120‧‧‧Gate insulation

130‧‧‧Semiconductor layer

140‧‧‧ protective layer

160‧‧‧ Drain electrode

190b‧‧‧Organic insulating film

200‧‧‧ the 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‧‧‧LCD layer

510‧‧‧LCD display device

512‧‧‧pixel electrode

512a‧‧‧Pixel Stem 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‧‧‧LCD display element

1400‧‧‧Transparent electrode (layer)

PX‧‧‧pixel

PE‧‧‧Pixel electrode

PA‧‧‧Main pixel electrode

PB‧‧‧ secondary pixel electrode

CE‧‧‧Common electrode

CA‧‧‧Main common electrode

CAL‧‧‧Left main common electrode

CAR‧‧‧ Right main common electrode

CB‧‧‧ Deputy common electrode

CBU‧‧‧ Upper common electrode

CBB‧‧‧ Underside common electrode

FIG. 1 is a schematic diagram of a liquid crystal display element of the present invention.

FIG. 1 is an enlarged view of a part of FIG. 1.

FIG. 2 is a cross-sectional view of a liquid crystal display element of the present invention.

FIG. 3 is an enlarged view of a part of FIG. 1.

FIG. 4 is a cross-sectional view of a liquid crystal display element of the present invention.

FIG. 5 is a schematic diagram of a liquid crystal display device according to the present invention.

FIG. 6 is an enlarged view of a part of FIG. 6.

FIG. 7 is a cross-sectional view of a liquid crystal display element of the present invention.

FIG. 9 is a polarizing microscope photograph of Example 1. FIG.

FIG. 10 is a polarizing microscope photograph of Comparative Example 2. FIG.

FIG. 11 is a schematic diagram showing an electrode structure and an arrangement of liquid crystal molecules of the oblique electric field type liquid crystal display device of the present invention.

FIG. 12 is a schematic diagram showing an electrode structure of an oblique electric field type liquid crystal display device divided into eight parts according to the present invention.

FIG. 13 is a schematic diagram of an electrode structure of a fish-bone type VA liquid crystal cell according to an embodiment.

<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≡C in such a manner that the oxygen atoms are not directly adjacent. -Substitution. One or two or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Each of the alkyl groups of R ^LC may be a branched group, or may be a linear group, and 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 groups (a), (b), and (c).

唍-2,6-二基。 (a) trans-1,4-cyclohexyl (one CH ₂ group present in this group or two or more adjacent CH ₂ groups may be substituted by an oxygen atom or a sulfur atom.), (b) 1,4-phenylene (one CH group present in this group or two or more non-adjacent CH groups may be substituted by a nitrogen atom.), (C) 1,4-bicyclic (2.2.2) phenylene Octyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or

唍 -2,6-diyl.

Each of the one or more hydrogen atoms contained in the aforementioned group (a), group (b) or group (c) may be substituted with a fluorine atom, a chlorine atom, -CF ₃ or -OCF ₃ .

In the general formula (LC), Z ^LC represents 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-.

In the general formula (LC), 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≡C in a manner that the oxygen atoms are not directly adjacent. -, -CF ₂ O-, -OCF ₂ -are 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 is a plurality of A ^LC1 in the general formula (LC), the plurality of A ^LC1s may be the same or different, and when there are a plurality of Z ^LCs , the plurality The Z ^{LCs present} 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 the general formula (LC1) or (LC2), R ^LC11 and R ^LC21 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or more CH ₂ groups in the alkyl group may not have an oxygen atom directly. Adjacent way is replaced by -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C-, and one or more hydrogen atoms in the alkyl group can be arbitrarily Substituted by a halogen atom. As the compound represented by the general formula (LC1) or (LC2), R ^LC11 and R ^{LC21 are} preferably each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and 2 carbon atoms. Alkenyl groups of ~ 7 are more preferably alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, and even more preferably straight-chain. The base preferably represents the following structure.

(In the formula, the right end is bonded to the ring structure.)

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

As a compound represented by general formula (LC1) or (LC2), it is preferable that A ^LC11 and A ^LC21 each independently have any one of the following structures.

In the general formula (LC1) or (LC2), X ^LC11 , X ^LC12 , X ^LC21 to X ^LC23 each independently represent a hydrogen atom, a chlorine atom, a fluorine atom, -CF ₃ or -OCF ₃ , and Y ^LC11 and Y ^LC21 are each independently Ground means 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} preferably each independently a fluorine atom, a cyano group, -CF ₃ or -OCF ₃ , more preferably a fluorine atom or -OCF ₃ , especially It is preferably a fluorine atom.

In the 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-. As the compounds represented by the general formula (LC1) or (LC2), Z ^LC11 and Z ^{LC21 are} preferably each independently a single bond, -CH ₂ CH _2- , -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF ₂ -or -CF ₂ O-, more preferably a single bond, -CH ₂ CH _2- , -OCH _2- , -OCF ₂ -or -CF ₂ O-, even more preferably a single bond , -OCH ₂ -or -CF ₂ O-.

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), m ^LC11 and m ^LC21 are each preferably independently 1, 2, or 3, and when attention is paid to low-temperature storage stability and response speed, 1 is more preferred. Or 2, when the case of the upper limit temperature of the nematic phase upper limit is improved, it is more preferably 2 or 3. When there are a plurality of A ^LC11 , A ^LC21 , Z ^LC11, and Z ^LC21 in the general formula (LC1) or (LC2), these may be the same or different.

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

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

烷-2,5-二基。又，通式(LC1-a)~(LC1-c)中，X^LC1b1、X^LC1b2、X^LC1c1~X^LC1c4各自獨立地表示氫原子、氯原子、氟原子、-CF₃或-OCF₃。作為通式(LC1-a)至通式(LC1-c)表示之化合物，X^LC1b1、X^LC1b2、X^LC1c1~X^LC1c4較佳各自獨立地為氫原子或氟原子。 In the general formulae (LC1-a) to (LC1-c), A ^LC1a1 , A ^LC1a2, and A ^LC1b1 represent trans-1,4-cyclohexyl, tetrahydropiperan-2,5-diyl, 1,3 -two

Alkan-2,5-diyl. In the general formulae (LC1-a) to (LC1-c), X ^LC1b1 , X ^LC1b2 , and X ^LC1c1 to X ^LC1c4 each independently represent a hydrogen atom, a chlorine atom, a fluorine atom, -CF ₃ or -OCF ₃ . As the compounds represented by the general formula (LC1-a) to the general formula (LC1-c), X ^LC1b1 , X ^LC1b2 , and X ^LC1c1 to X ^{LC1c4 are} preferably each independently a hydrogen atom or a fluorine atom.

The general formula (LC1) is also preferably one or two or more compounds selected from the group consisting of compounds represented by the following general formula (LC1-d) to general formula (LC1-p).

Formula (LC1-d) ~ (LC1 -p) ^{of, R LC11, Y LC11, X} LC11 and X ^LC12 each independently represents the aforementioned general formula (LC1) in the R ^LC11, Y ^LC11, X ^LC11 and X ^LC12 The same meaning. As the compounds represented by the general formulae (LC1-d) to (LC1-p), R ^{LC11 is} preferably each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and carbon atoms. Alkenyl groups of 2 to 7 are more preferably alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and alkenyl groups having 2 to 5 carbon atoms. X ^LC11 and X ^LC12 are each preferably a hydrogen atom or a fluorine atom. Y ^{LC11 is} preferably each independently a fluorine atom, -CF ₃ or -OCF ₃ .

烷-2,5-二基。 In the general formulae (LC1-d) to (LC1-p), A ^LC1d1 , A ^LC1f1 , A ^LC1g1 , A ^LC1j1 , A ^LC1k1 , A ^LC1k2 , A ^LC1m1 to A ^LC1m3 each independently represent 1,4-phenylene, Trans-1,4-cyclohexyl, tetrahydropiperan-2,5-diyl, or 1,3-di

Alkan-2,5-diyl.

In the general formulae (LC1-d) to (LC1-p), X ^LC1d1 , X ^LC1d2 , X ^LC1f1 , X ^LC1f2 , X ^LC1g1 , X ^LC1g2 , X ^LC1h1 , X ^LC1h2 , X ^LC1i1 , X ^LC1i2 , X ^LC1j1 to X ^{LC1j4 , X LC1k1, X LC1k2, X} LC1m1 and ^X LC1m2 each independently represent a hydrogen atom, a chlorine atom, a fluorine atom, -CF ₃ or -OCF _3. As the compounds represented by the general formulae (LC1-d) to (LC1-m), X ^LC1d1 to X ^{LC1m2 are} preferably each independently a hydrogen atom or a fluorine atom.

In the general formulae (LC1-d) to (LC1-p), Z ^LC1d1 , Z ^LC1e1 , Z ^LC1j1 , Z ^LC1k1 , and Z ^LC1m1 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-. As the compounds represented by the general formulae (LC1-d) to (LC1-p), Z ^LC1d1 to Z ^{LC1m1 are} preferably each independently a single bond, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -CF ₂ O- or -OCH _2- .

The compound represented by the general formulae (LC1-d) to (LC1-p) is preferably one selected from the group consisting of compounds represented by the following general formulae (LC1-1) to (LC1-45) Or two or more compounds. In the general formulae (LC1-1) to (LC1-45), R ^LC11 each independently represents an alkyl group having 1 to 7 carbon atoms.

The general formula (LC2) is preferably one or two 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 formulae (LC2-a) to (LC2-g), R ^LC21 , Y ^LC21 , X ^LC21 to X ^LC23 each independently represent R ^LC21 , Y ^LC21 , X ^LC21 to X ^LC23 in the general formula (LC2). The same meaning. As the compounds represented by the general formulae (LC2-a) to (LC2-g), R ^{LC21 is} preferably each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and carbon number. Alkenyl groups of 2 to 7 are more preferably alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and alkenyl groups having 2 to 5 carbon atoms. In addition, X ^LC21 to X ^{LC23 are} preferably each independently a hydrogen atom or a fluorine atom, and Y ^{LC21 is} preferably each independently a fluorine atom, -CF _3, or -OCF ₃ .

In the general formulae (LC2-a) to (LC2-g), X ^LC2d1 to X ^LC2d4 , X ^LC2e1 to X ^LC2e4 , X ^LC2f1 to X ^LC2f4, and X ^LC2g1 to X ^LC2g4 each independently represent a hydrogen atom, a chlorine atom, and a fluorine atom. , -CF ₃ or -OCF ₃ . As the compounds represented by the general formulae (LC2-a) to (LC2-g), X ^LC2d1 to X ^LC2g4 are each preferably a hydrogen atom or a fluorine atom.

In the general formulae (LC2-a) to (LC2-g), Z ^LC2a1 , Z ^LC2b1 , Z ^LC2c1 , Z ^LC2d1 , Z ^LC2e1 , Z ^LC2f1, and Z ^LC2g1 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-. As the compounds represented by the general formulae (LC2-a) to (LC2-g), Z ^LC2a1 to Z ^LC2g4 are each preferably -CF ₂ O- or -OCH _2- .

The compound represented by the aforementioned 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 R ^LC31 , R ^LC32 , R ^LC41 , R ^LC42 , R ^LC51, and R ^LC52 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more of the alkyl groups are -CH ₂ -It may be substituted with -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- in a way that the oxygen atoms are not directly adjacent, and one or more of the alkyl groups A hydrogen atom may be optionally substituted by a halogen atom, and A ^LC31 , A ^LC32 , A ^LC41 , A ^LC42 , A ^LC51, and A ^LC52 each independently represent any one of the following structures,

(In this structure, one or more of -CH ₂ -in cyclohexyl may be substituted by an oxygen atom, and one or more of -CH- in 1,4-phenylene may be replaced by a nitrogen atom. In addition, one or two or more hydrogen atoms in the structure may be substituted by a fluorine atom, a chlorine atom, -CF ₃ or -OCF _3. ), 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 oxygen atom, X ^LC41 represents hydrogen atom or fluorine atom, m ^LC31 , m ^LC32 , m ^LC41 , m ^LC42 , m ^LC51 and m ^LC52 Each independently represents 0 ~ 3, m ^LC31 + m ^LC32 , m ^LC41 + m ^LC42, and m ^LC51 + m ^LC52 are 1, 2 or 3, when there are a plurality of A ^LC31 ~ A ^LC52 , Z ^LC31 ~ Z ^LC52 These can be the same or different. ).

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

(In the formula, the right end is bonded to the ring structure.)

A ^LC31 to A ^{LC52 are} preferably each independently of the following structure,

Z ^LC31 to Z ^LC51 are each preferably a single bond, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH _2- , -CF ₂ O-, -OCF ₂ -or -OCH _2- .

It is preferable to contain at least one compound selected from the group of compounds represented by the general formula (LC3-1), the general formula (LC4-1), and the general formula (LC5-1) as the general formula (LC3), the general formula (LC4 ) And a compound represented by the general formula (LC5),

(In the formula, R ³¹ to R ³³ 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 alkenyl group 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 alkenyl group having 2 to 8 carbon atoms, Z ³¹ to Z ³³ represent single bonds, -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.).

In the general formulae (LC3-1) to (LC5-1), R ³¹ to R ³³ represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 1 to 8 carbon atoms. An alkoxy group or an alkenyl 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 more preferably an alkylene group having 2 to 5 carbon atoms 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 particularly preferably an alkyl group having 3 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 alkenyl group having 2 to 8 carbon atoms, preferably Represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 4 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms, and more preferably the carbon number Alkyl group 1 to 3 or alkoxy group having 1 to 3 carbon atoms, more preferably an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, particularly preferably an alkoxy group having 2 carbon atoms .

Z ³¹ to Z ³³ represent single bonds, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO-, -OCH ₂ -,- CH ₂ O-, -OCF ₂ -or -CF ₂ O-, preferably a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF ₂ -or- CF ₂ O-, more preferably a single bond or -CH ₂ O-.

The liquid crystal composition preferably contains 5 to 50% by mass of a compound selected from the group of compounds represented by the general formula (LC3-1), the general formula (LC4-1), and the general formula (LC5-1). It preferably contains 5 to 40% by mass, more preferably 5 to 30% by mass, more preferably 8 to 27% by mass, and even more preferably 10 to 25% by mass.

The compound represented by the general formula (LC3-1) is specifically preferably the following: Compounds represented by 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.)

The compound represented by general formula (LC4-1) is specifically preferably a compound represented by general formula (LC4-11) to general formula (LC4-14) described below.

(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 a fluorine atom.)

The compound represented by the general formula (LC5-1) is specifically preferably the general formula (LC5) described below. -11) to a compound represented by the general formula (LC5-14).

(Wherein 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 an oxygen atom .)

In the general formula (LC3-11), the general formula (LC3-13), the general formula (LC4-11), the general formula (LC4-13), the general formula (LC5-11), and the general formula (LC5-13), R ³¹ to R ^{33 are} preferably the same as those in the general formulae (LC3-1) to (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 even more preferably an alkyl group having 2 carbon atoms.

In the general formula (LC3-12), the general formula (LC3-14), the general formula (LC4-12), the general formula (LC4-14), the general formula (LC5-12), and the general formula (LC5-14), R ³¹ to R ^{33 are} preferably the same as those in the general formulae (LC3-1) to (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 even more preferably an alkyl group having 3 carbon atoms.

Among the general formulas (LC3-11) to (LC5-14), in order to increase the absolute value of the dielectric properties, the general formula (LC3-11), general formula (LC4-11), and general Formula (LC5-11), Formula (LC3-13), Formula (LC4-13) and Formula (LC5-13), more preferably Formula (LC3-11), Formula (LC4-11), General formula (LC5-11).

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

Furthermore, it is preferable to contain at least one compound selected from the group consisting of compounds represented by the general formula (LC3-2), the general formula (LC4-2), and the general formula (LC5-2) as the general formula (LC3), the general formula (LC4) and a compound represented by the general formula (LC5),

(In the formula, R ⁵¹ to R ⁵³ 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 alkenyl 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 alkenyl group having 2 to 8 carbon atoms, B ¹ to B ³ represent fluorine-substituted 1,4-phenylene or trans-1,4-cyclohexyl, and Z ⁴¹ to Z ⁴³ represent single bonds, -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 ⁴² represents hydrogen Atom or fluorine atom, Z ⁴⁴ represents -CH ₂ -or oxygen atom.).

In general formula (LC3-2), general formula (LC4-2), and general formula (LC5-2), R ⁵¹ to R ⁵³ represent an alkyl group having 1 to 8 carbon atoms, and an olefin having 2 to 8 carbon atoms. Group, alkoxy group having 1 to 8 carbon atoms or alkenyl 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 Alkyl group having 2 to 5 carbon atoms or alkenyl group having 2 to 4 carbon atoms, and even more preferably an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 carbon atoms, particularly preferably 3 to 6 carbon atoms. alkyl.

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 alkenyl group having 2 to 8 carbon atoms, preferably Represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 4 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms, and more preferably the carbon number Alkyl group 1 to 3 or alkoxy group having 1 to 3 carbon atoms, more preferably an alkyl group having 3 carbon atoms or an alkoxy group having 2 carbon atoms, particularly preferably an alkoxy group having 2 carbon atoms .

B ³¹ to B ³³ represent fluorine-substituted 1,4-phenylene or trans-1,4-cyclohexyl, preferably unsubstituted 1,4-phenylene or trans-1, 4-cyclohexyl, more preferably trans-1,4-cyclohexyl.

Z ⁴¹ to Z ⁴³ represent single bonds, -CH = CH-, -C≡C-, -CH ₂ CH ₂ -,-(CH ₂ ) _4- , -COO-, -OCO-, -OCH ₂ -,- CH ₂ O-, -OCF ₂ -or -CF ₂ O-, preferably a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF ₂ -or- CF ₂ O-, more preferably a single bond or -CH ₂ O-.

The compounds represented by the general formula (LC3-2), the general formula (LC3-3), the general formula (LC4-2), and the general formula (LC5-2) preferably contain 10 to 60% by mass of the liquid crystal composition, and more It preferably contains 20 to 50% by mass, more preferably 25 to 45% by mass, more preferably 28 to 42% by mass, and even more preferably 30 to 40% by mass.

The compound represented by general formula (LC3-2) is specifically preferably a compound represented by general formula (LC3-21) to general formula (LC3-29) described below.

Moreover, as a compound represented by general formula (LC3-3), the compound represented by general formula (LC3-31)-general formula (LC3-33) described below 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, and is preferably the same as the general formula (LC3-2 ) in R ⁵¹ and R ⁶¹ of the same embodiment aspect.)

The compound represented by general formula (LC4-2) is specifically preferably a compound represented by general formula (LC4-21) to general formula (LC4-26) described below.

(In the formula, R ⁵² represents an alkyl group having 1 to 5 carbon atoms or 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 a fluorine atom. (It is preferably the same embodiment as R ⁵² and R ⁶² in the general formula (LC4-2).)

The compound represented by general formula (LC5-2) is specifically preferably a compound represented by general formula (LC5-21) to general formula (LC5-26) described below.

(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 -or an oxygen atom. Is preferably the same embodiment as R ⁵³ and R ⁶³ in the general formula (LC5-2).)

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 Among the general formula (LC5-21), general formula (LC5-22), and general formula (LC5-25), R ⁵¹ to R ^{53 are} preferably general formula (LC3-2), general formula (LC4-2), and general formula (LC5-2). 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 even more preferably an alkyl group having 2 carbon atoms.

In 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 Among the general formula (LC5-23), general formula (LC5-24), and general formula (LC5-26), R ⁵¹ to R ^{53 are} preferably general formula (LC3-2), general formula (LC4-2), and general formula (LC5-2). 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 even more preferably an alkyl group having 3 carbon atoms.

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

The compound represented by the general formula (LC3-2), the general formula (LC4-2), and the general formula (LC5-2) may contain one or two or more compounds, and preferably contains B ¹ to B ^{3 to} represent 1,4-benzene. And B ¹ to B ^{3 each} represent at least one or more types of trans-1,4-cyclohexyl compounds.

In addition, as the compound represented by the general formula (LC3), others are preferably one or two or more compounds selected from the group of compounds represented by the following general formula (LC3-a) and the general formula (LC3-b).

(In the formula, 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 aforementioned general formula (LC3), and X ^LC3b1 to X ^LC3b6 represent hydrogen. Atom or fluorine atom, 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, m ^LC3b1 represents 0 or 1, when there are a plurality of A ^LC31 and ^In the case of Z ^LC31 , these may be the same or different.).

R ^LC31 and R ^LC32 each preferably independently represent 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 olefin having 2 to 7 carbon atoms. Oxygen.

烷-2,5-二基，更佳表示1,4-伸苯基、反式-1,4-伸環己基。 A ^LC31 preferably represents 1,4-phenylene, trans-1,4-cyclohexyl, tetrahydropiperan-2,5-diyl, 1,3-bis

Alkan-2,5-diyl, more preferably 1,4-phenylene and trans-1,4-cyclohexyl.

Z ^LC31 preferably represents a single bond, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH _2- , and more preferably represents a single bond.

The general formula (LC3-a) preferably represents 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 the aforementioned general formula (LC3).)

R ^LC31 and R ^{LC32 are} preferably each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an alkenyl group having 2 to 7 carbon atoms. More preferably, R ^LC31 represents carbon An alkyl group having 1 to 7 atoms, and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.

The general formula (LC3-b) preferably represents the following general formula (LC3-b1) to (LC3-b12), more preferably the general formula (LC3-b1), the general formula (LC3-b6), and the general formula (LC3-b8), general formula (LC3 -b11), more preferably the general formula (LC3-b1) and the general formula (LC3-b6), and the best formula (LC3-b1).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in the aforementioned general formula (LC3).)

R ^LC31 and R ^{LC32 are} preferably each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an alkenyl group having 2 to 7 carbon atoms. More preferably, R ^LC31 represents carbon An alkyl group having 2 or 3 atoms, and 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 (LC4-c), and the compound represented by the general formula (LC5) is preferably the following general formula (LC4) LC5-a) to compounds represented by the general formula (LC5-c).

(In the formula, R ^LC41 , R ^LC42, and X ^LC41 each independently represent the same meaning as R ^LC41 , R ^LC42, and X ^LC41 in the aforementioned general formula (LC4), and R ^LC51 and R ^LC52 each independently represent the same as the aforementioned general formula (LC5) R ^LC51 and R ^{LC52 have the} same meaning. 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 -CF ₂ O-.)

R ^LC41 , R ^LC42 , R ^LC51, and R ^LC52 each preferably independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group or carbon atom having 2 to 7 carbon atoms. Alkenyloxy groups of 2 to 7.

Z ^LC4a1 to Z ^LC5c1 each preferably represent a single bond, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH _2- , and more preferably a single bond.

The compound represented by the aforementioned general formula (LC) is also preferably 1 selected from compounds represented by the following general formula (LC6) (excluding compounds represented by general formula (LC1) to general formula (LC5).) One or two or more compounds.

In the 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≡C in such a manner that the oxygen atoms are not directly adjacent. -Substitution, in which one or more hydrogen atoms in the alkyl group may be optionally substituted with halogen. As the compound represented by the general formula (LC6), R ^LC61 and R ^{LC62 are} preferably each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an olefin having 2 to 7 carbon atoms. The group, as the alkenyl group, preferably represents any one of the following structures.

(In the formula, the right end is bonded to the ring structure.)

In the general formula (LC6), A ^LC61 to A ^LC63 each independently represent any one of the following structures. In this structure, one or more CH ₂ CH ₂ groups in cyclohexyl may be substituted by -CH = CH-, -CF ₂ O-, -OCF _2- , and 1,4-phenylene One or more CH groups may be substituted by a nitrogen atom.

As the compound represented by the general formula (LC6), it is preferable that each of A ^LC61 to A ^{LC63 is} independently any 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-, mLC61 represents 0 ~ 3. As the compound represented by the general formula (LC6), Z ^LC61 and Z ^{LC62 are} preferably each independently a single bond, -CH ₂ CH _2- , -COO-, -OCH _2- , -CH ₂ O-, -OCF _2- Or -CF ₂ O-.

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

[Polymerizable compound]

Examples of the polymerizable compound of 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 a difunctional or trifunctional group. The polymerizable compound having a reactive group may or may not contain a mesogen moiety.

In the polymerizable compound having a reactive group, the reactive group is preferably a photopolymerizable substituent. Especially when a vertical alignment film is generated by thermal polymerization, when the vertical alignment film material is thermally polymerized, since the reaction of a polymerizable compound having a reactive group can be suppressed, the reactive group is particularly preferably a photopolymerizable substituent. .

The polymerizable compound of the present invention is preferably a compound represented by the following general formula (P),

(In the above general formula (P), Z ^p1 represents a fluorine atom, a cyano group, a hydrogen atom, a hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 15 carbon atoms, and a hydrogen atom may be substituted with a halogen atom carbon atom. Alkyl groups having 1 to 15 carbon atoms, hydrogen atoms may be substituted with halogen atoms, alkenyl groups having 1 to 15 carbon atoms, hydrogen atoms may be substituted with alkenyl groups having 1 to 15 carbon atoms or -Sp ^p2 -R ^p2 ,

R ^p1 and R ^p2 each independently represent any one of the following formulae (RI) to (R-IX),

烷-2,5-二基，M^p2未經取代或亦可被碳原子數1~12之烷基、碳原子數1~12之鹵化烷基、碳原子數1~12之烷氧基、碳原子數1~12之鹵化烷氧基、鹵素原子、氰基、硝基或-R^p1取代， M^p1表示以下之式(i-11)~(ix-11)中的任一者，

In the formulae (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 a halogenated alkyl group having 1 to 5 carbon atoms, and W is Single bond, -O- or methylene, T is a single bond or -COO-, p, t and q each independently represent 0, 1 or 2, Sp ^p1 and Sp ^p2 represent a spacer group (spacer group ), Sp ^p1 and Sp ^p2 each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms, or -O- (CH ₂ ) _s- (where s represents an integer from 1 to 11, and the oxygen atom is bonded In the 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 ) zO- (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 C F ₂ -or -C≡C- (In the formula, each of R ^a independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the foregoing formula, z represents an integer of 1 to 4.), and M ^p2 represents 1 1,4-phenylene, 1,4-cyclohexyl, anthracene-2,6-diyl, phenanthrene-2,7-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl , Naphthalene-2,6-diyl, indane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or 1,3-diyl

Alkane-2,5-diyl, M ^{p2 is} unsubstituted or may also be alkyl having 1 to 12 carbon atoms, halogenated alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, Halogenated alkoxy, halogen atom, cyano, nitro or -R ^p1 substituted with 1 to 12 carbon atoms, and M ^p1 represents any one of the following formulae (i-11) to (ix-11),

(In the formula, it is bonded to Sp ^p1 in ★, and it is bonded to L ^p1 or L ^p2 in ★.), M ^p3 represents any one of the following formulas (i-13) to (ix-13),

(In the formula, it is bonded to Z ^p1 and ★ to L ^p2 .), M ^p2 to m ^p4 each independently represent 0, 1, 2, or 3, and m ^p1 and m ^p5 each independently represent 1 , 2 or 3, when there are a plurality of Z ^p1 , they may be the same or different, when there are a plurality of R ^p1 , they may be the same or different, when there are a plurality of R ^p2 In the case, they may be the same or different. When there is a plurality of Sp ^p1 , they may be the same or different. When there are a plurality of Sp ^p2 , they may be the same or different. 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. ). The polymerizable compound preferably contains one or two or more kinds.

In the general formula (P) of the present invention, Z ^{p1 is} preferably -Sp ^p2 -R ^p2 , and R ¹¹ and R ¹² are each preferably independently any one of formula (R-1) to formula (R-3) One.

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

In the general formula (P), L ^p1 is 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 ) zO- (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 is -OCH ₂ CH ₂ O-, _{-COOC 2 H 4 -, - OCOC} 2 H 4 -, - (CH 2) z -C (= O) -O -, - (CH 2) zO- (C = O) -, - O- (C = O)-(CH ₂ ) z-,-(C = O) -O- (CH ₂ ) z-, -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -C _{For 2} H ₄ OCO- or -C ₂ H ₄ COO-, z in the foregoing formula is preferably an integer of 1 to 4.

In addition, it is preferred that at least one of L ^p1 and L ^p2 in the general formula (P) is selected from-(CH ₂ ) _z -C (= O) -O-,-(CH ₂ ) zO- ( At least one of the group consisting of C = O)-and -O- (C = O)-(CH ₂ ) z-,-(C = O) -O- (CH ₂ ) z-.

Further, in the general formula (P), R ^p1 and R ^p2 are each preferably independently any one of the following formulae (R-1) to (R-15).

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

In addition, m ^{p3 of the} aforementioned general formula (P) represents 0, 1, 2 or 3; when m ^p3 is 1, M ^p2 is 1,4-phenylene; when m ^p3 is 2 or 3 , among a plurality of presence of at least transmitted preferred L M ^p2 and ^p1 and ^p1 of adjacent M M ^p2 is 1,4-phenylene.

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

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

The spacer groups (Sp ^p1 , Sp ^p2 , Sp ^p4 ) in the general formula (P) are preferably 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- The Z is preferably an integer of 1 to 10.

The polymerizable compound of the general formula (P) of the present invention is preferably at least one selected from the group consisting of compounds represented by the general formula (Pa), the general formula (Pb), the general formula (Pc), and the general formula (Pd). 1 compound.

In the general formulae (Pa) to (Pd), R ^p1 and R ^p2 each independently represent any one of the following formulae (RI) to (R-IX),

烷-2,5-二基，較佳為未經取代或經碳原子數1~12之烷基、碳原子數1~12之鹵化烷基、 碳原子數1~12之烷氧基、碳原子數1~12之鹵化烷氧基、鹵素原子、氰基、硝基或-R^p1取代， 環C表示以下之式(c-i)~(c-ix)的任一者，

In the formulae (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 a halogenated alkyl group having 1 to 5 carbon atoms, and W is Single bond, -O- or methylene, T is a single bond or -COO-, p, t and q each independently represent 0, 1 or 2, ring A and ring B each independently represent 1,4-benzene Base, 1,4-cyclohexyl, anthracene-2,6-diyl, phenanthrene-2,7-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2, 6-diyl, indane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or 1,3-diyl

Alkane-2,5-diyl is preferably unsubstituted or alkyl group having 1 to 12 carbon atoms, halogenated alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon Halogenated alkoxy, halogen atom, cyano, nitro or -R ^p1 substituted with 1 to 12 atoms, and ring C represents any one of the following formulae (ci) to (c-ix),

(In the formula, it is bonded to Sp ^p1 at ★ and L ^p5 or L ^p6 at ★★.)

Sp ^p1 and Sp ^p4 represent a spacer group, and X ^p1 to X ^p4 each preferably independently represent a hydrogen atom or a halogen atom,

L ^p4 , L ^p5 and L ^{p6 are} preferably 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-, In the formula, z is preferably 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), m ^p6 and m ^p7 each preferably independently represent 0, 1, 2 or 3. It is more preferable that m ^p6 + m ^p7 = 2 to 5.

In the compound represented by the general formula (Pd), m ^p12 and m ^p15 each independently represent 1, 2, or 3, m ^p13 preferably represents 0, 1, 2, or 3, and m ^p14 preferably represents 0 or 1. It is more preferable that m ^p12 + m ^p15 = 2 to 5. When there are a plurality of R ^p1 cases, they may be the same or different. When there are a plurality of R ^p1 cases, they may be the same or different. When there are a plurality of R ^p2 cases, they may be the same. It may be the same or different. When there is a plurality of Sp ^p1 , they may be the same or different. When there is a plurality of Sp ^p4 , they may be the same or different. When there is a plurality of L ^In the case of ^p4 and L ^p5 , they may be the same or different, and when there are a plurality of rings A to C, these may be the same or different.

The preferable structures of the compounds represented by the general formulae (P-a) to (P-d) of the present invention are exemplified below.

Preferred examples of the compound represented by the general formula (P-a) of the present invention include polymerizable compounds represented by the following formulae (P-a-1) to (P-a-31).

Preferred examples of the compound represented by the general formula (P-b) of the present invention include polymerizable compounds represented by the following formulae (P-b-1) to (P-b-34).

Preferred examples of the compound represented by the general formula (P-c) of the present invention include polymerizable compounds represented by the following formulae (P-c-1) to (P-c-52).

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

(In the compound represented by the general formula (P-d '), m ^{p10 more} preferably represents 2 or 3. Other symbols are the same as the general formula (pd), and are omitted.)

Preferred examples of the compound represented by the general formula (P-d) of the present invention include polymerizable compounds represented by the following formulae (P-d-1) to (P-d-31).

The "alkyl group having 1 to 15 carbon atoms" in the present invention is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the above 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 preferably independently an alkyl group having 1 to 8 carbon atoms. Is more preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the "alkyl group having 1 to 15 carbon atoms" in the present invention include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, and 3-pentyl. Base, isopentyl, neopentyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentayl, and the like. In the present specification, examples of the alkyl group are common, and they can be appropriately selected from the above examples according to the number of carbon atoms in each alkyl group.

As an example of the "alkoxy group having 1 to 15 carbon atoms" in the present invention, it is preferred that at least one oxygen atom in the substituent exists at a position directly bonded to the ring structure, and more preferably a methoxy group, Ethoxy, propoxy (n-propoxy, i-propoxy), butoxy, pentoxy, octyloxy, decoxy. In this specification, examples of the alkoxy group are common, and they can be appropriately selected from the above-mentioned examples according to the number of carbon atoms in each alkoxy group.

Examples of the "alkenyl group having 2 to 15 carbon atoms" in the present invention include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 1 , 3-butadienyl, 2-pentenyl, 3-pentenyl, 2-hexenyl and the like. In addition, as a more preferable alkenyl group in the present invention, the following formula (i) (vinyl), formula (ii) (1-propenyl), formula (iii) (3-butenyl), and formula (iv) (3-pentenyl) represents,

(In the above formulae (i) to (iv), * represents a site bonded to a ring structure.) However, when the liquid crystal composition of the present invention contains a polymerizable monomer, the formulae (ii) and the formulae are preferred. The structure represented by (iv) is more preferably the structure represented by formula (ii). In the present specification, examples of alkenyl groups are common, and they can be appropriately selected from the above examples according to the number of carbon atoms in each alkenyl group.

Among the polymerizable compounds of the present invention, as the polymerizable compound having a monofunctional group which is preferred for improving the solubility with low-molecular liquid crystal and suppressing crystallization, it is preferably represented by the following general formula (VI): Polymerizable compounds,

(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 represents an integer from 2 to 11) The oxygen atom is bonded to the aromatic ring.), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms. The alkylene group may be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent, or may be substituted with an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be replaced with an oxygen atom in a range where the oxygen atoms are not adjacent. ) Or a cyclic substituent, W represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups in the formula may be substituted for any hydrogen atom by -CH ₃ , -OCH ₃ , a fluorine atom or a cyano group.).

In the general formula (VI), X ³ represents a hydrogen atom or a methyl group. When the reaction rate is important, a hydrogen atom is preferred, and when a reduction in the reaction residual amount is important, a methyl group is preferred.

In the above 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 and an oxygen atom bond It is bound to an aromatic ring.) Since the length of the carbon chain affects Tg, when the content of the polymerizable compound is less than 10% by weight, it is preferably not too long, and is preferably a single bond or the number of carbon atoms. When the content of the polymerizable compound is less than 6% by weight, the alkylene group having 1 to 5 is more preferably a single bond or an alkylene group having 1 to 3 carbon atoms. When the content of the polymerizable compound is 10% by weight or more, an alkylene group having 5 to 10 carbon atoms is preferred. When Sp ³ represents -O- (CH ₂ ) _t- , t is preferably from 1 to 5, and more preferably from 1 to 3. In addition, since the number of carbon atoms affects the pretilt angle on the surface of the substrate containing the alignment film, it is preferable to use a plurality of polymerizable compounds having different carbon atom numbers of Sp ³ as needed to obtain the desired Pre-tilt angle.

In the above general formula (VI), V represents a straight-chain or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms. The alkyl group may be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent, or may be substituted with an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent) or The cyclic substituent is preferably substituted with two or more cyclic substituents.

More specifically, the polymerizable compound represented by the general formula (VI) may be a compound represented by the general formula (X1a).

(In the formula, A ¹ represents a hydrogen atom or a methyl group, and A ² represents a single bond or an alkylene group having 1 to 8 carbon atoms. (One or more methylene groups in the alkylene group may be an oxygen atom. In a manner that they are not directly bonded to each other, they are each independently replaced by an oxygen atom, -CO-, -COO-, or -OCO-, and one or more hydrogen atoms in the alkylene group can be independently replaced by fluorine atoms. , Methyl, or ethyl.), A ³ and A ⁶ each independently represent 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) In the manner that the oxygen atoms are not directly bonded to each other, each is independently replaced by an oxygen atom, -CO-, -COO-, or -OCO-, and one or more hydrogen atoms in the alkyl group may be independent of each other. Is substituted by a halogen atom or an alkyl group having 1 to 17 carbon atoms.), A ⁴ and A ⁷ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms (one of the alkyl groups) Or two or more methylene groups, each of which may be independently substituted by an oxygen atom, -CO-, -COO-, or -OCO- in a manner that oxygen atoms are not directly bonded to each other, and one or two of the alkyl groups are The above hydrogen atoms may each Is independently a halogen atom or an alkyl group having 1 to 9 carbon atoms, the substituent.), P represents ^{0 ~ 10, B 1, B} 2 and B ³ each independently represent a hydrogen atom, a straight-chain carbon atoms of 1 to 10, or Branched alkyl group (one or two or more methylene groups in the alkyl group can be independently bonded to each other by oxygen atoms, -CO-, -COO-, or -OCO -Substitution. One or two or more hydrogen atoms in the alkyl group 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 general formula (II-b).

The compound represented by the general formula (II-b) is specifically preferably a compound represented by the following formulae (II-q) to (II-z) and (II-aa) to (II-al).

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

The polymerizable compound represented by the general formula (VI) may be a compound represented by the general formula (X1b).

(Wherein A ⁸ represents a hydrogen atom or a methyl group, and the 6-membered rings T ¹ , T ^2, and T ³ each independently represent any of the following,

(Where q represents an integer from 1 to 4.), q represents 0 or 1, Y ¹ and Y ² each independently represents 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 each independently represents a single bond, and an alkylene group having 1 to 12 carbon atoms (1 of the alkylene group) Two or more methylene groups, each of which may be independently substituted by an oxygen atom, -CO-, -COO-, or -OCO- in a manner that oxygen atoms are not directly bonded to each other, and one or more of the alkylene groups Each of two or more hydrogen atoms may be independently substituted by a fluorine atom, a methyl group, or an ethyl group.), B ⁸ represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, or a terminal having propylene fluorene Alkyl or methacrylfluorene. ).

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

Further, the polymerizable compound represented by the general formula (VI) may specifically be a compound represented by the general formula (X1c),

(In the formula, R ⁷⁰ represents a hydrogen atom or a methyl group, and R ⁷¹ represents a hydrocarbon group having a condensed ring.). Exemplary compounds are shown below, but are not limited thereto.

Among the polymerizable compounds of the present invention, the polymerizable compound having a reactive group having a polyfunctionality which is preferable for improving the solubility with a low-molecular liquid crystal and suppressing crystallization is preferably represented by the following general formula (V). Polymerizable compounds,

(Wherein 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 -(In the formula, s represents an integer of 1 to 11, and an oxygen atom is bonded to an aromatic ring.), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or 5 to 30 carbon atoms Valent cyclic substituents, the alkylene group in the polyvalent alkylene group may be replaced by an oxygen atom in the range where the oxygen atoms are not adjacent, or may be an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be It is substituted by an oxygen atom in a range where the oxygen atoms are not adjacent.) Or a cyclic substituent, k represents an integer of 1 to 5. In all 1,4-phenylene groups, any hydrogen atom may be replaced by -CH ₃ , -OCH ₃ , a fluorine atom or a cyano group.).

In the above general formula (V), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, but when a reaction speed is important, a hydrogen atom is preferred, and when a reduction in a reaction residual amount is important, Methyl is preferred.

In the general formula (V), 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- (where s represents 2 to 11 An integer, an oxygen atom is bonded to an aromatic ring.) The pretilt angle of the liquid crystal display element of the present invention is affected by the number of carbon atoms, the content with the liquid crystal, the type of alignment film used, or the alignment processing conditions. It is preferred to use a person who spontaneously induces a pretilt angle on the surface of the alignment film depending on the molecular structure of the polymerizable compound. Therefore, it is not necessarily limited. For example, when the pretilt angle is about 5 degrees, the carbon chain is preferably not too long, more preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and more preferably Single bond or alkylene with 1 to 3 carbon atoms. In addition, if the pretilt angle is 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. When Sp ¹ and Sp ² represent -O- (CH ₂ ) _s- , the pretilt angle is also affected. Therefore, it is better to adjust the lengths of Sp ¹ and Sp ² as needed. When used, in order to increase the pretilt angle, s is preferably 1 to 5, and more preferably 1 to 3. In order to reduce 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, asymmetry of a molecule is exhibited, and pretilt is induced, so it is preferable.

Further, in the general formula (V), it is also preferable that Sp ¹ and Sp ² are the same. It is preferable to use two or more kinds of 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 .

In the above general formula (V), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms. An alkyl group may be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent, or an alkyl group having 5 to 20 carbon atoms (an alkylene group in the group may be replaced with an oxygen atom in a range where the oxygen atoms are not adjacent.), A ring Substituent substituents are preferably substituted by two or more cyclic substituents.

In the general formula (V), U specifically preferably represents the following formulae (Va-1) to (Va-13). In order to increase the anchoring force, biphenyl or the like having high linearity is preferred, and the formulae (Va-1) to (Va-6) are preferably expressed. The structures representing the formulae (Va-6) to (Va-11) are preferred in terms of high solubility with liquid crystals, and are preferably used in combination with the formulae (Va-1) to (Va-6).

(In the formula, both ends are bonded to Sp ¹ or Sp ^2. Z ^p1 and Z ^p2 each independently represent -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. All 1,4-phenylene groups in the formula can be replaced by any hydrogen atom It is -CH ₃ , -OCH ₃ , a fluorine atom, or a cyano group. Furthermore, one or more CH ₂ CH ₂ groups in the cyclohexyl group may be -CH = CH-, -CF ₂ O-, -OCF. ₂ -replaced.)

When U has a ring structure, it is preferable that at least one of the aforementioned Sp ¹ and Sp ² represents -O- (CH ₂ ) _s- (wherein s represents an integer of 1 to 7, and an oxygen atom is bonded to an aromatic ring. ), And preferably both are -O- (CH ₂ ) _s- .

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

The compound represented by the general formula (V) is specifically preferably a compound represented by the following general formula (Vb).

(Wherein 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 -(In the formula, 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-, -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, C represents 1,4-phenylene, trans-1,4-cyclohexyl, or a single bond, and all 1,4-phenylenes in the formula may have any hydrogen atom replaced by a fluorine atom.)

In the above general formula (Vb), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, preferably a diacrylate derivative both representing a hydrogen atom, or a dimethacrylate derivative each having a methyl group It is also preferably a compound in which one represents a hydrogen atom and the other represents a methyl group. The polymerization speed of these compounds is the fastest with diacrylate derivatives and slower with dimethacrylate derivatives. Asymmetric compounds are in the middle, which can be used in a better state according to their applications.

In the above 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-, and preferably at least one of them is -O. -(CH ₂ ) s-, more preferably, both represent -O- (CH ₂ ) s-. 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, preferably -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF ₂ -or a single bond, more preferably -COO-, -OCO- or a single bond, Especially preferred is a single key. In the above general formula (Vb), C represents 1,4-phenylene, trans-1,4-cyclohexyl, or a single bond in which any hydrogen atom may be substituted by a fluorine atom, preferably 1,4-phenylene. Phenyl or single bond. When C represents a ring structure other than a single bond, Z ^{1 is} also preferably a linking group other than a single bond, and when C is a single bond, Z ^{1 is} preferably a single bond.

According to the above, in the general formula (Vb), it is preferable that C represents a single bond and the ring structure is formed by two rings. As a polymerizable compound having a ring structure, specifically, the following general formula ( The compounds represented by V-1) to (V-6) are particularly preferably compounds represented by general formulae (V-1) to (V-4), and most preferably compounds represented by general formula (V-2).

In addition, in the general formula (Vb), compounds represented by the following general formulae (V1-1) to (V1-5) are preferable in terms of improving solubility with a liquid crystal composition, and particularly preferably the general formula (V1) -1).

In addition, the case where the general formula (Vb) is formed by three ring structures is also preferably used. The compounds represented by general formulae (V1-6) to (V1-13) are used to improve the solubility with the liquid crystal composition. Better. In addition, the compounds represented by the general formulae (V-1) to (V-6) having strong anchoring force with liquid crystals are also preferably the general formula (V1-) having weak anchoring force but good compatibility with liquid crystal compositions. 1) Compounds represented by (V1-5) are used in combination.

(In the formula, q1 and q2 each independently represent an integer of 1 to 12, and R ³ represents a hydrogen atom or a methyl group.)

As the compound represented by the general formula (V), specifically, the compound represented by the following general formula (Vc) is preferable in terms of increasing the reaction rate, and it is also preferable because the pretilt angle is thermally stabilized. In addition, the number of carbon atoms of Sp ¹ , Sp ² and Sp ³ can be adjusted as needed to obtain the desired pretilt angle. The relationship between the pretilt and the number of carbon atoms shows the same tendency as when the number of functional groups is two.

(Wherein 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, an alkylene group having 1 to 12 carbon atoms, or -O -(CH ₂ ) _s- (In the formula, s represents an integer of 2 to 7, and an oxygen atom is bonded to an aromatic ring.), 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 single bond, J represents 1,4-phenylene, trans (1,4-cyclohexyl or single bond, all 1,4-phenylenes in the formula may have any hydrogen atom replaced by a fluorine atom.)

It is also preferable to use a compound having a photo-alignment function as the polymerizable compound. Among them, a compound exhibiting photoisomerization is preferably used.

As the polymerizable compound having a photo-alignment function, specifically, the following compounds are preferable; 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 represents 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, trans-1,4-cyclohexyl (any hydrogen atom may be substituted by a fluorine atom.) Or a single bond.

Among them, a compound represented by the following general formula (Vn) is preferred.

(式中，Rn₁及Rn₂各自獨立地表示氫原子或甲基，式中，pn及qn各自獨立地表示1~12之整數。)

(In the formula, Rn ₁ and Rn ₂ each independently represent a hydrogen atom or a methyl group, and in the formula, pn and qn each independently represent an integer of 1 to 12.)

[Polymerization initiator]

As a polymerization method of the polymerizable compound used in the present invention, radical polymerization, anionic polymerization, and cationic polymerization can be used. The polymerization is preferably performed by radical polymerization, and more preferably, the freedom is performed by photo-fries rearrangement. Radical polymerization, radical polymerization using a photopolymerization initiator.

As the radical polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator can be used, and a photopolymerization initiator is preferred. Specifically, the following compounds are preferred.

啉基(4-硫代甲基苯基(thiomethylphenyl))丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-N-

啉基苯基)-丁酮、4'-苯氧基苯乙酮、4'-乙氧基苯乙酮等苯乙酮系；安息香、安息香異丙醚、安息香異丁醚、安息香甲醚、安息香乙醚等安息香系；2,4,6-三甲基苄醯基二苯基膦氧化物等醯基膦氧化物系； 二苯乙二酮、甲基苯基乙醛醯酯(methylphenylglyoxyester)系；二苯甲酮、鄰苄醯基苯甲酸甲酯、4-苯基二苯甲酮、4,4'-二氯二苯甲酮、羥基二苯甲酮、4-苄醯基-4'-甲基-二苯硫醚、丙烯酸化二苯甲酮、3,3',4,4'-四(三級丁基過氧化羰基)二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮、2,5-二甲基二苯甲酮、3,4-二甲基二苯甲酮等二苯甲酮系；2-異丙基9-氧硫

、2,4-二甲基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

等之9-氧硫

系；米其勒酮、4,4'-二乙基胺基二苯甲酮等胺基二苯甲酮系；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌等。其中，最佳為二苯乙二酮二甲基縮酮。 Preferred are: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diacetophenone dimethyl ketal, 1- (4-isopropyl (Phenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl-benzene Ketone, 2-methyl-2-N-

(4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1- (4-N-

(Phenylphenyl) -butanone, 4'-phenoxyacetophenone, 4'-ethoxyacetophenone and other acetophenone series; benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, Benzoin series such as benzoin ether; fluorenylphosphine oxide series such as 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide; diphendione, methylphenylglyoxyester series ; Benzophenone, methyl benzyl benzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzylfluorenyl-4 ' -Methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetrakis (tertiary-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl- Benzophenones such as 4-methoxybenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone; 2-isopropyl9-oxosulfone

2,4-dimethyl 9-oxosulfur

, 2,4-diethyl 9-oxysulfur

, 2,4-dichloro 9-oxysulfur

9-oxysulfur

Series; aminobenzophenone series such as Michelin, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9 , 10-phenanthrenequinone, camphorquinone, etc. Among them, diacetophenone dimethyl ketal is most preferred.

In consideration of the lifetime or reactivity of the radical, it is also preferable to use a plurality of polymerization initiators.

In addition, as a form of radical polymerization using photofries rearrangement without using the above-mentioned polymerization initiator, a polymerizable liquid crystal compound having a conjugated structure that absorbs ultraviolet rays may be contained and polymerized. For example, by using a polymerizable liquid crystal compound having a conjugated structure represented by the general formulae (X1c-1) to (X1c-4) instead of a polymerization initiator, the voltage retention of the liquid crystal element is not reduced, so it is preferable. . In order to promote polymerization, it is also preferable to use these in combination with a polymerization initiator.

[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, and the lower limit of the content of the polymerizable compound It is preferably 1% by mass or more, more preferably 2% by mass or more, and the upper limit value is preferably not more than 9% by mass, and more preferably not more than 7% by mass. The polymerizable liquid crystal composition used in the present invention preferably also contains the liquid crystal composition exemplified above and the polymerizable compound exemplified above 10% by mass and less than 40% by mass. The polymerizability in this case The lower limit value of the content of the compound is preferably 15% by mass or more, more preferably 20% by mass or more, and the upper limit value is preferably not more than 30% by mass, and more preferably not more than 25% by mass. 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 preferably has a uniaxial optical anisotropy or uniaxial refraction by containing a polymerizable compound of 0.5% by mass or more and less than 40% by mass. The polymer network in the direction of the anisotropy or easy alignment axis is more preferably formed in such a manner that the optical axis or the easy alignment axis of the polymer network and the easy alignment axis of the low-molecular liquid crystal are substantially the same. In addition, the polymer network also contains a polymer adhesive formed by combining a plurality of polymer networks to form a polymer film. The polymer adhesive is characterized in that it has a refractive index anisotropy that exhibits uniaxial alignment, and the low-molecular liquid crystal is dispersed in the film. The uniaxial optical axis of the film and the optical axis of the low-molecular liquid crystal are oriented substantially in the same direction. . Therefore, it is different from the polymer-dispersed liquid crystal or polymer network liquid crystal which is a light-scattering liquid crystal, and is characterized in that a high-contrast display can be obtained in a liquid crystal element that does not cause light scattering and uses polarized light, and Shorten the fall time and improve the responsiveness of the liquid crystal element. In addition, the polymerizable liquid crystal composition used in the present invention is formed of a polymer network layer on the entire liquid crystal element, which is different from the PSA (Polymer Sustained Alignment) in which a polymer thin film layer is formed on a liquid crystal element substrate to induce pretilt. Type liquid crystal composition.

Regardless of the concentration, it is preferable to contain at least two or more polymerizable compounds having different Tgs and adjust Tg as necessary. The polymerizable compound having a higher Tg (being a polymer precursor) is preferably a polymerizable compound having a molecular structure with a high crosslinking density and the number of functional groups is 2 or more. In addition, the precursor of the polymer having a low Tg is preferably a structure in which the number of functional groups is 1 or 2 or more, and the length of the molecule is increased by having an alkylene group or the like as a spacer between the functional groups. When adjusting the Tg of the polymer network in order to improve the thermal stability or impact resistance of the polymer network, it is preferable to appropriately adjust the ratio of the polyfunctional monomer to the monofunctional monomer. In addition, Tg is also related to the molecular-level thermal mobility in the main chain and side chains of the polymer network, which also affects the electro-optical characteristics. For example, if the crosslink density is increased, the molecular mobility of the main chain will decrease, the anchoring force with the low-molecular liquid crystal will increase, the driving voltage will become higher, and the fall time will be shorter. On the other hand, if the crosslink density is reduced to reduce Tg, the thermal mobility of the polymer main chain will be improved and it will be anchored with low molecular liquid crystals. The force decreases, the driving voltage decreases, and the falling time tends to be longer. In addition to the above Tg, the anchoring force at the polymer network interface will also be affected by the molecular mobility of the polymer side chain. The anchoring force at the polymer interface will be affected by the use of polyvalent branched alkyl groups and polyvalent groups. Alkyl polymerizable compounds are reduced. In addition, a polymerizable compound having a polyvalent branched alkylene group and a polyvalent alkyl group can effectively induce a pretilt angle at the substrate interface, and will act in a direction that reduces the anchoring force in the polar angle direction.

In a state where the polymerizable liquid crystal composition shows a liquid crystal phase, the polymerizable compound in the polymerizable liquid crystal composition is polymerized, thereby increasing the molecular weight of the polymerizable compound, and causing the liquid crystal composition and the polymerizable compound to undergo phase separation. The morphology separated into two phases largely differs depending on the type of liquid crystal compound or polymerizable compound contained. Phase separation structure can be formed by binodal decomposition, and spinodal decomposition can also be used to form phase separation structure. The binode decomposition generates numerous island-like polymerizable compound phases in the liquid crystal phase. The spinodal decomposition results in phase separation caused by fluctuations in the concentration of the liquid crystal phase and the polymerizable compound phase. To form a polymer network caused by bisection decomposition, it is preferable that the content of the low-molecular liquid crystal is at least 85% by mass or more. By using a polymerizable compound having a fast reaction rate, countless polymerizations having a size smaller than the wavelength of visible light are generated. The nucleus of the sex compound forms a nano-scale phase separation structure, so it is preferred. As a result, if the polymerization in the polymerizable compound phase proceeds, a polymer network having a void space smaller than the wavelength of visible light is formed depending on the phase separation structure. On the other hand, the voids in the polymer network are separated by the phase of the low-molecular liquid crystal phase. Cause: If the size of the gap is smaller than the wavelength of visible light, there will be no light scattering and high contrast, and the effect of the anchoring force from the polymer network will be stronger, the fall time will be shorter, and a high-speed response will be obtained. Liquid crystal display elements. The nucleation of the two-stage decomposed polymerizable compound phase may be affected by changes in the compatibility due to the type or combination of the compounds, or affected by parameters such as reaction speed and temperature. It is preferably adjusted as necessary. Regarding the reaction rate, in the case of ultraviolet polymerization, depending on the type and content of the functional group or photoinitiator of the polymerizable compound, and the intensity of ultraviolet irradiation, as long as the ultraviolet irradiation conditions are appropriately adjusted to promote reactivity, it is preferably UV radiation intensity of at least 20mW / cm ² or more. When the low-molecular-weight liquid crystal is 85% by mass or more, it is preferable to form a polymer network using a phase separation structure caused by spinodal decomposition. The spinodal decomposition can obtain phase separation caused by fluctuations in the concentration of two phases having periodicity. The fine structure is preferable because it is easy to form a uniform and uniform void space smaller than the wavelength of visible light. It is preferably formed as a polymer network. If the proportion of the polymerizable compound is less than 15% by mass, it is preferable to form a phase separation structure caused by binode decomposition, and if it is 15% by mass or more, it is preferable to form a phase separation structure caused by spinodal decomposition. When the content of the polymerizable compound increases, there is a phase transition temperature at which the low-molecular liquid crystal phase and the polymerizable compound phase undergo two-phase separation under the influence of temperature. If the temperature is higher than the two-phase separation transition temperature, an isotropic phase will appear, but if it is lower than this temperature, separation will occur, and a uniform phase separation structure cannot be obtained, which is not good. When two-phase separation occurs due to temperature, it is preferable to form a phase-separated structure at a temperature higher than the two-phase separation temperature. In either case, the same alignment state as that of the low-molecular liquid crystal is maintained, and a polymer network is formed at the same time. The formed polymer network exhibits optical anisotropy in a manner that mimics the alignment of low-molecular liquid crystals. Examples of the form of the liquid crystal layer in the polymer network include 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. A mixed structure, and a polymer network layer starting from the two substrate surfaces, and having a liquid crystal layer near the center of the opposite substrate. Regardless of the structure, it is preferable to induce a pretilt angle of 0 to 90 ° with respect to the interface of the liquid crystal element substrate by the action of the polymer network. The formed polymer network preferably has the function of coordinating the coexisting low-molecular liquid crystals along the alignment direction presented by the alignment film of the liquid crystal cell, and also preferably has the function of pre-tilting the low-molecular liquid crystals to the polymer interface direction. . The introduction of a polymerizable compound that pre-tilts the low-molecular-weight liquid crystal to the polymer interface is useful for improving transmittance or reducing the driving voltage of the liquid crystal element, so it is preferable. In addition, as for the function of having refractive index anisotropy and orienting the liquid crystal in the alignment direction, a polymerizable compound having a liquid crystal original group is preferably used. In addition, a polymer network may be formed by applying a voltage and simultaneously irradiating ultraviolet rays or the like to form a pretilt.

For a vertical alignment unit such as VA mode, a polymerizable compound having a polyvalent alkyl group or a polyvalent branched alkylene group which does not have a mesogen group and induces vertical alignment may be used, and it may be combined with a polymerizable compound having a mesogen group. It is also good to use. When the polymerizable liquid crystal composition is used to form a polymer network in a vertical alignment cell by phase separation polymerization, it is preferable to form a fibrous shape in a direction approximately the same as the direction in which the low-molecular liquid crystal is perpendicular to the liquid crystal cell substrate. Or columnar polymer networks. When a vertical alignment film is used and the vertical alignment film located on the surface of the unit substrate is subjected to a rubbing treatment or the like to induce tilted alignment of the liquid crystal to induce a pretilt angle, it is preferable that a fibrous or columnar polymer network is formed inclined with the The pre-tilt alignment of the low-molecular liquid crystals is in the same direction. The tilt of the polymer network can also select polymerizable compounds in a way that occurs spontaneously at the substrate interface. Alternatively, a voltage may be applied to bring the liquid crystal into a tilted alignment state, and a polymer network may be formed by irradiating ultraviolet rays or the like.

In addition, as a method of applying a voltage and inducing a pretilt angle at the same time, a voltage may be applied and polymerized simultaneously in a range of about 0.9 V lower than the critical voltage of the polymerizable liquid crystal composition and about 2 V higher than the critical voltage of the polymerizable liquid crystal composition. In the process of forming a polymer network, a voltage of more than a critical voltage is applied for a short time of several seconds to several tens of seconds, so that the critical voltage is not reached to form a polymer network. Because the fibrous or columnar polymer network is formed obliquely to induce a 90-degree angle with respect to the plane of the transparent substrate A pretilt angle of ~ 80 degrees is better, preferably a pretilt angle of 90 degrees to 85 degrees, preferably a pretilt angle of 89.9 degrees to 85 degrees, more preferably a pretilt angle of 89.9 degrees to 87 degrees, and more preferably Pre-tilt angle from 89.9 degrees to 88 degrees. A fibrous or columnar polymer network formed by any method is characterized in that two unit substrates are connected to each other. Thereby, the thermal stability of the pretilt angle can be improved, and the reliability of the liquid crystal display element can be improved.

In addition, as a method for inducing a pretilt angle of a low-molecular liquid crystal by forming an oblique alignment of a fibrous or columnar polymer network, the following method may be mentioned: a carbon of an alkylene group located between a functional group and a mesogen group A combination of a bifunctional acrylate having 6 or more atoms and a small pretilt induced angle and a bifunctional acrylate having a carbon number of 5 or more and a large pretilt induced angle of the alkylene group between the functional group and the mesogen. use. The desired pretilt angle can be induced near the interface by adjusting the blending ratio of these compounds.

In addition, 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% can be mentioned. In this case, the trans-form will have the same rod-like morphology as the low-molecular liquid crystal, which will affect the alignment state of the low-molecular liquid crystal. If the trans isomer contained in the polymerizable liquid crystal composition of the present invention is irradiated with ultraviolet rays from the upper surface of the unit in the form of parallel light, the long axis direction of the rod-shaped molecules will be uniformly parallel to the ultraviolet traveling direction. At the same time, the molecules are aligned in the direction of the major axis of the trans isomer. When the unit is irradiated with ultraviolet rays obliquely, the long axis of the molecules of the trans-isomer will face the oblique direction, and the liquid crystal will be aligned in the oblique direction of the ultraviolet rays. That is, a pretilt angle is induced, and a light alignment function is exhibited. If the polymerizable compound is crosslinked at this stage, the induced pretilt angle will be fixed due to the fibrous or columnar polymer network formed by the polymerized phase separation. Therefore, regarding the induction of the important pretilt angle in the VA mode, the following methods can be used to make the present invention as needed. Liquid crystal element: a method of applying a voltage and separating the polymerized phases at the same time; a method of adding a plurality of polymerizable compounds with different pretilt angles induced to separate the polymerized phases; a polymerizable compound with a reversible photo-alignment function A method for photo-alignment to align a low-molecular liquid crystal and a polymerizable liquid crystal compound in the direction of ultraviolet rays and perform a polymerization phase separation.

The polymerizable compound having a photo-alignment function is preferably a photoisomer compound that absorbs ultraviolet rays and becomes a trans isomer. Furthermore, the reaction rate of the polymerizable compound having a photo-alignment function is slower than that of a polymerizable compound having a photo-alignment function. Reaction rate of polymerizable compounds other than compounds. If it is irradiated with ultraviolet rays, if the polymerizable compound having a photo-alignment function is immediately converted into an isomer and aligned in the direction of travel of the light, the liquid crystal compound containing the polymerizable compound around will also be aligned in the same direction. At this time, the polymerization phase separation will proceed, and the long-axis direction of the low-molecular liquid crystal and the easy-alignment axis direction of the polymer network will be aligned in the same direction as the easy-alignment axis of the polymerizable compound having a photo-alignment function, and will be in the direction of the ultraviolet light. Induced pretilt angle.

In parallel alignment units such as IPS or FFS mode, a polymerizable liquid crystal composition is used to form a fibrous or columnar polymer network by phase separation polymerization. The low-molecular liquid crystal is aligned with the alignment film on the substrate surface of the liquid crystal cell. The alignment direction of the alignment is parallel, and the refractive index anisotropy or easy alignment axis direction of the formed fibrous or columnar polymer network is preferably the same direction as that of the low-molecular liquid crystal. Further, it is more preferable that the fibrous or columnar polymer network exists substantially in the entire cell except for the voids in which the low-molecular liquid crystal is dispersed. In order to induce the pretilt angle with respect to the direction of the polymer interface, it is preferable to use a polymerizable compound having no mesogen and having a polyvalent alkyl group or a polyvalent alkylene group and a polymerizable compound having a mesogen.

In addition, the electro-optical characteristics are affected by the surface area of the polymer network interface and the void spacing of the polymer network. It is important that light scattering does not occur. It is preferable to make the average void spacing small. At visible wavelengths. For example, there is a method of increasing the surface area of the interface and reducing the gap interval to increase the content of the monomer composition. Therefore, the polymerized phase separation structure is changed, and the interstitial space becomes finer, thereby forming a polymer network so as to increase the surface area of the interface, and the driving voltage and the fall time are reduced. 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 accelerating the phase separation speed and polymerizing it. The phase separation speed is greatly affected by the compatibility or polymerization speed of the low-molecular liquid crystal with the polymerizable compound. Since it depends very much on the molecular structure or content of the compound, it is preferable to adjust the composition and use it appropriately. In the case where the compatibility is high, it is preferable to use the polymerizable compound having a fast polymerization rate, and 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 speed becomes fast enough, so it is useful for producing the liquid crystal element of the present invention. As a method of reducing the compatibility, a method of polymerizing at a low temperature may be mentioned. If it is at a low temperature, the alignment order of the liquid crystal will be improved, and the compatibility between the liquid crystal and the monomer will be reduced, so the polymerization phase separation speed can be accelerated. Furthermore, as another method, a method of polymerizing a polymerizable liquid crystal composition at a temperature at which the polymerizable liquid crystal composition is brought into a supercooled state may be mentioned. In this case, as long as it is slightly lower than the melting point of the polymerizable liquid crystal composition, it is preferable to reduce the temperature by only a few degrees and accelerate the phase separation. As a result, a polymer phase separation structure equivalent to the case where a monomer composition with a content of tens of% is added to the liquid crystal is formed, that is, the surface area of the polymer network interface having a structure that functions to shorten the fall time. A polymer network structure with enlarged and finely spaced gaps. Therefore, in the polymerizable liquid crystal composition of the present invention, it is preferable to consider the alignment function, the cross-linking density, the anchoring force, and the gap interval, and to adjust the polymerizable liquid crystal composition appropriately so as to shorten the fall time.

In the liquid crystal device using the polymerizable liquid crystal composition of the present invention, a high contrast display is required. It is shown that light scattering must not occur. It is important to control the phase separation structure to form an appropriate polymer network layer structure in consideration of the above methods to obtain the target voltage-transmittance characteristics and switching characteristics. The specific description of the polymer network layer structure is as follows.

<Polymer Network Layer Continuous Structure>

It is preferable that the 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. The easy alignment axis or uniaxial optical axis of the polymer network and the easy alignment axis of the low-molecular liquid crystal are: In the same direction, it is preferable to form a polymer network by inducing the pretilt angle of the low-molecular liquid crystal. By making the average void space of the polymer network smaller than the wavelength of visible light, at least less than 450 nm, light scattering does not occur. , So it is better. When the response time (anchoring force) of the polymer network and the low-molecular liquid crystal is used to make the fall time of the response shorter than the response time of the low-molecular liquid crystal element, it is preferably set to a range of 50 nm to 450 nm. In order to reduce the influence of the cell thickness of the liquid crystal on the fall time, even if the cell thickness is thick, a fall time equivalent to that of the thin thickness is exhibited. It is preferable that the average gap interval be at least the lower limit of 200 nm and the upper limit of 450 nm. If the average gap interval is reduced, there is a problem that the driving voltage is increased. To suppress the increase of the driving voltage below 25V and shorten the fall response time, as long as the average gap interval is in the range of about 250nm to 450nm, the fall response time can be improved. It is preferably in a range of about 5 msec to about 1 msec. In addition, in order to suppress the increase in the driving voltage to within about 5 V, it is preferable to set the average gap interval to a range of about 300 nm to 450 nm. In addition, the average void interval of the polymer network can also be controlled, so that the falling response time is a high-speed response of 1 msec or less. Although the driving voltage may be increased to 30 V or higher, the average gap interval may be between 50 nm and 250 nm. When the average gap interval is 0.5 msec or less, the average gap interval is preferably between 50 nm and 200 nm. The average diameter of the polymer network is the opposite of the average void spacing. It is preferably in the range of 20nm to 700nm. When the content of the polymerizable compound increases, the average diameter tends to increase. If the reactivity is increased and the polymerization phase separation speed is increased, the density of the polymer network will increase, and the average diameter of the polymer network will decrease, so it is only necessary to adjust the phase separation conditions as needed. When the content of the polymerizable compound is 10% or less, the average diameter is preferably in a range of 20 nm to 160 nm, and when the average gap interval is in a range of 200 nm to 450 nm, the average diameter is preferably in a range of 40 nm to 160 nm. When the content of the polymerizable compound is more than 10%, a range of 50 nm to 700 nm is preferred, and a range of 50 nm to 400 nm is more preferred.

<Discontinuous Structure of Polymer Network Layer>

In contrast to a structure in which a polymer network layer is formed on the entire surface of the liquid crystal display element and the liquid crystal phase is continuous, if the content of the polymerizable compound becomes low and the amount required for the entire polymer network layer coating unit is insufficient, the polymer network Layers may form discontinuously. If the polarity of the surface of the substrate such as polyimide alignment film is high, the polymerizable compound will easily gather near the interface of the liquid crystal cell substrate, and the polymer network will grow from the substrate surface and form a polymer network layer by attaching to the substrate interface. It is formed by sequentially laminating a polymer network layer, a liquid crystal layer, a polymer network layer, and an opposite substrate from the surface of the unit substrate. If the layered structure of the polymer network layer / liquid crystal layer / polymer network layer is present and at least 0.5% (preferably 1% or more, more preferably 5% or more) of the cell thickness is formed in the direction of the cell cross section. The thickness of the polymer network layer will show the effect of shortening the fall time due to the anchoring force of the polymer network and the low-molecular liquid crystal, showing a better tendency. Among them, since the influence of the cell thickness becomes larger, when the fall time becomes longer if the cell thickness is increased, the polymer network layer thickness may be increased as needed. The structure of the polymer network in the polymer network layer, as long as the low-molecular liquid crystal and the easy-alignment axis or the uniaxial optical axis are oriented in the same direction, as long as the low-molecular liquid crystal is formed in a manner that induces a pretilt angle, that is, can. Average void The interval is preferably in a range of 90 nm to 450 nm.

For example, when the content of the polymerizable compound is from 1% by mass to 6% by mass, it is preferable to use a bifunctional monomer having a liquid crystal priming group having a high anchoring force, and it is preferable to use a structure having a short distance between functional groups and a polymerization rate. A fast bifunctional monomer, preferably at a low temperature below 0 ° C, forms a polymeric phase separation structure. When the content of the polymerizable compound is from 6% by mass to less than 10% by mass, a combination of the difunctional monomer and a monofunctional monomer having a weak anchoring force is preferred, and it is preferably at 25 ° C to-if necessary In the range of 20 ° C, a polymer phase separation structure is formed. In addition, if the melting point is equal to or higher than room temperature, if the melting point is lowered by about 5 ° C from the melting point, the same effect as that of low-temperature polymerization can be obtained, which is preferable. When the content of the polymerizable compound is 10% to 40% by mass, it is preferable because the polymer binder or the polymer network seriously affects the alignment or driving voltage of the low-molecular liquid crystal and increases the driving voltage. A polymerizable compound having a mesogen group having an alignment function of a low-molecular liquid crystal and a relatively weak anchoring force is used. For example, for a polymerizable compound having a weak anchoring force and having a mesogen group, it is effective to increase the number of carbons of the alkylene group located between the functional group and the mesogen group, and the number of carbons is preferably 5 to 10. In addition, if the polymerizable compound exceeds 30% by mass, the liquid crystal droplets may be dispersed in the polymer binder. In this case, a polymer binder having refractive index anisotropy is also preferred. And the alignment direction displayed by the alignment film on the substrate surface is consistent with the optical axis direction of the polymer adhesive.

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 faster τ d becomes. On the other hand, if the anchoring force at the interface between the liquid crystal composition and the polymer becomes large, τ r becomes low. In order to make the sum of τ d and τ r 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, preferably 2% by mass or more and 15% by mass or less. , More preferably 3% by mass or more and 8% by mass %the following.

When used in a TFT-driven liquid crystal display device, it is necessary to suppress flicker and improve the reliability of afterimages and the like caused by afterimages. The voltage retention ratio becomes an important characteristic. The reason why the voltage holding ratio is lowered is considered to be the ionic impurities contained in the polymerizable liquid crystal composition. In particular, moving ions can seriously affect the voltage holding rate. Therefore, it is preferable to obtain at least 10 ¹⁴ Ω. A specific resistance of cm or more is used to remove mobile ions by performing a purification process or the like. In addition, if a polymer network is formed by radical polymerization, the voltage retention rate may be reduced due to ionic impurities generated by a photopolymerization initiator and the like. It is preferable to select an organic acid or a low-molecular by-product amount. Less polymerization initiator.

[Liquid crystal display element]

The liquid crystal display element of the present invention contains a polymer or a copolymer in a liquid crystal composition. The liquid crystal composition is sandwiched between at least one transparent substrate having two electrodes. The content of the polymer or copolymer is the liquid crystal. The total mass of the composition and the polymer or copolymer is 0.5% by mass or more and less than 40% by mass. The polymer or copolymer forms a polymer network having a uniaxial refractive index anisotropy. Or easy to align the axis, and have two or more different alignment 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. When a voltage is applied to the alignment film disposed on the substrate and the electrode disposed on the substrate, the alignment of the liquid crystal molecules will be controlled. The polymer network or polymer adhesive has uniaxial refractive index anisotropy or easy alignment axis direction, preferably the optical network direction or easy alignment axis direction of the polymer network or polymer adhesive and low molecular liquid crystal The easy alignment axis direction is the same direction. In this regard, it is different from a light-scattering polymer network liquid crystal or a polymer-dispersed liquid crystal that does not have a uniaxial refractive index anisotropy or an easy alignment axis direction.

Moreover, it is preferable that the easy-alignment axis direction of the alignment film is the same as the easy-alignment axis direction of the polymer network or the polymer adhesive. By providing a polarizing plate, a retardation film, and the like, display is performed using this alignment state. As a liquid crystal display element, it can be applied to TN, STN, ECB, VA, VA-TN, IPS, FFS, π unit, OCB, cholesterol-type liquid crystal and other operating modes. Among them, VA, IPS, FFS, VA-TN, TN, and ECB are particularly preferred. In addition, the liquid crystal display element of the present invention is different from a PSA (Polymer Sustained Alignment) type liquid crystal display element having a polymer or copolymer on an alignment film in terms of a polymer or copolymer contained in a liquid crystal composition.

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, and as the lower limit, it is preferably 0.7% by mass. The above is preferably 0.9% by mass or more, and as the upper limit, it is preferably not more than 30% by mass, and more preferably not more than 20% by mass.

In the PSA type liquid crystal display element, a plurality of slits with a width of 3 to 5 μm are provided on the electrodes to tilt the liquid crystal toward the slit direction instead of the rubbing alignment process, thereby omitting the alignment process. In mass production technology, if a voltage of tens of volts is applied and ultraviolet rays are irradiated at the same time, the alignment of the liquid crystal will be stabilized by the polymer at the substrate interface to obtain a pretilt angle (inclination angle with respect to the substrate normal), forming Polymer film. The pretilt angle is induced by the effect of the polymer film. Using this phenomenon, it can be used in the manufacture of PSVA (polymer-stabilized vertical alignment) LCD or PSALCD. In addition, in order to improve the viewing angle, a pattern electrode designed to form multiple regions is used to divide the pretilt direction in one pixel into a plurality. When a liquid crystal with negative dielectric anisotropy is used, if a voltage equal to or higher than the saturation voltage is applied to the cell and the ultraviolet rays are irradiated in such a manner that the vertical alignment of the liquid crystal is converted to a bend alignment, a small amount of When the monomer in the liquid crystal is polymerized on the vertical alignment film, the following alignment film is formed: The slightly inclined liquid crystal alignment polymer for the bent deformation end stabilizes and induces a pretilt angle. Thereby, if the irradiation of ultraviolet rays is ended and the application of voltage is interrupted, a slightly inclined (pre-tilted) vertical alignment can be obtained. However, if this method is applied to a liquid crystal display element that can form a polymer network as a whole to improve the relaxation time of a response, a voltage of several tens of volts or more above the saturation voltage is applied for ultraviolet irradiation. The internet of things will stabilize the liquid crystal polymer in the state of parallel alignment. Because the refractive anisotropy or easy alignment axis of the polymer network is formed in such a manner that the liquid crystal molecules are maintained in a parallel alignment state, vertical alignment cannot be obtained.

In the vertical alignment type LCD, in order to make the tilt orientation of the tilt alignment consistent to a certain direction by applying a voltage, and to improve the transmittance and response time by giving a pretilt angle within 2 degrees with respect to the unit normal direction. Waiting for electro-optical characteristics. However, to form a slightly inclined polymer network by inducing a pretilt angle, it is considered that a voltage slightly higher than the critical voltage of the liquid crystal is applied to form the liquid crystal when the liquid crystal is tilted within 2 degrees. However, in liquid crystal display elements such as PVA (Patterned vertical alignment), where the oblique alignment direction is fixed by the shape of the electrodes, if a low voltage near the critical voltage is applied to form the refractive anisotropy or easy alignment axis of the polymer network, Because the tilt orientation of the liquid crystal is not fixed, the transmittance decreases. The reason is that if a voltage near the critical voltage is applied, it will only slightly change to form a bending alignment. The end of the bending deformation of the alignment film is approximately vertical, and the effect of the vertical alignment film is large. Therefore, the liquid crystal near the substrate interface will become a vertical alignment. , Which makes it impossible to specify the tilt alignment orientation near a substrate interface to a certain direction, which becomes unstable. On the other hand, if a high voltage equal to or higher than the saturation voltage of the electro-optical characteristics is applied, the liquid crystal near the interface of the substrate will become obliquely aligned and the electric field will be strong. Therefore, the influence of the electric field distribution caused by the pattern electrode will increase, and the orientation of the oblique orientation Changing to a certain direction can help improve the transmittance. However, since the polymer network of parallel alignment will be formed in the whole unit, As described above, vertical alignment cannot be obtained.

Since the orientation of the oblique alignment depends to a large extent on the type of the electrode pattern, for example, a Fishbone electrode as shown in FIG. 13 is repeatedly arranged with a plurality of fine wire electrodes with a width of about 3 to 5 μm and A linear slit having the same width as the wire electrode. In this pattern electrode, the liquid crystal on the wire electrode is aligned to form an oblique alignment direction of the liquid crystal, which is generally parallel to the slit direction. Therefore, it is necessary to have an alignment memory such as an oblique alignment orientation fixed toward the slit direction as a refractive anisotropy or easy alignment axis of the polymer network. In the case of the pattern electrode of Axially Symmetric Vertical Alignment, it is a sub-pixel structure composed of a dot electrode and a counter electrode of approximately a square shape. Although the central axis is vertically aligned even when a voltage is applied, the liquid crystal director is oriented obliquely and radially with the dot electrode of the central axis as a starting point. When the element is viewed from above, the oblique alignment orientation means that the liquid crystal axis is continuously aligned in a radial pattern from the central axis 360 degrees. If high-voltage is applied to stabilize a polymer in an alignment state in a part of the polymer network, a part of the polymer network is formed in a manner of stabilizing the radial inclined orientation. If the voltage does not reach the critical voltage during the irradiation of ultraviolet rays, thereby returning the liquid crystal to a substantially vertical alignment, and continuing to irradiate ultraviolet rays in this state, the refractive anisotropy of the polymer network will be formed in a manner of approximately vertical alignment. Or easy to align the axis, the radial tilted azimuth orientation can remain on the polymer network in the form of trajectory, which can take into account both the alignment control when the voltage is applied and the vertical alignment when no voltage is applied.

That is, in the liquid crystal display element of PVA, because two different polymer networks stabilizing the alignment state of the liquid crystal coexist, the influence of the polymer networks formed on the liquid crystal alignment is different. Polymer networks are: in order to stabilize the polymer in the alignment state obtained by applying a voltage above the critical voltage, the polymer is formed in a manner consistent with the alignment state of the liquid crystal. In the case of the refractive index anisotropy of the composite network or the easy alignment axis, the polymer network is formed in a manner consistent with the alignment state of the liquid crystal in order to stabilize the polymer in the alignment state obtained by applying a voltage that does not reach the critical voltage. Refractive index anisotropy of the road or easy alignment axis. For example, if only a polymer network is formed that stabilizes the liquid crystal alignment state before reaching a critical voltage, when the liquid crystal alignment is changed by the switching voltage, the liquid crystal alignment state is affected by the influence from the polymer network. It is different from the liquid crystal alignment state originally required for the liquid crystal display element. Therefore, the alignment after the alignment is changed when the PVA unit is switched will be deformed, and the desired alignment state cannot be obtained, which will affect the electro-optical effect and reduce the contrast and transmittance. . Therefore, by coexisting the polymer network, an alignment state obtained by applying a voltage above the critical voltage and an alignment state obtained by applying a voltage below the critical voltage, the two alignment states can change the orientation change between the two states. It is easy, and display characteristics become favorable. Therefore, in order to stabilize the liquid crystal alignment state above the critical voltage and the liquid crystal alignment state below the critical voltage, the polymer is stabilized, and the polymer network is formed so that the two alignment states coexist. The purpose of stabilizing the liquid crystal alignment state is to use a part of the polymerizable compound contained in the polymerizable liquid crystal composition, and use the remaining polymerizable compound in a polymer network formed to stabilize the liquid crystal alignment state before reaching a critical voltage. If a voltage higher than the critical voltage is applied and a voltage that does not reach the critical voltage is applied in the UV polymerization, although the alignment of the liquid crystal will change, alignment defects sometimes occur during this transition. If this alignment defect is stabilized by the polymer, As a result, the uniformity of the alignment state of the liquid crystal under a critical voltage is impaired, which causes a decrease in contrast or transmittance, which is not good. Especially when the voltage above the critical voltage is above the saturation voltage, if it becomes a voltage that does not reach the critical voltage during the irradiation of ultraviolet rays and causes the liquid crystal alignment to change, a large number of alignment defects will occur. Therefore, it is necessary to suppress the occurrence of alignment defects (toward faults) during the alignment transition by applying a voltage below the saturation voltage. (disclination)) At the same time, as described above, the tilt of the liquid crystal at the substrate interface is weakened, and the tilt direction becomes unstable, which is not good. In order to suppress the alignment defect caused by the alignment transition in the ultraviolet polymerization, it is preferable to apply an intermediate voltage that reduces the voltage above the threshold voltage in the ultraviolet polymerization to a voltage below the threshold voltage, at least for a time longer than the response time of the liquid crystal. The time for application is not to affect the formation of the polymer network, as long as it can suppress the occurrence of alignment defects, as long as it does not stabilize the alignment defect polymers, it depends on the liquid crystal. The reactivity of the polymerizable compound is preferably at least 5 seconds. In addition, the intermediate voltage is preferably at least the threshold voltage and below the saturation voltage, and is a voltage with intermediate gradient. The waveform is preferably a rectangular wave, and is preferably a step-shaped waveform in which the voltage gradually decreases in the order of a voltage above the critical voltage, an intermediate voltage, and a voltage below the critical voltage. The intermediate voltage may be a ramp wave that continuously reduces the voltage from a voltage above the threshold voltage to a voltage below the threshold voltage. In addition, if the alignment defect is not left after the polymer is stabilized by applying a method other than the intermediate voltage, the voltage above the threshold voltage can be removed in the middle of the ultraviolet irradiation, but the ultraviolet irradiation is interrupted in synchronization with the applied voltage, and the liquid crystal alignment will be applied again. It becomes a voltage below a critical voltage such as a substantially vertical alignment, but at this time, ultraviolet rays are irradiated again in synchronization with the voltage. That is, in the case of continuously irradiating ultraviolet rays, an intermediate voltage may be applied when the alignment of the liquid crystal during irradiation is changed. In the case of intermittently irradiating ultraviolet rays, when the alignment of the liquid crystal is changed, the ultraviolet rays are interrupted instantaneously, and ultraviolet rays may be irradiated again at the time point when the transition ends.

In addition, since a polymer network having a function of stabilizing these two different alignment states exists in a mixed state, the liquid crystal alignment state of the element after forming the polymer network when no voltage is applied, Will be affected by the polymer network that wants to maintain two different alignment states, the equilibrium of the influence of each polymer network will determine the liquid crystal alignment state when no voltage is applied state. For example, in a liquid crystal display element in the vertical alignment mode, if the influence of a polymer network that stabilizes the liquid crystal alignment state that does not reach the critical voltage is enhanced, the liquid crystal display element will display the original vertical alignment required to improve the liquid crystal display. The contrast is better. On the contrary, if the influence of the polymer network that stabilizes the liquid crystal alignment above the critical voltage is too strong, the pretilt angle of the liquid crystal will increase and the contrast will tend to decrease. In order to improve the transmittance or contrast of the liquid crystal display element and the display quality, it is important to balance the influence of the polymer networks that stabilize the two different liquid crystal alignment states. For example, in a PVA unit, if The polymer network acting in a manner that stabilizes the alignment state of the liquid crystal above the critical voltage has too much influence, and although the maximum transmittance will increase, the black level will increase, causing a decrease in contrast. In addition, if the polymer network acting in a manner that stabilizes the alignment state of the liquid crystal that does not reach the critical voltage has too strong influence, although a good black level can be obtained, it will cause the maximum transmittance to decrease and the contrast to decrease. Not good.

If a voltage that tilts the liquid crystal such as bending alignment is applied, and the orientation of the tilted alignment of the liquid crystal is fixed, the maximum transmittance will be improved. Therefore, if the liquid crystal is aligned above the critical voltage in order to make the tilted alignment orientation fixed, The effect of the stabilized polymer network is slight, and then a critical voltage is applied during the irradiation of ultraviolet rays to form a polymer network to stabilize the approximately vertical alignment state such as a good black level, which is good. The orientation of the black level and oblique alignment will become fixed, and the maximum transmittance will become higher. Therefore, high contrast can be obtained, display quality can be improved, and it becomes better. At this time, in order to make the influence of the polymer network formed by fixing the orientation of the tilt alignment to be slight, it is preferable to apply a voltage above the critical voltage to form the polymer network to make the tilt alignment not completely polymer stabilized. The voltage application time can be used to irradiate ultraviolet rays, and when a voltage below the critical voltage is applied, a substantially vertical alignment can be obtained to continue the ultraviolet rays irradiation.

[Manufacturing method of liquid crystal display element and role of polymer network]

The method for manufacturing a liquid crystal display element of the present invention is a method including the steps of applying a critical voltage to a polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes and having a polymerizable liquid crystal composition. The step of irradiating ultraviolet rays at the above voltage to cause polymerization phase separation, and the step of further irradiating the ultraviolet rays under the condition that the voltage does not reach the critical voltage in the state of ultraviolet rays irradiation. In this way, a polymer network that stabilizes the alignment state of the liquid crystal above the critical voltage and the alignment state of the liquid crystal that does not reach the critical voltage is formed, and a polymer network that stabilizes two different liquid crystal alignment states is formed. . In the case of a vertical alignment mode liquid crystal display element including a pattern electrode unit, it is preferable to apply a voltage equal to or higher than the critical voltage of the polymerizable liquid crystal composition and simultaneously irradiate ultraviolet rays to separate the polymerized phases. Under bending alignment deformation, the liquid crystal molecules in the polymerizable liquid crystal composition are inclinedly aligned in the range of 0 to 30 degrees relative to the plane of the transparent substrate in the vicinity of the plane of the transparent substrate, and it is preferable that the aforementioned voltage is not reached in the state of being irradiated with ultraviolet rays. In the step of critical voltage and further irradiating ultraviolet rays, the alignment is substantially vertical. Near the plane of the transparent substrate, the liquid crystal molecules are aligned at an angle of 80 to 90 degrees relative to the plane of the transparent substrate. The state where the liquid crystal molecules are aligned at an angle of 0 to 30 degrees with respect to the plane of the transparent substrate indicates a state where the birefringence of the liquid crystal is increased by the application of a voltage. If the orientation state of the liquid crystal is 0 degrees with respect to the plane of the transparent substrate, then The birefringence will be the largest and better, but even if it is aligned at an angle of 30 degrees relative to the plane of the substrate. In particular, the PVA unit is preferable because the tilt direction can be fixed. In any case, it is preferable to form a polymer network that stabilizes the alignment so that the tilted orientation of the liquid crystal caused by the applied voltage becomes a fixed direction.

At this time, in order to make the influence of the polymer network formed by obliquely aligning the orientation fixed, a voltage higher than the threshold voltage is applied to the ultraviolet rays to irradiate the liquid crystal. The bending alignment is deformed, but it is preferable that the time of this state is less than the time of applying the voltage below the critical voltage, and when the application of the voltage above the critical voltage is ended, the state of the alignment transition can be achieved. When the influence of the polymer network formed in order to make the tilt alignment orientation constant, the required black level cannot be obtained because the pretilt angle will increase. Therefore, in order to avoid this situation, if the A voltage below the critical voltage will be transformed from a bending alignment to a substantially vertical alignment, and it is only necessary to continue to irradiate ultraviolet rays, and it is preferable that the polymerizable compound remaining in the liquid crystal disappears. It is preferable to form a main polymer network in a step of causing the aforementioned voltage to reach a critical voltage and further irradiating ultraviolet rays in a state in which ultraviolet rays are irradiated. At this time, the magnitude of the pretilt angle will depend on the ratio of the time when the voltage above the critical voltage is applied to the time when the voltage below the critical voltage is applied. The time above the critical voltage application is due to the fact that there is no From the initial state of the formation of the polymer network to the start of the phase separation of the polymer and the formation of the polymer network at a part, it is preferable that the voltage can be restored from the bending alignment deformation to the substantially vertical alignment state when the application of voltage is stopped. The time for which a voltage above the critical voltage is applied is preferably 1 second to 15 seconds. When changing from this step to the next step, it is preferable to irradiate ultraviolet rays below a threshold voltage in a state where the alignment is changed to a substantially vertical alignment, and it is preferable to completely form a polymer network so that the polymerizable compounds remaining in the liquid crystal disappear. The state below the applied critical voltage is a substantially vertical alignment state, but it can also be deformed by a slight bending alignment to make the required black level and tilted alignment orientation fixed, and adjust the voltage as necessary. In addition, when the voltage below the critical voltage is applied, the formation of the polymer network may be substantially completed, and when the amount of the monomer remaining in the liquid crystal is in a trace amount, even if the residual monomer is polymerized, it will not affect the electro-optical characteristics. In this case, a voltage below the critical voltage may not be applied.

In addition, in the step of applying a voltage above the critical voltage and simultaneously irradiating ultraviolet rays to separate the polymerized phases, and then irradiating the ultraviolet rays with a voltage less than the critical voltage in the state of ultraviolet irradiation A step of applying an intermediate gradual voltage at least above the threshold voltage and below the saturation voltage in the state of irradiating ultraviolet rays may be provided. The intermediate gradual voltage is preferably less than the applied voltage of the first step and is above the critical voltage. The intermediate gradual voltage is applied in order to delay the transition from the bending alignment deformation to the substantially vertical alignment. Since the occurrence of alignment defects can be suppressed by the delay effect, it is preferably applied as needed.

Regarding the state where the liquid crystal molecules are aligned at an angle of 80 degrees to 90 degrees with respect to the plane of the transparent substrate, if the liquid crystal is oriented at 90 degrees with respect to the plane of the transparent substrate when no voltage is applied, the birefringence will become the smallest. The high contrast ratio of the display element is useful and preferable, but in order to tilt the alignment in a fixed direction when a voltage is applied, it is more preferable to tilt it within 89.9 degrees to 85 degrees with respect to the substrate plane in the form of a pretilt angle. If it is more than 80 degrees with respect to the plane of the substrate, the birefringence and the amount of light transmission will increase, which will cause the contrast of the display to decrease. It is not good. When the degree of the substrate is above 85 degrees, the black level of the display will become good. Since high contrast can be obtained, it is preferable. In addition, for liquid crystal display elements in the IPS (In-plane switching) display mode, the FFS (Fringe Field Switching) mode, and the TN (Twisted Nematic) mode, it is also preferable to apply a voltage equal to or higher than the threshold voltage of the polymerizable liquid crystal composition. In the step of simultaneously irradiating ultraviolet rays to cause polymerization phase separation, the liquid crystal molecules in the polymerizable liquid crystal composition are tilted with respect to the plane of the transparent substrate in the range of 0 to 90 degrees depending on the applied voltage. In the step of reducing the voltage to a threshold voltage and further irradiating ultraviolet rays in this state, depending on the applied voltage, the liquid crystal molecules are aligned at an angle of 0 to 30 degrees with respect to the plane of the transparent substrate in a pretilt angle.

The oblique alignment of the liquid crystal molecules with respect to the plane of the transparent substrate in a range of 0 to 90 degrees will cause it to form a polymer network and stabilize the alignment state of the liquid crystal upon application of a voltage. However, the prerequisite is that when the voltage application is stopped, the liquid crystal alignment state corresponding to the threshold voltage will be reached. In IPS In the case of the mode, the tilt angle of the properties of the alignment film used in the element has a great influence, which can be in the range of about 1 degree to 2 degrees. The tilt angle of the liquid crystal molecules with the pre-tilt angle including the twist alignment is preferably 0.5 degree to 3 It is preferably within 0 to 2 degrees. In the step of applying a voltage equal to or higher than the critical voltage of the polymerizable liquid crystal composition and simultaneously irradiating ultraviolet rays to separate the polymerized phases, it is preferable to apply a voltage such as a state of twisting deformation, and to apply the voltage in a state of ultraviolet rays. In the step in which the voltage does not reach the critical voltage and further irradiate ultraviolet rays, it is preferable that the voltage does not reach the critical voltage in a state where the torsional deformation is not stabilized by the polymer, and polymerization is performed under conditions of black display in parallel alignment. In the case of FFS mode, if a voltage above the critical voltage is applied, the alignment state of the liquid crystal will depend on the electric field distribution in the element. There are co-existing spray alignment, bending alignment, and twist alignment, but the spray alignment is mainly displayed. With torsional alignment. The inclination angle of the liquid crystal molecules in these states is in the range of 0 degrees to 45 degrees. If the alignment is stabilized by the polymer network, the same range is preferably stabilized. However, when the application of the voltage is stopped, it is preferable that "the alignment state of the liquid crystal corresponding to the critical voltage is not reached" is a prerequisite, and from these states, it is returned to a state of parallel alignment, and ultraviolet rays are irradiated. In the TN mode, a tilt angle in the range of 45 degrees to 90 degrees is preferred.

On the other hand, although a voltage that does not reach the critical voltage is applied to form a polymer network to stabilize the alignment state of the liquid crystal, in the case of IPS mode, FFS mode, and TN mode, the pretilt angle may be caused by the friction alignment process. It has about 1 degree to 3 degrees at the substrate interface. Therefore, it is better to form a polymer network to stabilize the liquid crystal alignment state after the voltage applied to the threshold voltage is not exceeded. The angle of liquid crystal alignment can also be tilted within this range. For other alignment processing methods such as light alignment films, the tilt angle of the liquid crystal molecules with pre-tilt angle containing twisted alignment is preferably 0.5 degrees to 3 degrees, and within 0 degrees to 2 degrees is useful for obtaining a wide viewing angle, and more preferably.

In addition, it is preferable that the applied voltage is an AC waveform, and that the polymerizable liquid crystal composition has a frequency that exhibits a range of dielectric properties. The waveform is preferably a rectangular wave with a high effective voltage when the spike voltage is fixed. The upper limit of the frequency is preferably a frequency in a range where a signal transmitted to a pixel by a driving circuit for a liquid crystal display element does not attenuate, and the frequency is at least 2 kHz or less. Regarding the frequency dependence of the dielectric coefficient displayed by the polymerizable liquid crystal composition before the ultraviolet rays are radiated, the frequency of the dielectric guideline display may be 10 kHz or less. The lower limit value may be a frequency at which flicker is generated when the element is driven, and the minimum flicker is sufficient in this case, and it is preferably at least 20 Hz or more.

The method for manufacturing a liquid crystal display element of the present invention is as described above, and is characterized in that a polymer network is formed to maintain two liquid crystal alignment states, and a polymer network formed to maintain each liquid crystal alignment state is formed to make a polymer The refractive index anisotropy or easy alignment axis of the network is consistent with the liquid crystal alignment direction above the critical voltage or the liquid crystal alignment direction that does not reach the critical voltage. Thereby, a state in which a polymer network that stabilizes the liquid crystal alignment when a voltage is applied and a polymer network that stabilizes the liquid crystal alignment when a voltage is not applied is generated, and the liquid crystal alignment state when no voltage is applied can be suppressed. Alignment distortion that occurs when the alignment is deformed due to the application of voltage improves the display characteristics such as increasing the contrast. On the other hand, if there is only a polymer network formed to maintain the liquid crystal alignment state when no voltage is applied, when changing to the liquid crystal alignment state when a voltage is applied, it is formed because of maintaining the liquid crystal alignment that does not reach the critical voltage. The polymer network has a strong influence, so when changing to the liquid crystal alignment state above the critical voltage, alignment distortion will occur, which will cause the transmittance to decrease. By forming a polymer network that stabilizes the liquid crystal alignment when a voltage is applied, a part of the polymer network can suppress the distortion of the alignment change caused by switching, and can obtain the originally required change of the liquid crystal alignment and improve the transmission. rate. In addition, in order to stabilize the alignment state of each liquid crystal when a voltage is applied and when no voltage is applied, the polymer network is characterized by: The same way of liquid crystal alignment makes the refractive index anisotropy or easy alignment axis of the polymer network.

In addition, the influence time of the polymer network formed to stabilize the liquid crystal state above the critical voltage can be changed by the application time of the voltage equal to or higher than the critical voltage in the ultraviolet rays, and the electro-optical characteristics can be changed. For example, when a polymer network is formed in a state where the liquid crystal alignment state when a voltage is applied includes a parallel alignment at an inclined orientation of 0 to 30 degrees with respect to the substrate plane, if the polymer network is shortened above the threshold voltage in ultraviolet irradiation The application time of the voltage is only a little because of the effect of maintaining the parallel alignment, so the liquid crystal will want to align with the effect of the polymer network that wants to maintain the vertical alignment. In addition, the influence of the two orientations from the polymer network that maintains two different orientations is balanced, and the angle of the pretilt as small as 1 degree or less relative to the normal direction of the transparent substrate is induced. As the application time of the voltage above the critical voltage in the ultraviolet rays is increased, the influence of the polymer network to maintain parallel alignment will be stronger, so the pretilt angle will be balanced by the force that maintains the vertical alignment and the force that maintains the parallel alignment. Increasing it can increase the pretilt angle, which is more than 10 degrees with respect to the normal direction of the transparent substrate. In addition, since the application time of a voltage equal to or higher than the critical voltage in the ultraviolet rays depends on the reactivity of the polymerizable liquid crystal composition to be used, it is preferably adjusted appropriately to obtain the desired pretilt angle. It is particularly preferable to obtain a pretilt angle in a range of 80 degrees to 90 degrees with respect to the substrate plane, more preferably 85 degrees to 89.9 degrees, and still more preferably 87 degrees to 89.9 degrees.

In order to maintain the alignment state of the liquid crystal (obtained by applying a voltage above the critical voltage), the polymer network formed in the vertical alignment mode using negative dielectric anisotropy should be in a parallel alignment state, or Tilt orientation with fixed azimuth. The alignment state obtained when the threshold voltage is not reached is preferably a substantially vertical alignment, particularly preferably a substantially vertical alignment at 80 to 90 degrees with respect to the substrate plane, and it is preferable that the display can obtain a good black level such as high contrast. Alignment state. In an IPS (In-plane switching) display mode using a lateral electric field using negative dielectric anisotropy or positive dielectric anisotropy, a liquid crystal alignment state obtained by applying a voltage equal to or higher than a threshold voltage in ultraviolet rays is preferred. To reverse the alignment. The alignment state obtained when the threshold voltage is not reached is preferably a parallel alignment with a fixed azimuth angle. In the FFS (Fringe Field Switching) mode, it is preferable that the alignment state obtained by irradiating ultraviolet rays with a voltage above a threshold voltage is at least any one of a bend alignment, a spray alignment, an inclined alignment, or a plurality of mixed alignment states. When the threshold voltage is not reached, the alignment is preferably substantially parallel. After the polymer network is formed to maintain the alignment state of the liquid crystal when the voltage is applied, the alignment state of the liquid crystal that does not reach the critical voltage is stabilized by the polymer, and the alignment can be easily changed. When the polymer network is formed, When the voltage is applied, the alignment state of the liquid crystal can achieve both high transmittance and high-speed response.

The voltage applied when irradiating ultraviolet rays is preferably adjusted appropriately so that the display of the liquid crystal display element after the polymer network is formed has a high contrast. Since it depends very much on the characteristics of the electro-optical effect of the polymerizable liquid crystal composition before ultraviolet rays, The voltage-transmittance characteristics exhibited by the polymerizable liquid crystal composition must be matched. The voltage above the critical voltage is preferably a voltage V10 or more with respect to the total transmittance change in the voltage-transmittance characteristic voltage of the polymerizable liquid crystal composition, and more preferably the total change in transmittance. The voltage V20 is more than 20%, and more preferably, the total change in transmittance is 50V or more. However, a voltage that is 6 times or less the critical voltage is preferred. Regarding the voltage applied above the threshold voltage applied in the irradiation of ultraviolet rays, an AC voltage is preferably applied, and a rectangular wave is preferably applied. The frequency is preferably a frequency at which flicker cannot be visually recognized. When an electronic circuit such as a TFT substrate is formed on a glass substrate, it is only required to be a frequency that does not cause a polymerization voltage attenuation, and is preferably about 30 Hz to 5 kHz.

Although the voltage applied during the irradiation of ultraviolet rays is above the critical voltage and does not reach the critical voltage Voltage, but as the voltage that does not reach the critical voltage, it only needs to be a range in which the alignment of the liquid crystal does not change due to the voltage, preferably 0V or more and less than 90% of the critical voltage, and preferably less than 80% The voltage is more preferably 70% or less. In addition, although the applied voltage is lower than the critical voltage during the irradiation of ultraviolet rays, it is preferable to return it to the liquid crystal alignment state when the liquid crystal display element is OFF. For example, in the vertical alignment mode, it can be restored to Vertical alignment. In FFS mode or IPS mode, it can be parallel alignment. In order to restore the liquid crystal alignment state when the liquid crystal display element is OFF, it is preferable that the polymer network that stabilizes the liquid crystal alignment when a voltage is applied is reduced to a voltage that does not reach the critical voltage in a state where the influence is slight.

Ultraviolet rays are irradiated after applying a voltage above the critical voltage, but if the voltage application time in the ultraviolet rays is prolonged, the influence of the polymer network that stabilizes the liquid crystal alignment when the voltage is applied in the ultraviolet rays will be increased without affecting The liquid crystal alignment state when the required liquid crystal display element is turned off is not good. Therefore, it is preferable to appropriately optimize the voltage in the most suitable ultraviolet irradiation to produce the liquid crystal display element of the present invention. In addition, when the voltage during the irradiation of ultraviolet rays does not reach the critical voltage, in order to adjust the response relaxation time of the liquid crystal of the polymerizable liquid crystal composition, the voltage may be gradually lowered during the irradiation of ultraviolet rays, so that the decrease time of the applied voltage is shorter than that of irradiation. The response relaxation time of the liquid crystal in the ultraviolet rays is long, so that the influence of the back flow generated during the response relaxation process is minimized, and the fall time of the applied voltage is preferably from 10 ms to 1,000 ms. On the contrary, it is also possible to lower it quickly, and it is preferably at least shorter than the relaxation time exhibited by the polymerizable liquid crystal composition, and preferably 100 ms or less.

In a state where a voltage above a critical voltage is applied, ultraviolet rays are irradiated to form a part of a polymer network of parallel alignment components, and continue to irradiate ultraviolet rays, and at the same time, the voltage does not reach the critical voltage, thereby returning the liquid crystal to a vertical alignment, and End of polymerization phase separation. Fishbone electrode liquid crystal In the unit, the pretilt angle can be changed by the ratio of the parallel alignment component to the vertical alignment component. If the voltage is removed during the initial formation of the polymer network, the orientation of the tilted alignment will be fixed, and the vertical alignment will be formed with residual monomers. And it can achieve vertical alignment and tilt alignment orientation at the same time, which is the alignment control technology of nano-phase-separated liquid crystal.

In addition, the so-called parallel alignment state means "after the application of a voltage, the negative dielectric anisotropic liquid crystals become substantially parallel alignment states", preferably in a range of 0.1 to 30 degrees with respect to the substrate surface, and more preferably in a range of 0.1 to 10 degrees. The range of degrees is tilted. Vertical alignment when no voltage is applied, which means "because of the vertical alignment film to become a substantially vertical alignment state", the liquid crystal alignment is preferably inclined from 80 to 89.9 degrees with respect to the substrate plane, and more preferably from 85 to 89.9 degrees .

In the case of positive dielectric anisotropic liquid crystals, if a voltage is applied, vertical alignment will be obtained, but the liquid crystal alignment state also includes tilting alignment of the liquid crystal with a range of 45 to 89.9 degrees with respect to the plane of the substrate. The parallel alignment when no voltage is applied means “the state becomes substantially parallel alignment due to the effect of the parallel alignment film”, and the liquid crystal alignment includes an alignment inclined by 0.1 to 30 degrees with respect to the substrate plane.

Therefore, the method for manufacturing a liquid crystal display element of the present invention preferably has the following steps: a light irradiation step: irradiating ultraviolet rays on the polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes; and a voltage applying step : Applying a voltage equal to or higher than the critical voltage of the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes, preferably at the time point when the light irradiation step is started, The voltage applied with the aforementioned voltage application step is applied. Therefore, the voltage applying step and the light irradiation step may be simultaneous, or the light irradiation step may be started later than the voltage applying step. Also, it is better than the orientation change when voltage is applied. At the stage where the alignment defect that has occurred has disappeared, the aforementioned light irradiation step is started.

For example, when alignment defects hardly occur when a voltage is applied, the voltage application step and the light irradiation step may be started (or performed) simultaneously, or the voltage application step and the light irradiation step may be interrupted or stopped at the same time. The aforementioned light irradiation step is performed in the ON state of the liquid crystal element. Before the alignment of the ON state in the middle of the polymerization step is about to stabilize due to the formation of the polymer network, the aforementioned voltage application step is interrupted. In the OFF state of the liquid crystal element, only the In the light irradiation step, the polymerizable compound remaining in the liquid crystal disappears. In addition, it is preferable to interrupt the ultraviolet radiation between the orientation transition from the ON state to the OFF state so that a polymer network is not formed.

"Is applied to a polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes with a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition, and the polymerizable liquid crystal composition is irradiated with ultraviolet rays The period (time) of the voltage above the threshold voltage of the object may be sufficient. In other words, "the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes is applied with a voltage equal to or higher than the critical voltage of the polymerizable liquid crystal composition, and simultaneously irradiated with ultraviolet rays to separate the polymerized phases" As long as the light irradiation step is performed while the voltage application step is in progress, the period of the light irradiation step and the period of the voltage application step preferably overlap.

In a preferable aspect of the method for manufacturing a liquid crystal display element of the present invention, as long as the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes is irradiated with ultraviolet light, the ultraviolet light may be irradiated. The orientation change from the ON state to the OFF state is sufficient. The voltage application step is preferably 3 to 30 seconds, more preferably 5 to 10 seconds. When the light irradiation is interrupted, it is better than the voltage application step just ended. Then set the interruption period of ultraviolet irradiation. After the alignment process of the liquid crystal is completed, the ultraviolet irradiation can be restarted when the alignment state is in a balanced state, and the foregoing light can be ended. Irradiation step.

In the method for manufacturing a liquid crystal display element of the present invention, it is preferable that a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition is applied to the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes. The period of time is shorter than the period of time when the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes is irradiated with ultraviolet rays.

In the method for manufacturing a liquid crystal display device of the present invention, a voltage applying 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 at least one transparent substrate having two electrodes. , Can be set to multiple times more than once (2 times, 3 times to 10 times). The magnitude of the applied voltage at this time may be the same or different. It is preferably different. As a form of this voltage applying step, it is preferable that the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes is irradiated with ultraviolet rays, and the polymerizable property is applied for a predetermined time. After the primary voltage (V ₁ ) equal to or higher than the critical voltage of the liquid crystal composition is used as the primary voltage, an intermediate voltage (V _m ) equal to or higher than the critical voltage and equal to or lower than the primary voltage (V ₁ ) is applied in a state of being irradiated with ultraviolet rays.

In the method for manufacturing a liquid crystal display element of the present invention, the following voltage application step may be performed more than once (two times, three times or more and 10 times or less): applying the polymerizable liquid crystal in a state of irradiating ultraviolet rays. Voltage below the critical voltage of the composition. The magnitude of the applied voltage at this time may be the same or different. In addition, when a voltage lower than the critical voltage is applied, the voltage may be lowered to a voltage lower than the critical voltage in stages, or may be continuously lowered to a voltage lower than the critical voltage.

In the above-mentioned preferred aspect, if a voltage not exceeding the critical voltage is applied in the UV polymerization after applying a voltage above the critical voltage, the liquid crystal alignment will change, but sometimes it is here An alignment defect occurs during the transition. If this alignment defect is stabilized by a polymer, the uniformity of the alignment state of the liquid crystal under the critical voltage will be impaired, which will cause the decrease in contrast or transmittance, which is not good. Especially when the voltage above the critical voltage is equal to or higher than the saturation voltage, if the voltage is changed to a voltage below the critical voltage during irradiation of ultraviolet rays, causing a liquid crystal alignment transition, a large number of alignment defects will occur. Therefore, it is necessary to suppress the occurrence of alignment defects during the alignment transition by applying a voltage below the saturation voltage, but at the same time, as described above, the tilt of the liquid crystal at the substrate interface becomes weaker and the direction of the tilt orientation becomes unstable. Not good. In order to suppress the alignment defects that occur during the alignment transition in UV polymerization, it is preferable to apply an intermediate voltage that reduces the voltage above the threshold voltage in UV polymerization to a voltage below the threshold voltage and applies it for at least the response time of the liquid crystal, as The time that does not affect the formation of the polymer network may be a time that suppresses the occurrence of alignment defects, and a time that does not stabilize the alignment defective polymer, depending on the reaction of the polymerizable compound in the liquid crystal. Performance, preferably at least within 5 seconds. In addition, the intermediate voltage is at least above the critical voltage and below the saturation voltage, and is preferably a voltage with an intermediate gradient. The waveform is preferably a rectangular wave, and is preferably a stepped waveform in which the voltage gradually decreases in the order of a voltage higher than the critical voltage, an intermediate voltage, and a voltage lower than the critical voltage. The intermediate voltage may be a ramp wave in which the voltage is continuously reduced from a voltage above the threshold voltage to a voltage below the threshold voltage. In addition, when the alignment defective polymer is stabilized without remaining by applying an intermediate voltage, the voltage above the threshold voltage is removed in the middle of the ultraviolet irradiation, but the ultraviolet irradiation is interrupted in synchronization with the applied voltage, and the liquid crystal alignment is applied again to become approximately vertical. A voltage below the critical voltage such as alignment, but at this time, ultraviolet rays can be irradiated again in synchronization with the voltage. That is, in the case of continuously irradiating ultraviolet rays, an intermediate voltage may be applied when the alignment of the liquid crystal during irradiation is changed. In the case of intermittently irradiating ultraviolet rays, when the alignment of the liquid crystal is changed, the irradiation of ultraviolet rays is temporarily interrupted, and You can irradiate ultraviolet rays at the time of completion.

It is preferred to form a polymer network that stabilizes the alignment so that the orientation of the oblique alignment of the liquid crystal formed by applying a voltage is a fixed direction. At this time, in order to make the influence of the polymer network formed by oblique alignment orientation fixed, a voltage higher than the critical voltage is applied to irradiate ultraviolet rays to deform the bend alignment of the liquid crystal, but it is preferable to make this state The time for which the voltage is less than the threshold voltage is applied, and when the application of the voltage above the threshold voltage is ended, it is sufficient that the orientation transition occurs. When the influence of the polymer network formed in order to make the tilt alignment orientation constant, the required black level cannot be obtained because the pretilt angle will increase. Therefore, in order to avoid this situation, if the A voltage below the critical voltage will be transformed from a bending alignment to a substantially vertical alignment, and it is only necessary to continue to irradiate ultraviolet rays, and it is preferable that the polymerizable compound remaining in the liquid crystal disappears. It is preferable to form a main polymer network in a step of causing the aforementioned voltage to reach a critical voltage and further irradiating ultraviolet rays in a state in which ultraviolet rays are irradiated. At this time, the magnitude of the pretilt angle will depend on the ratio of the time when the voltage above the critical voltage is applied to the time when the voltage below the critical voltage is applied. The time above the critical voltage application is due to the absence of any in the liquid crystal during the polymerization phase separation process. From the initial state of the formation of the polymer network to the start of the phase separation of the polymer and the formation of the polymer network at a part, it is preferable that the voltage can be restored from the bending alignment deformation to the substantially vertical alignment state when the application of voltage is stopped. The time for which a voltage above the critical voltage is applied is preferably 1 second to 15 seconds. When changing from this step to the next step, it is preferable to irradiate ultraviolet rays below a threshold voltage in a state where the alignment is changed to a substantially vertical alignment, and it is preferable to completely form a polymer network so that the polymerizable compounds remaining in the liquid crystal disappear. The state below the applied critical voltage is a substantially vertical alignment state, but it can also be deformed by a slight bending alignment to make the required black level and tilted alignment orientation fixed, and adjust the voltage as necessary. When a voltage below the critical voltage is applied In some cases, until the formation of the polymer network is almost completed, when the amount of monomers remaining in the liquid crystal is small and the electro-optical characteristics are not affected even if the residual monomers are polymerized, it may not be applied below the threshold voltage. Voltage.

In addition, between the step of applying a voltage equal to or higher than the critical voltage and simultaneously irradiating ultraviolet rays to separate the polymerized phases, and then irradiating the ultraviolet rays with the voltage not reaching the critical voltage and irradiating the ultraviolet rays, it may be set in a state of radiating ultraviolet rays. The step of applying an intermediate gradient voltage at least above the threshold voltage and below the saturation voltage. The intermediate gradual voltage is preferably less than the applied voltage of the first step and is above the critical voltage. The intermediate gradual voltage is applied in order to delay the transition from the bending alignment deformation to the substantially vertical alignment. Since the occurrence of alignment defects can be suppressed by the delay effect, it is preferably applied as needed.

One of the preferred embodiments of the method for manufacturing a liquid crystal display element of the present invention includes a light irradiation step of irradiating ultraviolet rays on a polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes, and applying the aforementioned polymerizability The voltage applying step of a voltage equal to or higher than the critical voltage of the liquid crystal composition includes the steps of starting the aforementioned light irradiation step in the aforementioned voltage applying step, lowering the voltage to a critical voltage in a state of irradiating ultraviolet rays, and further irradiating ultraviolet rays. In addition, it is preferable that the polymerizable liquid crystal composition is applied with a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition, as compared with irradiating the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes. UV time is short.

Thereby, since it can be changed from an alignment state above the threshold voltage to an alignment state below the threshold voltage, two types of liquid crystal alignment states can be irradiated with ultraviolet rays, which is preferable.

An example of the modification of the foregoing preferred embodiment is as follows: it has the following steps: A light irradiation step of irradiating a polymerizable liquid crystal composition sandwiched between at least one of two transparent substrates having electrodes with ultraviolet light; applying a first voltage of a first voltage (V1) which is above a threshold voltage of the polymerizable liquid crystal composition An application step; and a second voltage application step of applying a second voltage (V2) above a first voltage (V1) below a threshold voltage of the polymerizable liquid crystal composition, in the first voltage application step and / or a second voltage In the applying step, the aforementioned light irradiation step is started, and the step of irradiating ultraviolet rays to a voltage lower than a threshold voltage in a state of ultraviolet irradiation is included.

In addition, it is preferable that the polymerizable liquid crystal composition is applied with a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition, as compared with irradiating the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes. UV time is short.

One of other preferred embodiments of the manufacturing method of the present invention is a method for manufacturing a liquid crystal display element having a feature of applying the polymerizable liquid crystal composition sandwiched between at least one of two transparent substrates having electrodes. A voltage application step of a voltage higher than a critical voltage of the polymerizable liquid crystal composition, and a light irradiation step of starting the light irradiation step and irradiating the polymerizable liquid crystal composition with ultraviolet rays in the voltage application step, the light irradiation step includes ultraviolet rays During the interrupted period of ultraviolet irradiation, the voltage is lowered to a critical voltage in the state of ultraviolet irradiation, and further ultraviolet rays are irradiated. In addition, it is preferable that the polymerizable liquid crystal composition is applied with a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition, as compared with irradiating the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes. UV time is short. This will form a polymer network that maintains the alignment state above the critical voltage, but it can make the influence a bit Micro, which mainly forms a polymer network that maintains a state below the critical voltage, which can enhance its influence and is better. In the further-produced liquid crystal element, two states of the alignment state above the critical voltage and the alignment state below the critical voltage can be switched. If the polymerizable liquid crystal composition is applied for a longer time than the threshold voltage, the alignment state above the threshold voltage will be maintained, and the orientation state below the threshold voltage cannot be restored, and the ON-OFF switch cannot be obtained, so it is not good. .

The modified example of the above-mentioned preferred embodiment is a method for manufacturing a liquid crystal display element having a feature of applying the polymerizable liquid crystal composition to a polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes. A voltage application step of a voltage equal to or higher than the threshold voltage, and a light irradiation step of starting the light irradiation step and irradiating the polymerizable liquid crystal composition with ultraviolet rays in the voltage application step, and stopping the light irradiation step and the voltage application step at the same time. , Restarting the aforementioned light irradiation step, in a state where the ultraviolet rays are irradiated, the voltage does not reach the critical voltage, and further ultraviolet rays are irradiated. In addition, although the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes is irradiated with ultraviolet rays and interrupted, it is preferable that the total polymerizable liquid crystal composition is applied with the polymerizability longer than the polymerizable liquid crystal composition. The voltage of the liquid crystal composition is longer than the threshold voltage. Thereby, it is preferable to prevent the alignment defects that occur when the alignment transitions from above the critical voltage to below the critical voltage to be maintained by the formed polymer network, and to obtain a liquid crystal device with high contrast and high-speed response.

One of other preferred embodiments of the manufacturing method of the present invention is a method for manufacturing a liquid crystal display device having the steps of applying the polymerization to a polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes. A voltage application step of a voltage equal to or higher than the critical voltage of the liquid crystal composition; a light irradiation step of starting the light irradiation step in the voltage application step; and irradiating the polymerizable liquid crystal composition with ultraviolet light; Voltage is not reached A step of applying a third voltage (V3) to the threshold voltage and further irradiating ultraviolet rays; and making the voltage below the third voltage (V3) (the third voltage (V3) does not reach the threshold voltage) in a state of irradiating ultraviolet rays. Step of 4 voltage (V4) and further irradiation with ultraviolet rays. In addition, it is preferable that the polymerizable liquid crystal composition is applied with a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition, as compared with irradiating the polymerizable liquid crystal composition sandwiched between at least one of the two transparent substrates having electrodes. UV time is short.

Thereby, even if the alignment of the liquid crystal element in the ON state and the alignment of the OFF state of the obtained liquid crystal element will form a polymer network, it can also be made similar to the respective alignment states of the liquid crystal before polymerization, which can obtain high contrast and display high speed. A responsive liquid crystal element is preferred.

The scope of the present invention is not limited to the preferred embodiments of the present invention described above. The above-mentioned light irradiation step (including the first and second steps) and the voltage application step are the same as those described in the polymerization phase separation step of the present invention, and therefore are omitted here.

The distance (d) between the substrates of the liquid crystal display element of the present invention is preferably in a range of 2 to 5 μm, and more preferably 3.5 μm or less. Generally speaking, the birefringence is adjusted so that the product of the birefringence of the liquid crystal composition and the cell thickness is around 0.275. However, since the polymerizable liquid crystal composition of the present invention forms a polymer network after polymerized phase separation, When an electric field is applied, the birefringence of a liquid crystal display device is lowered by the anchoring force of the polymer network and the optical properties of the polymer network. Therefore, the liquid crystal composition and the polymer composition or the polymerizable liquid crystal composition The product of the birefringence (Δn) of the contained liquid crystal composition and the distance (d) between the substrates is particularly preferably 0.3 to 0.4 μm if the driving voltage increases within about 5 V due to the formation of the polymer network. The range is more preferably within the range of 0.30 to 0.35 μm if there is an increase within about 3 V, and the range is particularly preferably within the range of 0.29 to 0.33 μm if the drive voltage is increased within 1 V. By making the substrate pitch of the liquid crystal display element The product of the birefringence (Δn) from the (d) and the liquid crystal composition and the distance (d) between the substrates are within the above ranges, respectively. The transmittance will be as high as that of the case with only low-molecular-weight liquid crystals. Reproducible display. The birefringence of the liquid crystal composition used for the polymerizable liquid crystal composition is preferably set so that the product of the cell thickness (d) and the birefringence (Δn) becomes 1 to 1.9 times 0.275.

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

(Vth is the critical voltage, 1Kii and 2Kii are the elastic constants, i is 1, 2, or 3, Δε is the dielectric conductivity, <r> is the average void space at the interface of the transparent polymer material, and A is the high transparency The anchoring force of the molecular substance on the liquid crystal composition, d represents the distance between the substrates with transparent electrodes)

According to this, the driving voltage of the light-scattering liquid crystal display element depends on the average gap interval of the transparent polymer material interface, the distance between the substrates, the elastic constant of the liquid crystal composition or the dielectric anisotropy, and the liquid crystal composition and transparency. Anchoring energy between polymer materials.

Among them, the parameter that can be controlled by the liquid crystal display device of the present invention is the anchoring force between the physical properties of the liquid crystal and the polymer. Because the anchoring force depends very much on the molecular structure of the polymer and the Molecular structure, so if a polymerizable compound with a strong anchoring force is selected, the response time can be increased to less than 1.5ms, but at the same time the driving voltage can be increased to more than 30V. Therefore, it is preferred that the driving voltage be less than 30V and the response speed The liquid crystal compound and the polymerizable compound are appropriately selected so that the composition becomes 1.5 ms or less, and the composition is adjusted. It is preferable to appropriately blend a polymer precursor having a strong anchoring force and a polymer precursor having a weak anchoring force and adjust the composition in such a manner that the driving voltage and the response speed reach a balance. On the other hand, as the physical properties of the liquid crystal composition required to reduce the driving voltage, it is particularly preferable to set the dielectric anisotropy to 6 or more if it is a P-type liquid crystal, and to set the dielectric anisotropy to -3 if it is an N-type liquid crystal. the following. The birefringence is preferably 0.09 or more. In addition, 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. Among them, the concentration of the polymer precursor affects the retardation of the liquid crystal element, so it is preferred to use the appropriate increase or decrease of the birefringence of the liquid crystal composition in a manner to obtain the required retardation.

The liquid crystal display element of the present invention is preferably obtained by irradiating energy rays while making the liquid crystal composition at -50 ° C to 30 ° C, polymerizing a polymerizable compound, and forming a refractive index anisotropy in the liquid crystal composition. Or a polymer network with easy alignment. The upper limit of the polymerization temperature is 30 ° C, preferably 20 ° C to -10 ° C. As described in the following examples, the present inventors have discovered that depending on the composition of the polymerizable compound, τ d can be further accelerated by low-temperature polymerization and normal-temperature polymerization. The reason is considered to be: 1) polymerization in a state where the alignment of the liquid crystal molecules is increased due to low temperature; 2) the compatibility between the polymer polymerized by the low temperature polymerization and the liquid crystal composition is reduced, making phase separation easier, The polymerization phase separation speeds up, and the interstitial space of the polymer network becomes fine. 3) Even if a polymerizable compound with a relatively low anchoring force is used, the interstitial space is fine and the influence of the anchoring force becomes strong. Refractive index anisotropic polymer network, etc.

The liquid crystal display element of the present invention is preferably formed to have a uniaxial refractive index. The anisotropic or easy-alignment polymer network or polymer binder's optical axis direction or easy-alignment axis direction forms a pretilt angle with respect to the transparent substrate, and preferably has the following structure, that is, by adjusting the electric field strength The low-molecular liquid crystal alignment is controlled so that it is inclined with respect to the substrate surface to apply a voltage to the liquid crystal layer and simultaneously irradiate energy rays, thereby polymerizing a polymerizable compound and obtaining refractive index anisotropy or A structure made of polymers that can be easily aligned in the axial direction. In the vertically aligned VA mode, by applying a voltage such that the pretilt angle within 20 degrees with respect to the normal direction of the substrate is within 20 degrees, it not only has protrusions or the like equivalent to those currently used in VA mode cells or PSA liquid crystals. The effect of the fine polymer protrusions and the high-speed response that PSA cannot achieve are particularly preferable. In addition, by applying an electric field from a plurality of directions to polymerize the polymer to form multiple regions, the viewing angle can be improved, and it is more preferable. In addition, the alignment film is subjected to a light alignment process or a friction alignment process in such a manner that the low-molecular liquid crystal induces a pretilt angle at the interface of the vertical alignment film at the substrate interface, thereby defining the tilt direction of the low-molecular liquid crystal alignment and suppressing the occurrence of switching Alignment defects are therefore preferred, and it is also preferred to perform the alignment process using pattern electrodes that are tilted in a plurality of directions. Regarding the aforementioned liquid crystal layer, an AC electric field is suitably applied to a liquid crystal composition containing a polymerizable compound in a temperature range of -50 ° C to 30 ° C, and ultraviolet rays or electron beams are irradiated to thereby make a polymer network having refractive index anisotropy. It is formed in the liquid crystal so that its optical axis direction forms a pretilt angle with respect to the substrate surface. If the polymer phase is separated in an orientation state in which the dielectric anisotropy of the low-molecular liquid crystal is used to induce a pretilt angle by applying an electric field, the optical axis of the polymer network after polymerization can be inclined with respect to the substrate surface. The liquid crystal element is more preferably configured to polymerize the polymerizable compound. In addition, it is also preferable that the polymer network obtained by stabilizing the alignment state of the applied voltage and the polymer network obtained by stabilizing the alignment state of the unapplied voltage are compounded to induce a pretilt angle.

The two substrates used in the liquid crystal display element of the present invention can be made of flexible transparent materials such as glass or plastic. 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 produced by, for example, a pigment dispersion method, a printing method, a plating method, or a dyeing method. If a color filter manufacturing method using a pigment dispersion method is described as an example, a hardening coloring composition for a color filter is coated on the transparent substrate, patterned, and then hardened by heating or light. . This step is performed separately for three colors of red, green, and blue, whereby a pixel portion for a color filter can be manufactured. In addition, a pixel electrode provided with active elements such as a TFT and a thin film diode may be provided on the substrate.

The substrates are faced so that the transparent electrode layer becomes the inside. At this time, the interval between the substrates can be adjusted through the spacer. At this time, it is preferable to adjust so that the thickness of the obtained light control layer becomes 1-100 micrometers. More preferably, it is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy of the liquid crystal Δn and the cell thickness d so that the contrast ratio becomes the maximum, and set it to 1 at 550 nm according to the display mode. / 2 or 1/4. When there are two polarizing plates, the polarization axis of each polarizing plate can be adjusted to adjust the viewing angle or contrast to be good. Also, a retardation film for extending the viewing angle can be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and columnar spacers made of a photoresist material. Then, a sealing agent such as an epoxy-based thermosetting composition is screen-printed on the substrate in a shape provided with a liquid crystal injection port, the substrates are bonded to each other, and the sealing agent is thermally cured by heating.

As a method for sandwiching the polymerizable liquid crystal composition between two substrates, a general vacuum injection method or an ODF method can be used. In the manufacturing steps of the liquid crystal display element of the ODF method, use a dispenser to draw epoxy-based light and heat and use a sealant such as hardening to draw a closed-loop dam shape on either the bottom plate or the front plate. After a predetermined amount of the polymerizable liquid crystal composition is dropped on the substrate under the outgassing, the front plate and the bottom plate are bonded, whereby a liquid crystal display element can be manufactured. The polymerizable liquid crystal composition used in the present invention is applicable because the dropping of the liquid crystal-monomer composite material in the ODF step can be performed stably.

As a method for polymerizing a polymerizable compound, in order to obtain a good alignment property of liquid crystals, a moderate polymerization rate is desired. Therefore, it is preferable to polymerize a polymer by irradiating ultraviolet rays or electron beams which are active energy rays in a single or combined use or sequentially Methods. When using ultraviolet light, a polarized light source or a non-polarized light source can be used. When the polymerizable liquid crystal composition is polymerized while being sandwiched between two substrates, at least the substrate on the irradiation surface side must have moderate transparency to active energy rays. In addition, it is preferable that an AC electric field is applied to the polymerizable liquid crystal composition containing the polymerizable compound in a temperature range of -50 ° C to 20 ° C, and ultraviolet rays or electron beams are irradiated. The applied AC electric field is preferably an AC with 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 the pretilt angle desired by the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the liquid crystal display element of the transverse electric field type MVA mode, from the viewpoint of alignment stability and contrast, it is preferable to control the pretilt angle to 80 to 89.9 degrees.

The temperature at the time of irradiation is preferably within a temperature range of -50 ° C to 30 ° C of the polymerizable liquid crystal composition. As a lamp generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used. In addition, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength range of the liquid crystal composition, and it is preferable to eliminate ultraviolet rays less than 365 nm before use. The intensity of the irradiated ultraviolet rays is preferably 0.1 mW / cm ² to 100 W / cm ² , and more preferably 2 mW / cm ² to 50 W / cm ² . The energy of the irradiated ultraviolet rays can be appropriately adjusted, and is preferably 10 mJ / cm ² to 500 J / cm ² , and more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiated with ultraviolet rays, the intensity can also be changed. The time for irradiating ultraviolet rays can be appropriately selected according to the intensity of the ultraviolet rays irradiated, preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.

(Transverse 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 cross-sectional view showing an example of a 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 a surface thereof; a second substrate 7 provided separately from the first substrate and having a light alignment layer formed on the surface; and filled in the first substrate 2 The liquid crystal layer 5 between the substrate 2 and the second substrate 7 and in contact with the pair of alignment layers has a thin film transistor provided as an active device between the alignment layer 4 (4a, 4b) and the first substrate 2 and shared. The electrode 22 and the electrode layer 3 of the pixel electrode.

FIG. 1 is a diagram schematically showing the configuration of a liquid crystal display element. In FIG. 1, each component is separately described for convenience of explanation. The structure of a liquid crystal display element 10 according to an embodiment of the present invention is as described in FIG. 1. The liquid crystal display element 10 includes a polymerizable liquid crystal composition sandwiched between a first transparent insulating substrate 2 and a second transparent insulating substrate 7 arranged opposite to each other. Or the liquid crystal layer 5) is a liquid crystal display element having a lateral electric field method (an example in the figure is the FFS mode as one of the IPS modes). An electrode layer 3 is formed on a surface of the first transparent insulating substrate 2 on the liquid crystal layer 5 side. In addition, between the liquid crystal layer 5 and the first transparent insulating substrate 2 and between the liquid crystal layer 5 and the second transparent insulating substrate 7, there are respectively a contact with the polymerizable liquid crystal composition constituting the liquid crystal layer 5 to induce horizontal alignment. In the alignment film 4 (4a, 4b), the liquid crystal molecules in the polymerizable liquid crystal composition are aligned 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 by a pair of polarizing plates 1 and 8. In FIG. 1, a color filter 6 is provided between the second substrate 7 and the alignment film 4. In addition, as a form of the liquid crystal display element of the present invention, it may be The so-called integrated color filter (COA) may include a color filter between an electrode layer containing a thin film transistor and a liquid crystal layer, or a color filter between the electrode layer containing a thin film transistor and a second substrate.

That is, a liquid crystal display element 10 according to an embodiment of the present invention is a laminated layer including a first polarizing plate 1, a first substrate 2, an electrode layer 3 containing a thin film transistor, an alignment film 4, and a liquid crystal containing a polymerizable liquid crystal composition. The structure of the layer 5, the alignment film 4, the color filter 6, the second substrate 7, and the second polarizing plate 8.

The first substrate 2 and the second substrate 7 can be made of flexible transparent materials such as glass or plastic, and one of them can also be an opaque material such as silicon. The two substrates 2 and 7 are adhered together by a sealing material such as an epoxy-based thermosetting composition and a sealing material arranged in a peripheral area, and glass particles, plastic particles, alumina particles, etc. may be disposed therebetween. Granular spacers or spacers made of resin formed by photolithography to maintain the distance between substrates.

FIG. 2 is an enlarged plan view of an area surrounded by a line II of the electrode layer 3 formed on the substrate 2 in FIG. 1. FIG. 3 is a cross-sectional view obtained by cutting the liquid crystal display element shown in FIG. 1 along the III-III line direction in FIG. 2. As shown in FIG. 2, in the electrode layer 3 containing a thin film transistor formed on the surface of the first substrate 2, a plurality of gate wirings 24 for supplying a scanning signal and a plurality of data wirings 25 for supplying a display signal cross each other. The grounds are arranged in a matrix. Note that only a pair of gate wirings 24 and a pair of data wirings 25 are shown in FIG. 2.

A unit pixel of a liquid crystal display device is formed by an area surrounded by a plurality of gate wirings 24 and a plurality of data wirings 25. A pixel electrode 21 and a 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 near the intersection where the gate wiring 24 and the data wiring 25 cross each other. This thin film transistor is connected to the pixel electrode 21 as a switching 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. This common line is connected to the common electrode 22 to the common electrode. 22 Supply common signal.

A preferred aspect of the thin film transistor structure is shown in FIG. 3, for example, which has a gate electrode 11 formed on the surface of the substrate 2 and a gate provided so as to cover the gate electrode 11 and cover substantially the entire surface of the substrate 2 An electrode insulating layer 12, a semiconductor layer 13 formed on the surface of the gate insulating layer 12 and facing the gate electrode 11, a protective layer 14 provided so as to cover a part of the surface of the semiconductor layer 13, and covering the protective layer 14 and the drain electrode 16 provided on one side end of the semiconductor layer 13 and in contact with the gate insulating layer 12 formed on the surface of the substrate 2 to cover the protective layer 14 and the other of the semiconductor layer 13 A source electrode 17 provided at a side end portion and in contact with the gate insulating layer 12 formed on the surface of the substrate 2 and an insulating protection layer 18 provided to cover the drain electrode 16 and the source electrode 17. An anodized film (not shown) may be formed on the surface of the gate electrode 11 to eliminate the step difference from the gate electrode.

The semiconductor layer 13 may be made of amorphous silicon, polycrystalline silicon, or the like. However, if a transparent semiconductor film such as ZnO, IGZO (In-Ga-Zn-O), or ITO is used, it is possible to suppress the damage of photocarriers caused by light absorption, thereby increasing From the viewpoint of a large element aperture ratio, it is also preferable.

In addition, in order to reduce the width or height of the Schottky barrier, an ohmic contact layer 15 may be provided between the semiconductor layer 13 and the drain electrode 16 or the source electrode 17. As the ohmic contact layer, a material to which impurities such as phosphorus are added at a high concentration such as n-type amorphous silicon or n-type polycrystalline silicon 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 particularly preferably Al or The wiring of its alloy. The insulating protection layer 18 is a layer having an insulating function, and is formed of a silicon nitride, a silicon dioxide, a silicon oxynitride film, or the like.

In the embodiment shown in FIG. 2 and FIG. 3, the common electrode 22 is a flat electrode formed on substantially the entire surface of the gate insulating layer 12. On the other hand, the pixel electrode 21 is an insulation protection formed on the common electrode 22. Comb electrodes on layer 18. That is, the common electrode 22 is disposed closer to the first substrate 2 than the pixel electrode 21, and these electrodes are disposed 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 of the opening in the unit pixel area becomes larger, and the aperture ratio and transmittance increase.

Regarding the pixel electrode 21 and the common electrode 22, in order to form a fringe electric field between these electrodes, the electrode-to-electrode distance (also referred to as the minimum separation distance) between the pixel electrode 21 and the common electrode 22: R It is formed to be smaller than the distance between the first substrate 2 and the second substrate 7: G. Here, the distance between electrodes: R represents the distance in the horizontal direction on the substrate between the electrodes. In FIG. 3, since the flat common electrode 22 overlaps the comb pixel electrode 21, an example of the distance between electrodes: R = 0 is revealed, and the minimum separation distance: R is smaller than the distance between the first substrate 2 and the second substrate 7 (i.e., Cell gap): G, thus forming a fringe electric field E. Therefore, the FFS-type liquid crystal display element can use a horizontal electric field formed in a direction perpendicular to the line where the pixel electrodes 21 form a comb shape, and a parabolic electric field. The electrode width of the comb-shaped portion of the pixel electrode 21: 1 and the width of the gap between the comb-shaped portion of the pixel electrode 21: m is preferably formed to a width to the extent that the generated electric field can drive all the liquid crystal molecules in the liquid crystal layer 5. 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, the liquid crystal display element of the present invention may be different from FIG. 3 and formed such that the distance between electrodes (also referred to as the minimum separation distance) between the pixel electrode 21 and the common electrode 22: R is greater than that between the first substrate 2 and the second substrate 7 Distance: G (IPS method). to In this case, for example, a configuration in which the comb-shaped pixel electrode and the comb-shaped common electrode are alternately provided on substantially the same plane may be mentioned.

A preferred form of the liquid crystal display element of the present invention is preferably an FFS liquid crystal display element using a fringe electric field. If the shortest separation distance d between the common electrode 22 and the pixel electrode 21 is shorter than the distance between the alignment films 4 (the distance between the substrates) The shortest separation distance D can form a fringe electric field between the common electrode and the pixel electrode, and can efficiently utilize the horizontal and vertical alignment of the liquid crystal molecules. In the case of the FFS-type liquid crystal display device of the present invention, if a voltage is applied to liquid crystal molecules arranged in a long axis direction parallel to the alignment direction of the alignment layer, a parabolic electric field will occur between the pixel electrode 21 and the common electrode 22 The potential lines are formed to the upper portions of the pixel electrode 21 and the common electrode 22, and the long axes of the liquid crystal molecules in the liquid crystal layer 5 are aligned along the formed electric field. Therefore, liquid crystal molecules can be driven even with low dielectric anisotropy.

From the viewpoint of preventing light leakage, the color filter 6 of the present invention preferably forms a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 23. In addition, the color filter 6 usually includes three types of filter pixels of R (red), G (green), and B (blue) to form one point of an image or an image. For example, these three types of filters are arranged along the extension direction of the gate wiring. The color filter 6 can be produced by, for example, a pigment dispersion method, a printing method, an electrographic method, or a dyeing method. If a color filter manufacturing method using a pigment dispersion method is described as an example, a hardening coloring composition for a color filter is coated on the transparent substrate, patterned, and then heated or irradiated with light. To harden. This step is performed separately for three colors of red, green, and blue, whereby a pixel portion for a color filter can be manufactured. In addition, it may be a so-called integrated color filter provided with pixel electrodes provided with active elements such as TFTs and thin film diodes on the substrate.

A polymerizable liquid crystal composition constituting the liquid crystal layer 5 is provided on the electrode layer 3 and the color filter 6 One of the alignment films 4 is directly abutted to induce one of the horizontal alignments.

In addition, the polarizing plate 1 and the polarizing plate 8 can adjust the polarizing axis of each polarizing plate to adjust the viewing angle or contrast to be good. It is preferable that the transmission axes have a mutually perpendicular manner in a manner that the transmission axes operate in a normally black mode. Transmission axis. It is particularly preferable that either of the polarizing plate 1 and the polarizing plate 8 is disposed so as to have a transmission axis parallel to the alignment direction of the liquid crystal molecules. In addition, 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 becomes maximum. Moreover, a retardation film for widening the viewing angle can also be used.

As another embodiment of the liquid crystal display device, in the case of the IPS method, the shortest separation distance d between the adjacent common electrode and the pixel electrode is greater than the shortest separation distance G between the liquid crystal alignment films. Structure, etc .: When the common electrode and the pixel electrode are formed on the same substrate and the common electrode and the pixel electrode are alternately arranged, the shortest separation distance d between the adjacent common electrode and the pixel electrode is greater than the shortest separation distance G between the liquid crystal alignment films. .

In the method for manufacturing a liquid crystal display element of the present invention, it is preferable that a substrate with an electrode layer and / or a surface of the substrate be formed with a film, and then a pair of substrates be separated and faced such that the film becomes an inner side, and a liquid crystal composition be filled between the substrates. . At this time, it is preferable to adjust the substrate interval via a spacer.

The distance between the substrates (to obtain the average thickness of the liquid crystal layer, also referred to as the separation distance between the films) is preferably adjusted to 1 to 100 μm. The average separation distance between the coatings is more preferably 1.5 to 10 μm.

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

The FFS liquid crystal display element described with reference to FIGS. 1 to 3 is an example, as long as it is not Without departing from the technical idea of the present invention, it can be implemented in various other forms.

Hereinafter, another embodiment of the liquid crystal display element of the present invention will be described using FIGS. 4 and 5.

For example, FIG. 4 is another embodiment of a plan view obtained by enlarging the area surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 1. As shown in FIG. 4, the pixel electrode 21 may be configured to have a slit. In addition, a slit pattern may be formed so as to have an inclined angle with respect to the gate wiring 24 or the data wiring 25.

The pixel electrode 21 shown in FIG. 4 is a shape obtained by cutting out an approximately rectangular frame-shaped cutout portion from an electrode of an approximately rectangular flat plate. A comb-teeth common electrode 22 is formed on one surface of the pixel electrode 21 with an insulating protective layer 18 (not shown) interposed therebetween. In addition, when the shortest separation distance R between the adjacent common electrode and the pixel electrode is smaller than the shortest separation distance G between the alignment layers, it becomes the FFS method, and when R is greater than G, it becomes the IPS method. The surface of the pixel electrode is preferably covered with a protective insulating film and an alignment film layer. In addition, similar to the above, a storage capacitor 23 may be provided in a region surrounded by the plurality of gate wirings 24 and the plurality of data wirings 25 to store display signals supplied through the data wirings 25. In addition, the shape of the cutout portion is not particularly limited, and the cutout portion may be a well-known shape such as an oval, a circle, a rectangle, a rhombus, a triangle, or a parallelogram. When the shortest separation distance R between the adjacent common electrode and the pixel electrode is larger than the shortest separation distance G between the alignment layers, the display device will be an IPS display device.

FIG. 5 is different from the embodiment of FIG. 3 and is another example of a cross-sectional view obtained by cutting the liquid crystal display element shown in FIG. 1 along the III-III line direction in FIG. 2. The first substrate 2 on which an alignment layer 4 and an electrode layer 3 containing a thin film transistor 20 are formed on the surface, and the first substrate 2 on which an alignment layer 4 is formed on the surface. The two substrates 8 are separated at predetermined intervals D into alignment layers facing each other, and the space is filled with a liquid crystal layer 5 containing a liquid crystal composition. A gate insulating layer 12, a common electrode 22, an insulating protection layer 18, a pixel electrode 21, and an alignment layer 4 are sequentially laminated on a part of the surface of the first substrate 2. Also, as shown in FIG. 4, the pixel electrode 21 is formed in a shape in which a triangular cutout portion is cut out at the central portion and both ends of the flat plate body, and a rectangular cutout portion is cut out in the remaining area. The pixel electrode 21 has a structure in which a comb-shaped common electrode is arranged in a substantially elliptical cutout portion substantially in parallel and closer to the first substrate side than the pixel electrode.

In the example shown in FIG. 5, a common electrode 22 having a comb shape or a slit is used, and the distance R between the pixel electrode 21 and the common electrode 22 is α (in addition, the distance between the electrodes is shown in FIG. 5 for convenience). The horizontal component is denoted as R). In addition, although an example in which the common electrode 22 is formed on the gate insulating layer 12 is shown in FIG. 3, the common electrode 22 may be formed on the first substrate 2 as shown in FIG. 5 with the gate insulating layer 12 interposed therebetween. A pixel electrode 21 is provided. The electrode width of the pixel electrode 21: 1. The electrode width of the common electrode 22: n and the distance between the electrodes: R are preferably adjusted appropriately to a width to which the generated electric field can drive all the liquid crystal molecules in the liquid crystal layer 5. When the shortest separation distance R between the adjacent common electrode and the pixel electrode is smaller than the shortest separation distance G between the alignment layers, it becomes the FFS method, and when R is greater than G, it becomes the IPS method. In addition, in FIG. 5, the positions of the pixel electrode 21 and the common electrode 22 in the thickness direction are different. The positions of the two electrodes in the thickness direction may be the same or the common electrode may be provided on the liquid crystal layer 5 side.

(Vertical electric field type)

Another preferred embodiment of the present invention is a vertical electric field type liquid crystal display element using a liquid crystal composition. FIG. 6 is a diagram schematically showing a configuration of a vertical electric field type liquid crystal display element. In addition, in FIG. 7, each component is described separately for convenience of explanation. FIG. 7 is formed from FIG. 6. The top view of the electrode layer 300 (or the thin film transistor layer 300) containing the thin film transistor on the substrate surrounded by the VII line is enlarged. FIG. 8 is a cross-sectional view obtained by cutting the liquid crystal display element shown in FIG. 6 along the direction of line VIII-VIII in FIG. 7. Hereinafter, a vertical electric field type liquid crystal display element of the present invention will be described with reference to FIGS. 6 to 9.

The structure of the liquid crystal display element 1000 of the present invention is, as described in FIG. 6, a liquid crystal display element having a second substrate 800, a first substrate 200, and a polymerization sandwiched between the first substrate 200 and the second substrate 800. Liquid crystal composition (or liquid crystal layer 500), and the orientation of liquid crystal molecules in the polymerizable liquid crystal composition when no voltage is applied is substantially perpendicular to the substrates 200 and 800, and the second substrate 800 is provided with a transparent conductive material A transparent electrode (layer) 600 (also referred to as a common electrode 600) is configured, and the first substrate 200 includes a pixel electrode made of a transparent conductive material and a thin film electrode for controlling the pixel electrode included in each pixel. Crystal thin film transistor layer 300. As shown in FIGS. 6 and 8, the second substrate 800 and the first substrate 200 may be sandwiched by a pair of polarizing plates 100 and 900. In FIG. 6, a color filter 700 is provided between the first substrate 200 and the common electrode 600. In addition, a pair of alignment films 400 are formed on the surfaces of the transparent electrodes (layers) 600 and 1400 adjacent to the liquid crystal layer 500 of the present invention and in direct contact with the polymerizable liquid crystal composition constituting the liquid crystal layer 500.

That is, the liquid crystal display element 1000 of the present invention includes a first polarizing plate 100, a first substrate 200, an electrode layer containing a thin film transistor (or a thin film transistor layer) 300, a photo-alignment film 400, The structure of the liquid crystal composition-containing layer 500, the alignment film 400, the common electrode 600, the color filter 700, the second substrate 800, and the second polarizing plate 900. The alignment film 400 is preferably a photo-alignment film.

The alignment film is made by using an alignment treatment (mask rubbing or light alignment) In the fabricated liquid crystal cell, a vertical alignment film slightly inclined (0.1 to 5.0 °) with respect to the normal direction of the glass substrate is formed on the inner side (the liquid crystal layer side) of the transparent electrode of the liquid crystal cell.

The polymerizable monomers are aligned in the vertical direction by the alignment regulatory force of the vertical alignment film, and the polymerizable monomers are polymerized and fixed by irradiating ultraviolet light to form a polymer network. It is inferred that the polymer network formed in this way has the following four structures: (1) forming a polymer network across the upper and lower substrates; (2) forming a polymer network from the upper (lower) substrate toward the liquid crystal, But to the halfway point; (3) forming a polymer network only near the surface of the alignment film (mainly a monofunctional monomer); (4) the polymer networks are bonded to each other in the liquid crystal layer (not floating) )). These forms are mixed with "the refractive index anisotropy of the polymer network or easy alignment axis formed to stabilize the orientation state above the critical voltage" and "the refractive index anisotropy or easy of the polymer network The alignment axis is formed as a polymer network that stabilizes two different alignment states below the critical voltage.

It is considered that the anisotropic polymer network formed in this way will be substantially completely separated from the liquid crystal layer, and the liquid crystal molecules are aligned between these polymer networks. It is obviously different from the molecular arrangement structure of so-called polymer network type liquid crystals in which liquid crystal molecules are mixed with a polymer network and light scattering occurs when no voltage is applied, and it also has a biased alignment film that is also used by PSA and the like. The structure of the nearby alignment sustaining layer is completely different.

As an example, a polymer network and a liquid crystal molecule arrangement structure obtained by a method using an alignment film are disclosed. On the other hand, even in the so-called MVA method or PVA, which has a structure such as a barrier wall or a slit, only the pre-tilt of the polymer network or liquid crystal molecules near the substrate interface is applied by the structure or the slit. The oblique electric field strength is slightly different, so it is inferred that it has the structure shown in the figure above.

In a VA type liquid crystal display device having liquid crystal molecules arranged by such a polymer network and liquid crystal molecules, the anchoring force to the liquid crystal molecules when no voltage is applied will be due to the anchoring force of the liquid crystal alignment film and the polymer network. The synergistic effect of the effect is stronger, and as a result, the response speed when the voltage is turned off can be accelerated.

(Transverse / oblique electric field type)

As a novel display technology that does not perform complicated steps such as mask rubbing or mask irradiation on the alignment film, and can simply divide the liquid crystal display region by a simple method dedicated to the electrode structure, it is proposed to make the oblique electric field and the transverse electric field act. On the liquid crystal layer.

FIG. 11 is a plan view schematically showing a minimum unit configuration of a pixel PX, which is one of the TFT liquid crystal display elements using the above technology. The structure and operation of the lateral / oblique electric field mode liquid crystal display device will be briefly described below.

The pixel electrode PE includes a main pixel electrode PA and a sub-pixel electrode PB. The main pixel electrodes PA and the sub pixel electrodes PB are electrically connected to each other, and the main pixel electrodes PA and the sub pixel electrodes PB are both disposed on the array substrate AR. The main pixel electrode PA extends in a second direction Y, and the sub pixel electrode PB extends in a first direction X different from the second direction Y. In the illustrated example, the pixel electrode PE is formed in an approximately cross shape. The sub pixel electrode PB is coupled to a substantially central portion of the main pixel electrode PA, and the main pixel electrode PA extends to both sides thereof, that is, to the left and right of the pixel PX. These main pixel electrodes PA and sub-pixel electrodes PB are substantially perpendicular to each other. The pixel electrode PE is electrically connected to a switching element that is 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 are provided in the pair. To the substrate CT. The main common electrode CA extends in the second direction Y. The main common electrode CA is disposed on both sides of the main pixel electrode PA. At this time, in the X-Y plane, the main common electrodes CA are not overlapped with the main pixel electrode PA, and an interval of approximately equal length is formed between each of the main common electrodes CA and the main pixel electrode PA. That is, the main pixel electrode PA is located at a substantially intermediate position of the adjacent main common electrode CA. The secondary common electrode CB extends in the first direction X. The sub common electrode CB is disposed on both sides of the sub pixel electrode PB. At this time, in the X-Y plane, the sub-common electrodes CB do not overlap with the sub-pixel electrodes PB, and an interval of approximately equal length is formed between each of the sub-common electrodes CB and the sub-pixel electrodes PB. That is, the sub-pixel electrode PB is located at a substantially intermediate position of the adjacent sub-common electrode CB.

In the example shown in the figure, the main common electrode CA is formed in a strip shape extending linearly in the second direction Y. The auxiliary common electrode CB is formed in a strip shape extending linearly in the first direction X. In addition, the main common electrode CA is arranged parallel to each other at intervals along the first direction X. In order to distinguish these, the main common electrode on the left in the figure is referred to as CAL, and the main common electrode on the right in the figure is referred to as CAR. In addition, the secondary common electrodes CB are arranged parallel to each other at intervals along the second direction Y. In order to distinguish these, the secondary common electrode on the upper side in the figure is referred to as CBU, and the secondary common electrode on the lower side in the figure is referred to as 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 arranged across the boundary between the pixel PX shown on the left and a pixel (not shown) on the left, and the main common electrode CAR is arranged across the pixel PX shown on the right and a pixel on the right (not shown) ). CBU and CBB Do not place it between the pixel PX and the adjacent pixels. That is, the sub-common electrode CBU is disposed across the boundary between the pixel PX and its upper pixel (not shown), and the sub-common electrode CBB is disposed across the pixel PX and its lower pixel (not shown) (Shown).

In the example shown in the figure, four areas divided by the pixel electrode PE and the common electrode CE in one pixel PX are formed as openings or transmission portions that are mainly helpful for 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 a 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. The 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 a part of the common electrode.

FIG. 12 is a schematic diagram of an electrode structure of an oblique electric field mode liquid crystal cell divided into eight parts. In this way, a further wide viewing angle can be achieved by dividing one pixel into eight parts.

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 no electric field is formed between the pixel electrode PE and the common electrode CE (at the time of OFF), as shown by the dotted line in FIG. 11, the liquid crystal molecules LM of the liquid crystal layer LQ The long axis is aligned so as to face 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 an OFF state corresponds to the initial alignment state, and the alignment direction of the liquid crystal molecules LM during the OFF state corresponds to the initial alignment direction. Strictly speaking, the liquid crystal molecules LM are not only aligned parallel to the X-Y plane, but have pre-tilt in most cases. Therefore, the initial alignment direction of the liquid crystal molecules LM in a strict sense is a direction obtained by orthographically projecting the alignment direction of the liquid crystal molecules LM when it is OFF to the X-Y plane.

Both the first alignment processing direction PD1 and the second alignment processing direction PD2 are directions substantially parallel to the second direction Y. At the time of OFF, the liquid crystal molecules LM are initially aligned so that their long axes face a direction substantially parallel to the second direction Y, as indicated by the dotted lines in FIG. 11. 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 shown in the figure, when the first alignment processing direction PD1 and the second alignment processing direction PD2 are parallel and facing the same, the cross section of the liquid crystal layer LQ, the liquid crystal molecules LM are approximately horizontal near the middle of the liquid crystal layer LQ (preliminary). (The inclination angle is about zero) alignment, with this as a boundary, is aligned near the first alignment film AL1 and near the second alignment film AL2 so as to have a pretilt angle such as symmetry (jet alignment). In the state in which the liquid crystal molecules LM are jet-aligned in this manner, the liquid crystal molecules LM near the first alignment film AL1 and the liquid crystal molecules LM near the second alignment film AL2 will be received even in a direction inclined with respect to the substrate normal direction. Optical compensation. Therefore, when the first alignment processing direction PD1 and the second alignment processing direction PD2 are parallel to each other and face the same, there is less light leakage in the case of black display, a high contrast ratio can be achieved, and display quality can be improved. In addition, when the first alignment processing direction PD1 and the second alignment processing direction PD2 are parallel and opposite to each other, the liquid crystal molecules LM are near the first alignment film AL1 and the second alignment film AL2 in the cross section of the liquid crystal layer LQ. The vicinity and the middle portion of the liquid crystal layer LQ are aligned so as to have a substantially uniform pretilt angle (horizontal alignment). A part of the backlight light from the backlight 4 passes through the first polarizing plate PL1 and is incident on 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. The polarization state of such linearly polarized light hardly changes when passing through the liquid crystal display panel LPN when it is OFF. Therefore, the linearly polarized light passing through the liquid crystal display panel LPN is absorbed by the second polarizing plate PL2 (black display) which has a cross nicol positional relationship with the first polarizing plate PL1.

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 pixel electrode PE and the common electrode CE are formed substantially parallel to the substrate. Transverse electric field (or oblique electric field). The liquid crystal molecule LM is affected by an electric field and its long axis rotates in a plane substantially parallel to the X-Y plane as shown by the solid line in the figure.

In the example shown in FIG. 11, in a region between the pixel electrode PE and the main common electrode CAL, the liquid crystal molecules LM in the lower half region rotate clockwise with respect to the second direction Y, and are aligned so as to face the In the lower left, the liquid crystal molecules LM in the upper half region are rotated counterclockwise with respect to the second direction Y, and are aligned so as to face the upper left in the figure. In the region between the pixel electrode PE and the main common electrode CAR, the liquid crystal molecules LM in the lower half region are rotated counterclockwise with respect to the second direction Y, and are aligned so as to be toward the lower right in the figure, and in the upper half region. The liquid crystal molecules LM rotate in a clockwise direction with respect to the second direction Y, and are aligned so as to face the upper right in the figure. In this way, 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, and in each alignment A domain is formed in the direction. That is, a plurality of domains are formed in one pixel PX.

At this ON, linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1 will be incident on the liquid crystal display panel LPN, and its polarization state will change according to the alignment state of the liquid crystal molecules LM when passing through the liquid crystal layer LQ. . At this time, at least a part of the light passing through the liquid crystal layer LQ passes through the second polarizing plate PL2 (white display). According to this structure, since four domains can be formed in one pixel, the viewing angles in four directions can be optically compensated to achieve a wide viewing angle. Therefore, it is possible to realize a display without gradual inversion and high transmittance, and to provide a liquid crystal with good display quality. Display device. In addition, by setting the areas of the openings in the four areas divided by the pixel electrode PE and the common electrode CE in a pixel to be approximately the same, the transmittance of each area can be approximately the same, and the light passing through the openings can be mutually Optical compensation is performed to achieve uniform display over a wide viewing angle range.

(Fishbone electrode)

FIG. 13 shows the described fishbone-type electrode structure. A liquid crystal layer is sealed between two glass substrates which are bonded to each other with a predetermined cell gap. Transparent electrodes made of ITO are formed on the facing surfaces of the two substrates facing each other. A common substrate was formed on a counter substrate using a glass substrate having a thickness of about 0.7 mm. The transparent electrode is provided with a slit portion 512c from which a part of the electrode material (ITO) is removed. The slit portion 512c having a cross shape connecting the midpoints of the opposite sides of the rectangular unit and having a width of about 3 to 5 μm functions as an alignment regulation structure, and the slit portion with a width of 5 μm extends in a direction inclined by 45 ° from the slit portion 512 c. A plurality of 512c are formed with a pitch of 8 μm, and these function as auxiliary alignment control factors that suppress the disorder of the azimuth direction when tilted. The width of the pixel electrode for display is 3 μm. The pixel stem electrode 512a and the pixel branch electrode 512b have an angle of 45 degrees, and at the same time have a structure in which the branch electrode is extended in four directions which are different every 90 degrees with the pixel center as a symmetrical center. Although the liquid crystal molecules are tilted due to the application of voltage, the orientation of the tilted alignment is the same as the directions of the four directions. Therefore, a region divided into four is formed in one pixel to increase the viewing angle of the display.

[Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples. In addition, "%" in the composition of the following examples and comparative examples means "mass%."

[Example 1]

A composition (Δn0.103, viscosity η 16.5, Δε-3.1) shown below (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. The polymerizable compounds (V1-1-1) and (V1-1-2) were uniformly dissolved at room temperature, and it was confirmed with a polarizing microscope that a nematic liquid crystal phase was displayed. A polymerization photoinitiator Irgacure 651 was mixed with this solution to prepare a polymerizable liquid crystal composition. The composition table of the prepared polymerizable liquid crystal composition is shown in Table 1.

In order to obtain a uniaxial alignment (horizontal alignment) of the liquid crystal, a vertical alignment (PVA) unit of a fishbone pattern electrode coated with a polyimide vertical alignment film with a cell gap of 3.6 μm was used. The obtained polymerizable liquid crystal composition was poured into a cell. A plurality of slits are engraved in the cell so that the liquid crystal will be tilted and aligned in the direction of the slits due to the applied voltage. The wire electrode width and slit width of the fish-bone pattern electrode are both 3.5 μm, and the length of the wire electrode is 100 μm.

After the injection, the injection port was sealed with a sealing agent 3026E (manufactured by threebond). Apply a rectangular wave voltage of 2.45V at a frequency of 1kHz, and simultaneously use an ultraviolet LED light source with a wavelength of 365nm to irradiate ultraviolet light with an intensity of 15mW / cm ² for 12 seconds, and then continue to irradiate the ultraviolet light to make the voltage 0V, so that It returned to the vertical alignment, and was irradiated with ultraviolet rays for 68 seconds from the point when the voltage was returned to 0V, to obtain a fishbone-type PVA unit. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components. The ultraviolet irradiation time was 80 seconds as a whole.

After the ultraviolet irradiation is completed, a voltage is applied to the cell to arrange the slit direction at 45 degrees with respect to either of the two polarizing axes of the orthogonal polarizing plate so that the bright field of view becomes the brightest. The liquid crystal of the cell is observed with a polarizing microscope. Alignment state. In a state where no voltage is applied, it can be confirmed that the light is in a dark field and is almost completely vertically aligned. If the voltage is applied slowly, make sure that the part of the slit The direct alignment changes to an oblique alignment, and the brightness gradually increases. In this unit, in order to confirm the orientation of the tilted alignment of the liquid crystal, in a state where the voltage of 7.5V is applied to the tilted alignment, the slit direction is minimized with respect to the two polarization axes of the orthogonal polarizing plate so that the transmittance is minimized. One is parallel. As shown in the polarizing microscope photograph in FIG. 9, if the oblique alignment orientation is directed toward the slit direction, a black line will be observed in the slit and the line electrode, but if the polarization direction is consistent with the slit direction, it will be in the narrow direction. Numerous black lines were observed in the seam and the wire electrode, and it was confirmed that the orientation of the oblique alignment was consistent with the direction of the slit. From this, it can be seen that if a voltage is applied to the liquid crystal to align the liquid crystal obliquely, the transmittance will be improved because the liquid crystal will be inclined toward the slit direction.

After applying a rectangular wave of 60 Hz and measuring the voltage-transmittance characteristics, the result showed that the maximum transmittance T100 was 65%, which was a value close to the transmittance of the liquid crystal display of 69%.

<LCN-1>

[Comparative Example 1]

The composition of Comparative Example 1 of Table 1 was injected into the cell in the same manner as in Example 1. Before the ultraviolet irradiation, a voltage of 15V was applied and waited for several minutes until the alignment defect disappeared. Then, the voltage was set to 0V. Then, after confirming that the liquid crystals are aligned in the direction of the slits with a polarizing microscope, ultraviolet rays are irradiated for 80 seconds. After the irradiation is completed, a voltage of 9V is applied to the unit where the polymer network is formed to align the liquid crystal obliquely. If the polarization direction is consistent with the slit direction, an innumerable number will be observed in part when observed with a polarization microscope. The black line, the part where the orientation of the oblique alignment coincides with the direction of the slit, and the bright part where the oblique alignment deviates from the slit direction are mixed, and the entire slit does not become a black line, and the oblique alignment is observed to be different. If the voltage is measured to increase the transmittance slowly, the maximum transmittance T100 is 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 cells. Before the ultraviolet irradiation, a voltage of 15V was applied to the unit, and waited for several minutes until the alignment defect disappeared. Then, the voltage of Table 2 was applied to each cell, and it was confirmed with a polarizing microscope that the liquid crystals were aligned toward the slits. The orientation is tilted, and ultraviolet rays are irradiated for 80 seconds while a voltage is applied. In order to observe the alignment of the liquid crystal using a polarizing microscope, after the irradiation is completed, a voltage of 9V is applied to the cell to tilt the liquid crystal. If the polarization direction is consistent with the slit direction, numerous black lines will be observed in a part. The part where the orientation of the oblique alignment coincides with the direction of the slit and the bright part where the oblique alignment orientation deviates from the direction of the slit are mixed, and the entire slit does not become a black line. The orientation to tilt is different. If the voltage is measured to increase the transmittance, the maximum transmittance T100 is 40.3% in Comparative Example 2 and 36.1% in Comparative Example 3. Compared with Comparative Example 1, T100 is increased, but the tilt orientation of the liquid crystal is not all the same. It is low toward the slit.

[Comparative Example 4]

The composition of Comparative Example 4 of Table 1 was injected into the cell in the same manner as in Example 1. Before the ultraviolet irradiation, a voltage of 15V was applied to the unit, and waited for several minutes until the alignment defect disappeared. Then, the voltage of Table 2 was applied to the cell, and the polarizing microscope was used to confirm that the liquid crystals were aligned uniformly in the direction of the slits. The UV rays were irradiated for 80 seconds while the voltage was applied. If the alignment of the liquid crystal is observed using a polarizing microscope, a bright field of view is displayed in the state where no voltage is applied. If the minimum transmittance T0 is measured, it is 39.6%. The polymer network is formed to maintain the alignment state above the critical voltage. The alignment state of the parallel liquid crystals is stabilized, and black of dark field cannot be obtained. When the maximum transmittance T100 is measured by an applied voltage, it is 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 cells.

After the injection, the glass unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). An ultraviolet LED light source with a wavelength of 365 nm was used to irradiate ultraviolet rays with an intensity of 15 mW / cm ² at 25 ° C for 80 seconds. Using a rectangular wave with a frequency of 1kHz and 2.39V ~ 7.5V as the voltage, from the time point of starting ultraviolet irradiation to 5 seconds to 15 seconds, after adjusting the time appropriately, the polymerization voltage is 0V under the state of ultraviolet irradiation to make it Returning to the vertical alignment, a fishbone-type PVA unit was prepared. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components.

After the ultraviolet rays were irradiated, the slit direction was arranged at an angle of 45 degrees with respect to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cells was observed with a polarizing microscope. In a state where no voltage is applied, it can be confirmed that it is a dark field of view and is almost in a vertical alignment state. If the voltage is applied slowly, it is confirmed that the slit portion changes from vertical alignment to oblique alignment, and the brightness gradually increases. In order to confirm the orientation of the oblique alignment, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction was made the same as that of the polarizing plate so that the transmittance was minimized. If the orientation of the oblique alignment is directed toward the slit direction, a black line will be observed between the slit and the wire electrode. If the polarization direction is made the same as the slit direction, countless black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment faces the slit direction.

After applying a rectangular wave of 60 Hz and measuring the voltage-transmittance characteristics, the maximum transmittance T100 was displayed as 60% or more, which was a value close to the transmittance of the liquid crystal display of 69%.

[Example 6]

The composition of Example 6 in Table 1 was injected into the cell in the same manner as in Example 1.

After the injection, the glass unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). An ultraviolet LED light source with a wavelength of 365 nm was used to irradiate ultraviolet rays with an intensity of 15 mW / cm ² at 25 ° C for 80 seconds. A rectangular wave with a frequency of 1kHz and 2.45V was used as the voltage, and after applying 12 seconds from the time point when ultraviolet irradiation was started, the voltage was set to 0V in the state of ultraviolet irradiation, and the voltage was returned to the vertical alignment to obtain a fishbone PVA. unit. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components.

After the ultraviolet rays were irradiated, the slit direction was arranged at an angle of 45 degrees with respect to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cells was observed with a polarizing microscope. In a state where no voltage is applied, it can be confirmed that it is a dark field of view and is almost in a vertical alignment state. If the voltage is applied slowly, it is confirmed that the slit portion changes from vertical alignment to oblique alignment, and the brightness gradually increases. In order to confirm the orientation of the oblique alignment, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction was made the same as that of the polarizing plate so that the transmittance was minimized. Even if the polymerizable compound and the liquid crystal composition are changed, if the oblique alignment orientation is aligned toward the slit direction, a black line is observed in the slit and the wire electrode uniformly. If the polarization direction is made the same as the slit direction, countless black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment faces the slit direction.

After applying a rectangular wave of 60 Hz and measuring the voltage-transmittance characteristics, the maximum transmittance T100 was displayed as 60% or more, which was a value close to the transmittance of the liquid crystal display of 69%.

[Example 7]

The composition of Example 7 in Table 1 was injected into the cell in the same manner as in Example 1.

After the injection, the glass unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). An ultraviolet LED light source with a wavelength of 365 nm was used to irradiate ultraviolet rays with an intensity of 15 mW / cm ² at 25 ° C for 80 seconds. A rectangular wave with a frequency of 1kHz and 2.45V was used as the voltage, and after applying for 8 seconds from the time point when the ultraviolet irradiation was started, the voltage was 0V under the state of ultraviolet irradiation, and the voltage was returned to the vertical alignment to obtain a fishbone PVA. unit. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components. After the ultraviolet rays were irradiated, the linear direction of the slits was inclined by 45 degrees with respect to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cells was observed with a polarizing microscope. In a state where no voltage is applied, it can be confirmed that it is a dark field of view and is almost in a vertical alignment state. If the voltage is applied slowly, it is confirmed that the slit portion changes from vertical alignment to oblique alignment, and the brightness gradually increases. In order to confirm the orientation of the oblique alignment, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction was made the same as that of the polarizing plate so that the transmittance was minimized. Even if the polymerizable compound and the liquid crystal composition are changed, if the oblique alignment orientation is aligned toward the slit direction, a black line is observed in the slit and the wire electrode uniformly. If the polarization direction is made the same as the slit direction, countless black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment faces the slit direction.

After applying a rectangular wave of 60 Hz and measuring the voltage-transmittance characteristics, the maximum transmittance T100 was shown to be 65.4% or more, which is a value close to the transmittance of the liquid crystal display of 69%.

[Example 8]

The composition of Example 8 of Table 1 was injected into the cell in the same manner as in Example 1.

After the injection, the glass unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). An ultraviolet LED light source with a wavelength of 365 nm was used to irradiate ultraviolet rays with an intensity of 15 mW / cm ² at 25 ° C for 1200 seconds. A rectangular wave with a frequency of 1kHz and 3.4V was used as the voltage, and after applying 100 seconds from the time point when ultraviolet irradiation was started, the voltage was set to 0V under the state of ultraviolet irradiation, and the voltage was returned to the vertical alignment to obtain a fish-bone PVA. unit. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components.

To confirm the oblique alignment direction as in Example 7, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction and the polarizing plate direction were made the same to minimize the transmittance. Even if the polymerizable compound and the liquid crystal composition are changed, if the oblique alignment orientation is aligned toward the slit direction, a black line is observed in the slit and the wire electrode uniformly. If the direction of polarized light matches the direction of the slit, Numerous black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment is consistent with the direction of the slit.

After applying a rectangular wave of 60 Hz and measuring the voltage-transmittance characteristics, the result shows that the maximum transmittance T100 is 64.3% or more, which is a value close to the transmittance of the liquid crystal display of 69%.

[Example 9]

The composition of Example 9 in Table 1 was adjusted in the same manner as in Example 1.

After coating the polyimide alignment film to obtain the homeotropic alignment of the liquid crystal, the friction alignment process is performed so that the pretilt angle is about 1 ° with respect to the normal direction of the substrate surface. The parallel friction alignment with ITO is used. The obtained polymerizable liquid crystal composition is injected into the cell by a vacuum injection method. After the injection, the glass unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). At 25 ° C., an ultraviolet ray with an intensity of 15 mW / cm ^{2 was} irradiated for 80 seconds. A rectangular wave with a frequency of 1kHz and 12V was used as the voltage, and the time was changed from 2 seconds to 10 seconds from the start of the ultraviolet irradiation time. After the ultraviolet irradiation, the voltage was set to 0V, and the voltage was restored to the vertical alignment. Fishbone type PVA unit. This makes it possible to form two differently oriented polymer networks: a polymer network with parallel alignment components and a polymer network with vertical alignment components. After the ultraviolet rays were irradiated, the rubbing alignment axis was arranged parallel to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cell was observed with a polarizing microscope.

Unit numbers 1 to 2 are dark fields of view. Even if the unit is rotated toward the azimuth direction, the black level of the dark field of view does not change. It is a vertical alignment. Make sure that the direction of the optical axis of the polymer network and the direction of the easy alignment axis of the liquid crystal are perpendicular to the unit. surface. On the other hand, if the unit numbers 3 to 4 are rotated toward the azimuth direction, they have an orientation that can obtain the same dark field of view as the unit numbers 1 and 2 and an azimuth that is slightly brighter. Unit number 5 is different from other units, even if the unit is turned The azimuth direction does not show the azimuth of the dark field of view, which is slightly brighter than the dark field of view of unit numbers 1 to 4. It was confirmed that the fall time was shortened by the effect of the anchoring force of the polymer network formed so that the optical axis direction of the polymer network coincided with the easy-alignment axis of the liquid crystal. The cell numbers 1 to 5 are arranged so as to be inclined by 45 degrees with respect to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cell is observed with a polarizing microscope. In the absence of applied voltage, a dark field of view is displayed (except for cell number 5). If the voltage is applied slowly, it changes to a bright field of view. In the configuration state of this unit, measure the electro-optical characteristics and summarize the results in Table 3.

If the voltage application time during the ultraviolet irradiation is changed from 2 seconds to 10 seconds, the pretilt angle is increased from 1.9 ° to 22.4 °. As the pretilt angle increases, Toff (relaxation time) increases from 3.8ms to 7.7ms, and the minimum transmittance T0 increases from 0.01% to 5.26%. In particular, if the voltage application time is 10 seconds, T0 increases sharply. On the other hand, the driving voltage V90 is reduced from 8.1V to 5.5V. At the time point when UV irradiation was started, a voltage of 12V showing parallel alignment was applied, leaving a trajectory of the polymer network that stabilized the parallel alignment. If the voltage was 0V during UV irradiation, the vertical alignment would be stabilized. A polymer network, but mixed with a polymer network showing (a) a component that stabilizes parallel alignment and (b) a component that stabilizes vertical alignment, as the voltage application time becomes longer, (a) The influence gradually increases and the pretilt angle increases. This result shows that the balance between the anchoring force of the polymer network that wants to become parallel alignment and the anchoring force of the polymer network that wants to become vertical alignment will determine the pretilt angle. If the voltage is applied for more than 10 seconds, the influence of (a) will increase, and it will be oriented in the direction of parallel alignment. T0 will be above 0.1%, and the contrast will decrease. If the application time of the polymerization voltage is 7 seconds or less, the influence of (a) is only slightly. Therefore, T0 is 0.1% or less, showing a good value, and high contrast can be obtained.

[Example 10]

The polymerizable liquid crystal composition of Example 6 was used, and the production of the unit was the same as that of Example 7. As shown in Table 4, after the application of the voltage, the irradiation of ultraviolet rays was stopped, and the voltage-transmittance characteristics during the ultraviolet irradiation were measured. Then, the ultraviolet rays were irradiated with the remaining time so that the total irradiation time became 80 seconds, and the voltage after the ultraviolet irradiation was measured. -Transmittance characteristics. The influence of the polymer network showing (a) a component that stabilizes parallel alignment and (b) a component that stabilizes vertical alignment was measured by measuring the voltage-transmittance during ultraviolet irradiation. Table 4 shows the voltage-transmittance characteristics and response time after applying a voltage to the same cell, and the voltage-transmittance characteristics and response time after the polymerization voltage was set to 0V and the remaining time was irradiated with ultraviolet rays. Comparing the voltage-transmittance characteristics (V90, T0, T100) after the voltage is applied to the cell numbers 1 to 5, almost the same characteristics are displayed. In addition, the voltage-transmittance characteristics (V90, T0, T100) after the ultraviolet irradiation is completed are also substantially the same. However, T0 and the pretilt angle after the voltage is applied to the cell number 6 are sharply increased compared to the cell numbers 1 to 5. This is due to the increase in the parallel alignment stabilizing component of (a). Therefore, in order to obtain a dark field of view showing a good black level, it is necessary to appropriately adjust the polymerization voltage application time such that T0 does not increase. In Example 10, the polymerization application time is preferably within 10 seconds. Comparing the voltage-transmittance characteristics of the unit numbers 1 to 5 after the ultraviolet irradiation is completed, a good value of 0.1% or less can be obtained. Good T0, but the unit number 6 is further increased than T0 after the application of the polymerization voltage, and the influence of (a) is increased. As a result, the pretilt angle is large, which makes the response time longer, which is not suitable for a display element. That is, in the case of the vertical alignment unit, the polymerization voltage application time is adjusted so as not to sacrifice the range of the black level (0.1% or less), thereby obtaining a voltage-transmittance with a Toff of 4ms or less and a maximum transmittance T100. characteristic.

[Example 11]

The polymerizable liquid crystal composition of Example 1 was used, and the production of the unit was the same as that of Example 1.

After the injection, the injection port was sealed with a sealing agent 3026E (manufactured by threebond). Apply a rectangular wave voltage of 1kHz and 2.45V, and use an ultraviolet LED light source with a wavelength of 365nm at the same time. After irradiating ultraviolet rays with an intensity of 15mW / cm ² for 12 seconds, the voltage should be 0.9V in the state of continuous ultraviolet rays. It was returned to the vertical alignment, and ultraviolet rays were irradiated for 68 seconds from the time point when the voltage was restored to 0.9 V to obtain a fishbone-type PVA unit. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components.

After the ultraviolet irradiation is completed, the slit direction is arranged to be inclined with respect to any one of the cross polarizers. 45 degrees, observe the liquid crystal alignment state of the cell with a polarizing microscope. In a state where no voltage is applied, it can be confirmed that the light is in a dark field and is almost completely vertically aligned. If the voltage is applied slowly, it is confirmed that the slit portion changes from vertical alignment to oblique alignment, and the brightness gradually increases. In order to confirm the orientation of the oblique alignment, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction was made the same as that of the polarizing plate so that the transmittance was minimized. If the orientation of the oblique alignment is directed toward the slit direction, a black line will be observed between the slit and the wire electrode. If the polarization direction is made the same as the slit direction, countless black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment faces the slit direction.

After applying a 60-Hz rectangular wave to measure the voltage-transmittance characteristics, the result showed that the maximum transmittance T100 was 63% or more, which was a value close to the transmittance of the liquid crystal display of 69%.

[Example 12-15]

The composition of Example 6 in Table 1 was injected into the cell in the same manner as in Example 1.

After the injection, the glass unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). Regarding ultraviolet irradiation conditions, an ultraviolet LED light source with a wavelength of 365 nm was used, and ultraviolet rays with an intensity of 15 mW / cm ^{2 were} irradiated at 25 ° C for 80 seconds. On the other hand, the voltage application condition is a rectangular wave voltage having a frequency of 1 kHz and a primary voltage as described in Table 5 under the aforementioned ultraviolet irradiation conditions. After applying the ultraviolet irradiation for 6 seconds from the time point of starting the ultraviolet irradiation, the ultraviolet irradiation is performed. In this state, the primary voltage described in Table 5 is replaced with the intermediate voltage described in Table 5. After applying for 1 second, ultraviolet rays are irradiated, and at the same time, the intermediate voltage described in Table 5 is replaced with the secondary voltage described in Table 5. (Below the liquid crystal threshold voltage), and in a state where the liquid crystal is returned to the vertical alignment, a fishbone-type PVA unit is obtained. This makes it possible to form a polymer network of row alignment components and a polymer network of vertical alignment components.

After the ultraviolet rays were irradiated, the slit direction was arranged at an angle of 45 degrees with respect to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cells was observed with a polarizing microscope. In a state where no voltage is applied, it can be confirmed that it is a dark field of view and is almost in a vertical alignment state. If the voltage is applied slowly, it is confirmed that the slit portion changes from vertical alignment to oblique alignment, and the brightness gradually increases. In order to confirm the orientation of the oblique alignment, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction was made the same as that of the polarizing plate so that the transmittance was minimized. If the orientation of the oblique alignment is directed toward the slit direction, a black line will be observed between the slit and the wire electrode. When the voltage was removed, it was confirmed that the alignment defects that sometimes occurred were not subjected to polymer stabilization. If the polarization direction is made the same as the slit direction, countless black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment faces the slit direction. A rectangular wave of 60 Hz was applied and the voltage-transmittance characteristics were measured. As a result, the maximum transmittance T100 was as described in Table 5 for the element characteristics, and showed a value close to that of the liquid crystal display of 69%.

[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 unit was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by threebond). Regarding the ultraviolet irradiation conditions, an ultraviolet LED light source with a wavelength of 365 nm was used, and ultraviolet rays with an intensity of 15 mW / cm ^{2 were} irradiated at 25 ° C for 80 seconds. As described later, a period of interruption of ultraviolet rays was set (in addition, 80 seconds did not include ultraviolet rays. During the outage). On the other hand, the voltage application condition is a rectangular wave voltage with a frequency of 1 kHz and the primary voltage described in the production conditions in Table 5 under the aforementioned ultraviolet irradiation conditions. After applying the ultraviolet irradiation for 10 seconds, The voltage and ultraviolet rays were removed at the same time. Without applying the intermediate voltage described in Table 5, the ultraviolet irradiation was interrupted for one second, and then returned to the vertical alignment state, and then the ultraviolet rays were irradiated to obtain a fishbone-type PVA unit. This makes it possible to form a polymer network of parallel alignment components and a polymer network of vertical alignment components.

After the ultraviolet rays were irradiated, the slit direction was arranged at an angle of 45 degrees with respect to any of the orthogonal polarizing plates, and the liquid crystal alignment state of the cells was observed with a polarizing microscope. In a state where no voltage is applied, it can be confirmed that it is a dark field of view and is almost in a vertical alignment state. If the voltage is applied slowly, it is confirmed that the slit portion changes from vertical alignment to oblique alignment, and the brightness gradually increases. In order to confirm the orientation of the oblique alignment, a voltage of 7.5 V was applied to make the oblique alignment state, and the slit direction was made the same as that of the polarizing plate so that the transmittance was minimized. If the orientation of the oblique alignment is directed toward the slit direction, a black line will be observed between the slit and the wire electrode. When the voltage was removed, it was confirmed that the alignment defects that sometimes occurred were not subjected to polymer stabilization. If the polarization direction is made the same as the slit direction, countless black lines are observed in the slit and the wire electrode, and it is confirmed that the orientation of the oblique alignment faces the slit direction. A rectangular wave of 60 Hz was applied and the voltage-transmittance characteristics were measured. As a result, the maximum transmittance T100 was as shown in Table 5, and a value close to that of the liquid crystal display of 69% was displayed.

(Table 5 Production conditions)

(Table 6 Element characteristics)

In this specification or the examples, the abbreviation "Gap" in the examples of the examples indicates the cell gap (µm), and "V90" indicates the driving voltage (V), Ton (on-time millisecond), and Toff (off-time millisecond).

Claims (21)

A method for manufacturing a liquid crystal display element, comprising the steps of applying a voltage equal to or higher than a threshold voltage of the polymerizable liquid crystal composition to a polymerizable liquid crystal composition sandwiched between at least one transparent substrate having two electrodes, and A step of simultaneously irradiating ultraviolet rays to separate polymerized phases, and then a step of irradiating ultraviolet rays so that the voltage does not reach a critical voltage, and further radiating ultraviolet rays. For example, in the method for manufacturing a liquid crystal display element according to the scope of patent application, in the step of applying a voltage equal to or higher than the critical voltage of the polymerizable liquid crystal composition and simultaneously irradiating ultraviolet rays to separate the polymerized phase, the liquid crystal in the polymerizable liquid crystal composition is separated. The molecules are aligned at an angle of 0 to 30 degrees with respect to the plane of the transparent substrate, and in the step of irradiating ultraviolet rays so that the voltage does not reach a critical voltage and further radiating ultraviolet rays, the liquid crystal molecules are inclined 80 degrees to 90 degrees with respect to the plane of the transparent substrate Degree alignment. For example, in the method for manufacturing a liquid crystal display device according to the scope of claims 1 or 2, in the step of applying a voltage equal to or higher than the critical voltage of the polymerizable liquid crystal composition and simultaneously irradiating ultraviolet rays to separate the polymerized phase, the polymerizable liquid crystal composition is The liquid crystal molecules are aligned at an angle ranging from 0 to 90 degrees with respect to the plane of the transparent substrate, and in the step of irradiating ultraviolet rays so that the voltage does not reach a critical voltage and further radiating ultraviolet rays, the liquid crystal molecules are inclined at 0 degrees with respect to the plane of the transparent substrate Alignment to 30 degrees. For example, the method for manufacturing a liquid crystal display device according to any one of claims 1 to 3, wherein the applied voltage is an AC waveform, and the polymerizable liquid crystal composition has a frequency that exhibits a range of dielectric properties. For example, the method for manufacturing a liquid crystal display device according to any one of claims 1 to 4, wherein the voltage equal to or higher than the critical voltage is the total change in transmittance with respect to the voltage-transmittance characteristic voltage of the polymerizable liquid crystal composition. Will be above 10% voltage V10. For example, the method for manufacturing a liquid crystal display device according to any one of claims 1 to 5, wherein the voltage that does not reach the critical voltage is a voltage that is 0 V or more and less than 90% of the critical voltage. For example, the method for manufacturing a liquid crystal display device according to any one of claims 1 to 6, using one or two or more compounds selected from the compounds represented by the following general formula (V) and general formula (VI) Compounds, as polymerizable compounds in the polymerizable liquid crystal composition,

(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- (where s represents an integer from 1 to 11 and the oxygen atom is bonded to the aromatic ring), U represents a straight or branched polyvalent alkylene group having 2 to 20 carbon atoms or 5 to 6 carbon atoms Polyvalent cyclic substituents of 30, the alkylene groups in polyvalent alkylene groups may be replaced by oxygen atoms in the range where the oxygen atoms are not adjacent, or by alkyl groups having 5 to 20 carbon atoms (the alkylene groups in the group It may be substituted by an oxygen atom in the range where the oxygen atoms are not adjacent) or a cyclic substituent. K represents an integer of 1 to 5, and all 1,4-phenylene groups in the formula may be substituted with any hydrogen atom. _3, -OCH _3, a fluorine atom or 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 represents an integer from 2 to 11) , The oxygen atom is bonded to the aromatic ring), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms, and The alkylene group may be substituted by an oxygen atom in a range where the oxygen atoms are not adjacent, or may be substituted by an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be replaced by an oxygen atom in a range where the oxygen atoms are not adjacent) or Substituted by a cyclic substituent, W represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms; all 1,4-phenylene groups in the formula may be substituted with -CH ₃ or -OCH ₃ , fluorine atom or cyano). For example, in the method for manufacturing a liquid crystal display device under the scope of claim 7, one or two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² are used as the polymerizable compound. For example, in the method for manufacturing a liquid crystal display device with the scope of patent application No. 7 or 8, it uses two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² as the polymerizable compound, among which the two or more The compounds have different Sp ¹ and Sp ² . For example, the method for manufacturing a liquid crystal display element according to any one of claims 1 to 9, using a liquid crystal compound represented by the following general formula (LC) as a liquid crystal compound in a polymerizable liquid crystal composition,

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms, and one or more CH ₂ groups in the alkyl group may be -O-,- CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- substitution. One or more hydrogen atoms in the alkyl group can be arbitrarily substituted with a halogen atom. 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-cyclohexyl (existing in this group) Among them, one CH ₂ group or two or more adjacent CH ₂ groups may be substituted by an oxygen atom or a sulfur atom), (b) 1,4-phenylene (one CH group in this group or Non-adjacent two or more CH groups may be substituted by a nitrogen atom), (c) 1,4-bicyclo (2.2.2) octyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or

唍 -2,6-diyl, one or more of the hydrogen atoms contained in the group (a), the group (b) or the group (c) may each be a fluorine atom, a chlorine atom, -CF ₃ or- OCF ₃ substitution, Z ^LC represents 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-, and 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; the alkane One or more CH ₂ groups in the group may be -O-, -CH = CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF ₂ -substitution, one or more of the hydrogen atoms in the alkyl group can be arbitrarily substituted with a halogen atom, a represents an integer of 1 to 4, and when a represents 2, 3, or 4 In the case where there is a plurality of A ^LC1 in the general formula (LC), the plurality of A ^LC1s may be the same or different. When the case of a plurality of Z ^LCs , the plurality of Z ^LCs may be the same or Can be different). For example, the method for manufacturing a liquid crystal display element according to any one of claims 1 to 10, wherein the unit 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 liquid crystal display element includes a polymer or copolymer in a liquid crystal composition sandwiched between at least one transparent substrate having two electrodes, and the content of the polymer or copolymer is the liquid crystal composition and the polymer or polymer. The total mass of the copolymer is more than 0.5% by mass and less than 40% by mass, the polymer or copolymer forms a polymer network having a uniaxial refractive index anisotropy or an easily-aligned axis, and It has two or more different alignment states. For example, the liquid crystal display element of the scope of application for patent No. 12 has the following tilt alignment as two or more different alignment states of the polymer network: relative to the plane of the transparent substrate, the tilt is in the range of 0 to 30 degrees Alignment and tilt alignment in the range of 80 degrees to 90 degrees with respect to the plane of the transparent substrate. For example, the liquid crystal display element of the patent application No. 12 or 13 has an electrode having a shape capable of dividing the display pixel of the liquid crystal display element into a plurality of regions. In a region divided according to the shape of the electrode, the following are provided: The oblique alignment is two or more different alignment states of the polymer network: the oblique alignment in the range of 0 to 30 degrees relative to the plane of the transparent substrate, and the oblique alignment of the oblique alignment is fixed in the azimuth direction, and relative to the plane of the transparent substrate. The plane of the transparent substrate is obliquely aligned in the range of 80 degrees to 90 degrees. The liquid crystal molecules in the liquid crystal composition when no voltage is applied have vertical or parallel alignment. For example, the liquid crystal display element in any one of claims 12 to 14, the optical axis direction of the polymer network or the easy alignment axis direction is consistent with the alignment of the liquid crystal molecules in the liquid crystal composition, and has the following tilt Alignment is two or more different alignment states: inclined orientation in the range of 0 to 30 degrees with respect to the plane of the transparent substrate, and inclined orientation in the range of 80 to 90 degrees with respect to the plane of the transparent substrate. At this time, the liquid crystal molecules in the liquid crystal composition have a pretilt angle of 0 degrees to 90 degrees with respect to the plane of the transparent substrate. For example, the liquid crystal display element according to any one of claims 12 to 15, wherein a polymer network layer having a thickness of at least 0.5% or more of the cell thickness is formed in the cell cross-section direction. For example, the liquid crystal display device according to any one of claims 12 to 16 uses one or two or more compounds selected from the compounds represented by the following general formula (V) and general formula (VI) as polymerization. Polymerizable compound in a liquid crystal composition,

(Wherein 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 -(In the formula, s represents an integer from 1 to 11, and an oxygen atom is bonded to an aromatic ring), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent group having 5 to 30 carbon atoms Cyclic substituents, the alkylene group in the polyvalent alkylene group may be replaced by an oxygen atom in the range where the oxygen atoms are not adjacent, or the alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be an oxygen atom Non-adjacent ranges are substituted by oxygen atoms) or cyclic substituents. K represents an integer of 1 to 5. All 1,4-phenylene groups in the formula can be replaced by -CH ₃ or -OCH. ₃ , fluorine atom or cyano)

(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 represents an integer from 2 to 11) , The oxygen atom is bonded to the aromatic ring), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent group having 5 to 30 carbon atoms, and The alkylene group may be replaced by an oxygen atom in a range where the oxygen atoms are not adjacent, or an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be replaced by an oxygen atom in a range where the oxygen atoms are not adjacent) or a ring Substituent substitution, W represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 15 carbon atoms. All 1,4-phenylene groups in the formula may be substituted with any of the hydrogen atoms -CH ₃ , -OCH ₃ , Fluorine atom or cyano). For example, the liquid crystal display device of the 17th patent application range uses one or two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² as the polymerizable compound. For example, a liquid crystal display device with a patent scope of item 17 or 18 uses two or more compounds represented by the same general formula (V) as Sp ¹ and Sp ² as the polymerizable compound, and the two or more compounds are mutually Sp ¹ and Sp ^{2 are} different. For example, the liquid crystal display device according to any one of the claims 12 to 19 uses a liquid crystal compound represented by the following general formula (LC) 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, and one or more CH ₂ groups in the alkyl group may be -O-,- CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- substitution. One or more hydrogen atoms in the alkyl group can be arbitrarily substituted with a halogen atom. 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-cyclohexyl (existing in this group) Among them, one CH ₂ group or two or more adjacent CH ₂ groups may be substituted by an oxygen atom or a sulfur atom), (b) 1,4-phenylene (one CH group in this group or Non-adjacent two or more CH groups may be substituted by a nitrogen atom), (c) 1,4-bicyclo (2.2.2) octyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or

唍 -2,6-diyl, one or more of the hydrogen atoms contained in the group (a), the group (b) or the group (c) may each be a fluorine atom, a chlorine atom, -CF ₃ or- OCF ₃ substitution, Z ^LC represents 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-, and 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; the alkane One or more CH ₂ groups in the group may be -O-, -CH = CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF ₂ -substitution, one or more of the hydrogen atoms in the alkyl group can be arbitrarily substituted with a halogen atom, a represents an integer of 1 to 4, and when a represents 2, 3, or 4 In the case where there is a plurality of A ^LC1 in the general formula (LC), the plurality of A ^LC1s may be the same or different. When the case of a plurality of Z ^LCs , the plurality of Z ^LCs may be the same or Can be different). For example, the liquid crystal display element according to any one of claims 12 to 20, wherein the unit structure is a VA mode, an IPS mode, an FFS mode, a VA-TN mode, a TN mode, or an ECB mode.