WO2017051709A1 - 液晶表示素子 - Google Patents
液晶表示素子 Download PDFInfo
- Publication number
- WO2017051709A1 WO2017051709A1 PCT/JP2016/076253 JP2016076253W WO2017051709A1 WO 2017051709 A1 WO2017051709 A1 WO 2017051709A1 JP 2016076253 W JP2016076253 W JP 2016076253W WO 2017051709 A1 WO2017051709 A1 WO 2017051709A1
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- liquid crystal
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- compound
- hydrogen
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- C09K19/3001—Cyclohexane rings
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- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
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- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- B32—LAYERED PRODUCTS
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- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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- 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
- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13712—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering the liquid crystal having negative dielectric anisotropy
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- 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
- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13775—Polymer-stabilized liquid crystal layers
Definitions
- the present invention relates to a polymer-supported alignment type liquid crystal display element, a liquid crystal composition having a negative dielectric anisotropy used in this element, and a liquid crystal alignment film.
- the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) mode.
- the classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film insulator), MIM (metal film insulator), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process.
- the classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.
- the liquid crystal display element contains a liquid crystal composition having a nematic phase.
- This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationships in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device.
- the temperature range of the nematic phase is related to the temperature range in which the device can be used.
- a preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about ⁇ 10 ° C. or less.
- the viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small 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 optical anisotropy or a small optical anisotropy, ie an appropriate 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 value for this product depends on the type of operating mode. This value is about 0.45 ⁇ m for a mode element such as TN, about 0.30 ⁇ m to about 0.40 ⁇ m for a VA mode element, and about 0.20 ⁇ m for an IPS mode or FFS mode element. To about 0.30 ⁇ m.
- a composition having a large optical anisotropy is preferable for a device having a small cell gap.
- a large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable.
- 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 device used in a liquid crystal projector, a liquid crystal television, and the like.
- a polymer-supported alignment (PSA) type liquid crystal display element In a general-purpose liquid crystal display element, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film.
- PSA polymer-supported alignment
- a polymer is combined with an alignment film.
- a composition to which a small amount of a polymerizable compound is added is injected into the device.
- the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device.
- the polymerizable compound polymerizes to form a polymer network in the composition.
- the alignment of liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened, and image burn-in is improved.
- Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
- a composition having a positive dielectric anisotropy is used for an AM device having a TN mode.
- a composition having a negative dielectric anisotropy is used in an AM device having a VA mode.
- a composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode.
- a composition having positive or negative dielectric anisotropy is used in a polymer-supported orientation type AM device.
- An example of a liquid crystal composition having negative dielectric anisotropy is disclosed in Patent Document 1 below.
- liquid crystal alignment film plays such a role.
- This alignment film is one of the important elements related to the display quality of the element, and the role of the alignment film has become important year by year as the quality of the element increases.
- the liquid crystal alignment film is prepared from a liquid crystal alignment agent.
- the alignment agent mainly used is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. This solution is applied to a substrate, and the coating film is heated to form a polyimide thin film.
- the thin film is given a function of aligning liquid crystal molecules in a certain direction by rubbing treatment.
- the rubbing process is a process of rubbing the surface of polyimide in one direction using a cloth in which fibers of nylon, rayon, polyester or the like are implanted, and is used industrially. By this treatment, the liquid crystal molecules can be uniformly aligned on the alignment film.
- One object of the present invention is a liquid crystal display device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
- Another object is a liquid crystal alignment film that contributes to a short response time.
- Another object is a liquid crystal composition used for such a device.
- Other objectives are: high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high heat resistance
- the liquid crystal composition satisfies at least one of characteristics such as high stability and a large elastic constant.
- Another object is a liquid crystal composition having an appropriate balance between at least two of these properties.
- the present invention provides an electrode group formed on one or both of a pair of opposed substrates, a plurality of active elements connected to the electrode group, and opposing surfaces of the pair of substrates.
- a liquid crystal alignment film formed between the pair of substrates, wherein the liquid crystal alignment film is selected from polyorganosiloxane, polyamic acid, polyamic acid ester, and polyimide.
- a polymer-supported alignment type liquid crystal display device comprising a polymer, wherein the liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (1) as a first component. It is related with the liquid crystal composition contained and the liquid crystal aligning film contained in this element.
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine;
- ring A and ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4 -Phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or tetrahydropyran-2,5-diyl;
- ring B is 2,3-difluoro-1,4-phenylene, 2 -Chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene 2,6-diyl or 7,8-be difluorochroman-2,6-diyl,;
- One advantage of the present invention is a liquid crystal display device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. Another advantage is a liquid crystal alignment film that contributes to a short response time. Another advantage is a liquid crystal composition used in such a device. Another advantage is the high maximum temperature of the nematic phase, the low minimum temperature of the nematic phase, small viscosity, suitable optical anisotropy, negative large dielectric anisotropy, large specific resistance, high stability against ultraviolet light, high heat resistance The liquid crystal composition satisfies at least one of characteristics such as high stability and a large elastic constant. Another advantage is a liquid crystal composition having an appropriate balance between at least two of these properties.
- liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
- “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules.
- “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal phase, but has a composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products.
- This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a rod-like molecular structure.
- the “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.
- a liquid crystalline compound having alkenyl is not polymerizable in that sense.
- the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. If necessary, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor are added to the liquid crystal composition.
- the ratio of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive even when the additive is added.
- the ratio of the additive is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or additive is calculated based on the total weight of the liquid crystal compound. Weight parts per million (ppm) may be used.
- the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
- the upper limit temperature of the nematic phase may be abbreviated as “the upper limit temperature”.
- “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”.
- High voltage holding ratio means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large voltage holding ratio even at a temperature close to.
- the expression “increasing the dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, this value increases positively, and the composition having a negative dielectric anisotropy. For objects, this means that this value increases negatively.
- the expression “at least one 'A' may be replaced by 'B'” means that the number of 'A' is arbitrary. When the number of “A” is one, the position of “A” is arbitrary, and when the number of “A” is two or more, the positions can be selected without limitation. This rule also applies to the expression “at least one 'A' is replaced by 'B'”.
- the expression “in alkyl, at least one —CH 2 — may be replaced by —O— or —S—” includes —OCH 3 , —CH 2 OCH 3 , —CH 2 OCH 2 CH Groups such as 2 OCH 3 , —SCH 2 CH 2 CH 3 , —CH 2 CH 2 SCH 3 , —CH 2 OCH 2 CH 2 SCH 3 and the like are included.
- Compound (1) The compound represented by Formula (1) may be abbreviated as Compound (1). At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
- the symbol of the terminal group R 1 is used for a plurality of compounds.
- two groups represented by two arbitrary R 1 may be the same or different.
- R 1 of the compound (1-1) is ethyl and R 1 of the compound (1-2) is ethyl.
- R 1 of compound (1-1) is ethyl and R 1 of compound (1-2) is propyl.
- This rule also applies to symbols such as other end groups.
- Formula (1) when a is 2, two rings A exist. In this compound, the two rings represented by the two rings A may be the same or different.
- This rule also applies to any two rings A when a is greater than 2.
- This rule also applies to symbols such as Z 1 and ring C.
- This rule also applies to the two —Sp 2 —P 5 groups in the compound (3-27).
- 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 divalent groups such as tetrahydropyran-2,5-diyl.
- This rule also applies to linking groups such as carbonyloxy (—COO— and —OCO—).
- the present invention includes the following items.
- Item 1 An electrode group formed on one or both of a pair of substrates disposed opposite to each other, a plurality of active elements connected to the electrode group, and formed on each surface of the pair of substrates facing each other
- a polymer-supported alignment type liquid crystal display device comprising a combination, wherein the liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (1) as a first component.
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine;
- ring A and ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4 -Phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or tetrahydropyran-2,5-diyl;
- ring B is 2,3-difluoro-1,4-phenylene, 2 -Chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene 2,6-diyl or 7,8-be difluorochroman-2,6-diyl,;
- Item 2. The liquid crystal display device according to item 1, wherein the first component is at least one compound selected from the group of compounds represented by formulas (1-1) to (1-21).
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.
- Item 3. The liquid crystal display element according to item 1 or 2, wherein the ratio of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.
- Item 4. The liquid crystal display element according to any one of items 1 to 3, wherein the liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (2) as the second component.
- R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine Or alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine;
- Ring D and Ring E are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;
- Z 3 is a single bond, ethylene, or carbonyloxy;
- c is 1 2, or 3.
- Item 5. The liquid crystal display device according to item 4, wherein the second component is at least one compound selected from the group of compounds represented by formulas (2-1) to (2-13).
- R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.
- Item 6 The liquid crystal display device according to item 4 or 5, wherein the ratio of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.
- Item 7. The liquid crystal display device according to any one of items 1 to 6, wherein the liquid crystal composition contains at least one polymerizable compound selected from the group of compounds represented by formula (3) as an additive component.
- 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, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen.
- ring G may be 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, -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, 1,3-dioxane-2,5-
- P 1 , P 2 , and P 3 are each independently a polymerizable group selected from the group of groups represented by Formula (P-1) to Formula (P-5).
- Item 8. A liquid crystal display device according to Item 7.
- M 1 , M 2, and M 3 are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or at least one hydrogen is fluorine or chlorine, 1-5 alkyl substituted with
- Item 9 The liquid crystal display device according to item 7 or 8, wherein the additive component is at least one polymerizable compound selected from the group of compounds represented by formulas (3-1) to (3-27).
- the additive component is at least one polymerizable compound selected from the group of compounds represented by formulas (3-1) to (3-27).
- P 4 , P 5 and P 6 are independently from the group of groups represented by formula (P-1) to formula (P-3).
- Selected polymerizable groups are: In formulas (P-1) to (P-3), M 4 , M 5 , and M 6 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine And in Formulas (3-1) to (3-27), Sp 1 , Sp 2 , and Sp 3 are each independently a single bond or a carbon number of 1 To alkylene, in which at least one —CH 2 — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH 2 — CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, in which at least one hydrogen may be replaced with fluorine or chlorine.
- Item 10 The liquid crystal display device according to any one of items 7 to 9, wherein the ratio of the additive component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.
- the liquid crystal alignment film contains at least one polymer selected from the polyamic acid, the polyamic acid ester, and the polyimide as a main component, and contains the polyorganosiloxane as a subcomponent.
- the liquid crystal display element according to any one of the above.
- Item 13 Item 1.
- the polyorganosiloxane contained in the liquid crystal alignment film contains at least one group selected from the group of groups represented by formulas (X 1 -1) to (X 1 -7). 13.
- the liquid crystal display element according to any one of items 12.
- the asterisk indicates a bonding site;
- Z 6 is —O— or a single bond;
- Z 7 is a single bond having 1 to C carbon atoms.
- R 6 alkylene, or a divalent group having 1 to 20 carbon atoms including at least one selected from the group consisting of —O—, —S—, —COO—, —OCO—, and —NR 6 —, wherein And R 6 is hydrogen or alkyl having 1 to 6 carbon atoms; h is 1, 2, or 3; i is an integer of 0 to 6, and when i is 0, Z 6 is a single bond J is an integer from 0 to 6;
- Item 14 The liquid crystal display element according to any one of items 1 to 13, wherein the liquid crystal alignment film contains a polyorganosiloxane containing a group represented by the formula (X 1 -7) according to item 13.
- Item 15 The liquid crystal display device according to any one of items 1 to 11, wherein the polyamic acid, polyamic acid ester, or polyimide has an alicyclic structure.
- Item 16 A liquid crystal composition used for the liquid crystal display element according to any one of items 1 to 15.
- Item 17. The liquid crystal composition according to item 16, wherein the elastic constant (K11) is 11 pN or more and the elastic constant (K33) is 11 pN or more at 25 ° C.
- Item 18. A liquid crystal alignment film used for the liquid crystal display element according to any one of items 1 to 15.
- Item 19 The liquid crystal alignment film according to Item 18, wherein the volume resistivity ( ⁇ ) at 25 ° C. is 1.0 ⁇ 10 14 ⁇ cm or more.
- Item 20 The liquid crystal alignment film according to Item 19, wherein the dielectric constant ( ⁇ ) at 25 ° C. is in the range of 3 to 5.
- the present invention includes the following items.
- A) The above composition further containing at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor.
- C) The above-mentioned composition further containing a polymerizable compound, and a polymer-supported orientation type AM device containing this composition.
- the liquid crystal composition contained in the liquid crystal display element of the present invention will be described in the following order.
- Sixth, additives that may be added to the composition will be described.
- Seventh a method for synthesizing the component compounds will be described.
- Eighth, the use of the composition will be described.
- Ninth, a liquid crystal alignment film will be described.
- This composition contains a plurality of liquid crystal compounds.
- the composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like.
- This composition is classified into a composition A and a composition B from the viewpoint of a liquid crystal compound.
- the composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (1) and the compound (2).
- the “other liquid crystal compound” is a liquid crystal compound different from the compound (1) and the compound (2). Such compounds are mixed into the composition for the purpose of further adjusting the properties.
- Composition B consists essentially of a liquid crystalline compound selected from compound (1) and compound (2).
- the term “substantially” means that the composition may contain an additive but no other liquid crystal compound.
- Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A.
- the composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.
- the main characteristics of the component compounds and the main effects of the compounds on the composition and the device will be explained.
- the main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention.
- L means large or high
- M means moderate
- S means small or low.
- L, M, and S are classifications based on qualitative comparison among the component compounds, and the symbol 0 (zero) means that the dielectric anisotropy is extremely small.
- Compound (1) increases the dielectric anisotropy and decreases the minimum temperature.
- Compound (2) decreases the viscosity or increases the maximum temperature.
- Compound (3) gives a polymer by polymerization, and this polymer shortens the response time of the device and improves image burn-in.
- a desirable ratio of the first component is approximately 10% by weight or more for increasing the dielectric anisotropy, and approximately 90% by weight or less for decreasing the minimum temperature.
- a more desirable ratio is in the range of approximately 20% by weight to approximately 85% by weight.
- a particularly desirable ratio is in the range of approximately 30% by weight to approximately 85% by weight.
- a desirable ratio of the second component is approximately 10% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 90% by weight or less for increasing the dielectric anisotropy.
- a more desirable ratio is in the range of approximately 15% by weight to approximately 75% by weight.
- a particularly preferred ratio is in the range of approximately 15% by weight to approximately 60% by weight.
- Compound (3) is added to the composition for the purpose of adapting to a polymer-supported orientation type device.
- a desirable ratio of the additive is approximately 0.03% by weight or more for aligning liquid crystal molecules, and approximately 10% by weight or less for preventing display defects of the device.
- a more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
- a particularly preferred ratio is in the range of approximately 0.2% by weight to approximately 1% by weight.
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons. Or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R 1 or R 2 is alkyl having 1 to 12 carbons for increasing the stability, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.
- R 3 and R 4 are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine 12 alkyls or alkenyls having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
- Desirable R 3 or R 4 is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability.
- Alkyl is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.
- Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl or pentyl for decreasing the viscosity.
- Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
- Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
- the preferred configuration of —CH ⁇ CH— in these alkenyls depends on the position of the double bond.
- Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
- Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
- Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.
- alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl for increasing the dielectric anisotropy.
- alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl, or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
- Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or Tetrahydropyran-2,5-diyl.
- Preferred examples of “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- 3-fluoro-1,4-phenylene.
- Preferred ring A or ring C is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy.
- 1,4-phenylene As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Tetrahydropyran-2,5-diyl is Or And preferably It is.
- Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl.
- Preferred ring B is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. In order to increase the anisotropy, 7,8-difluorochroman-2,6-diyl.
- Ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.
- Preferred ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.
- Z 1 and Z 2 are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Desirable Z 1 or Z 2 is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.
- Z 3 is a single bond, ethylene or carbonyloxy. Desirable Z 3 is a single bond for increasing the stability.
- A is 0, 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less.
- Preferred a is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
- Preferred b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.
- c is 1, 2 or 3.
- Preferred c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
- P 1 , P 2 and P 3 are independently a polymerizable group.
- Preferred P 1 , P 2 or P 3 is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). More desirable P 1 , P 2 or P 3 is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P 1 , P 2 or P 3 is a group represented by the formula (P-1) or the formula (P-2). Most preferred P 1 , P 2 or P 3 is a group represented by the formula (P-1).
- a preferred group represented by the formula (P-1) is —OCO—CH ⁇ CH 2 or —OCO—C (CH 3 ) ⁇ CH 2 .
- the wavy lines in the formulas (P-1) to (P-5) indicate the binding sites.
- M 1 , M 2 and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine A substituted alkyl of 1 to 5 carbon atoms.
- Preferred M 1 , M 2 or M 3 is hydrogen or methyl for increasing the reactivity. More preferred M 1 is hydrogen or methyl, and more preferred M 2 or M 3 is hydrogen.
- 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, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine. Further, it may be substituted with alkyl having 1 to 12 carbons.
- Preferred ring F and ring I are 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, At least one hydrogen is fluorine, chlorine,
- Z 4 and Z 5 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO— may be substituted, and at least one —CH 2 —CH 2 — may be —CH ⁇ CH—, —C (CH 3 ) ⁇ CH—, —CH ⁇ C (CH 3 ) —, or —C (CH 3 ) ⁇ C (CH 3 ) — may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine.
- Preferred Z 4 or Z 5 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. Further preferred Z 4 or Z 5 is a single bond.
- D is 0, 1, or 2.
- Preferred d is 0 or 1.
- e, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 1 or greater.
- Preferred e, f, or g is 1 or 2.
- the first component is a compound (1) having a large negative dielectric anisotropy.
- Desirable compounds (1) are the compounds (1-1) to (1-21) described in item 2. More desirable compound (1) is compound (1-1), compound (1-2), compound (1-3), compound (1-5), compound (1-7), compound (1-8), Compound (1-11), Compound (1-15), Compound (1-18), or Compound (1-19).
- the total proportion of these compounds is preferably in the range of 50% to 100% by weight based on the weight of the first component.
- the total proportion of these compounds is preferably in the range of 10% to 90% by weight based on the weight of the liquid crystal composition.
- the total proportion of these compounds is more preferably in the range of 20% to 85% by weight based on the weight of the liquid crystal composition.
- the second component is a compound (2) having a very small dielectric anisotropy.
- Desirable compounds (2) are the compounds (2-1) to (2-13) described in item 5.
- at least one of the second components is the compound (2-1), the compound (2-3), the compound (2-5), the compound (2-6), or the compound (2-7). It is preferable. It is preferable that at least two of the second components are the compound (2-1) and the compound (2-3), or the combination of the compound (2-1) and the compound (2-5).
- the additive component is a polymerizable compound (3).
- Desirable compound (3) is the compound (3-1) to the compound (3-27) according to item 9.
- at least one of the additive components is compound (3-1), compound (3-2), compound (3-24), compound (3-25), compound (3-26), or compound (3-27) is preferred.
- At least two of the additive components are compound (3-1) and compound (3-2), compound (3-1) and compound (3-18), compound (3-2) and compound (3-24), Compound (3-2) and Compound (3-25), Compound (3-2) and Compound (3-26), Compound (3-25) and Compound (3-26), or Compound (3-18) and A combination of compounds (3-24) is preferred.
- additives that may be added to the composition will be described.
- Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like.
- An optically active compound is added to the composition for the purpose of inducing a helical structure in liquid crystal molecules to give a twist angle. Examples of such a compound are the compound (4-1) to the compound (4-5).
- a desirable ratio of the optically active compound is approximately 5% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.
- an antioxidant is added to the composition in order to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature.
- a preferred example of the antioxidant is a compound (5) wherein z is an integer of 1 to 9.
- preferred z is 1, 3, 5, 7, or 9. Further preferred z is 7. Since the compound (5) in which z is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time.
- a desirable ratio of the antioxidant is approximately 50 ppm or more for achieving this effect, and approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature.
- a more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.
- the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving this effect, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.
- a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element.
- a preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight.
- an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition.
- a desirable ratio of the antifoaming agent is approximately 1 ppm or more for achieving this effect, and approximately 1000 ppm or less for preventing display defects.
- a more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.
- a polymerizable compound is used for adapting to a polymer-supported orientation type element.
- Compound (3) is suitable for this purpose.
- a polymerizable compound different from the compound (3) may be added to the composition together with the compound (3).
- Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate derivatives.
- a desirable ratio of the compound (3) is 10% by weight or more based on the total weight of the polymerizable compound. A more desirable ratio is 50% by weight or more. A particularly desirable ratio is 80% by weight or more. The most preferred ratio is 100% by weight.
- a polymerizable compound such as compound (3) is polymerized by ultraviolet irradiation.
- the polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator.
- a suitable initiator such as a photopolymerization initiator.
- Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature.
- Irgacure 651 registered trademark; BASF
- Irgacure 184 registered trademark; BASF
- Darocur 1173 registered trademark; BASF
- a desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight based on the weight of the polymerizable compound.
- a more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.
- a polymerization inhibitor When storing a polymerizable compound such as compound (3), a polymerization inhibitor may be added to prevent polymerization.
- the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
- the composition mainly has a minimum temperature of about ⁇ 10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20.
- a device containing this composition has a large voltage holding ratio.
- This composition is suitable for an AM device.
- This composition is particularly suitable for a transmissive AM device.
- a composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds.
- a composition having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error.
- This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.
- This composition can be used for an AM device. Further, it can be used for PM elements.
- This composition can be used for an AM device or a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA.
- Use in an AM device having a TN, OCB, IPS, or FFS mode is particularly preferable.
- the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate.
- These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device.
- NCAP non-curvilinear-aligned-phase
- PD polymer-dispersed
- This alignment film contains polyorganosiloxane, polyamic acid, polyamic acid ester, polyimide, or a mixture of these polymers.
- the polyorganosiloxane is produced by hydrolyzing an organosilicon compound such as chlorosilane or alkoxysilane.
- Polyorganosiloxane may be abbreviated as “polysiloxane”.
- Polyamic acid, polyamic acid ester, or polyimide is generally a product obtained by a condensation reaction of tetracarboxylic dianhydride and diamine, or an ester derivative thereof, depending on the degree of condensation, polyamic acid, polyamic acid ester, or Called polyimide. These may be abbreviated as “polyamic acid or a derivative thereof”.
- Preferred polysiloxanes have a carboxyl group, a hydroxyalkyl group, an amino group, an alkylamino group, a mercapto group, an epoxy group, or a polymerizable unsaturated bond.
- the raw material of the polysiloxane containing a carboxyl group is 4- (trimethoxysilyl) pentanoic acid.
- the raw material for the hydroxyalkyl group is 4-hydroxypropyltriethoxysilane or the like.
- the raw material for the amino group is 3-aminopropyltrimethoxysilane or the like.
- the raw material for the alkylamino group is N- [3- (trimethoxysilyl) propyl] -1-butanamine and the like.
- the raw material for the mercapto group is 3-mercaptopropyltrimethoxysilane or the like.
- the raw material for the epoxy group is 3-glycidoxypropyltrimethoxysilane or the like.
- the raw material for the polymerizable unsaturated bond is 3- (trimethoxysilyl) propyl methacrylate, ⁇ -methylene- ⁇ -butyrolactone, or the like.
- polysiloxanes contain at least one group selected from the group of groups represented by formulas (X 1 -1) to (X 1 -7).
- the asterisk represents a bonding site;
- Z 6 is —O— or a single bond;
- Z 7 is a single bond having 1 carbon atom 6 alkylene, or a divalent group having 1 to 20 carbon atoms and having at least one group selected from the group of —O—, —S—, —COO—, —OCO—, and —NR 6 —;
- R 6 is hydrogen or alkyl having 1 to 6 carbons;
- h is 1, 2, or 3, i is an integer from 0 to 6, and when i is 0, Z 6 is J is an integer from 0 to 6;
- the polysiloxane having a group represented by the formula (X 1 -1) or the formula (X 1 -2) is a silane having such a group, such as chlorosilane, alkoxysilane, alone or with other silanes. Produced by hydrolyzing the mixture.
- silanes are 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
- JP2013-064968A paragraphs 0048 to 0068, and the like.
- Preferred groups represented by the formula (X 1 -1) or (X 1 -2) are as follows.
- a polysiloxane having a group represented by the formula (X 1 -3) or the formula (X 1 -4) hydrolyzes a silane having an epoxy corresponding to a diol alone or in a mixture with other silanes, It is produced by opening an epoxy.
- a polysiloxane having a group represented by the formula (X 1 -5) hydrolyzes a silane having a monovalent group derived from a corresponding acid anhydride alone or in a mixture with other silanes, Produced by ring opening of the acid anhydride moiety.
- JP2013-057815 paragraphs 0061 to 0067, and the like.
- polysiloxane having a group represented by the formula (X 1 -6) see JP2013-057815, paragraphs 0026 to 0060, and the like.
- ⁇ -Methylene- ⁇ -butyrolactone is polymerizable.
- a polysiloxane having a group represented by the formula (X 1 -7) hydrolyzes a silane having a monovalent group derived from ⁇ -methylene- ⁇ -butyrolactone alone or in a mixture with other silanes. And further by ring opening of the acid anhydride moiety.
- a preferred polyamic acid or derivative thereof has an alicyclic structure.
- alicyclic structures are bicyclo [2.2.2] octene or cyclobutane.
- bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride or 1,2, 3,4-Cyclobutanetetracarboxylic dianhydride is used as the starting material.
- An amine having an alicyclic structure such as 1,4-diaminocyclohexane may be used as a starting material. For details, see JP2013-080193A, paragraphs 0156 to 0175, and the like.
- the liquid crystal alignment film contains at least one polymer selected from the group consisting of polysiloxane, polyamic acid, polyamic acid ester, and polyimide.
- the main component is polyamic acid or a derivative thereof, and the subcomponent is polysiloxane.
- the proportion of polyamic acid or its derivative is 50% by weight or more, and the proportion of polysiloxane is less than 50% by weight. That is, the ratio is 100-50 / 0- ⁇ 50.
- a preferred ratio is 97 to 70/3 to 30.
- a more desirable ratio is from 95 to 80/5.
- a preferred alignment film contains a polysiloxane containing at least one group selected from the group of groups represented by formulas (X 1 -1) to (X 1 -7).
- a more preferred alignment film contains polysiloxane containing a group represented by the formula (X 1 -7).
- the present invention will be described in more detail with reference to examples. The invention is not limited by these examples.
- the present invention includes a mixture of composition M1 and composition M2.
- the present invention also includes a mixture in which at least two of the compositions of the composition examples are mixed.
- the present invention also includes a liquid crystal aligning agent containing the polysiloxane synthesized in Synthesis Examples 1 to 3, and a liquid crystal aligning agent containing the polysiloxane described in Synthesis Examples 25 to 45 and a polyamic acid or a derivative thereof.
- the synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound, composition, and device were measured by the methods described below.
- NMR analysis DRX-500 manufactured by Bruker BioSpin Corporation was used for measurement.
- the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature, 500 MHz, and 16 times of integration.
- Tetramethylsilane was used as an internal standard.
- CFCl 3 was used as an internal standard and the number of integrations was 24.
- s is a singlet
- d is a doublet
- t is a triplet
- q is a quartet
- quint is a quintet
- sex is a sextet
- m is a multiplet
- br is broad.
- GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
- the carrier gas is helium (2 mL / min).
- the sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C.
- capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used.
- the column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min.
- a sample was prepared in an acetone solution (0.1% by weight), and 1 ⁇ L thereof was injected into the sample vaporizing chamber.
- the recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof.
- the obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.
- capillary column As a solvent for diluting the sample, chloroform, hexane or the like may be used.
- the following capillary column may be used.
- HP-1 from Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by SGE International Pty.
- a capillary column CBP1-M50-025 length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m
- Shimadzu Corporation may be used.
- the ratio of the liquid crystal compound contained in the composition may be calculated by the following method.
- a liquid crystal compound (mixture) is detected by a gas chromatograph (FID).
- the area ratio of peaks in the gas chromatogram corresponds to the ratio (weight ratio) of liquid crystal compounds.
- the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the peak area ratio.
- Measurement sample When measuring the characteristics of the composition or the device, the composition was used as it was as a sample.
- a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation.
- (Extrapolated value) ⁇ (Measured value of sample) ⁇ 0.85 ⁇ (Measured value of mother liquid crystal) ⁇ / 0.15.
- the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed.
- the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.
- the following mother liquid crystals were used.
- the ratio of the component compounds is shown by weight%.
- Measurement method The characteristics were measured by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B) deliberated and established by the Japan Electronics and Information Industry Association (JEITA), or a modified method thereof. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.
- JEITA Japan Electronics and Information Industry Association
- nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid.
- the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
- T C Minimum temperature of nematic phase
- a sample having a nematic phase is placed in a glass bottle and placed in a freezer at 0 ° C., ⁇ 10 ° C., ⁇ 20 ° C., ⁇ 30 ° C. and ⁇ 40 ° C. for 10 days. After storage, the liquid crystal phase was observed. For example, when the sample remained in a nematic phase at ⁇ 20 ° C. and changed to a crystalline or smectic phase at ⁇ 30 ° C., the TC was described as ⁇ 20 ° C.
- the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.
- Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s: An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
- Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s): The measurement was performed according to the method described in M. ⁇ Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 ⁇ m. This element was applied stepwise in increments of 1 volt within a range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
- the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and the element was sealed with an adhesive that was cured with ultraviolet rays.
- Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of the liquid crystal molecules was measured.
- 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After baking this glass substrate, the obtained alignment film was rubbed. A sample was put 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 the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of the liquid crystal molecules was measured.
- Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
- the light source was a halogen lamp.
- a sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed.
- the voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V.
- the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
- a voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum.
- the threshold voltage was expressed as a voltage when the transmittance reached 10%.
- VHR-1 Voltage holding ratio
- the TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. . This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed.
- the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- Area B was the area when it was not attenuated.
- the voltage holding ratio was expressed as a percentage of area A with respect to area B.
- VHR-2 Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured in the same procedure as above except that it was measured at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.
- VHR-3 Voltage holding ratio
- the TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 ⁇ m.
- a sample was injected into this element and irradiated with light for 20 minutes.
- the light source was an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source was 20 cm.
- a decaying voltage was measured for 16.7 milliseconds.
- a composition having a large VHR-3 has a large stability to ultraviolet light.
- VHR-3 is preferably 90% or more, and more preferably 95% or more.
- VHR-4 Voltage holding ratio
- the TN device injected with the sample was heated in a constant temperature bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured to determine the stability against heat. Evaluated. In the measurement of VHR-4, a voltage decaying for 16.7 milliseconds was measured. A composition having a large VHR-4 has a large stability to heat.
- 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 the maximum, and the transmittance was 0% when the light amount was the minimum.
- the response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; millisecond).
- Composition containing a polymerizable compound A sample was put in the device produced in Example 1 described later, and this device was sealed using an adhesive that was cured with ultraviolet rays. This device was irradiated with ultraviolet rays of 25 mW / cm 2 for 400 seconds while applying a voltage of 15 V to produce a PAS device.
- An EXERCURE 4000-D type mercury xenon lamp manufactured by HOYA CANDEO OPTRONICS Co., Ltd. was used for ultraviolet irradiation.
- a rectangular wave 60 Hz, 10 V, 0.5 seconds
- 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 the maximum, and the transmittance was 0% when the light amount was the minimum.
- the response time was expressed as the time required for the transmittance to change from 0% to 90% (rise time; millisecond).
- Elastic constant (K11: spray elastic constant, K33: bend elastic constant; measured at 25 ° C .; pN):
- an EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used. Using. A sample was put in a vertical alignment element in which the distance between two glass substrates (cell gap) was 20 ⁇ m. A 20 to 0 volt charge was applied to the device, and the capacitance and applied voltage were measured. Fitting the measured values of capacitance (C) and applied voltage (V) using “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), formulas (2.98) and (2.101) on page 75 The value of the elastic constant was obtained from the formula (2.100).
- Pretilt angle (°) A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used to measure the pretilt angle.
- Alignment stability (change in liquid crystal alignment angle; °): The change in the liquid crystal alignment axis on the electrode side of the liquid crystal display element described later was evaluated.
- the liquid crystal orientation angle ⁇ (before) on the electrode side before stress application was measured, and then a rectangular wave 4.5 V, 60 Hz was applied to the element for 20 minutes, then shorted for 1 second, and again after 1 second and 5 minutes.
- the liquid crystal alignment angle ⁇ (after) on the side was measured. From these values, the change ⁇ (°) in the liquid crystal alignment angle after 1 second and after 5 minutes was calculated using the following equation.
- ⁇ (°) ⁇ (after) ⁇ (before) (Formula 2)
- volume resistivity ( ⁇ ; measured at 25 ° C .; ⁇ ⁇ cm): A polyimide film was formed on the entire glass substrate with ITO, and Al was evaporated on the alignment film surface of this substrate to form an upper electrode ( Electrode area 0.23 cm 2 ). A voltage of 3 V was applied between the ITO electrode and the upper electrode, and the volume resistivity was calculated from the current value after 300 seconds.
- d is the film thickness of the polyimide film
- ⁇ 0 the vacuum dielectric constant
- S the electrode area.
- the compounds contained in the composition were represented by symbols based on the definitions in Table 3 below.
- Table 3 the configuration regarding 1,4-cyclohexylene is trans.
- the number in parentheses after the compound symbol indicates the chemical formula to which the compound belongs.
- the symbol ( ⁇ ) means other liquid crystal compounds.
- the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive.
- composition M1 to M15 containing the polymerizable compound has been described above.
- devices having various alignment films were prepared, and these liquid crystal compositions were injected.
- the polymerizable compound was polymerized by irradiating the device with ultraviolet rays. Finally, the response time of this device was measured.
- the production of an element having an alignment film will be described in the following order: polysiloxane, modified polysiloxane, polyamic acid, polyimide, liquid crystal aligning agent, and liquid crystal display element.
- SiO 2 conversion concentration is the concentration expressed in terms of silicon atoms of the alkoxysilane to SiO 2.
- siloxane (1) was obtained as a viscous transparent liquid. This compound is abbreviated as siloxane (1).
- Liquid crystal display element Two substrates were prepared on which ITO electrode patterns having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 3.5 ⁇ m were formed.
- the alignment agent (S-1) prepared from alkoxysilane in Synthesis Example 1 was spin-coated on the ITO surface of the substrate. It dried for 5 minutes with an 80 degreeC hotplate, and baked for 30 minutes with 180 degreeC hot-air circulation type oven, and obtained the oriented film (film thickness of 100 nm). After spraying 3.5 ⁇ m bead spacers on the alignment film of one substrate, a sealant was printed thereon.
- the other substrate was bonded with the alignment film surface inside, and the sealing agent was cured to produce a device.
- the composition M1 was injected into this device. After conversion to a PSA element by irradiating with ultraviolet rays, the response time was measured. The results are summarized in Table 5.
- Example 2 to 24 Using the aligning agents (S-2) to (S-24) instead of the aligning agent (S-1), a liquid crystal display device having various alignment films was produced in the same manner as in Example 1.
- the orientation agents (S-2) and (S-3) were prepared from alkoxysilanes.
- the aligning agents (S-4) to (S-24) were prepared from modified polysiloxane and polyamic acid (or polyimide).
- Each of the compositions M1 to M15 was injected into the device described in Example 1, irradiated with ultraviolet rays, and then the response time was measured. The results are summarized in Table 5.
- the response time is short. As can be seen from Table 5, the response time ranged from 3.6 ms to 6.1 ms. From this result, it can be said that the response time was able to be within such an optimal range even though the types of the liquid crystal composition and the alignment film were very different. This is a feature of the present invention that should be noted.
- the liquid crystal display element of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.
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Abstract
Description
式(1)において、R1およびR2は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、炭素数2から12のアルケニルオキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルであり;環Aおよび環Cは独立して、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、またはテトラヒドロピラン-2,5-ジイルであり;環Bは、2,3-ジフルオロ-1,4-フェニレン、2-クロロ-3-フルオロ-1,4-フェニレン、2,3-ジフルオロ-5-メチル-1,4-フェニレン、3,4,5-トリフルオロナフタレン-2,6-ジイル、または7,8-ジフルオロクロマン-2,6-ジイルであり;Z1およびZ2は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり;aは、0、1、2、または3であり;bは、0または1であり;そして、aおよびbの和は3以下である。
式(1)において、R1およびR2は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、炭素数2から12のアルケニルオキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルであり;環Aおよび環Cは独立して、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、またはテトラヒドロピラン-2,5-ジイルであり;環Bは、2,3-ジフルオロ-1,4-フェニレン、2-クロロ-3-フルオロ-1,4-フェニレン、2,3-ジフルオロ-5-メチル-1,4-フェニレン、3,4,5-トリフルオロナフタレン-2,6-ジイル、または7,8-ジフルオロクロマン-2,6-ジイルであり;Z1およびZ2は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり;aは、0、1、2、または3であり;bは、0または1であり;そして、aおよびbの和は3以下である。
式(1-1)から式(1-21)において、R1およびR2は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、炭素数2から12のアルケニルオキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルである。
式(2)において、R3およびR4は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数2から12のアルケニルであり;環Dおよび環Eは独立して、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、または2,5-ジフルオロ-1,4-フェニレンであり;Z3は、単結合、エチレン、またはカルボニルオキシであり;cは、1、2、または3である。
式(2-1)から式(2-13)において、R3およびR4は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数2から12のアルケニルである。
式(3)において、環Fおよび環Iは独立して、シクロヘキシル、シクロヘキセニル、フェニル、1-ナフチル、2-ナフチル、テトラヒドロピラン-2-イル、1,3-ジオキサン-2-イル、ピリミジン-2-イル、またはピリジン-2-イルであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;環Gは、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-1,2-ジイル、ナフタレン-1,3-ジイル、ナフタレン-1,4-ジイル、ナフタレン-1,5-ジイル、ナフタレン-1,6-ジイル、ナフタレン-1,7-ジイル、ナフタレン-1,8-ジイル、ナフタレン-2,3-ジイル、ナフタレン-2,6-ジイル、ナフタレン-2,7-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、またはピリジン-2,5-ジイルであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;Z4およびZ5は独立して、単結合または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-、-C(CH3)=CH-、-CH=C(CH3)-、または-C(CH3)=C(CH3)-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;P1、P2、およびP3は独立して、重合性基であり;Sp1、Sp2、およびSp3は独立して、単結合、または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;dは、0、1、または2であり;e、f、およびgは独立して、0、1、2、3、または4であり、そしてe、f、およびgの和は1以上である。
式(P-1)から式(P-5)において、M1、M2、およびM3は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から5のアルキルである。
式(3-1)から式(3-27)において、P4、P5、およびP6は独立して、式(P-1)から式(P-3)で表される基の群から選択された重合性基であり:
式(P-1)から式(P-3)において、M4、M5、およびM6は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から5のアルキルであり;式(3-1)から式(3-27)において、Sp1、Sp2、およびSp3は独立して、単結合、または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよい。
式(X1-1)から式(X1-7)において、星印は結合する部位を示し;Z6は、-O-または単結合であり;Z7は、単結合、炭素数1から6のアルキレン、または-O-、-S-、-COO-、-OCO-、および-NR6-の群から選択された少なくとも1つを含む炭素数1から20の二価基であり、ここでR6は、水素または炭素数1から6のアルキルであり;hは1、2、または3であり;iは、0から6の整数であり、iが0の場合、Z6は単結合であり;jは、0から6の整数である。
または
であり、好ましくは
である。
1)誘電率(ε∥)の測定:よく洗浄したガラス基板にオクタデシルトリエトキシシラン(0.16mL)のエタノール(20mL)溶液を塗布した。ガラス基板をスピンナーで回転させたあと、150℃で1時間加熱した。2枚のガラス基板の間隔(セルギャップ)が4μmであるVA素子に試料を入れ、この素子を紫外線で硬化する接着剤で密閉した。この素子にサイン波(0.5V、1kHz)を印加し、2秒後に液晶分子の長軸方向における誘電率(ε∥)を測定した。
2)誘電率(ε⊥)の測定:よく洗浄したガラス基板にポリイミド溶液を塗布した。このガラス基板を焼成した後、得られた配向膜にラビング処理をした。2枚のガラス基板の間隔(セルギャップ)が9μmであり、ツイスト角が80度であるTN素子に試料を入れた。この素子にサイン波(0.5V、1kHz)を印加し、2秒後に液晶分子の短軸方向における誘電率(ε⊥)を測定した。
1)重合性化合物を含まない組成物:2枚のガラス基板の間隔(セルギャップ)が4μmであり、ラビング方向がアンチパラレルであるノーマリーブラックモード(normally black mode)のVA素子に試料を入れた。この素子を紫外線で硬化する接着剤を用いて密閉した。この素子に矩形波(60Hz、10V、0.5秒)を印加した。この際に、素子に垂直方向から光を照射し、素子を透過した光量を測定した。この光量が最大になったときが透過率100%であり、この光量が最小であったときが透過率0%であるとみなした。応答時間は透過率90%から10%に変化するのに要した時間(立ち下がり時間;fall time;ミリ秒)で表した。
カラムはHSPgel RT MB-M(Waters製)を使用し、前記の混合溶液を展開剤として、カラム温度50℃、流速0.40mL/minの条件で測定した。標準ポリスチレンは東ソー(株)製TSK標準ポリスチレンを用いた。
後述する液晶表示素子の輝度-電圧特性(B-V特性)を測定し、これをストレス印加前の輝度-電圧特性:B(before)とした。次に、素子に4.5V、60Hzの交流を20分間印加した後、1秒間ショートし、再び輝度-電圧特性(B-V特性)を測定した。これをストレス印加後の輝度-電圧特性:B(after)とした。輝度変化率ΔB(%)は、これらの値から、次の式を用いて算出した。
ΔB(%)=[B(after)-B(before)]/B(before) (式1)
この測定は国際公開2000-43833号を参考に行った。電圧0.75VにおけるΔB(%)の値が小さいほど、AC残像の発生が少ないといえる。
Δφ(°)=φ(after)-φ(before) (式2)
これらの測定はJ. Hilfiker, B. Johs, C. Herzinger, J. F. Elman, E. Montbach, D. Bryant, and P. J. Bos Thin Solid Films, 455-456, (2004) 596-600を参考に行った。Δφが小さいほうが液晶配向軸の変化率が小さく、液晶配向軸の安定性が良いといえる。
全面ITO付きガラス基板にポリイミド膜を成膜し、この基板の配向膜面に、Alを蒸着し、上部電極とした(電極面積0.23cm2)。ITO電極と上部電極との間に、1V・周波数1kHzの交流電圧を印加し、この膜の電気容量(C)を測定した。この値から、以下の式を用いてこの膜の誘電率(ε)を計算した。
ε=(C×d)/(ε0×S) (式3)
ここで、dはポリイミド膜の膜厚であり、ε0は真空の誘電率であり、Sは電極面積である。
BCS:2-ブトキシエタノール
HG:2-メチル-2,4-ペンタンジオール(別名:ヘキシレングリコール)
TEOS:テトラエトキシシラン
C18:オクタデシルトリエトキシシラン
ACPS:3-アクリロキシプロピルトリメトキシシラン
UPS:3-ウレイドプロピルトリエトキシシラン
MPMS:3-メタクリロキシプロピルトリメトキシシラン
3-HB(2F,3F)-O2 (1-1) 10%
5-HB(2F,3F)-O2 (1-1) 10%
3-H2B(2F,3F)-O2 (1-3) 8%
5-H2B(2F,3F)-O2 (1-3) 8%
3-HDhB(2F,3F)-O2 (1-13) 5%
3-HBB(2F,3F)-O2 (1-15) 8%
4-HBB(2F,3F)-O2 (1-15) 5%
5-HBB(2F,3F)-O2 (1-15) 5%
V-HBB(2F,3F)-O2 (1-15) 5%
V2-HBB(2F,3F)-O2 (1-15) 5%
3-HH-4 (2-1) 14%
V-HHB-1 (2-5) 11%
3-HBB-2 (2-6) 6%
NI=89.4℃;Tc<-30℃;Δn=0.109;Δε=-3.8;Vth=2.24V;η=24.6mPa・s;VHR-1=99.2%;VHR-2=98.1%;VHR-3=97.9%.
この組成物に化合物(3-2)を0.4重量%の割合で添加した。
MAC-BB-MAC (3-2)
3-HB(2F,3F)-O2 (1-1) 10%
V-HB(2F,3F)-O2 (1-1) 7%
3-BB(2F,3F)-O2 (1-5) 7%
V2-BB(2F,3F)-O1 (1-5) 7%
3-B(2F,3F)B(2F,3F)-O2 (1-6) 3%
2-HHB(2F,3F)-O2 (1-7) 5%
3-HHB(2F,3F)-O2 (1-7) 10%
3-HBB(2F,3F)-O2 (1-15) 10%
V-HBB(2F,3F)-O2 (1-15) 8%
2-HH-3 (2-1) 14%
3-HB-O1 (2-2) 5%
3-HHB-1 (2-5) 3%
3-HHB-O1 (2-5) 3%
3-HHB-3 (2-5) 5%
2-BB(F)B-3 (2-7) 3%
NI=72.5℃;Tc<-20℃;Δn=0.112;Δε=-3.9;Vth=2.14V;η=22.8mPa・s.
この組成物に化合物(3-1)を0.3重量%の割合で添加した。
MAC-B(2F)B-MAC (3-1)
3-HB(2F,3F)-O4 (1-1) 6%
3-H2B(2F,3F)-O2 (1-3) 8%
3-H1OB(2F,3F)-O2 (1-4) 5%
3-BB(2F,3F)-O2 (1-5) 10%
3-HHB(2F,3F)-O2 (1-7) 7%
V-HHB(2F,3F)-O2 (1-7) 7%
V-HHB(2F,3F)-O4 (1-7) 7%
3-HBB(2F,3F)-O2 (1-15) 6%
V-HBB(2F,3F)-O2 (1-15) 6%
1V2-HBB(2F,3F)-O2 (1-15) 5%
3-HH-V (2-1) 11%
1-BB-3 (2-3) 6%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 4%
3-HBB-2 (2-6) 5%
3-B(F)BB-2 (2-8) 3%
NI=87.7℃;Tc<-30℃;Δn=0.129;Δε=-4.4;Vth=2.17V;η=26.2mPa・s.
この組成物に化合物(3-3)を0.3重量%の割合で添加した。
MAC-B(F)B-MAC (3-3)
3-HB(2F,3F)-O2 (1-1) 7%
1V2-HB(2F,3F)-O2 (1-1) 7%
3-BB(2F,3F)-O2 (1-5) 8%
3-HHB(2F,3F)-O2 (1-7) 5%
5-HHB(2F,3F)-O2 (1-7) 4%
3-HH1OB(2F,3F)-O2 (1-10) 5%
2-BB(2F,3F)B-3 (1-11) 4%
2-HBB(2F,3F)-O2 (1-15) 3%
3-HBB(2F,3F)-O2 (1-15) 8%
4-HBB(2F,3F)-O2 (1-15) 5%
V-HBB(2F,3F)-O2 (1-15) 8%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (2-5) 3%
NI=78.2℃;Tc<-30℃;Δn=0.109;Δε=-3.3;Vth=2.08V;η=16.3mPa・s.
この組成物に化合物(3-1)を0.3重量%、化合物(3-2)を0.03重量%の割合で添加した。
MAC-B(2F)B-MAC (3-1)
AC-VO-BB-OV-AC (3-2)
3-HB(2F,3F)-O4 (1-1) 15%
3-chB(2F,3F)-O2 (1-2) 7%
2-HchB(2F,3F)-O2 (1-8) 8%
3-HBB(2F,3F)-O2 (1-15) 8%
5-HBB(2F,3F)-O2 (1-15) 7%
V-HBB(2F,3F)-O2 (1-15) 5%
3-dhBB(2F,3F)-O2 (1-16) 5%
5-HH-V (2-1) 18%
7-HB-1 (2-2) 5%
V-HHB-1 (2-5) 7%
V2-HHB-1 (2-5) 7%
3-HBB(F)B-3 (2-13) 8%
NI=98.5℃;Tc<-30℃;Δn=0.112;Δε=-3.2;Vth=2.47V;η=23.5mPa・s.
この組成物に化合物(3-24)を0.3重量%の割合で添加した。
3-H2B(2F,3F)-O2 (1-3) 18%
5-H2B(2F,3F)-O2 (1-3) 17%
3-DhHB(2F,3F)-O2 (1-12) 5%
3-HHB(2F,3CL)-O2 (1-18) 5%
3-HBB(2F,3CL)-O2 (1-19) 8%
5-HBB(2F,3CL)-O2 (1-19) 7%
3-HH-V (2-1) 11%
3-HH-VFF (2-1) 7%
F3-HH-V (2-1) 10%
3-HHEH-3 (2-4) 4%
3-HB(F)HH-2 (2-9) 3%
3-HHEBH-3 (2-10) 5%
NI=78.2℃;Tc<-30℃;Δn=0.084;Δε=-2.6;Vth=2.45V;η=22.5mPa・s.
この組成物に化合物(3-25)を0.3重量%の割合で添加した。
3-H2B(2F,3F)-O2 (1-3) 7%
V-HHB(2F,3F)-O2 (1-7) 8%
2-HchB(2F,3F)-O2 (1-8) 8%
3-HH1OB(2F,3F)-O2 (1-10) 5%
2-BB(2F,3F)B-3 (1-11) 7%
2-BB(2F,3F)B-4 (1-11) 7%
3-HDhB(2F,3F)-O2 (1-13) 3%
3-DhH1OB(2F,3F)-O2 (1-14) 4%
4-HH-V (2-1) 15%
3-HH-V1 (2-1) 6%
1-HH-2V1 (2-1) 5%
3-HH-2V1 (2-1) 5%
V2-BB-1 (2-3) 5%
1V2-BB-1 (2-3) 5%
3-HHB-1 (2-5) 6%
3-HB(F)BH-3 (2-12) 4%
NI=87.5℃;Tc<-30℃;Δn=0.115;Δε=-2.0;Vth=2.82V;η=17.2mPa・s.
この組成物に化合物(3-25)を0.3重量%、化合物(3-2)を0.1重量%の割合で添加した。
AC-VO-BB-OV-AC (3-2)
V-HB(2F,3F)-O2 (1-1) 8%
3-H2B(2F,3F)-O2 (1-3) 10%
3-BB(2F,3F)-O2 (1-5) 10%
2O-BB(2F,3F)-O2 (1-5) 3%
2-HHB(2F,3F)-O2 (1-7) 4%
3-HHB(2F,3F)-O2 (1-7) 7%
V-HHB(2F,3F)-O2 (1-7) 5%
2-BB(2F,3F)B-3 (1-11) 6%
2-BB(2F,3F)B-4 (1-11) 6%
3-HDhB(2F,3F)-O2 (1-13) 6%
2-HBB(2F,3F)-O2 (1-15) 5%
3-HBB(2F,3F)-O2 (1-15) 6%
3-dhBB(2F,3F)-O2 (1-16) 4%
3-HH1OCro(7F,8F)-5 (1-21) 4%
3-HH-V (2-1) 11%
1-BB-5 (2-3) 5%
NI=70.9℃;Tc<-20℃;Δn=0.129;Δε=-4.4;Vth=1.74V;η=27.2mPa・s.
この組成物に化合物(3-26)を0.2重量%、化合物(3-18)を0.2重量%の割合で添加した。
MAC-BB(F)B-MAC (3-18)
3-HB(2F,3F)-O2 (1-1) 7%
V-HB(2F,3F)-O2 (1-1) 8%
3-H2B(2F,3F)-O2 (1-3) 8%
3-BB(2F,3F)-O2 (1-5) 10%
2-HHB(2F,3F)-O2 (1-7) 4%
3-HHB(2F,3F)-O2 (1-7) 7%
V-HHB(2F,3F)-O2 (1-7) 6%
3-HDhB(2F,3F)-O2 (1-13) 6%
2-HBB(2F,3F)-O2 (1-15) 5%
3-HBB(2F,3F)-O2 (1-15) 6%
V-HBB(2F,3F)-O2 (1-15) 5%
V2-HBB(2F,3F)-O2 (1-15) 4%
3-HEB(2F,3F)B(2F,3F)-O2
(1-17) 3%
3-H1OCro(7F,8F)-5 (1-20) 3%
3-HH-O1 (2-1) 5%
1-BB-5 (2-3) 4%
V-HHB-1 (2-5) 4%
5-HBBH-3 (2-11) 5%
NI=81.5℃;Tc<-30℃;Δn=0.122;Δε=-4.7;Vth=1.76V;η=31.8mPa・s.
この組成物に化合物(3-1)を0.4重量%の割合で添加した。
MAC-B(2F)B-MAC (3-1)
V-HB(2F,3F)-O4 (1-1) 14%
V-H1OB(2F,3F)-O2 (1-4) 3%
3-BB(2F,3F)-O2 (1-5) 10%
3-HHB(2F,3F)-O2 (1-7) 7%
V2-HHB(2F,3F)-O2 (1-7) 7%
V-HH1OB(2F,3F)-O2 (1-10) 6%
V-HBB(2F,3F)-O4 (1-15) 9%
1V2-HBB(2F,3F)-O2 (1-15) 5%
3-HH-V (2-1) 13%
1-BB-3 (2-3) 3%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 4%
V-HBB-2 (2-6) 5%
1-BB(F)B-2V (2-7) 6%
5-HBBH-1O1 (-) 4%
NI=93.6℃;Tc<-30℃;Δn=0.125;Δε=-3.9;Vth=2.20V;η=29.9mPa・s.
この組成物に化合物(3-1)を0.3重量%、化合物(3-24)を0.1重量%の割合で添加した。
MAC-B(2F)B-MAC (3-1)
3-HB(2F,3F)-O4 (1-1) 6%
3-H2B(2F,3F)-O2 (1-3) 8%
3-H1OB(2F,3F)-O2 (1-4) 4%
3-BB(2F,3F)-O2 (1-5) 7%
3-HHB(2F,3F)-O2 (1-7) 10%
V-HHB(2F,3F)-O2 (1-7) 7%
V-HHB(2F,3F)-O4 (1-7) 7%
3-HBB(2F,3F)-O2 (1-15) 6%
V-HBB(2F,3F)-O2 (1-15) 6%
1V2-HBB(2F,3F)-O2 (1-15) 5%
2-HH-3 (2-1) 12%
1-BB-3 (2-3) 6%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 4%
3-HBB-2 (2-6) 5%
3-B(F)BB-2 (2-7) 3%
NI=92.8℃;Tc<-20℃;Δn=0.126;Δε=-4.4;Vth=2.19V;η=26.0mPa・s.
この組成物に化合物(3-2)を0.2重量%の割合で添加した。
MAC-BB-MAC (3-2)
3-HB(2F,3F)-O2 (1-1) 5%
1V2-HB(2F,3F)-O2 (1-1) 7%
V2-BB(2F,3F)-O2 (1-5) 8%
3-HHB(2F,3F)-O2 (1-7) 5%
5-HHB(2F,3F)-O2 (1-7) 4%
3-HH1OB(2F,3F)-O2 (1-10) 5%
2-BB(2F,3F)B-3 (1-11) 4%
2-HBB(2F,3F)-O2 (1-15) 3%
3-HBB(2F,3F)-O2 (1-15) 8%
4-HBB(2F,3F)-O2 (1-15) 5%
V-HBB(2F,3F)-O2 (1-15) 8%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (2-5) 5%
NI=81.7℃;Tc<-20℃;Δn=0.110;Δε=-3.2;Vth=2.12V;η=15.8mPa・s.
この組成物に化合物(3-1)を0.4重量%の割合で添加した。
MAC-B(2F)B-MAC (3-1)
3-HB(2F,3F)-O2 (1-1) 7%
1V2-HB(2F,3F)-O2 (1-1) 7%
3-BB(2F,3F)-O2 (1-5) 8%
3-HHB(2F,3F)-O2 (1-7) 5%
5-HHB(2F,3F)-O2 (1-7) 4%
3-HH1OB(2F,3F)-O2 (1-10) 5%
2-BB(2F,3F)B-3 (1-11) 4%
2-HBB(2F,3F)-O2 (1-15) 3%
3-HBB(2F,3F)-O2 (1-15) 8%
4-HBB(2F,3F)-O2 (1-15) 5%
V-HBB(2F,3F)-O2 (1-15) 8%
3-HH-V (2-1) 33%
V-HHB-1 (2-5) 3%
NI=76.0℃;Tc<-30℃;Δn=0.107;Δε=-3.2;Vth=2.08V;η=16.0mPa・s.
この組成物に化合物(3-1)を0.35重量%、化合物(3-25)を0.1重量%の割合で添加した。
MAC-B(2F)B-MAC (3-1)
3-HB(2F,3F)-O4 (1-1) 6%
3-H2B(2F,3F)-O2 (1-3) 8%
3-H1OB(2F,3F)-O2 (1-4) 4%
3-BB(2F,3F)-O2 (1-5) 7%
V-HHB(2F,3F)-O2 (1-7) 7%
V-HHB(2F,3F)-O4 (1-7) 7%
3-HH2B(2F,3F)-O2 (1-9) 7%
5-HH2B(2F,3F)-O2 (1-9) 3%
3-HBB(2F,3F)-O2 (1-15) 6%
V-HBB(2F,3F)-O2 (1-15) 6%
1V2-HBB(2F,3F)-O2 (1-15) 5%
2-HH-3 (2-1) 12%
1-BB-5 (2-3) 12%
3-HHB-1 (2-5) 4%
3-HHB-O1 (2-5) 3%
3-HBB-2 (2-6) 3%
NI=83.6℃;Tc<-30℃;Δn=0.122;Δε=-4.4;Vth=2.13V;η=22.9mPa・s.
この組成物に化合物(3-2)を0.1重量%、化合物(3-24)を0.3重量%の割合で添加した。
AC-VO-BB-OV-AC (3-2)
2-H1OB(2F,3F)-O2 (1-4) 6%
3-H1OB(2F,3F)-O2 (1-4) 4%
3-BB(2F,3F)-O2 (1-5) 3%
2-HH1OB(2F,3F)-O2 (1-10) 14%
3-HBB(2F,3F)-O2 (1-15) 11%
V-HBB(2F,3F)-O2 (1-15) 10%
V-HBB(2F,3F)-O4 (1-15) 6%
2-HH-3 (2-1) 5%
3-HH-VFF (2-1) 30%
1-BB-3 (2-3) 5%
3-HHB-1 (2-5) 3%
3-HBB-2 (2-6) 3%
NI=77.8℃;Tc<-20℃;Δn=0.105;Δε=-3.2;Vth=2.17V;η=18.9mPa・s.
この組成物に化合物(3-2)を0.1重量%、化合物(3-25)を0.3重量%の割合で添加した。
AC-VO-BB-OV-AC (3-2)
[合成例1]
温度計、還流管を備え付けた200mL(ミリリットル)の四つ口反応フラスコ中で、HG(22.5g)、BCS(7.5g)、TEOS(28.3g)、C18(1.7g)、およびACPS(14.1g)を混合して、アルコキシシランの溶液を調製した。この溶液に、HG(11.2g)、BCS(3.7g)、水(10.8g)、および蓚酸(0.2g;触媒)の溶液を、室温下で30分かけて滴下した。この溶液を30分間撹拌してから1時間還流させた後に放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。この溶液(10.0g)に、BCS(20.0g)を混合し、SiO2換算濃度が4重量%である配向剤(S-1)を調製した。
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中で、HG(21.1g)、BCS(7.0g)、TEOS(19.2g)、C18(1.7g)、およびACPS(23.4g)を混合して、アルコキシシランの溶液を調製した。この溶液に、HG(10.5g)、BCS(3.5g)、水(10.8g)、および蓚酸(0.9g;触媒)を混合した溶液を、室温下で30分かけて滴下した。この溶液を30分間撹拌してから1時間還流させた。次に、UPS含有量92重量%のメタノール溶液(1.2g)、HG(0.5g)、およびBCS(0.2g)の混合物を加えた。30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。この溶液(10.0g)に、BCS(20.0g)を混合し、SiO2換算濃度が4重量%である配向剤(S-2)を調製した。
温度計、還流管を備え付けた200mLの四つ口反応フラスコ中で、HG(20.2g)、BCS(6.7g)、TEOS(27.9g)、C18(1.7g)、およびMPMS(17.4g)を混合して、アルコキシシランの溶液を調製した。この溶液に、HG(10.0g)、BCS(3.4g)、水(10.8g)、および蓚酸(0.9g;触媒)の溶液を、室温下で30分かけて滴下した。この溶液を30分間撹拌してから1時間還流させた後、UPS含有量92重量%のメタノール溶液(0.6g)、HG(0.3g)およびBCS(0.1g)の混合物を加えた。30分間還流させてから放冷してSiO2換算濃度が12重量%のポリシロキサン溶液を得た。この溶液(10.0g)に、BCS(20.0g)を混合し、SiO2換算濃度が4重量%である配向剤(S-3)を調製した。
[合成例4]
撹拌機、温度計、滴下漏斗および還流冷却管を備えた反応容器に、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン(100.0g)、メチルイソブチルケトン(500g)、およびトリエチルアミン(10.0g)を入れ、室温で混合した。脱イオン水(100g)を滴下漏斗より30分かけて滴下した。この混合物を80℃で6時間加熱した。反応終了後、有機層を分離し、0.2重量%硝酸アンモニウム水溶液により洗浄後の水が中性になるまで洗浄したのち、減圧下で溶媒および水を留去することにより、エポキシ基を有するポリシロキサンを粘調な透明液体として得た。この化合物をシロキサン(1)と略す。
100mLの三口フラスコに、上記のシロキサン(1)(9.8g)、メチルイソブチルケトン(28.0g)、化合物(CA1-1)(5.0g)、化合物(CA3-1)(3.3g)、およびU-CAT 18X(4級アミン塩;エポキシ化合物の硬化促進剤;サンアプロ社/東京)(0.20g)を入れ、80℃で12時間撹拌した。反応終了後、メタノールで再沈殿を行い、沈殿物を酢酸エチルに溶解させた。この溶液を3回水洗し、溶媒を留去することにより、化合物(A-1)(14.5g)を無色粉末として得た。Mw:6,500。
化合物(CA1-1)の代わりに化合物(CA1-2)(4.0g)を用いたこと以外は合成例5と同様に操作して、化合物(A-2)(12.8g)の無色粉末を得た。Mw:6,000。
化合物(CA1-1)の代わりに化合物(CA1-3)(6.8g)用いたこと以外は合成例5と同様に操作して、化合物(A-3)(14.7g)の無色粉末を得た。Mw:8,100。
化合物(CA1-1)の代わりに化合物(CA1-4)(5.6g)を用いたこと以外は合成例5と同様に操作して、化合物(A-4)(15.0g)の無色粉末を得た。Mw:7,500。
100mLの三口フラスコに、合成例4で得たシロキサン(1)(9.8g)、メチルイソブチルケトン28g、化合物(CA1-1)(10g)およびU-CAT 18X(合成例5を参照)(0.20g)を入れ、80℃で12時間撹拌した。反応終了後、メタノールで再沈殿を行い、沈殿物を酢酸エチルに溶解して、この溶液を3回水洗し、溶媒を留去することにより、化合物(A-5)(16.0g)を無色粉末として得た。Mw:、8,500。
化合物(CA1-1)の代わりに化合物(CA1-5)(4.1g)を用いたこと以外は合成例5と同様に操作して化合物(A-6)(12.4g)の無色粉末を得た。Mw:6,200。
化合物(CA3-1)の代わりに化合物(CA3-2)(3.6g)を用いたこと以外は合成例5と同様に操作して、化合物(A-7)(13.4g)の無色粉末を得た。Mw:7,900。
100mLの三口フラスコに、合成例4で得たシロキサン(1)(9.8g)、メチルイソブチルケトン(28.0g)、化合物(CA1-1)(8.0g)、化合物(CA3-2)(1.4g)、およびU-CAT 18X(合成例5を参照)(0.20g)を入れ、80℃で12時間撹拌した。反応終了後、メタノールで再沈殿を行い、沈殿物を酢酸エチルに溶解させた。この溶液を3回水洗し、溶媒を留去することにより、化合物(A-8)(13.9g)を無色粉末として得た。Mw:8,900。
100mLの三口フラスコに、合成例4で得たシロキサン(1)(9.8g)、メチルイソブチルケトン(28.0g)、化合物(CA1-1)(2.0g)、化合物(CA3-2)(5.8g)、およびU-CAT 18X(合成例5を参照)(0.20g)を入れ、80℃で12時間撹拌した。反応終了後、メタノールで再沈殿を行い、沈殿物を酢酸エチルに溶かした。この溶液を3回水洗し、溶媒を留去することにより、化合物(A-9)(13.4g)を無色粉末として得た。Mw:7,600。
100mLの三口フラスコに、合成例4で得たシロキサン(1)(9.8g)、メチルイソブチルケトン(28.0g)、化合物(CA1-1)(8.0g)、化合物(CA3-3)(2.6g)、およびU-CAT 18X(合成例5を参照)(0.20g)を入れ、80℃で12時間撹拌した。反応終了後、メタノールで再沈殿を行い、沈殿物を酢酸エチルに溶かした。この溶液を3回水洗し、溶媒を留去することにより、化合物(A-10)(15.5g)を無色粉末として得た。Mw:9,200。
化合物(CA1-1)の代わりに化合物(CA1-6)(6.1g)を用いたこと以外は合成例5と同様に操作して、化合物(A-11)(18.4g)の無色粉末を得た。Mw:7,300。
化合物(CA1-1)の代わりに化合物(CA1-7)(5.7g)を用いたこと以外は合成例5と同様に操作して、化合物(A-12)(17.5g)の無色粉末を得た。Mw:7,600。
化合物(CA1-1)の代わりに化合物(CA1-8)(7.2g)を用いたこと以外は合成例5と同様に操作して、化合物(A-13)(19.1g)の無色粉末を得た。Mw:7,000。
化合物(CA1-1)の代わりに化合物(CA1-9)(6.2g)を用いたこと以外は合成例5と同様に操作して、化合物(A-14)(18.1g)の無色粉末を得た。Mw:6,900。
化合物(CA1-1)の代わりに化合物(CA1-10)(7.0g)を用いたこと以外は合成例5と同様に操作して、化合物(A-15)(19.4g)の無色粉末を得た。Mw:7,500。
化合物(CA1-1)の代わりに化合物(CA1-11)(8.4g)を用いたこと以外は合成例5と同様に操作して、化合物(A-16)(20.1g)の無色粉末を得た。Mw:7,300。
化合物(CA1-1)の代わりに化合物(CA1-12)(7.2g)を用いたこと以外は合成例5と同様に操作して、化合物(A-17)(19.5g)の無色粉末を得た。Mw:7,300。
[合成例22]
1,2,3,4-シクロブタンテトラカルボン酸二無水物(19.61g)(0.1モル)と4,4’-ジアミノ-2,2’-ジメチルビフェニル(21.23g)(0.1モル)とをN-メチル-2-ピロリドン(367.6g)に溶解させ、室温で6時間撹拌した。反応混合物を大過剰のメタノール中に注ぎ、生成物を沈澱させた。沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥することにより、ポリアミック酸(PA-1)(35.0g)得た。
2,3,5-トリカルボキシシクロペンチル酢酸二無水物(22.4g;0.1モル)とシクロヘキサンビス(メチルアミン)(14.23g;0.1モル)とをN-メチル-2-ピロリドン(329.3g)に溶解させ、60℃で6時間撹拌した。反応混合物を大過剰のメタノール中に注ぎ、生成物を沈澱させた。沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥することにより、ポリアミック酸(PA-2)(32.0g)を得た。
[合成例24]
合成例23で得たポリアミック酸(PA-2)(17.5g)にN-メチル-2-ピロリドン(232.5g)、ピリジン(3.8g)、および無水酢酸(4.9g)を添加し、120℃で4時間撹拌してイミド化を行った。反応混合物を大過剰のメタノール中に注ぎ、生成物を沈澱させた。沈殿物をメタノールで洗浄し、減圧下で15時間乾燥することにより、ポリイミド(PI-1)(15.0g)を得た。
[合成例25]
合成例22で得たポリアミック酸(PA-1)を含有する溶液を、これに含有されるポリアミック酸(PA-1)に換算して1,000重量部に相当する量をとり、化合物(A-1)(100重量部)を加え、さらにN-メチル-2-ピロリドンおよびブチルセロソルブを加えて、溶媒組成がN-メチル-2-ピロリドン:ブチルセロソルブ=50:50(重量比)、固形分濃度が4.0重量%の溶液とした。この溶液を孔径10.2μmのフィルターで濾過することにより、配向剤(S-4)を得た。表4を参照のこと。
変性ポリシロキサンとポリアミック酸(または、ポリイミド)とを表4のように組み合わせ、合成例25と同様にして同様に操作して、配向剤(S-5)から(S-24)を調製した。
[実施例1]
画素サイズが100μm×300μmで、ライン/スペースがそれぞれ3.5μmのITO電極パターンが形成されている基板を2枚用意した。合成例1でアルコキシシランから調製した配向剤(S-1)を、基板のITO面にスピンコートした。80℃のホットプレートで5分間乾燥し、180℃の熱風循環式オーブンで30分間焼成して、配向膜(膜厚100nm)を得た。一方の基板の配向膜上に3.5μmのビーズスペーサーを散布した後、その上からシール剤を印刷した。他方の基板を、配向膜面を内側にして張り合わせ、シール剤を硬化させて素子を作製した。この素子に組成物M1を注入した。紫外線を照射することによってPSA素子に変換したあと、応答時間を測定した。結果を表5にまとめた。
配向剤(S-1)の代わりに、配向剤(S-2)から(S-24)を用いて、実施例1同様に操作して、種々の配向膜を有する液晶表示素子を作製した。すでに記載したように、配向剤(S-2)および(S-3)はアルコキシシランから調製した。配向剤(S-4)から(S-24)は、変性ポリシロキサンとポリアミック酸(または、ポリイミド)とから調製した。実施例1に記載した素子に組成物M1からM15の各組成物を注入し、紫外線を照射した後、応答時間を測定した。結果を表5にまとめた。
Claims (20)
- 対向配置されている一対の基板の一方または両方に形成されている電極群と、前記電極群に接続された複数のアクティブ素子と、前記一対の基板の対向しているそれぞれの面に形成された液晶配向膜と、前記一対の基板の間に挟持された液晶組成物とを有し、前記液晶配向膜が、ポリオルガノシロキサン、ポリアミック酸、ポリアミック酸エステル、およびポリイミドから選択された少なくとも1つの重合体を含有し、前記液晶組成物が、第一成分として式(1)で表される化合物の群から選択された少なくとも1つの化合物を含有する高分子支持配向型の液晶表示素子。
式(1)において、R1およびR2は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、炭素数2から12のアルケニルオキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルであり;環Aおよび環Cは独立して、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、またはテトラヒドロピラン-2,5-ジイルであり;環Bは、2,3-ジフルオロ-1,4-フェニレン、2-クロロ-3-フルオロ-1,4-フェニレン、2,3-ジフルオロ-5-メチル-1,4-フェニレン、3,4,5-トリフルオロナフタレン-2,6-ジイル、または7,8-ジフルオロクロマン-2,6-ジイルであり;Z1およびZ2は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり;aは、0、1、2、または3であり;bは、0または1であり;そして、aおよびbの和は3以下である。 - 液晶組成物の重量に基づいて、第一成分の割合が10重量%から90重量%の範囲である、請求項1または2に記載の液晶表示素子。
- 液晶組成物が、第二成分として式(2)で表される化合物の群から選択された少なくとも1つの化合物を含有する、請求項1から3のいずれか1項に記載の液晶表示素子。
式(2)において、R3およびR4は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数2から12のアルケニルであり;環Dおよび環Eは独立して、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、または2,5-ジフルオロ-1,4-フェニレンであり;Z3は、単結合、エチレン、またはカルボニルオキシであり;cは、1、2、または3である。 - 液晶組成物の重量に基づいて、第二成分の割合が10重量%から90重量%の範囲である、請求項4または5に記載の液晶表示素子。
- 液晶組成物が、添加物成分として式(3)で表される化合物の群から選択された少なくとも1つの重合性化合物を含有する、請求項1から6のいずれか1項に記載の液晶表示素子。
式(3)において、環Fおよび環Iは独立して、シクロヘキシル、シクロヘキセニル、フェニル、1-ナフチル、2-ナフチル、テトラヒドロピラン-2-イル、1,3-ジオキサン-2-イル、ピリミジン-2-イル、またはピリジン-2-イルであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;環Gは、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-1,2-ジイル、ナフタレン-1,3-ジイル、ナフタレン-1,4-ジイル、ナフタレン-1,5-ジイル、ナフタレン-1,6-ジイル、ナフタレン-1,7-ジイル、ナフタレン-1,8-ジイル、ナフタレン-2,3-ジイル、ナフタレン-2,6-ジイル、ナフタレン-2,7-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、またはピリジン-2,5-ジイルであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;Z4およびZ5は独立して、単結合または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-、-C(CH3)=CH-、-CH=C(CH3)-、または-C(CH3)=C(CH3)-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;P1、P2、およびP3は独立して、重合性基であり;Sp1、Sp2、およびSp3は独立して、単結合、または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;dは、0、1、または2であり;e、f、およびgは独立して、0、1、2、3、または4であり、そしてe、f、およびgの和は1以上である。 - 添加物成分が、式(3-1)から式(3-27)で表される化合物の群から選択された少なくとも1つの重合性化合物である、請求項7または8に記載の液晶表示素子。
式(3-1)から式(3-27)において、P4、P5、およびP6は独立して、式(P-1)から式(P-3)で表される基の群から選択された重合性基であり:
式(P-1)から式(P-3)において、M4、M5、およびM6は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から5のアルキルであり;式(3-1)から式(3-27)において、Sp1、Sp2、およびSp3は独立して、単結合、または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよい。 - 液晶組成物の重量に基づいて、添加物成分の割合が0.03重量%から10重量%の範囲である、請求項7から9のいずれか1項に記載の液晶表示素子。
- 前記液晶配向膜が、前記ポリアミック酸、前記ポリアミック酸エステル、および前記ポリイミドから選択された少なくとも1つの重合体を主成分として含有し、前記ポリオルガノシロキサンを副成分として含有する、請求項1から10のいずれか1項に記載の液晶表示素子。
- 前記液晶配向膜に含有されるポリオルガノシロキサンが、カルボキシル基、ヒドロキシアルキル基、-NHR5、メルカプト基、エポキシ基、または重合性不飽和結合を含有し、R5は、水素または炭素数1から6のアルキルである、請求項1から11のいずれか1項に記載の液晶表示素子。
- 前記液晶配向膜に含有されるポリオルガノシロキサンが、式(X1-1)から式(X1-7)で表される基の群から選択された少なくとも1つの基を含有する、請求項1から12のいずれか1項に記載の液晶表示素子。
式(X1-1)から式(X1-7)において、星印は結合する部位を示し;Z6は、-O-または単結合であり;Z7は、単結合、炭素数1から6のアルキレン、または-O-、-S-、-COO-、-OCO-、および-NR6-の群から選択された少なくとも1つを含む炭素数1から20の二価基であり、ここでR6は、水素または炭素数1から6のアルキルであり;hは1、2、または3であり;iは、0から6の整数であり、iが0の場合、Z6は単結合であり;jは、0から6の整数である。 - 前記液晶配向膜が、請求項13に記載の式(X1-7)で表される基を含有するポリオルガノシロキサンを含有する、請求項1から13のいずれか1項に記載の液晶表示素子。
- ポリアミック酸、ポリアミック酸エステル、またはポリイミドが脂環式構造を有する、請求項1から11のいずれか1項に記載の液晶表示素子。
- 請求項1から15のいずれか1項に記載の液晶表示素子に使用される、液晶組成物。
- 25℃において、弾性定数(K11)が11pN以上であり、弾性定数(K33)が11pN以上である、請求項16に記載の液晶組成物。
- 請求項1から15のいずれか1項に記載の液晶表示素子に使用される、液晶配向膜。
- 25℃における体積抵抗率(ρ)が1.0×1014Ωcm以上である、請求項18に記載の液晶配向膜。
- 25℃における誘電率(ε)が3から5の範囲である、請求項19に記載の液晶配向膜。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/762,560 US20180258348A1 (en) | 2015-09-25 | 2016-09-07 | Liquid crystal display device |
EP16848497.0A EP3355107B1 (en) | 2015-09-25 | 2016-09-07 | Liquid crystal display element |
CN201680056143.1A CN108139629A (zh) | 2015-09-25 | 2016-09-07 | 液晶显示元件 |
KR1020187008488A KR20180056663A (ko) | 2015-09-25 | 2016-09-07 | 액정 표시 소자 |
JP2017541506A JPWO2017051709A1 (ja) | 2015-09-25 | 2016-09-07 | 液晶表示素子 |
TW105130378A TWI696687B (zh) | 2015-09-25 | 2016-09-21 | 聚合物穩定配向型的液晶顯示元件、液晶組成物以及液晶配向膜 |
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Cited By (3)
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JPWO2017195585A1 (ja) * | 2016-05-10 | 2018-05-24 | Dic株式会社 | 液晶表示素子 |
CN110753738A (zh) * | 2017-07-25 | 2020-02-04 | Dic株式会社 | 液晶组合物及液晶显示元件 |
JP2020042068A (ja) * | 2018-09-06 | 2020-03-19 | Dic株式会社 | 液晶表示素子 |
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CN114806598A (zh) * | 2022-05-20 | 2022-07-29 | 北京八亿时空液晶科技股份有限公司 | 一种具有高对比度的负性液晶组合物及其应用 |
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US20180258348A1 (en) | 2018-09-13 |
JPWO2017051709A1 (ja) | 2018-08-16 |
TW201725257A (zh) | 2017-07-16 |
EP3355107A4 (en) | 2019-05-15 |
CN108139629A (zh) | 2018-06-08 |
EP3355107A1 (en) | 2018-08-01 |
TWI696687B (zh) | 2020-06-21 |
EP3355107B1 (en) | 2020-06-17 |
KR20180056663A (ko) | 2018-05-29 |
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