Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a method of manufacturing a horizontal alignment type liquid crystal display device.
• it contains an alignment control layer-forming monomer having an aromatic ester that generates light fleece rearrangement upon light irradiation, and the action of this compound can achieve horizontal alignment of liquid crystal molecules without using an alignment film such as polyimide.
• the present invention relates to a method of manufacturing a liquid crystal display device using a liquid crystal composition having positive or negative dielectric anisotropy.
• phase change PC
• TN twisted nematic
• STN super twisted nematic
• EOB electrically controlled birefringence
• OCB optically compensated bend
• IPS modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment).
• PM passive matrix
• AM active matrix
• PM is classified into static, multiplex, etc.
• AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc.
• TFT thin film transistor
• MIM metal insulator metal
• the classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process.
• Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.
• the liquid crystal display element contains a liquid crystal composition having a nematic phase.
• This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained.
• the association between the two properties is summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices.
• the temperature range of the nematic phase is related to the usable temperature range of the device.
• the preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower.
• the viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.
• the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required.
• the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
• the appropriate product value depends on the type of operating mode. This value is about 0.45 ⁇ m in a device of mode such as TN. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m in the VA mode device and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m in the IPS mode or FFS mode device.
• compositions with large optical anisotropy are preferred for small cell gap devices.
• the large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, positive or negative large dielectric anisotropy is preferred.
• the large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at the initial stage is preferred. After prolonged use, compositions having high specific resistance are preferred.
• the stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal monitor, a liquid crystal television, etc.
• an AM device having a TN mode a composition having positive dielectric anisotropy is used.
• a composition having negative dielectric anisotropy is used.
• an AM device having an IPS mode or an FFS mode a composition having positive or negative dielectric anisotropy is used.
• a composition having positive or negative dielectric anisotropy is used in an AM element of a polymer sustained alignment (PSA) type.
• PSA polymer sustained alignment
• a liquid crystal display device of the polymer supported alignment (PSA) type a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the device.
• the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device.
• the polymerizable compound polymerizes to form a polymer network in the composition.
• the polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.
• Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
• Patent Documents 1 to 4 On the other hand, PSA type liquid crystal display devices in which an alignment film is not formed in advance even in the VA mode have been proposed. This technique is not easy to obtain uniform vertical alignment because it does not use an alignment film such as conventional polyimide. In order to solve such a problem, a method has been proposed in which the ultraviolet light exposure to the polymerizable compound contained in the liquid crystal composition is performed a plurality of times and the intensity and the wavelength are changed. (Patent Documents 5 to 6)
• the object of the present invention is that in the production of a horizontal alignment type liquid crystal display device in which an alignment film such as polyimide is not formed in advance, an ultraviolet irradiation step is further added to the step of exposing the liquid crystal composition containing a horizontal alignment control agent to ultraviolet light. It is an object of the present invention to provide a method of increasing the uniformity of the horizontal alignment of liquid crystal molecules by the addition.
• Patent Documents 1 and 2 Alignment of liquid crystal using a low molecular weight compound having a cinnamate group, a polyvinyl cinnamate, a low molecular weight compound having a chalcone structure, a low molecular weight compound or a polymerizable compound, or a low molecular weight compound having an azobenzene structure or a dendrimer instead of an alignment film such as polyimide Methods for controlling have been reported (Patent Documents 1 and 2). In the methods of Patent Documents 1 and 2, first, the low molecular weight compound, the polymerizable compound and the polymer are dissolved in the liquid crystal composition as an additive. Next, a thin film of the additive is formed on the substrate by phase separation of the additive.
• the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition.
• the low molecular weight compound or polymer is dimerized or isomerized by this linear polarization, the molecules are aligned in a certain direction.
• IPS and FFS a device of horizontal alignment mode
• VA vertical alignment mode
• a dendrimer having azobenzene as a partial structure is dissolved in a liquid crystal composition as an additive.
• a thin film of the compound is formed on the substrate by phase separation of the compound.
• the liquid crystal composition is aligned vertically to the substrate.
• linearly polarized light is irradiated without heating the substrate.
• the dendrimer is dimerized or isomerized by this linear polarization, its molecules are aligned in the horizontal direction with respect to the substrate.
• Horizontal alignment mode devices such as IPS and FFS can be manufactured.
• the dendrimer and the liquid crystal composition have to be properly combined so that the dissolution and the phase separation of the dendrimer can easily proceed.
• Patent Document 5 discloses a method of performing ultraviolet light exposure having different polymerization rates three times on a liquid crystal display element including a liquid crystal composition having a non-liquid crystal polymerizable compound.
• the liquid crystal alignment applied here is vertical alignment, and relates to a vertical alignment type liquid crystal display element, and there is no suggestion or description about application to the horizontal alignment type liquid crystal display element of the present application.
• Patent Document 6 discloses a method in which a liquid crystal display element including a liquid crystal composition having a plurality of polymerizable compounds having different ultraviolet absorption peak wavelengths is exposed to ultraviolet light having different wavelength ranges twice.
• the liquid crystal alignment applied here is vertical alignment, and relates to a vertical alignment type liquid crystal display element, and there is no suggestion or description about application to the horizontal alignment type liquid crystal display element of the present application.
• the present invention contains an alignment control layer-forming monomer having an aromatic ester which generates light fleece dislocation upon irradiation with ultraviolet light, and utilizes a liquid crystal composition having positive or negative dielectric anisotropy, and ultraviolet light under specific conditions. It has been found that the problem can be solved by polymerizing by exposure, and the present invention has been completed.
• the present invention includes the following aspects and the like.
• the liquid crystal layer comprises a liquid crystal composition, which is a method of manufacturing a horizontal alignment type liquid crystal display device;
• the liquid crystal composition contains a liquid crystal compound having a positive or negative dielectric anisotropy has a transition temperature T NI from a nematic phase to an isotropic phase, as the first additive, the light irradiation Containing at least one alignment control layer-forming monomer which causes any of photo-fries rearrangement, photo-isomerization, photo-dimerization or photo-decomposition;
• the liquid crystal layer is maintained at a temperature range of T NI or higher, and A first ultraviolet radiation having a peak at 340nm from 280 nm, illuminance in the range of 2 mW / cm 2 of 200 mW
• the first additive according to [1] is an alignment control layer-forming monomer represented by the formula (A) having an aromatic ester which generates a light fleece rearrangement upon light irradiation,
• P 10 and P 20 independently represent a polymerizable group;
• M 10 , M 20 and M 30 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine.
• Z 10 , Z 20 and Z 30 independently represent a single bond, -COO-, -OCO-, -OCOO, -OCO-CH 2 CH 2- , -CH 2 CH 2 -COO-, -CH 2 O- , -OCH 2 -, - CF 2 O -, - OCF 2 -, - C ⁇ C -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 - or -CF 2 CF 2- is;
• a 10 and A 30 are independently
• Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 and Y 27 are each independently hydrogen or fluorine , Difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons, and at least one of Y 20 and Y 27 is hydrogen,
• Y 28 , Y 29 , Y 30 , Y 31 , Y 32 and Y 33 are each independently hydrogen, fluorine, or 1 to 5 carbon atoms
• at least one of Y 28 and Y 31 is hydrogen
• n 10 is independently an integer of 0 to 3
• In ultraviolet irradiation the
• a first ultraviolet radiation having a peak at 340nm from 280 nm, illuminance in the range of 2 mW / cm 2 of 100 mW / cm 2 , and the polarized irradiation in a range from 1 J / cm 2 to an exposure amount of 13J / cm 2;
• the liquid crystal layer is kept in a temperature range from room temperature (25 ° C.) to less than T NI , and the second ultraviolet light having a peak at 330 nm to 400 nm is 1 J / cm at an illuminance of 1 mW / cm 2 to 100 mW / cm 2.
• irradiation ranging from cm 2 to an exposure amount of 14J / cm 2, according to [1], the production method of a horizontal alignment type liquid crystal display device.
• the liquid crystal layer to hold the T NI + 5 ° C. below the temperature range from above T NI, a first ultraviolet radiation having a peak at 340nm from 280 nm, illuminance is 2 mW / cm Polarized irradiation within a range of 2 to 100 mW / cm 2 and an exposure dose of 1 J / cm 2 to 11 J / cm 2 ;
• the liquid crystal layer is kept in a temperature range of room temperature (25 ° C.) to 45 ° C.
• the second ultraviolet light having a peak at 330 nm to 400 nm is 1 J / cm at an illuminance of 1 mW / cm 2 to 50 mW / cm 2.
• P 10 and P 20 independently represent acryloyloxy, methacryloyloxy, ⁇ -fluoroacrylate, trifluoromethylacrylate, vinyl, vinyloxy, epoxy;
• Z 10 , Z 20 and Z 30 independently represent a single bond, -COO-, -OCO-, -OCOO-, -OCO-CH 2 CH 2- , -CH 2 CH 2 -COO-, -CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2
• At least one of Y 14 and Y 19 is hydrogen although it may be substituted by alkyl, or alkoxy having 1 to 5 carbon atoms
• Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 and Y 27 are each independently hydrogen or fluorine , Difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons, but at least one of Y 20 and Y 27 is hydrogen
• Y 28 , Y 29 , Y 30 , Y 31 , Y 32 and Y 33 are each independently hydrogen, fluorine, or 1 to 5 carbon atoms
• at least one of Y 28 and Y 31 is hydrogen
• n 10 is an independently integers of from 0 to 3, the manufacturing method of
• R 10 is independently hydrogen, fluorine, methyl or trifluoromethyl
• R 31 is independently hydrogen or methyl
• Z 10 , Z 20 and Z 30 independently represent a single bond, -COO-, -OCO-, -OCOO-, -OCO-CH 2 CH 2- , -CH 2 CH 2 -C
• the ratio of the alignment control layer-forming monomer is in the range of 0.1 parts by weight to 10.0 parts by weight when the total amount of liquid crystal compounds is 100 parts by weight, [1] to [5] ] The manufacturing method of the horizontal alignment type liquid crystal display element of any one of a 1 item.
• the liquid crystal composition contains at least one compound selected from the group of compounds represented by formulas (2) to (4):
• the manufacturing method of a horizontal alignment type liquid crystal display element as described.
• R 11 and R 12 independently represent alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one of —CH 2 — is replaced by —O—
• at least one hydrogen may be replaced by fluorine
• Ring B 1 , ring B 2 , ring B 3 and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl
• liquid crystal composition further contains at least one compound selected from the group of compounds represented by formulas (9) to (15): The manufacturing method of the horizontal alignment type liquid crystal display element of description.
• R 15 and R 16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, at least one of —CH 2 — is replaced by —O—
• at least one hydrogen may be replaced by fluorine
• R 17 is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—
• At least one hydrogen may be replaced by fluorine
• Ring E 1 , ring E 2 , ring E 3 , and ring E 4 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene,
• the liquid crystal composition further contains a polymerizable compound represented by the formula (16 ⁇ ) as a second additive, and forms an alignment control layer comprising a copolymer produced by polymerizing these compounds.
• a method for producing a horizontal alignment type liquid crystal display device according to any one of [1] to [10].
• Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine May be replaced by Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl,
• the ratio of the second additive in the liquid crystal composition is in the range of 0.03 parts by weight to 10 parts by weight based on 100 parts by weight of the total amount of liquid crystal compounds [11] to [11] 12]
• a display device comprising: a horizontal alignment type liquid crystal display element obtained by the manufacturing method according to any one of [1] to [13]; and a backlight.
• This example also includes the following section.
• A It further contains at least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, and an antifoamer.
• the above liquid crystal composition (B) A polymerizable composition prepared by adding a polymerizable compound different from the compound (A) or the compound (16 ⁇ ) to the liquid crystal composition described above. (C) A polymerizable composition prepared by adding the compound (A) and the compound (16 ⁇ ) to the above liquid crystal composition. (D) A liquid crystal composite prepared by polymerizing a polymerizable composition.
• (E) A polymer supported alignment type device containing this liquid crystal complex.
• (F) A polymerizable composition prepared by adding the compound (A), the compound (16 ⁇ ), and a polymerizable compound different from the compound (A) or the compound (16 ⁇ ) to the liquid crystal composition described above is used A polymer-supported oriented device manufactured by
• the liquid crystal display element including the liquid crystal composition including the alignment control layer forming monomer is exposed to ultraviolet light under different conditions to obtain a horizontal alignment type liquid crystal display element having excellent transmittance characteristics and contrast ratio. It can be realized. Furthermore, in the manufacture of a horizontal alignment type liquid crystal display element, the step of forming an alignment film becomes unnecessary, and the manufacturing cost of the liquid crystal display element can be reduced.
• liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
• “Liquid crystal display element” is a generic term for liquid crystal display panels and liquid crystal display modules.
• the “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but has a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a generic term for compounds mixed in a substance.
• This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod like.
• the "polymerizable compound” is a compound to be added for the purpose of forming a polymer in the composition.
• the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor and a polar compound are added to the liquid crystal composition as necessary. Ru.
• the proportion of the liquid crystal compound is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive even when the additive is added.
• the proportion of the additive is expressed as a weight percentage (part by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used.
• the proportion of the polymerization initiator is exceptionally expressed based on the weight of the polymerizable compound.
• the compound represented by formula (A) may be abbreviated as "compound (A)".
• the compound (A) means one compound represented by formula (A), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound etc. selected from the group of compounds represented by formula (2).
• Symbols such as B 1 , C 1 , D 1 and E 1 surrounded by a hexagon correspond to ring B 1 , ring C 1 , ring F and the like, respectively.
• the hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a fused ring such as a naphthalene ring.
• the straight line crossing one side of the hexagon is that any hydrogen on the ring is — (L 10 )
• n 11 represents that it may be replaced by a group such as-or -Sp 1 -P 1 .
• a subscript such as 'f' indicates the number of groups replaced. When the subscript is 0, there is no such replacement. When the subscript 'f' is 2 or more, a plurality of -Sp 1 -P 1 exists on the ring F. The plurality of groups represented by -Sp 1 -P 1 may be identical or different.
• the symbol of the terminal groups R 11 was used in a plurality of component compounds.
• two groups represented by any two R 11 may be identical or different.
• R 11 of compound (2) is ethyl and R 11 of compound (3) is ethyl.
• R 11 of compound (2) is ethyl and R 11 of compound (3) is propyl.
• This rule also applies to symbols such as other end groups, rings, linking groups and the like.
• Formula (8) when i is 2, two rings D 1 exist. In this compound, two groups represented by two rings D 1 may be identical or different. This rule applies to any two rings D 1 when i is greater than two. This rule also applies to symbols such as other rings and linking groups.
• the expression "at least one 'A'” means that the number of 'A' is arbitrary.
• the expression “at least one 'A' may be replaced by 'B'” when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Even in the case of three or more, their positions can be selected without limitation.
• This rule also applies to the expression "at least one 'A' has been replaced by 'B'".
• the expression “at least one A may be replaced by B, C or D” means that when at least one A is replaced by B, at least one A is replaced by C, and When one A is replaced with D, it is meant to include the case where more than one A is replaced with at least two of B, C and D.
• two successive -CH 2 -be replaced by -O- to be -O-O- it is also not preferable that —CH 2 — of the methyl moiety (—CH 2 —H) is replaced by —O— to form —O—H.
• the alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl.
• the configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to raise the upper limit temperature of the nematic phase.
• 2-fluoro-1,4-phenylene means the following two divalent groups.
• fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric bivalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
• a liquid crystal composition is added with an alignment control layer-forming monomer which causes light fleece dislocation, photoisomerization, photodimerization or photolysis upon light irradiation.
• the composition is enclosed in a device.
• the alignment control layer-forming monomer contributes to the alignment control of liquid crystal molecules because the structure is changed directionally by irradiation with polarized light. Further, since it has a polymerizable group, the polymer composed of the orientation control layer forming monomer has a role as an orientation control film.
• a compound having an aromatic ester which produces a light fleece rearrangement is described.
• the compound having an aromatic ester which produces light fleece rearrangement means a compound which absorbs ultraviolet light and radical cleavage of the aromatic ester site causes rearrangement to a hydroxy ketone.
• a radical is formed by photolysis of the aromatic ester site upon irradiation with ultraviolet light, resulting in light fleece rearrangement.
• photolysis of the aromatic ester site occurs when the polarization direction of polarized ultraviolet light and the long axis direction of the aromatic ester site are the same. After photolysis, they recombine and tautomerization produces hydroxyl groups in the molecule. It is considered that this hydroxyl group causes an interaction at the substrate interface, and the monomer for forming an orientation control layer is easily adsorbed to the substrate interface side with anisotropy. Moreover, since it has a polymerizable group, it is immobilized by polymerization. This property can be used to prepare a thin film capable of aligning liquid crystal molecules. In order to prepare this thin film, the ultraviolet light to be irradiated is suitably linear polarized light.
• the alignment control layer-forming monomer is added in the range of 0.1 parts by weight to 10 parts by weight when the total amount of liquid crystal compounds is 100 parts by weight. Heat the composition. This composition is injected into an element not having an alignment film. Next, the device is irradiated with linearly polarized light while warming the device to cause light fleece rearrangement and polymerization of the alignment control layer-forming monomer. The light-fleece-disposed alignment control layer-forming monomer is aligned in a certain direction, and the thin film formed after polymerization has a function as a liquid crystal alignment film.
• the orientation control layer forming monomer is referred to as a compound (A) in the present specification. Further, the compound (A-1), the compound (A-2) and the compound (A-3) may be referred to separately as necessary when referring to details of the structure.
• Compound (A) 2. Synthesis of compound (A), as a composition containing compound (A) Liquid Crystal Composition, Device Containing the Composition The liquid crystal display element will be described in order.
• Compound (A) 1-1.
• Compound (A) an example of a liquid crystal composition using the same
• P 10 and P 20 are each independently a polymerizable group, preferably acryloyloxy, methacryloyloxy, ⁇ -fluoroacrylate, trifluoromethylacrylate, vinyl, vinyloxy, epoxy.
• M 10 , M 20 and M 30 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine.
• Z 10 , Z 20 and Z 30 independently represent a single bond, -COO-, -OCO-, -OCOO-, -OCO-CH 2 CH 2- , -CH 2 CH 2 -COO-, -CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - C ⁇ C -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 - or -CF 2 CF 2- , preferably Single bond, -COO -, - OCO -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 - , -C ⁇ C-, or -CH 2 CH 2- .
• a 10 and A 30 are independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1 , 5-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, biphenylene-4,4'-diyl or 1,3-dioxane-2,5-diyl, which In phenylene, any hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or P 10 -Sp 10 -Z 10 - may be replaced by, in this 2,7-diyl, any The hydrogen
• a 20 independently represents 1,4-phenylene represented by the formula (A20-1), pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6 represented by the formula (A20-2) -Diyl, naphthalene-1,5-diyl, biphenylene-4,4'-diyl represented by formula (A20-3), or fluorene-2,7-diyl represented by formula (A20-4), preferably 1,4-phenylene represented by (A20-1), naphthalene-2,6-diyl represented by the formula (A20-2), biphenylene-4,4′-diyl represented by the formula (A20-3) or the formula (A20-) 4) fluorene-2,7-diyl, more preferably 1,4-phenylene represented by formula (A20-1), biphenylene-4,4′-diyl represented by formula (A20-3), or Fluorene shown in
• Y 10 , Y 11 , Y 12 and Y 13 are each independently hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoro Acetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons, and at least one of Y 10 and Y 13 is hydrogen.
• Preferred Y 10 , Y 11 , Y 12 and Y 13 are each independently hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, carbon number 1 to 5 Or C 1 -C 5 alkoxy, but at least one of Y 10 and Y 13 is hydrogen. More preferable Y 10 , Y 11 , Y 12 and Y 13 are each independently hydrogen, fluorine, hydroxy, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons However, at least one of Y 10 and Y 13 is hydrogen.
• Y 14 , Y 15 , Y 16 , Y 17 , Y 18 and Y 19 are each independently hydrogen, fluorine or C 1 to 5 carbon atoms. Although it is alkyl or alkoxy having 1 to 5 carbon atoms, at least one of Y 14 and Y 19 is hydrogen.
• Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 and Y 27 are each independently hydrogen or fluorine , Difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons, but at least one of Y 20 and Y 27 is hydrogen.
• Y 28 , Y 29 , Y 30 , Y 31 , Y 32 and Y 33 are each independently hydrogen, fluorine, or 1 to 5 carbon atoms Although it is alkyl, at least one of Y 28 and Y 31 is hydrogen.
• n 10 is independently an integer of 0 to 3.
• R 10 is hydrogen, fluorine or methyl, preferably hydrogen or methyl.
• R 31 is hydrogen or methyl, preferably hydrogen.
• L 10 is independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, preferably hydrogen, fluorine, trifluoromethyl, 1 to carbon atoms 5 alkyl or alkoxy having 1 to 5 carbon atoms.
• n 11 is independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.
• the compound (A) is characterized by having an aromatic ester site that causes photofries rearrangement and a polymerizable group.
• the compound (A) is useful because when a light fleece dislocation is generated by ultraviolet irradiation, the polar group interacts non-covalently with the substrate surface.
• One of the applications is an additive for a liquid crystal composition used in a liquid crystal display device.
• the compound (A) is added for the purpose of controlling the alignment of liquid crystal molecules.
• Such an additive has high solubility in a liquid crystal composition, is chemically stable under sealed conditions in the device, and preferably has a high voltage holding ratio when used in a liquid crystal display device. .
• the compound (A) fulfills such properties to a considerable extent.
• Preferred examples of the compound (A) will be described.
• Preferred alignment control layer-forming monomers are compounds (A-1-1) to compounds (A-1-10), compounds (A-2-1), compounds (A-2-2) and compounds as described below (A-3-1).
• N and m in the following compounds are independently 2 to 6, and R 10 is independently hydrogen, methyl, fluorine or trifluoromethyl.
• Y 10 is hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons.
• Y 20 is hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons.
• Synthesis of Compound (A) A synthesis method of the compound (A) will be described.
• the compound (A) can be prepared according to WO 1995/22586, JP 2005-206579, WO 2006/049911, Macromolecules, 26, 1244-1247 (1993), JP 2003-238491, International Synthesis is performed according to the methods described in JP 2010/133278 A, JP 2000-178233 A, JP 2012-1623 A, and JP 2011-227187 A.
• An orientation control monomer having an ⁇ -fluoroacrylate group is synthesized according to the method described in JP-A-2005-112850.
• An orientation control monomer having an ⁇ -trifluoromethyl acrylate group is synthesized according to the method described in JP-A-2004-175728.
• the compound (A) having a tolan structure is synthesized according to WO 2001/053248.
• Compounds for which the synthetic method has not been described can be synthesized by appropriately combining known methods of organic synthetic chemistry.
• Organic Synthesis (Organic Syntheses, John Wiley & Sons, Inc.), “Organic Reactions” (Organic Reactions, John Wiley & Sons, Inc.), “Comprehensive Organic Synthesis” (Comprehensive Organic Synthesis, Pergamon Press You may refer to books such as “New Experimental Chemistry Course” (Maruzen).
• the liquid crystal composition contains the compound (A) as an alignment control layer-forming monomer.
• the compound (A) has at least an aromatic ester which produces a light-fleece rearrangement upon irradiation with light.
• Examples of the compound (A) are the compound (A-1), the compound (A-2) or the compound (A-3).
• the compound (A) controls the alignment of liquid crystal molecules by directed isomerization by light fleece dislocation caused by polarized light irradiation and noncovalent interaction with the substrate of the device.
• This composition contains the compound (A) as the component A, and further contains a liquid crystal compound selected from the components B, C, D and E shown below.
• the preferred proportion of the compound (A) is about 0.1 parts by weight or more, based on 100 parts by weight of the total amount of liquid crystal compounds in order to obtain high reactivity to ultraviolet light, and it is dissolved in a liquid crystal composition To less than about 7 parts by weight.
• a further preferred ratio is in the range of about 0.3 parts by weight to about 7 parts by weight.
• the most preferred ratio is in the range of about 0.3 parts by weight to about 5 parts by weight.
• the preferable ratio is in the range of about 0.3 parts by weight to about 7 parts by weight.
• Component B to Component E Component B which is a liquid crystal compound is compounds (2) to (4).
• Component C is compounds (5) to (7).
• Component D is a compound (8).
• Component E is compounds (9) to (15).
• This composition may contain other liquid crystal compounds different from the compounds (2) to (15).
• compositions with appropriately selected components have high upper limit temperature, low lower limit temperature, small viscosity, suitable optical anisotropy (ie large optical anisotropy or small optical anisotropy), positive or negative large dielectric constant It has anisotropy, high specific resistance, stability to heat or ultraviolet light, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).
• suitable optical anisotropy ie large optical anisotropy or small optical anisotropy
• positive or negative large dielectric constant It has anisotropy, high specific resistance, stability to heat or ultraviolet light, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).
• Component B is a compound in which the two end groups are alkyl or the like.
• Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can.
• R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH 2 — is —O And at least one hydrogen may be replaced by fluorine.
• the component B is a compound close to neutrality because the absolute value of the dielectric anisotropy is small.
• the compound (2) is mainly effective in reducing the viscosity or adjusting the optical anisotropy.
• the compounds (3) and (4) are effective in extending the temperature range of the nematic phase or in adjusting the optical anisotropy by raising the upper limit temperature.
• the content of component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on the weight of the liquid crystal composition.
• the component C which is a liquid crystal compound is a compound having a fluorine, chlorine or a fluorine-containing group at the right end.
• Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113), and compounds (7-1) to (7-61). .
• R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— , at least one hydrogen may be replaced by fluorine;
• X 11 is fluorine, chlorine, -OCF 3, -OCHF 2, -CF 3, -CHF 2, -CH 2 F, -OCF 2 CHF 2 or, -OCF is a 2 CHFCF 3.
• Component C is used when preparing a composition for modes such as IPS, FFS, OCB, etc. because the dielectric anisotropy is positive and the stability to heat, light, etc. is very excellent.
• the content of component C is suitably in the range of 1% by weight to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight to 95%. It is in the range of%.
• the content of component C is preferably 30% by weight or less based on the weight of the liquid crystal composition.
• Component D which is a liquid crystal compound is a compound (8) in which the right terminal group is —C ⁇ N or —C ⁇ C—C ⁇ N.
• compounds (8-1) to (8-64) can be mentioned.
• R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— At least one hydrogen may be replaced by fluorine;
• -X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N.
• Component D is mainly used when preparing a composition for a mode such as TN since the dielectric anisotropy is positive and the value thereof is large. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.
• the content of component D is suitably in the range of 1% by weight to 99% by weight, preferably 10% by weight, based on the weight of the liquid crystal composition. It is in the range of 97% by weight, more preferably in the range of 40% to 95% by weight.
• the content of component D is preferably 30% by weight or less based on the weight of the liquid crystal composition.
• Component E which is a liquid crystal compound is compounds (9) to (15). These compounds, as in 2,3-difluoro-1,4-phenylene, have phenylene in which the lateral position is replaced by two fluorine or chlorine.
• Preferred examples of component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compounds (11-1) and compounds (12-1) to (12-). 3), compounds (13-1) to (13-11), compounds (14-1) to (14-3), and compounds (15-1) to (15-3).
• R 15 and R 16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — is — R 17 may be replaced by O ⁇ and at least one hydrogen may be replaced by fluorine; R 17 is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, In alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— and at least one hydrogen may be replaced by fluorine.
• Component E has a large negative dielectric anisotropy.
• Component E is used when preparing a composition for modes such as IPS, VA, PSA and the like. As the content of component E is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, the smaller the content, the better, as long as the required value of the threshold voltage of the device is satisfied. Considering that the dielectric anisotropy is about -5, the content is preferably 40% by weight or more in order to achieve sufficient voltage driving.
• the compound (9) is a bicyclic compound, it is mainly effective in reducing the viscosity, adjusting the optical anisotropy or increasing the dielectric anisotropy.
• the compounds (10) and (11) are tricyclic compounds, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy.
• Compounds (12) to (15) have the effect of increasing the dielectric anisotropy.
• the content of component E is preferably 40% by weight or more, more preferably 50% by weight, based on the weight of the liquid crystal composition. To 95% by weight.
• the content of component E is preferably 30% by weight or less based on the weight of the liquid crystal composition.
• liquid crystal composition satisfying at least one of the properties such as specific resistance, high stability to ultraviolet light, high stability to heat, and a large elastic constant. If necessary, liquid crystal compounds different from the components B, C, D, and E may be added.
• the polymerizable compound (16 ⁇ ), which is the above-mentioned second additive having a role as a reactive monomer, may be added to the composition for the purpose of increasing the reactivity (polymerizability).
• P 11 , P 12 and P 13 are independently a polymerizable group.
• Preferred P 11 , P 12 or P 13 is a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-5). Further preferred P 11 , P 12 or P 13 is a group (P-1), a group (P-2) or a group (P-3).
• the wavy lines in group (P-1) to group (P-5) indicate the binding site.
• M 11 , M 12 and M 13 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine
• C 1 -C 5 alkyl substituted by Preferred M 11 , M 12 or M 13 is hydrogen or methyl to increase the reactivity.
• Further preferred M 11 is methyl, further preferred M 12 or M 13 is hydrogen.
• Preferred Sp 11 , Sp 12 or Sp 13 is a single bond.
• ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is fluorine or chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen It may be substituted by C1-12 alkyl substituted by fluorine or chlorine.
• Preferred ring F or ring I is phenyl.
• Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl in these rings
• At least one hydrogen is fluorine, chlorine,
• Preferred Z 7 or Z 8 is a single bond,-(CH 2 ) 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-.
• Further preferred Z 22 or Z 23 is a single bond.
• u is 0, 1 or 2.
• Preferred u is 0 or 1.
• f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
• Preferred f, g or h is 1 or 2.
• Preferred second additives are compounds represented by Formula (16 ⁇ -1) to Formula (16 ⁇ -27).
• P 11 , P 12 and P 13 independently represent a group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-3), wherein M 11 and M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine:
• a polymerizable compound such as a first additive or a second additive used in the present liquid crystal composition is added for the purpose of forming a polymer in the liquid crystal composition.
• the compounds (A) may be used alone or in combination of two or more.
• a copolymer may be produced from the compound (A) and the compound (16 ⁇ ).
• the compound (A) is immobilized in the state where the polar group interacts non-covalently with the substrate surface. This further improves the ability of the liquid crystal molecules to orient, and at the same time prevents the compound (A) from diffusing into the liquid crystal composition.
• the compound (A) gives a polymer by polymerization. Since the polymers are arranged, the liquid crystal molecules can be provided with an appropriate pretilt angle on the substrate surface.
• the polymer stabilizes the orientation of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.
• Preferred examples of the compound (16 ⁇ ) are acrylate compounds, methacrylate compounds, vinyl compounds, vinyloxy compounds, propenyl ether compounds, epoxy compounds (oxiranes, oxetanes), and vinyl ketone compounds. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
• the liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and dissolved together by heating. Depending on the application, additives may be added to the composition. Examples of the additives are a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, an antifoamer and the like. Such additives are well known to those skilled in the art and are described in the literature.
• the polymerizable compound By adding the polymerization initiator, the polymerizable compound can be rapidly polymerized. By optimizing the reaction temperature, the amount of remaining polymerizable compound can be reduced.
• photo radical polymerization initiators are TPO, 1173, 4265, 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959 from the Omnirad series of IGM Resins.
• photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture It is.
• polymerization After adding a photo radical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiation with ultraviolet light. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image sticking to the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator.
• the preferred wavelength of the light to be irradiated will be described later.
• a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
• the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
• polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butyl catechol, 4-methoxyphenol, phenothiazine and the like.
• the optically active compound has an effect of preventing reverse twist by inducing a helical structure to liquid crystal molecules to give a necessary twist angle.
• the helical pitch can be adjusted by adding an optically active compound.
• Two or more optically active compounds may be added in order to adjust the temperature dependency of the helical pitch.
• the optically active compounds the following compounds (Op-1) to (Op-18) can be mentioned.
• ring J is 1,4-cyclohexylene or 1,4-phenylene
• R 28 is alkyl having 1 to 10 carbons.
• Antioxidants are effective to maintain a large voltage holding ratio.
• Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF Corporation) be able to.
• UV absorbers are effective to prevent the lowering of the upper limit temperature.
• Preferred examples of the UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
• AO-3 and (AO-4) the following compounds (AO-3) and (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (trade name: BASF Corporation) And 1,4-diazabicyclo [2.2.2] octane (DABCO).
• Light stabilizers such as sterically hindered amines are preferred to maintain high voltage holding rates.
• the following compounds AO-5) and (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF) can be mentioned.
• a heat stabilizer is also effective for maintaining a large voltage holding ratio, and IRGAFOS 168 (trade name: BASF) can be mentioned as a preferable example.
• Defoamers are effective to prevent foaming.
• Preferred examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.
• R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, -COOR 41 , or -CH 2 CH 2 COOR 41 , wherein R 41 is 1 carbon To 20 alkyl.
• R 42 is alkyl having 1 to 20 carbons.
• R 43 is hydrogen, methyl or O ⁇ , (oxygen radical), the ring K is 1,4-cyclohexylene or 1,4-phenylene, z is 1, Or three.
• Liquid crystal display device The liquid crystal composition described above has an operation mode such as PC, TN, STN, OCB or PSA and can be used for a liquid crystal display element driven by an active matrix system.
• This composition can be used also for a liquid crystal display element driven by a passive matrix method, having an operation mode such as PC, TN, STN, OCB, VA, IPS and the like.
• These elements can be applied to any of reflective, transmissive, and semi-transmissive types.
• This composition includes an NCAP (nematic curvilinear aligned phase) element produced by microencapsulating a nematic liquid crystal, a polymer dispersed liquid crystal display element (PDLCD) produced by forming a three-dimensional network polymer in the liquid crystal, and a polymer It can also be used as a network liquid crystal display (PNLCD).
• NCAP network curvilinear aligned phase
• PLCD polymer dispersed liquid crystal display element
• PLCD network liquid crystal display
• a liquid crystal display element in a PSA mode is produced.
• the elements in the PSA mode can be driven by a driving method such as an active matrix or passive matrix. Such an element can be applied to any of reflective, transmissive and semi-transmissive types.
• a device in the polymer dispersed mode can also be produced.
• the alignment film is a film for aligning liquid crystal molecules in a certain direction.
• a thin film of polyimide is used.
• a composition containing a compound (A) as an alignment control layer forming monomer is used.
• the compound (A) gives a polymer by polymerization.
• This polymer has the function of an alignment film and can be used instead of the alignment film.
• An example of a method of manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate does not have an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. The compound (A) is added to this composition.
• Additives may be further added as needed.
• the composition is injected into the device. This element is heated to a transition temperature (T NI ) of the liquid crystal composition from the nematic phase to the isotropic phase to change the liquid crystal composition to the isotropic phase, and then the first step of polarized ultraviolet irradiation is performed.
• the polarized light to be irradiated here is ultraviolet light having a peak in the range of wavelength 280 nm to wavelength 340 nm.
• light irradiation of the second stage is performed in the state of from room temperature (25 ° C.) to less than the TNI temperature.
• non-polarized ultraviolet light is preferred.
• More preferable non-polarized ultraviolet light may have a peak in the range of wavelength 330 nm to wavelength 400 nm.
• the polymerizable compound is reacted by ultraviolet irradiation. Such a two-step reaction produces an orientation control layer that induces uniform horizontal orientation in liquid crystal molecules, and a target element is produced.
• the liquid crystal layer is maintained in a temperature range above the transition temperature (T NI ) of the liquid crystal composition to the isotropic phase, and irradiation is performed with polarized ultraviolet light having a peak in the wavelength range of 280 nm to 340 nm.
• the aromatic ester site of the compound (A) is photolyzed to form a radical to undergo light fleece rearrangement.
• the photolysis of the aromatic ester site occurs when the polarization direction of polarized ultraviolet light and the long axis direction of the aromatic ester site are the same. After photolysis, they recombine and tautomerization produces hydroxyl groups in the molecule.
• this hydroxyl group causes an interaction at the substrate interface, and the monomer for forming an orientation control layer is easily adsorbed to the substrate interface side with anisotropy. Moreover, since it has a polymerizable group, it is immobilized by polymerization. This polymer serves as an alignment control layer that uniformly aligns liquid crystal molecules.
• the liquid crystal layer is kept in a temperature range from room temperature (25 ° C.) to less than T NI and a second ultraviolet ray having a peak at a wavelength of 330 nm to a wavelength of 400 nm is irradiated in a non-polarized state, it remains in the alignment control layer It is believed that some of the aromatic ester sites undergo photofleece rearrangement, or that an unreacted orientation control layer-forming monomer is polymerized along the orientation control layer. Since the light fleece dislocation here occurs inside the polymer directed by the first ultraviolet light, it is considered that the dislocation reaction tends to proceed in the direction in which the anisotropy of the orientation control layer increases.
• additional polymerization of the unreacted orientation control layer forming monomer also contributes to imparting anisotropy to the orientation control layer.
• Such an increase in the anisotropy of the alignment control layer means that the alignment control force acting on the liquid crystal molecules is increased.
• Such an effect of the polymer additionally stabilizes the alignment of the liquid crystal molecules, thereby improving the contrast of the device. Response time is reduced. Since image sticking is a malfunction of liquid crystal molecules, the effect of the polymer is to simultaneously improve the sticking. Since the polymerization is carried out in such two steps, the amount of unreacted matter is extremely small. Therefore, an element having a large voltage holding ratio can be obtained.
• ultraviolet light is irradiated in at least two steps.
• the preferred intensity of the first step ultraviolet light is in the range of about 2mW / cm 2 to about 200mW / cm 2
• the preferred dose (the product of the intensity (unit: mW / cm 2 ) and the irradiation time (unit: second) is , 1 J / cm 2 to 15 J / cm 2 .
• Ultraviolet light having a peak in the range of 280 nm to 340 nm and peaks in the vicinity of 313 nm and in the vicinity of 335 nm is preferred. This ultraviolet light may be called "first ultraviolet light".
• the ultraviolet rays polymerize most of the polymerizable compounds.
• further preferred illuminance is in the range of about 2 mW / cm 2 to about 100 mW / cm 2, more preferably the exposure dose is in the range of 1 J / cm 2 of 13J / cm 2.
• a more preferred illumination intensity is in the range of about 2 mW / cm 2 to about 100 mW / cm 2 , and a more preferred exposure dose is in the range of 1 J / cm 2 to 11 J / cm 2 .
• the preferred UV intensity of the second stage is in the range of about 1 mW / cm 2 to about 200 mW / cm 2 , and the preferred exposure dose is in the range of 1 J / cm 2 to 15 J / cm 2 .
• a more preferred illumination intensity is in the range of about 1 mW / cm 2 to about 100 mW / cm 2 , and a more preferred exposure dose is in the range of 1 J / cm 2 to 14 J / cm 2 .
• a further preferred illumination intensity is in the range of about 1 mW / cm 2 to about 50 mW / cm 2 , and a further preferred exposure dose is in the range of 1 J / cm 2 to 14 J / cm 2 .
• Ultraviolet light having a peak in the range of 330 nm to 400 nm and peaks in the vicinity of 335 nm and in the vicinity of 365 nm is preferred. This ultraviolet light may be called "second ultraviolet light”. This ultraviolet light can cause additional fleece dislocations. Moreover, the unreacted orientation control layer formation monomer (A) can be converted into a polymer.
• the orientation control layer is a thin film containing small asperities according to observation with a scanning electron microscope.
• the polymer of the polymerizable compound is observed as a layer formed by deposition from the substrate surface.
• the height of the cross section of this thin film is defined as the thickness of the orientation control layer.
• the film thickness is on average about 1 nm to about 100 nm, preferably about 5 nm to about 70 nm. When the film thickness is about 5 nm or more, it is preferable because horizontal alignment characteristics can be maintained. When the film thickness is 100 nm or less, the drive voltage can be appropriately reduced, which is preferable.
• liquid crystal molecules are substantially horizontally aligned with respect to the substrate surface when no voltage is applied.
• a horizontal alignment film such as polyimide is disposed between the color filter substrate and the liquid crystal layer or between the array substrate and the liquid crystal layer.
• such an alignment film is not required on at least one substrate side.
• liquid crystal molecules are horizontally aligned with respect to the substrate by the action of the alignment control layer.
• the angle between the liquid crystal molecules and the substrate is 0 ° or more and 5 ° or less. Preferably it is 0 degrees or more and 3 degrees or less.
• a wide viewing angle can be achieved by combining such horizontal orientation with a comb electrode.
• the present invention will be described in more detail by way of examples (including synthesis examples and usage examples). The invention is not limited by these examples.
• the invention also includes mixtures prepared by mixing at least two of the compositions of the Use Examples.
• the compound (A) was synthesized by the procedure shown in the synthesis example and the like.
• the compound synthesized was identified by a method such as NMR analysis. The characteristics were measured by the following method.
• NMR analysis For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. In the 19 F-NMR measurement, CFCl 3 was used as an internal standard, and the integration was performed 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.
• GC-2010 type gas chromatograph made by Shimadzu Corporation was used.
• capillary columns DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. were used.
• Helium (1 ml / min) was used as a carrier gas.
• the temperature of the sample vaporization chamber was set to 300 ° C.
• the temperature of the detector (FID) portion was set to 300 ° C.
• the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ l of the resulting solution was injected into the sample vaporization chamber.
• GCSolution system made by Shimadzu Corporation etc. was used.
• HPLC analysis For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. As a column, YMC YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m) was used. The eluate was used by appropriately mixing acetonitrile and water. As a detector, a UV detector, an RI detector, a CORONA detector, etc. were used suitably. When a UV detector was used, the detection wavelength was 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 ⁇ L of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.
• Ultraviolet-visible spectroscopy For measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length: 1 cm) for measurement.
• Measurement sample When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.
• Measurement method The measurement of the characteristics was performed by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. there were. A thin film transistor (TFT) was not attached to the TN device used for the measurement.
• JEITA Japan Electronics and Information Technology Industries Association
• Phase structure The sample was placed on a hot plate (Metler FP-52 hot stage) equipped with a polarization microscope and a melting point measuring apparatus. While heating this sample at a rate of 3 ° C./min, phase states and changes thereof were observed with a polarization microscope to identify the type of phase.
• a hot plate Metal FP-52 hot stage
• Transition temperature (° C)
• a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system, or a high-sensitive differential scanning calorimeter manufactured by SSI Nano Technology Inc., X-DSC7000 was used.
• the temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the transition point was determined by extrapolating the start point of the endothermic peak or exothermic peak associated with the phase change of the sample.
• the melting point of the compound and the polymerization initiation temperature were also measured using this apparatus.
• the temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "the lower limit temperature of the liquid crystal phase”.
• the temperature at which a compound transitions from liquid crystal phase to liquid may be abbreviated as the "clearing point”.
• the crystal is designated C.
• the smectic phase is represented by S and the nematic phase is represented by N.
• a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished among the smectic phases, they are represented as S A , S B , S C or S F , respectively.
• the liquid (isotropic) was designated as I.
• the transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0 ° C., and the transition temperature from nematic phase to liquid is 100.0 ° C.
• T NI or NI Maximum temperature of nematic phase
• the sample was placed on the hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid.
• the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature”.
• TNI When the sample is a mixture of a liquid crystal compound and a base liquid crystal, it is indicated by the symbol TNI .
• TNI When the sample is a mixture of a liquid crystal compound and a compound such as component B, C or D, it is indicated by the symbol NI.
• Viscosity Bulk viscosity; ;; measured at 20 ° C .; mPa ⁇ s
• an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
• the measurement method of characteristics may be different between the sample with positive dielectric anisotropy and the sample with negative dielectric anisotropy.
• the measuring methods when the dielectric anisotropy is positive are described in the items (8a) to (12a).
• the terms (8b) to (12b) are described.
• Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s) Positive dielectric anisotropy: The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degree and a distance between two glass substrates (cell gap) of 5 ⁇ m. The device was applied stepwise in steps of 0.5 V in the range of 16 V to 19.5 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
• the peak current and peak time of transient current generated by this application were measured. These measurements and M.
• the rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The value of dielectric anisotropy required for this calculation was determined by the method described below using the device for which this rotational viscosity was measured.
• Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s
• Negative dielectric anisotropy Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 ⁇ m. The device was applied stepwise in the range of 39 to 50 volts in increments of 1 volt. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of transient current generated by this application were measured.
• the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and this device was sealed with an adhesive cured with ultraviolet light.
• Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of liquid crystal molecules was measured.
• 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 ⁇ m and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of liquid crystal molecules was measured.
• Threshold voltage (Vth; measured at 25 ° C .; V) Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / ⁇ n ( ⁇ m) and the twist angle is 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 90% transmittance.
• Threshold voltage (Vth; measured at 25 ° C .; V) Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.
• the rise time ( ⁇ r: millisecond) is the time taken for the transmittance to change from 90% to 10%.
• the fall time ( ⁇ f: millisecond) is the time taken for the transmittance to change from 10% to 90%.
• the response time is represented by the sum of the rise time and the fall time obtained in this manner.
• a rectangular wave 60 Hz, 10 V, 0.5 seconds was applied to this element.
• the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum.
• the response time is represented by the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).
• Pretilt angle (degree) For measurement of the pretilt angle, Opti-Pro manufactured by Shintech Co., Ltd. was used.
• the first additive is selected from the compounds shown below.
• the compounds in the composition are represented by symbols based on the definitions in 1) to 5) of Table 2 below.
• Table 2 the configuration for 1,4-cyclohexylene is trans.
• the numbers in parentheses after the symbols correspond to the compound numbers.
• the symbol (-) means other liquid crystal compounds.
• the proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition.
• Example 1 To 100 parts by weight of the above composition (M1), 0.5 parts by weight of a compound (A-1-3-1) was added as an alignment control layer-forming monomer. As an antioxidant, R 40 is a heptyl group - was added, compound a (AO-1) at a rate of 150ppm (C 7 H 15).
• This composition is applied to a liquid crystal element (hereinafter sometimes referred to as an IPS element or simply an element) having a comb-like electrode having no alignment film in which the distance between two glass substrates (cell gap) is 3.2 ⁇ m. The injection was performed at the upper temperature limit of the nematic phase).
• polarized ultraviolet rays having peaks at wavelengths of 313 nm, 335 nm and 365 nm as the first ultraviolet rays were irradiated at 10 J / cm 2 from the normal direction to the device (the illuminance at wavelength 313 nm was 3 mW / cm 2 ( measured with Ushio Inc. UIT-150 and UVD-S313).
• a UV irradiation lamp USH-250BY manufactured by Ushio Inc. was used.
• As an exposure unit, ML-251A / B manufactured by USHIO INC. Was used.
• the polarized ultraviolet light was formed using a wire grid polarizer (ProFlux UVT260A manufactured by Polatechno Co., Ltd.).
• the IPS device is cooled to room temperature (25 ° C.), and while the liquid crystal layer is kept at room temperature (25 ° C.), black light manufactured by Eye Graphics Co., Ltd., F40T10 (peak wavelengths 335 nm and 365 nm) is used as the second ultraviolet light Irradiate the device with 5.4 J / cm 2 from the normal direction (in a wavelength of 365 nm, the illuminance is 3 mW / cm 2.
• UIT-150 manufactured by Ushio Inc. It measured using UVD-S365.), And performed the horizontal orientation process of the element.
• the element on which the orientation control layer was formed was set in a polarization microscope to observe the orientation state of the liquid crystal.
• the polarizer and the analyzer of the polarization microscope were arranged such that their transmission axes were orthogonal to each other.
• the alignment direction of the liquid crystal molecules is parallel to the transmission axis of the polarizer of the polarization microscope, that is, the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degrees.
• the element was placed on the horizontal rotation stage of a polarizing microscope. Light was irradiated from the lower side of the element, that is, from the polarizer side, and the presence or absence of light transmitted through the analyzer was observed.
• the orientation of the light transmitted through the analyzer was determined to be "good” because almost no light was observed. In addition, when the light which permeate
• the element was rotated on the horizontal rotation stage of the polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 degree.
• the intensity of light transmitted through the analyzer increases as the angle formed by the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules increases, and is approximately maximized when the angle is 45 degrees. confirmed.
• the liquid crystal molecules were aligned in a direction substantially horizontal to the main surface of the substrate of the device, and it was judged to be “horizontal alignment”.
• the ratio of the brightness when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degree to the brightness when 45 degrees ((light The light transmission intensity in the transmission state) / (light transmission intensity in the black state) was taken using a multimedia display tester 3298 manufactured by Yokogawa Electric Corporation, and was as good as about 1300.
• the alignment control layer on the element substrate was observed with a scanning electron microscope, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.
• Comparative Example 1 The composition used in Example 1 was injected at 90 ° C. (above the upper limit temperature of the nematic phase) into an IPS device having no alignment film in which the distance between two glass substrates (cell gap) is 3.2 ⁇ m. While the liquid crystal layer is maintained at 90 ° C., polarized ultraviolet light having peaks at wavelengths of 313 nm, 335 nm and 365 nm is irradiated at 10 J / cm 2 from the normal direction to the device as the first ultraviolet light (the illuminance at 313 nm is 3 mW The device was subjected to horizontal alignment processing only with a change of 1 / cm 2 ).
• the element on which the alignment control layer was formed was set in a polarization microscope, and the alignment state of the liquid crystal was observed in the same manner as in Example 1.
• Light was irradiated from the lower side of the element, that is, from the polarizer side, and the presence or absence of light transmitted through the analyzer was observed.
• the orientation was determined to be "slightly poor" as light passing through the analyzer was slightly observed.
• the element was rotated on the horizontal rotation stage of the polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 °. Yes, it was determined that the "horizontal orientation".
• the ratio of the brightness when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degree to the brightness when it is 45 degrees
• the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.
• Comparative Example 2 The composition used in Example 1 was injected at 90 ° C. (above the upper limit temperature of the nematic phase) into an IPS device having no alignment film in which the distance between two glass substrates (cell gap) is 3.2 ⁇ m. While the liquid crystal layer is maintained at 90 ° C., polarized ultraviolet light having peaks at wavelengths of 313 nm, 335 nm and 365 nm is irradiated at 10 J / cm 2 from the normal direction to the device as the first ultraviolet light (the illuminance at 313 nm is 3 mW / Cm 2 ).
• the IPS element is cooled to room temperature (25 ° C.), and the second-step exposure is irradiated with 5.4 J / cm 2 non-polarized light from the normal direction to the element using the same light source as the first ultraviolet
• the illuminance at a wavelength of 313 nm was 8 mW / cm 2 ), and the device was subjected to horizontal alignment processing.
• the element on which the alignment control layer was formed was set in a polarization microscope, and the alignment state of the liquid crystal was observed in the same manner as in Example 1. Light was irradiated from the lower side of the element, that is, from the polarizer side, and the presence or absence of light transmitted through the analyzer was observed.
• the orientation was determined to be "slightly poor” as light passing through the analyzer was slightly observed.
• the element was rotated on the horizontal rotation stage of the polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 °. Yes, it was determined that the "horizontal orientation".
• the ratio of the brightness when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degree to the brightness when 45 degrees is an example.
• it was inferior to Example 1 with about 720.
• the alignment control layer on the element substrate was observed with a scanning electron microscope, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.
• Comparative Example 3 The composition used in Example 1 was injected at 90 ° C. (above the upper limit temperature of the nematic phase) into an IPS device having no alignment film in which the distance between two glass substrates (cell gap) is 3.2 ⁇ m. While the liquid crystal layer is maintained at 90 ° C., non-polarized ultraviolet light having peaks at wavelengths of 313 nm, 335 nm and 365 nm as the first ultraviolet light is irradiated with 10 J / cm 2 from the normal direction Was 8 mW / cm 2 ).
• the device While maintaining the liquid crystal layer at 90 ° C., 5.4 J / cm 2 polarized light is irradiated from the normal direction to the element using the same light source as the first ultraviolet light (illuminance at a wavelength of 313 nm) 3mW / cm 2 ), the device was subjected to horizontal alignment processing. Next, the element on which the alignment control layer was formed was set in a polarization microscope, and the alignment state of the liquid crystal was observed in the same manner as in Example 1. Light was irradiated from the lower side of the element, that is, from the polarizer side, and the presence or absence of light transmitted through the analyzer was observed. The orientation was determined to be "slightly poor" as light passing through the analyzer was slightly observed.
• the element was rotated on the horizontal rotation stage of the polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 °. Yes, it was determined that the "horizontal orientation".
• the ratio of the brightness when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degree to the brightness when 45 degrees is an example.
• it was inferior to about 800 in Example 1.
• the alignment control layer on the element substrate was observed with a scanning electron microscope, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.
• Example 2 An IPS device was produced in the same manner as in Example 1 except that the amount of the compound (A-1-3-4) was changed to 3 parts by weight as a monomer for forming an orientation control layer. Further, the first ultraviolet ray and the second ultraviolet ray were irradiated in the same manner as in Example 1 to perform horizontal alignment treatment. The uniformity of orientation of the obtained element was "good” as in Example 1, and was "horizontal orientation". When the uniformity of the horizontal alignment was measured in the same manner as in Example 1, the ratio of luminance was as good as about 1000. Observation of the orientation control layer on the element substrate with a scanning electron microscope revealed that the film thickness was about 48 nm, and most of the orientation control layer-forming monomer was consumed.
• Example 3 An IPS device was produced in the same manner as in Example 1 except that the amount of the compound (A-1-3-14) was changed to 3 parts by weight as a monomer for forming an orientation control layer. Further, the first ultraviolet ray and the second ultraviolet ray were irradiated in the same manner as in Example 1 to perform horizontal alignment treatment. The uniformity of orientation of the obtained element was "good” as in Example 1, and was "horizontal orientation". When the uniformity of horizontal alignment was measured in the same manner as in Example 1, the luminance ratio was as good as about 1040. Observation of the orientation control layer on the element substrate with a scanning electron microscope revealed that the film thickness was about 48 nm, and most of the orientation control layer-forming monomer was consumed.
• Example 4 An IPS device was produced in the same manner as in Example 1 except that the amount of the compound (A-2-2-2) was changed to 0.5 parts by weight as a monomer for forming an orientation control layer. Further, the second ultraviolet rays were irradiated in the same manner as in Example 1 except that the exposure amount of the first ultraviolet rays was set to 0.9 J / cm 2, and the horizontal alignment process was performed. The uniformity of orientation of the obtained element was "good” as in Example 1, and was "horizontal orientation". When the uniformity of horizontal alignment was measured in the same manner as in Example 1, the luminance ratio was as good as about 1,100. When the alignment control layer on the element substrate was observed with a scanning electron microscope, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.
• Example 5 An IPS device is produced in the same manner as in Example 4 except that the amount of the compound (A-2-2-2) is 10 parts by weight as a monomer for forming an orientation control layer. Further, the first ultraviolet light and the second ultraviolet light are irradiated in the same manner as in Example 1 to perform horizontal alignment processing. The uniformity of the horizontal orientation of the resulting device tends to be the same as in Example 1.
• Example 1 had almost no light leakage.
• Comparative Examples 1 to 3 light leakage was slightly observed. The light leakage is considered to be caused by the lack of the alignment control force of the alignment control layer. From the observation of the thickness of the orientation control layer, it is considered that almost all the monomers for forming the orientation control layer in Examples and Comparative Examples are converted to polymers.
• the difference in the luminance ratio between the example and the comparative example is that the aromatic ester site remaining in the orientation control layer is subjected to light fleece rearrangement by the second ultraviolet irradiation, or the orientation control layer-forming monomer which has not reacted is oriented It is inferred that the anisotropy (alignment regulating force) of the orientation control layer is increased because the polymerization is performed along the control layer.
• the second ultraviolet irradiation step of the present invention is considered to contribute to the improvement of the uniformity of the horizontal alignment. The same effect is obtained even when the dielectric anisotropy of the liquid crystal composition is positive. Therefore, it can be concluded that the liquid crystal display device manufactured by the method of the present invention has uniform horizontal alignment. Since this device prevents light leakage, it can be said that the device is excellent in characteristics such as contrast.
• the liquid crystal display device manufactured by the method of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.

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