WO2015008846A1 - 液晶表示素子、液晶配向処理剤、及び液晶配向膜 - Google Patents
液晶表示素子、液晶配向処理剤、及び液晶配向膜 Download PDFInfo
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- WO2015008846A1 WO2015008846A1 PCT/JP2014/069107 JP2014069107W WO2015008846A1 WO 2015008846 A1 WO2015008846 A1 WO 2015008846A1 JP 2014069107 W JP2014069107 W JP 2014069107W WO 2015008846 A1 WO2015008846 A1 WO 2015008846A1
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- 0 C*[N+](CC[N+](C)[O-])[O-] Chemical compound C*[N+](CC[N+](C)[O-])[O-] 0.000 description 7
- SEAWNFIMLZVETF-UHFFFAOYSA-N CO[NH+](CC[NH+]([O-])O[U])[O-] Chemical compound CO[NH+](CC[NH+]([O-])O[U])[O-] SEAWNFIMLZVETF-UHFFFAOYSA-N 0.000 description 1
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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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/32—Cellulose ether-esters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/0422—Sugars
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
- G02F1/13347—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals working in reverse mode, i.e. clear in the off-state and scattering in the on-state
Definitions
- the present invention relates to a transmission / scattering type liquid crystal display element that becomes transparent when no voltage is applied and is in a scattering state when a voltage is applied, a liquid crystal aligning agent for the element, and a liquid crystal alignment film.
- a TN (Twisted Nematic) mode has been put to practical use as a liquid crystal display element using a liquid crystal material.
- this mode light is switched by utilizing the optical rotation characteristics of the liquid crystal, and it is necessary to use a polarizing plate when used as a liquid crystal display element.
- the use efficiency of light is lowered by using a polarizing plate.
- As a liquid crystal display element having a high light utilization efficiency without using a polarizing plate there is a liquid crystal display element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state.
- PDLC Dispersed Liquid Crystal
- PNLC Polymer network liquid crystal
- a liquid crystal display element using these includes a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates.
- the liquid crystal composition is disposed, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and is manufactured through a process of forming a cured product composite of the liquid crystal and the polymerizable compound. It is a liquid crystal display element. And this liquid crystal display element controls the permeation
- liquid crystal molecules are oriented in a random direction when no voltage is applied, and thus becomes clouded (scattered).
- a normal type element that is transmitted and becomes a transmission state.
- it is necessary to always apply a voltage in order to obtain a transmissive state. Therefore, in applications that are often used in a transparent state, for example, when used in a window glass, power consumption is low. large.
- a reverse type element has been reported that is in a transmission state when no voltage is applied to a normal type element and in a scattering state when a voltage is applied (see Patent Documents 1 and 2).
- a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that aligns the liquid crystal vertically is used.
- the vertical liquid crystal alignment film is a highly hydrophobic film, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, a large amount of a polymerizable compound (also referred to as a curing agent) for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film must be introduced into the liquid crystal composition used for the reverse type element.
- an object of the present invention is to provide a liquid crystal display element having the above-described characteristics. That is, the object of the present invention is that the vertical alignment of the liquid crystal is high and has good optical properties, that is, transparency when no voltage is applied and scattering property when a voltage is applied. It is to provide a liquid crystal display element having high adhesion. Furthermore, the present invention provides a liquid crystal alignment film for the liquid crystal display element and a liquid crystal alignment treatment agent used for forming the liquid crystal alignment film.
- the present inventor has a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polysiloxane polymer having a side chain having a specific structure.
- a liquid crystal display element having high adhesion between a layer and a liquid crystal alignment film, high vertical alignment of liquid crystal, and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when a voltage is applied It was found that it can be obtained.
- a liquid crystal composition comprising a liquid crystal and a polymerizable compound that is polymerized by active energy rays or heat is disposed between two substrates provided with electrodes, and a liquid crystal alignment film is provided on at least one of the substrates.
- a liquid crystal display element in which a cured product composite of a liquid crystal and a polymerizable compound is formed by curing a part or the whole of the liquid crystal composition exhibiting liquid crystallinity.
- a liquid crystal display element which is formed from a liquid crystal aligning agent containing the components (A) and (B).
- Component (A) Cellulosic polymer having a structure represented by the following formula [1].
- X 1 , X 2 , X 3 , X 4 , X 5 and X 6 each independently represent at least one group selected from the group consisting of the following formulas [1a] to [1m].
- N represents an integer of 100 to 1000000.
- X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , and X 14 are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group, and butyl. And at least one selected from the group consisting of groups, n represents an integer from 0 to 3, and m represents an integer from 0 to 3.
- a 1 represents at least one structure selected from the group consisting of structures represented by the following formulas [2-1] and [2-2].
- a 2 represents a hydrogen atom or a carbon number of 1 to 5
- a 3 represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. (However, m + n + p is 4.)
- Y 1 is selected from the group consisting of a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO—, and —OCO—.
- Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
- Y 3 represents a single bond, — (CH 2 ) c — (c Is an integer of 1 to 15, and represents at least one selected from the group consisting of —O—, —CH 2 O—, —COO—, and —OCO—
- Y 4 represents a benzene ring, a cyclohexane ring, and a heterocycle At least one divalent cyclic group selected from the group consisting of a ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group has 1
- Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, or 1 carbon atom. And at least one selected from the group consisting of an alkoxyl group having ⁇ 18 and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, n represents an integer of 0-4.
- Y 7 is a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— and —OCO—
- Y 8 represents at least one linking group selected from the group consisting of: an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.
- B 1 is an organic group having 2 to 12 carbon atoms having at least one selected from the group consisting of vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacryl group, acrylic group, ureido group and cinnamoyl group.
- B 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- B 3 represents an alkyl group having 1 to 5 carbon atoms
- m represents an integer of 1 or 2
- n represents 0 to Represents an integer of 2.
- p represents an integer of 0 to 3, where m + n + p is 4.
- D 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- D 2 represents an alkyl group having 1 to 5 carbon atoms.
- N represents an integer of 0 to 3.
- the liquid crystal according to (1) wherein the ratio of the component (A) to the component (B) is 0.1 to 9 parts by mass of the component (A) with respect to 1 part by mass of the component (B).
- (3) The alkoxysilane represented by the formula [2b] of the component (B) is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris ( The above (1) which is at least one selected from the group consisting of 2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate Or a liquid crystal display device according to (2).
- the alkoxysilane represented by the formula [2b] of the component (B) is 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane and 2
- the liquid crystal display device according to the above (1) or (2) which is at least one selected from the group consisting of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- the component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [2a], or an alkoxy represented by the formula [2a] and the formula [2b] or the formula [2c]
- the liquid crystal display element according to any one of (1) to (5), further comprising a solvent in the liquid crystal aligning agent.
- a solvent methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1, 4-butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene
- the liquid crystal aligning agent contains an adhesive compound having at least one selected from the group consisting of structures represented by the following formulas [B1] to [B8]: (7)
- the liquid crystal display element in any one of.
- B 1 represents a hydrogen atom or a benzene ring.
- B 2 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring.
- B 3 represents a carbon number of 1 to And at least one selected from the group consisting of 18 alkyl groups, fluorine-containing alkyl groups having 1 to 18 carbon atoms, alkoxyl groups having 1 to 18 carbon atoms, and fluorine-containing alkoxyl groups having 1 to 18 carbon atoms.
- the liquid crystal alignment treatment agent further comprises at least one generator selected from the group consisting of a photo radical generator, a photo acid generator, and a photo base generator, according to the above (1) to (8).
- the liquid crystal display element in any one.
- (11) A liquid crystal alignment film used for the liquid crystal display element according to any one of (1) to (10) above, and a liquid crystal formed from a liquid crystal alignment treatment agent containing the component (A) and the component (B) Alignment film.
- a liquid crystal layer and a vertical liquid crystal alignment are obtained by using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polysiloxane polymer having a side chain having a specific structure. It is possible to provide a liquid crystal display device having high adhesion to a film, high liquid crystal vertical alignment, and good optical characteristics, that is, good transparency when no voltage is applied and good scattering characteristics when a voltage is applied.
- the liquid crystal display element of the present invention can be suitably used for a reverse type element that is in a transmissive state when no voltage is applied and is in a scattering state when a voltage is applied. It is used as a dimming window or an optical shutter element for controlling blocking.
- the liquid-crystal aligning agent used for the liquid crystal display element of this invention is the cellulose polymer (it is also called a specific cellulose polymer) which is a component (A), and the polysiloxane polymer (specific) which is a component (B). (Also referred to as polysiloxane polymer).
- This specific cellulosic polymer has high transparency. Therefore, the vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent is difficult to absorb light such as ultraviolet rays, and promotes the reaction of the polymerizable compound in the liquid crystal composition by irradiation of active energy rays when producing a liquid crystal display element. can do.
- the structure represented by the formula [2-1] is at least selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring at the side chain site.
- the specific side chain structure represented by the formula [2-1] can obtain high vertical alignment even if the amount of the side chain structure introduced is small. Therefore, the liquid crystal display element using the vertical liquid crystal alignment film having the specific side chain structure represented by the formula [2-1] has higher adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.
- the liquid crystal display element of the present invention uses a vertical liquid crystal alignment film obtained from a liquid crystal aligning agent containing a specific cellulose polymer and a specific polysiloxane polymer having a specific side chain structure, and the vertical alignment of the liquid crystal is high. High, good optical properties, that is, transparency when no voltage is applied and scattering property when a voltage is applied, and further, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high.
- the liquid crystal display element of the present invention comprises a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by liquid crystal and ultraviolet light between the pair of substrates.
- the liquid crystal composition is formed by irradiating with ultraviolet rays in a state where at least one of the substrates has a liquid crystal alignment film that aligns liquid crystal vertically and part or all of the liquid crystal composition exhibits liquid crystallinity It is manufactured through a process of curing a product and forming a cured product composite of liquid crystal and a polymerizable compound, and is preferably used as a reverse type element that is in a transmission state when no voltage is applied and in a scattering state when a voltage is applied. it can.
- the specific cellulose polymer is a polymer having a structure represented by the following formula [1].
- X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are each independently at least one selected from the group consisting of the following formulas [1a] to [1m] Indicates a group.
- n represents an integer of 100 to 1000000. Among these, n is preferably 100 to 500,000 from the viewpoint of the solubility of the specific cellulose polymer in a solvent and the handleability when it is prepared as a liquid crystal aligning agent. More preferred is 100 to 100,000.
- X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 and X 14 are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group and butyl group. At least one selected from the group consisting of
- n represents an integer of 0 to 3. Among these, an integer of 0 or 1 is preferable.
- m represents an integer of 0 to 3. Among these, an integer of 0 or 1 is preferable.
- X 1 , X 2 , X 3 , X 4 , X 5 and X 6 each independently represent at least one group selected from the group consisting of the formulas [1a] to [1m]. May be one type or two or more types. In particular, it is preferable to use two or more types from the viewpoint of the solubility of the specific cellulose polymer in a solvent and the coating properties of the liquid crystal aligning agent. Particularly preferably, the formula [1a] and the formulas [1b] to [1m] are used. Furthermore, it is preferable to use Formula [1a], Formula [1c], Formula [1d], Formula [1e], Formula [1h], or Formula [1i].
- Specific examples of the specific cellulose polymer include the following, but are not limited to these examples.
- Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.
- the method for introducing the structures represented by the formulas [1b] to [1m] is not particularly limited, and an existing method can be used.
- formula [1b] a method of reacting cellulose and benzyl chloride in the presence of an alkali
- formula [1c] a method of reacting cellulose and a halogen compound having X 7 in the presence of an alkali
- formula [1d] a method of reacting cellulose and an acid chloride compound having X 8 in the presence of an alkali
- a method of reacting cellulose and acetic anhydride When introducing the formula [1e], a method of reacting cellulose and a halogen compound having X 9 —OH in the presence of an alkali,
- formula [1f] a method of reacting cellulose and a halogen compound having X 10 —COOH in the presence of an alkali
- formula [1e] a method of reacting cellulose and a halogen compound having X 10 —
- the specific cellulose polymer is soluble in the solvent of the specific cellulose polymer, the coating property of the liquid crystal aligning agent, and the optical properties of the liquid crystal display element and the adhesion properties between the liquid crystal layer and the vertical liquid crystal alignment film.
- the type one type or a mixture of two or more types can be used.
- the polysiloxane polymer is at least selected from the group consisting of an alkoxysilane represented by the following formula [2a], an alkoxysilane represented by the following formula [2b], and an alkoxysilane represented by the following formula [2c]. It is a polysiloxane obtained by polycondensing one kind.
- a 1 represents at least one structure selected from the group consisting of structures represented by Formula [2-1] or Formula [2-2] below. Among these, the structure represented by the formula [2-1] is preferable from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained.
- a 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
- a 3 represents an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
- m represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
- n represents an integer of 0-2.
- p represents an integer of 0 to 3.
- an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3. Note that m + n + p is 4.
- Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO—, and —OCO.
- at least one linking group selected from the group consisting of: Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO. -Is preferred. More preferred is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
- Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
- Y 3 is at least selected from the group consisting of a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— and —OCO—.
- One kind of linking group is shown.
- a single bond — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
- Y 4 is at least one divalent cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
- X 4 may be an organic group selected from organic groups having 17 to 51 carbon atoms having a steroid skeleton.
- Y 5 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms.
- a benzene ring or a cyclohexane ring is preferable.
- Y 6 is at least selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
- an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
- n represents an integer of 0 to 4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
- (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred.
- Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).
- Y 7 represents a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, At least one linking group selected from the group consisting of —COO— and —OCO—; Of these, a single bond, —O—, —CH 2 O—, —CONH—, —CON (CH 3 ) — or —COO— is preferable. More preferably, they are a single bond, —O—, —CONH— or —COO—.
- Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Of these, an alkyl group having 8 to 18 carbon atoms is preferable.
- the specific side chain structure in the present invention as described above, the specific side chain structure represented by the formula [2-1] is preferably used from the viewpoint that a high and stable vertical alignment of liquid crystal can be obtained.
- alkoxysilane represented by the formula [2a] include alkoxysilanes represented by the following formulas [2a-1] to [2a-32].
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group having 1 to 3 carbon atoms.
- M represents an integer of 2 or 3.
- n represents an integer of 0 or 1. .
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group having 1 to 3 carbon atoms.
- R 3 represents —O—, —COO—, —OCO—, —CONH—.
- R 4 represents at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, and a fluorine-containing alkoxy group, and m is 2 or 3.
- N represents an integer of 0 or 1)
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group having 1 to 3 carbon atoms.
- R 3 represents —O—, —COO—, —OCO—, —CONH—.
- R 4 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, a fluorine-containing alkoxy group, a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, This represents at least one selected from the group consisting of a formyl group, an acetyl group, an acetoxy group and a hydroxyl group, m represents an integer of 2 or 3, and
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group having 1 to 3 carbon atoms.
- R 3 represents — O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —OCH 2 —, —CH 2 O—, —COOCH 2 And at least one selected from the group consisting of — and —CH 2 OCO—, wherein R 4 is selected from the group consisting of alkyl groups having 1 to 12 carbon atoms, alkoxy groups, fluorine-containing alkyl groups, and fluorine-containing alkoxy groups. (At least 1 type is shown, m shows the integer of 2 or 3. n shows the integer of 0 or 1.)
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group having 1 to 3 carbon atoms.
- M represents an integer of 2 or 3.
- n represents an integer of 0 or 1.
- B 4 represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
- B 3 represents a 1,4-cyclohexylene group or a 1,4-phenylene group
- B 2 represents Represents an oxygen atom or —COO— * (where a bond marked with “*” is bonded to B 3 ),
- B 1 is an oxygen atom or —COO— * (note that “*” is attached)
- the bond is bonded to (CH 2 ) a 2 ).
- the alkoxysilane represented by the above formula [2a] is used for the solubility of the specific polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
- B 1 represents an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group, or a cinnamoyl group.
- a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group is preferable as a substituent from the viewpoint of availability. More preferably, they are a methacryl group, an acryl group, or a ureido group.
- B 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
- B 3 represents an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
- m represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
- n represents an integer of 0-2. Of these, 0 or 1 is preferable.
- p represents an integer of 0 to 3. Among these, an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3.
- m + n + p is 4.
- alkoxysilane represented by the formula [2b] include, for example, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxy Ethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) Propyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxy
- Ethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate or 3- (trimethoxysilyl) propyl methacrylate is preferred.
- 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxy which undergoes a crosslinking reaction by heat Silane is preferred.
- the alkoxysilane represented by the formula [2b] has properties such as the solubility of the specific polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the situation, one kind or a mixture of two or more kinds can be used.
- D 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the hydrogen atom of these alkyl groups may be substituted with a halogen atom, a nitrogen atom, an oxygen atom or a sulfur atom. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
- D 2 represents an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
- n represents an integer of 0 to 3. Of these, 0 or 1 is preferable.
- alkoxysilane represented by the formula [2c] include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane.
- examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and examples of the alkoxysilane represented by the formula [2c] include these It is preferable to use alkoxysilane.
- the alkoxysilane represented by the formula [2c] has properties such as the solubility of the specific polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the situation, one type or a mixture of two or more types can be used.
- the specific polysiloxane polymer includes at least one selected from the group consisting of the alkoxysilane represented by the formula [2a], the alkoxysilane represented by the formula [2b], and the alkoxysilane represented by the formula [2c]. It is a polysiloxane obtained by condensation. Specifically, it is obtained by polycondensing polysiloxane obtained by polycondensation of one kind of alkoxysilane represented by the formula [2a] and two kinds of alkoxysilanes represented by the formulas [2a] and [2b].
- Polysiloxane polysiloxane obtained by polycondensation of two alkoxysilanes represented by formula [2a] and formula [2c], and 3 represented by formula [2a], formula [2b] and formula [2c] It is a polysiloxane obtained by polycondensation of a kind of alkoxysilane.
- polysiloxane obtained by polycondensation of plural types of alkoxysilanes is preferable. That is, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by the formulas [2a] and [2b], and two types of alkoxysilanes represented by the formulas [2a] and [2c] Or a polysiloxane obtained by polycondensation of three types of alkoxysilanes represented by the formulas [2a], [2b] and [2c]. Of these, polysiloxanes obtained by polycondensation of three types of alkoxysilanes represented by formula [2a], formula [2b] and formula [2c] are preferred.
- the alkoxysilane represented by the formula [2a] is preferably 1 to 40 mol% in all alkoxysilanes. Of these, 1 to 30 mol% is preferable. Further, the alkoxysilane represented by the formula [2b] is preferably 1 to 70 mol% in all alkoxysilanes. Of these, 1 to 60 mol% is preferable. Furthermore, the alkoxysilane represented by the formula [2c] is preferably 1 to 99 mol% in all alkoxysilanes. Among these, 1 to 80 mol% is preferable.
- the method for producing the specific polysiloxane polymer is not particularly limited.
- a method obtained by polycondensing an alkoxysilane represented by formula [2a] in a solvent a method obtained by polycondensing two types of alkoxysilanes represented by formula [2a] and formula [2b]
- Examples thereof include a method obtained by polycondensation of alkoxysilane in a solvent.
- the specific polysiloxane polymer of the present invention can be obtained as a solution obtained by polycondensing these alkoxysilanes and uniformly dissolved in a solvent.
- the method for polycondensing the specific polysiloxane polymer is not particularly limited. For example, a method in which an alkoxysilane is hydrolyzed and polycondensed in an alcohol solvent or a glycol solvent can be mentioned. At that time, the hydrolysis / polycondensation reaction may be partially hydrolyzed or completely hydrolyzed.
- acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkaline such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine Catalysts such as compounds; metal salts such as hydrochloric acid, nitric acid, oxalic acid, etc.
- the hydrolysis / polycondensation reaction can also be promoted by heating a solution in which the alkoxysilane is dissolved.
- the heating temperature and heating time in that case can be suitably selected according to the objective. For example, conditions such as heating and stirring at 50 ° C. for 24 hours and then stirring for 1 hour under reflux conditions may be mentioned.
- a method in which a polycondensation reaction is carried out by heating a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to a solvent to prepare a solution of oxalic acid in advance, alkoxysilane is mixed in a state where the solution is heated.
- the amount of oxalic acid used in the above reaction is preferably 0.2 to 2.0 mol with respect to 1 mol of all alkoxy groups in the alkoxysilane.
- This reaction can be carried out at a solution temperature of 50 to 180 ° C., but is preferably carried out under reflux for several tens of minutes to several tens of hours so as not to cause evaporation or volatilization of the solvent.
- a plurality of alkoxysilanes represented by the formula [2a], the formula [2b] and the formula [2c] are used, a plurality of the alkoxysilanes are mixed in advance. Even if it reacts using a mixture, you may react, adding multiple types of alkoxysilane sequentially.
- the solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even if it is a solvent in which an alkoxysilane does not melt
- an alcohol is generally generated by a polycondensation reaction of alkoxysilane, and therefore, an alcohol solvent, a glycol solvent, a glycol ether solvent, a solvent having good compatibility with alcohol, and the like are used.
- solvent used in such a polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol, diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4 -Glucol solvents such as pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Recall monopropyl ether, ethylene glycol monobut
- the concentration of silicon atoms contained in all alkoxysilanes charged as raw materials in terms of SiO 2 is 20% by mass or less. Is preferred. In particular, the content is preferably 5 to 15% by mass.
- the polysiloxane polymer solution obtained by the above method may be used as the specific polysiloxane polymer as it is, or if necessary, the polysiloxane polymer obtained by the above method. These solutions can be concentrated, diluted by adding a solvent, or substituted with another solvent to be used as a specific polysiloxane polymer.
- a solvent used for dilution a solvent used for a polycondensation reaction or other solvents may be used.
- the additive solvent is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and one or two or more types can be arbitrarily selected and used.
- the additive solvent examples include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate;
- ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
- ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate
- the polysiloxane polymer is mixed before mixing the other polymer with the polysiloxane polymer.
- the alcohol generated during the polycondensation reaction of the coalescer is preferably distilled off at normal pressure or reduced pressure.
- the liquid crystal aligning agent in the present invention is a coating solution for forming a liquid crystal alignment film, the specific cellulose polymer as the component (A), and the formula [2-1] and the formula [B] as the component (B).
- 2-2] is a coating solution containing a specific polysiloxane polymer having at least one specific side chain structure selected from the group consisting of the structure represented by 2-2] and a solvent.
- the ratio of the specific cellulose polymer and the specific polysiloxane polymer in the liquid crystal alignment treatment agent is 0.01 to 99 mass% with respect to 1 part by mass of the specific polysiloxane polymer. Part is preferred. Among these, 0.1 to 9 parts by mass is more preferable, and 0.1 to 3 parts by mass is more preferable.
- All the polymer components in the liquid crystal aligning agent may all be a specific cellulose polymer and a specific polysiloxane polymer, or other polymers may be mixed.
- examples of other polymers include polysiloxane polymers having no specific side chain represented by the formula [2-1] or the formula [2-2].
- at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyamide, polyester, polyamic acid and polyimide can also be mixed.
- the content of the other polymer is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of all the polymers including the specific cellulose polymer and the specific polysiloxane polymer. Of these, 1 to 10 parts by mass is preferable.
- Content of the solvent in a liquid-crystal aligning agent can be suitably selected from a viewpoint of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness.
- the content of the solvent in the liquid crystal alignment treatment agent is preferably 50 to 99.9% by mass.
- 60 to 99% by mass is preferable, and 65 to 99% by mass is more preferable.
- the solvent used for the liquid crystal aligning agent is not particularly limited as long as the solvent dissolves the specific cellulose polymer and the specific polysiloxane polymer.
- the solvent used for the liquid crystal aligning agent may be a polycondensation solution of the specific polysiloxane polymer as it is, or a new solvent may be added to the polycondensation solution of the specific polysiloxane polymer, Furthermore, the polycondensation solution of the specific polysiloxane polymer may be replaced with a new solvent.
- the new solvent is not particularly limited as long as it is a solvent that dissolves the specific cellulose polymer and the specific polysiloxane polymer. Although the specific example is given to the following, it is not limited to these examples.
- a 1 represents an alkyl group having 1 to 3 carbon atoms.
- a 2 represents an alkyl group having 1 to 3 carbon atoms.
- a 3 represents an alkyl group having 1 to 4 carbon atoms.
- One or two kinds of the above-mentioned solvents are used depending on the solubility of the specific cellulose polymer and the specific polysiloxane and the coating properties and surface smoothness characteristics of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied.
- the above can be mixed and used.
- the liquid crystal alignment treatment agent in the present invention includes at least one selected from the group consisting of structures represented by the following formulas [B1] to [B8] for the purpose of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to introduce a compound having a certain property (also referred to as a specific adhesion compound). It is preferable that two or more structures represented by the formulas [B1] to [B8] are included in the adhesive compound.
- B 1 represents a hydrogen atom or a benzene ring.
- B 2 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring.
- B 3 represents a carbon number of 1 to And at least one selected from the group consisting of 18 alkyl groups, fluorine-containing alkyl groups having 1 to 18 carbon atoms, alkoxyl groups having 1 to 18 carbon atoms, and fluorine-containing alkoxyl groups having 1 to 18 carbon atoms.
- M 1 represents at least one structure selected from the group consisting of structures represented by the following formulas [a-1] to [a-7].
- the formula [a-1], the formula [a-2], the formula [a-3], the formula [a-5] or the formula [a- 6] is preferable.
- a structure represented by the formula [a-1], the formula [a-3], the formula [a-5] or the formula [a-6] is more preferable.
- a 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
- a 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
- a 3 , A 5 , A 6 and A 9 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
- a 4 , A 7 and A 8 each independently represents an alkylene group having 1 to 3 carbon atoms. Among these, an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound.
- M 2 represents a single bond, —CH 2 —, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH.
- 2 represents at least one linking group selected from the group consisting of —COO—, —OCO—, —CON (CH 3 ) —, and —N (CH 3 ) CO—.
- a single bond —CH 2 —, —O—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO— is preferred. More preferably, they are a single bond, —CH 2 —, —O—, —NH—, —CONH—, —CH 2 O—, —OCH 2 —, —COO— or —OCO—. Particularly preferred is a single bond, —O—, —CONH—, —OCH 2 —, —COO— or —OCO—.
- M 3 represents an alkylene group having 1 to 20 carbon atoms, — (CH 2 —CH 2 —O) p — (p represents an integer of 1 to 10), — (CH 2 —O— ) Q- (q represents an integer of 1 to 10) and at least one selected from the group consisting of organic groups having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms.
- any —CH 2 — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO 2 —, —CF 2 —, — C (CF 3) 2 -, - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si (CH 3) may be replaced by 2 O-, bonded to any carbon atom
- the hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.
- an alkylene group having 1 to 20 carbon atoms — (CH 2 —CH 2 —O) p — (p represents an integer of 1 to 10), — ( CH 2 —O—) q — (q represents an integer of 1 to 10) or structures represented by the following formulas [c-1] to [c-5] are preferable.
- an alkylene group having 1 to 15 carbon atoms — (CH 2 —CH 2 —O) p — (p represents an integer of 1 to 10), — (CH 2 —O—) q — (q is An integer of 1 to 10), and a structure represented by the following formula [c-1], formula [c-3], formula [c-4], or formula [c-5].
- an alkylene group having 1 to 15 carbon atoms, — (CH 2 —CH 2 —O) p — (p represents an integer of 1 to 10), formula [c-1], formula [c-4] Or it is a structure shown by Formula [c-5].
- M 4 represents at least one linking group selected from the group consisting of a single bond, —CH 2 —, —OCH 2 —, and O—CH 2 —CH 2 —.
- a structure represented by a single bond, —CH 2 — or —OCH 2 — is preferable from the viewpoint of easy synthesis of the adhesive compound.
- M 5 represents at least one structure selected from the group consisting of the structures represented by Formulas [b-1] to [b-8].
- the structure represented by the formula [b-1], the formula [b-2], or the formula [b-6] is preferable from the viewpoint of easy synthesis of the adhesive compound.
- n represents an integer of 1 to 3. Especially, 1 or 2 is preferable from the point of the ease of the synthesis
- m represents an integer of 1 to 3. Especially, 1 or 2 is preferable from the point of the ease of the synthesis
- the specific adhesive compound it is preferable to use at least one compound selected from the group consisting of compounds represented by the following formulas [6-1] and [6-5]. (N represents an integer of 1 to 10. m represents an integer of 1 to 10.)
- adhesion compounds include those shown below.
- trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, etc.
- the content of the specific adhesive compound in the liquid crystal aligning agent is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
- the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.
- the specific adhesion compound may be used singly or in combination of two or more depending on the vertical alignment property of the liquid crystal when the vertical liquid crystal alignment film is formed, and the characteristics such as the optical characteristics of the liquid crystal display element. it can.
- the liquid crystal alignment treatment agent in the present invention has at least one specific selected from the group consisting of a photo radical generator, a photo acid generator and a photo base generator for the purpose of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to introduce a generator.
- the photo radical generator is not particularly limited as long as it generates radicals by ultraviolet rays, and examples thereof include tert-butylperoxy-iso-butrate, 2,5-dimethyl-2,5-bis (benzoyldioxy).
- the photoacid generator and photobase generator are not particularly limited as long as they generate an acid or a base by ultraviolet rays.
- triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivatives examples thereof include compounds, diaryl iodonium salts, triaryl sulfonium salts, triaryl phosphonium salts, and iron arene complexes.
- the content of the specific generator in the liquid crystal aligning agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of all the polymer components.
- the specific generating agent can be used singly or in combination of two or more depending on the vertical alignment property of the liquid crystal when the vertical liquid crystal alignment film is formed, and further the optical characteristics of the liquid crystal display element. .
- the liquid crystal aligning agent in the present invention is selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. It is preferable to introduce a compound having at least one selected substituent (collectively referred to as a specific crosslinking compound). It is necessary to have two or more of these substituents in the crosslinkable compound.
- crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-amin
- the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4]. Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
- the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5]. Specific examples include crosslinkable compounds represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication No. WO2012 / 014898 (2012.2.2 publication). .
- Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
- a melamine resin such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
- -Formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like Specifically, a melamine derivative in which a hydrogen atom of an amino group is substituted with a methylol group and / or an alkoxymethyl group, a benzoguanamine derivative, glycoluril, or the like can be used.
- the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer
- Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
- Methoxy-methylated melamines such as 8 substituted MW-30 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712; Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254; butoxymethylated melamine such as Cymel 506, 508; carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated etoxy Methylated benzoguanamine; methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10; butoxymethylated benzoguanamine such
- Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like. More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication No. WO2011 / 132751.
- the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components.
- 0.1 to 50 parts by mass is more preferable, and 1 to 30 parts by mass is most preferable, with respect to 100 parts by mass of all polymer components.
- the nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] can also be added to the liquid crystal aligning agent.
- This amine compound may be added directly to the liquid crystal aligning agent, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent.
- the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific cellulose polymer and the specific polysiloxane polymer.
- coating a liquid crystal aligning agent, and surface smoothness can be used for a liquid-crystal aligning agent, unless the effect of this invention is impaired.
- a compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate can also be used.
- the compound that improves the film thickness uniformity and surface smoothness of the vertical liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
- F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.
- the compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
- the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the liquid crystal aligning agent may be deteriorated.
- the liquid crystal alignment treatment agent includes a dielectric material for changing the electrical properties such as the dielectric constant and conductivity of the vertical liquid crystal alignment film, as long as the effects of the present invention are not impaired. A conductive substance may be added.
- the liquid crystal composition in the present invention is a liquid crystal composition containing at least a liquid crystal and a polymerizable compound that undergoes a polymerization reaction with ultraviolet rays.
- nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used.
- those having negative dielectric anisotropy are preferable.
- those having a large dielectric anisotropy and a large refractive index anisotropy are preferred.
- two or more kinds of liquid crystals can be mixed and used according to the respective physical property values of the phase transition temperature, dielectric anisotropy and refractive index anisotropy.
- liquid crystal display element As an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also referred to as VHR). Therefore, as the liquid crystal, it is preferable to use a fluorine-based or chlorine-based liquid crystal that has high electrical resistance and does not decrease VHR due to active energy rays such as ultraviolet rays. Furthermore, the liquid crystal display element can also be made into a guest-host type element by dissolving a dichroic dye in a liquid crystal composition. In this case, an element is obtained that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied.
- the direction of the liquid crystal director (orientation direction) changes by 90 degrees depending on the presence or absence of voltage application. Therefore, this liquid crystal display element can obtain a higher contrast than the conventional guest-host type element that switches between random alignment and vertical alignment by utilizing the difference in light absorption characteristics of the dichroic dye.
- the liquid crystal is colored when aligned in the horizontal direction and becomes opaque only in the scattering state. Therefore, as the voltage is applied, it is possible to obtain an element that switches from colorless and transparent when no voltage is applied to a colored opaque and colored transparent state.
- Any polymerizable compound may be used as long as it can form a cured product of the liquid crystal composition (for example, a polymer network) by a polymerization reaction with ultraviolet rays.
- a monomer of the polymerizable compound may be introduced into the liquid crystal composition, or a polymer obtained by polymerizing this monomer in advance may be introduced into the liquid crystal composition.
- a polymer even when a polymer is used, it is necessary to have a site that undergoes a polymerization reaction with ultraviolet rays.
- a monomer is introduced into the liquid crystal composition, and irradiation of ultraviolet rays at the time of preparing the liquid crystal display device is performed.
- a method of forming a cured product by polymerization reaction is preferred.
- the polymerizable compound may be any compound as long as it dissolves in the liquid crystal.
- the polymerizable compound is not particularly limited as long as it is a compound that causes a polymerization reaction by ultraviolet rays. At that time, the polymerization may proceed in any reaction form to form a cured product (cured product composite) of the liquid crystal composition.
- Specific reaction formats include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction.
- the reaction form of a polymeric compound is radical polymerization.
- the following radical type polymerizable compounds (monomers) and oligomers thereof can be used as the polymerizable compounds. Further, as described above, a polymer obtained by polymerizing these monomers can also be used.
- monofunctional polymerizable compounds examples include 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate 2-ethoxyethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl Acrylate, lauryl acrylate, morpholine acrylate, phenoxyethyl acrylate, phenoxy Xydiethylene glycol acrylate
- bipolymerizable compound examples include 4,4′-diaacryloyloxystilbene, 4,4′-diaacryloyloxydimethylstilbene, 4,4′-diacryloyloxydiethylstilbene, 4 , 4'-Diacryloyloxydipropylstilbene, 4,4'-Diacryloyloxydibutylstilbene, 4,4'-Diacryloyloxydipentylstilbene, 4,4'-Diacryloyloxydihexylstilbene, 4,4'-di Acryloyloxydifluorostilbene, 2,2,3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate Acrylate, diethylene glycol dimethacrylate, 1,4-butane All dimethacrylate, 1,3-but
- polyfunctional polymerizable compound also referred to as polyfunctional monomer
- examples of the polyfunctional polymerizable compound include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy.
- Pentaacrylate trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate or 2,2,3,3,4,4 -Hexafluoropentanediol-1,5-dimeta Relate, or the like of these oligomers and the like.
- the radical type polymerizable compound may be used alone or in combination of two or more depending on the optical characteristics of the liquid crystal display element and the adhesion characteristics between the liquid crystal layer and the vertical liquid crystal alignment film.
- a radical initiator that generates radicals by ultraviolet rays (also referred to as a polymerization initiator) is introduced into the liquid crystal composition for the purpose of promoting radical polymerization of the polymerizable compound. It is preferable.
- tert-butylperoxy-iso-butarate 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ ⁇ - (tert-butyldioxy) -iso-propoxy] benzene, Di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, ⁇ - (iso-propylphenyl) -iso-propyl hydroperoxide, 2,5-dimethylhexane , Tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) valerate, cyclohexanone peroxide, 2 , 2 ', 5,5'-tetra (tert-butyl peroxid
- the polymerizable compound the following ionic polymerizable compounds can also be used. Specifically, it is a compound having at least one cross-linking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. More specifically, a melamine derivative, a benzoguanamine derivative, glycoluril, etc. in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group or both are mentioned. These melamine derivatives and benzoguanamine derivatives may be oligomers. These preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring.
- melamine derivatives and benzoguanamine derivatives include, for example, MX-750 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring in the commercial product; methoxymethyl per triazine ring MW-30 with an average of 5.8 groups substituted (manufactured by Sanwa Chemical Co., Ltd.); methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated butoxymethylated melamines such as Cymel 235, 236, 238, 212, 253, 254; butoxymethylated melamines such as Cymel 506, 508; methoxymethylated isobutoxymethylated containing carboxyl groups such as Cymel 1141; Melamine; Metoki like Cymel 1123 Methylated ethoxymethylated benzoguanamine; methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, but
- Examples of the benzene having a hydroxyl group or an alkoxyl group or a phenolic compound include 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis. (Sec-butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
- a compound containing an epoxy group or an isocyanate group and having a crosslinking group can also be used as the ionic polymerizable compound.
- an ion initiator that generates an acid or a base by the following ultraviolet rays can be introduced for the purpose of promoting the polymerization reaction.
- a triazine compound, an acetophenone derivative compound, a disulfone compound, a diazomethane compound, a sulfonic acid derivative compound, a diaryliodonium salt, a triarylsulfonium salt, a triarylphosphonium salt, an iron arene complex, or the like may be used. However, it is not limited to these.
- diphenyl iodonium chloride diphenyl iodonium trifluoromethanesulfonate
- diphenyl iodonium mesylate diphenyl iodonium tosylate
- diphenyl iodonium bromide diphenyl iodonium tetrafluoroborate
- diphenyl iodonium hexafluoroantimonate diphenyl iodonium hexafluoroarsenate.
- the amount of the polymerizable compound introduced into the liquid crystal composition is not particularly limited, but when the amount of the polymerizable compound introduced is large, the polymerizable compound does not dissolve in the liquid crystal or the temperature at which the liquid crystal composition exhibits a liquid crystal phase. Or the change between the transparent state and the scattering state of the element becomes small, and the optical characteristics deteriorate. Further, when the amount of the polymerizable compound introduced is small, the curability of the liquid crystal layer is lowered, and further, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered, and the liquid crystal orientation is not affected by mechanical external pressure. It becomes easy to get confused.
- the introduction amount of the polymerizable compound is preferably 1 to 50 parts by mass, and more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the liquid crystal. Particularly preferred is 11 to 30 parts by mass. Further, the amount of the radical initiator or ionic initiator that promotes the reaction of the polymerizable compound is not particularly limited, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal. 0.05 to 5 parts by mass is more preferable. Particularly preferred is 0.05 to 3 parts by mass.
- the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate.
- a plastic substrate such as an acrylic substrate, a polycarbonate substrate, and a PET (polyethylene terephthalate) substrate, and those The film can be used.
- a plastic substrate or a film is preferable.
- a substrate on which a metal or dielectric multilayer film such as a silicon wafer or aluminum is formed can be used as long as the substrate is only on one side.
- the substrates has a vertical liquid crystal alignment film that vertically aligns liquid crystal molecules.
- This vertical liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate and baking it, followed by alignment treatment by rubbing treatment or light irradiation.
- the vertical liquid crystal alignment film in the present invention can be used as the vertical liquid crystal alignment film without these alignment treatments.
- the application method of the liquid crystal aligning agent is not particularly limited, but industrially includes screen printing, offset printing, flexographic printing, ink jet method, dipping method, roll coater method, slit coater method, spinner method, spray method, etc. Depending on the kind of the substrate and the desired thickness of the vertical liquid crystal alignment film, it can be appropriately selected.
- the liquid crystal alignment treatment agent After the liquid crystal alignment treatment agent is applied on the substrate, it is heated by a heating means such as a hot plate, a heat circulation oven, an IR (infrared) oven, etc., depending on the type of the substrate and the solvent used for the liquid crystal alignment treatment agent.
- the vertical liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 300 ° C., preferably 30 to 250 ° C.
- the treatment is preferably performed at a temperature of 30 to 150 ° C.
- the thickness of the vertical liquid crystal alignment film after firing is preferably 5 to 500 nm because if it is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the element may be lowered. More preferably, it is 10 to 300 nm, and particularly preferably 10 to 250 nm.
- the liquid crystal composition used in the liquid crystal display element of the present invention is the liquid crystal composition as described above, and a spacer for controlling the electrode gap (also referred to as a gap) of the liquid crystal display element may be introduced therein. it can.
- the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when a glass substrate is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed is prepared, and a sealant is applied to four pieces of one side of the substrate except for a part, and then the vertical liquid crystal alignment film is formed. An empty cell is manufactured by attaching the substrate on the other side so that the surface is on the inside. A method of obtaining a liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied can be mentioned.
- a plastic substrate or film is used as the substrate, a pair of substrates with a vertical liquid crystal alignment film is prepared, and the liquid crystal composition is formed on one substrate by ODF (One Drop Filling) method or inkjet method.
- ODF One Drop Filling
- a liquid crystal composition injection cell is obtained by dropping an object and then bonding the other substrate together.
- the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, it is not necessary to apply the sealing agent to the four pieces of the substrate.
- the gap of the liquid crystal display element can be controlled by the spacer or the like.
- Examples of the method include a method of introducing a spacer having a target size into the liquid crystal composition as described above, and a method of using a substrate having a column spacer having a target size.
- the gap can be controlled without introducing a spacer.
- the size of the gap of the liquid crystal display element is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m. Particularly preferred is 5 to 20 ⁇ m. If the gap is too small, the contrast of the liquid crystal display element is lowered. If the gap is too large, the driving voltage of the element is increased.
- the liquid crystal display element of the present invention can be obtained by curing the liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of liquid crystal and a polymerizable compound.
- the liquid crystal composition is cured by at least one of ultraviolet irradiation and heating in the liquid crystal composition injection cell.
- the light source of the ultraviolet irradiation device used at that time include a metal halide lamp and a high-pressure mercury lamp.
- the wavelength of ultraviolet light is preferably 250 to 400 nm. Of these, 310 to 370 nm is preferable.
- the temperature is 40 to 120 ° C., preferably 60 to 80 ° C. Further, both the ultraviolet treatment and the heat treatment may be performed simultaneously, or the heat treatment may be performed after the ultraviolet treatment. In the present invention, it is preferable to cure the liquid crystal composition only by ultraviolet treatment.
- a liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polysiloxane polymer having a side chain having a specific structure is a liquid crystal display element.
- this device can be suitably used for reverse-type devices that become transparent when no voltage is applied, and scatter when voltage is applied, and control the transmission and blocking of light for display purposes. It is useful as a light control window or an optical shutter element.
- the liquid crystal display element of the present invention is a liquid crystal display element used in transportation equipment and transportation machines such as automobiles, railways, and aircrafts, specifically, light used for light control windows and room mirrors that control transmission and blocking of light. It can be suitably used for a shutter element or the like.
- this element has good transparency when no voltage is applied and good scattering characteristics when a voltage is applied, so when used for a glass window of a vehicle, compared to using a conventional reverse type element, The efficiency of taking in light at night is high, and the effect of preventing glare from outside light is also enhanced. Therefore, it is possible to further improve the safety when driving a vehicle and the comfort when riding.
- this element is made of film and pasted on a vehicle glass window, the low reverse adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is less likely to cause defects and deterioration. Reliability is higher than
- the liquid crystal display element of the present invention can be used for a light guide plate of a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode) display, or a back plate of a transparent display using these displays.
- a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode) display
- a back plate of a transparent display using these displays a back plate of a transparent display using these displays.
- CE-1 Hydroxyethyl cellulose (manufactured by WAKO)
- CE-2 Hydroxypropyl methylcellulose phthalate (manufactured by ACROS) (Alkoxysilane monomer)
- E1 alkoxysilane represented by the following formula [E1]
- E2 octadecyltriethoxysilane
- E3 3-methacryloxypropyltrimethoxysilane
- E4 3-ureidopropyltriethoxysilane
- E5 tetraethoxysilane
- S1 Photoradical generator represented by the following formula [S1]
- S2 Photoradical generator represented by the following formula [S2]
- ⁇ Synthesis Example 3> Prepare a solution of alkoxysilane monomer by mixing ECS (29.2 g), E1 (4.10 g) and E5 (38.8 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, a solution prepared by mixing ECS (12.1 g), water (10.8 g) and oxalic acid (0.50 g) as a catalyst in advance at 25 ° C. was added dropwise over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes.
- Examples 1 to 15 and Comparative Examples 1 to 5 are production examples of a liquid crystal alignment treatment agent. This liquid crystal alignment treatment agent was also used for the production of a liquid crystal display element and its evaluation. Tables 2 to 4 collectively show the liquid crystal aligning agents obtained in the examples and comparative examples, composition ratios, and the like.
- the liquid crystal display element before processing was obtained.
- the liquid crystal display element before this treatment was irradiated with ultraviolet rays of 7 J / cm 2 in terms of 365 nm using a metal halide lamp with an illuminance of 60 mW while cutting a wavelength of 350 nm or less.
- the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ° C. Thereby, a liquid crystal display element (reverse type element) was obtained.
- liquid crystal display elements plastic substrates
- the liquid crystal aligning agents obtained in Examples and Comparative Examples were pressure filtered through a membrane filter having a pore diameter of 1 ⁇ m to produce a liquid crystal display element.
- this liquid crystal aligning agent is washed with pure water on a 150 ⁇ 150 mm PET (polyethylene terephthalate) substrate with ITO electrodes (length: 150 mm, width: 150 mm, thickness: 0.2 mm) on the ITO surface.
- An ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm is coated with a bar coater and heat-treated on a hot plate at 100 ° C. for 5 minutes and in a heat-circulating clean oven at 150 ° C. for 1 minute.
- the liquid crystal display element before this treatment was irradiated with ultraviolet rays of 7 J / cm 2 in terms of 365 nm using a metal halide lamp with an illuminance of 60 mW while cutting a wavelength of 350 nm or less.
- the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ° C. Thereby, a liquid crystal display element (reverse type element) was obtained.
- the evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better the evaluation (the transmittance values are shown in Tables 8 to 10).
- the scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element by AC driving and visually observing the alignment state of the liquid crystal. Specifically, a device in which the element was clouded, that is, a device having a scattering characteristic, was considered excellent in the present evaluation (good display in Tables 8 to 10).
- the evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better this evaluation was (the transmittance values are shown in Tables 8 and 9).
- the scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element by AC driving and visually observing the alignment state of the liquid crystal. Specifically, the element in which the element was clouded, that is, the element in which the scattering characteristics were obtained was considered to be excellent in the present evaluation (good display in Tables 8 and 9).
- Example 1 EC-2 (11.0 g) and PB (14.2 g) were added to CE-2 (1.10 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (1) (13.8 g) obtained in Synthesis Example 1 was added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (1).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 2 Using the liquid crystal aligning agent (1) obtained in Example 1 and the liquid crystal composition (2), a liquid crystal display element (glass substrate, plastic substrate) was produced and evaluated.
- Example 3> To CE-2 (1.40 g), ECS (15.1 g), PGME (15.1 g) and BCS (10.7 g) were added and stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (1) (14.3 g), S2 (0.156 g) and M2 (0.467 g) obtained in Synthesis Example 1 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours.
- a liquid crystal aligning agent (2) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 4 EC-2 (1.63 g), BCS (6.00 g) and EC (5.30 g) were added to CE-2 (1.65 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (1) (13.8 g), S1 (0.165 g) and M2 (0.165 g) obtained in Synthesis Example 1 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (3) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 5 PGME (28.7 g), BCS (5.70 g) and EC (5.70 g) were added to CE-2 (1.00 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (19.4 g) obtained in Synthesis Example 2 was added to this solution and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (4).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 6 PGME (21.8 g), ECS (10.9 g) and EC (5.40 g) were added to CE-2 (0.95 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (18.5 g), S2 (0.159 g) and M1 (0.634 g) obtained in Synthesis Example 2 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (5) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 7 PGME (27.9 g) and BCS (8.60 g) were added to CE-1 (0.50 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (23.6 g), S2 (0.233 g) and M3 (0.500 g) obtained in Synthesis Example 2 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (6) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 8 PGME (28.4 g) and PB (8.40 g) were added to CE-1 (0.65 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (21.7 g), S2 (0.033 g), M2 (0.975 g) and K1 (0.163 g) obtained in Synthesis Example 2 were added to this solution at 25 ° C. Was stirred for 5 hours to obtain a liquid crystal aligning agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 9 EC-2 (11.0 g) and PB (14.2 g) were added to CE-2 (1.10 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, to this solution, the polysiloxane solution (3) (13.8 g) obtained in Synthesis Example 3 was added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 10 Using the liquid crystal aligning agent (8) obtained in Example 9 and the liquid crystal composition (2), a liquid crystal display element (glass substrate, plastic substrate) was produced and evaluated.
- Example 12 To CE-2 (1.65 g), ECS (17.8 g), PGME (17.8 g) and EC (5.30 g) were added and stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (3) (11.3 g) obtained in Synthesis Example 3 was added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (10). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 13 PGME (25.6 g) and BCS (11.2 g) were added to CE-2 (0.65 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (4) (21.7 g) obtained in Synthesis Example 4 was added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 14 PGME (34.3 g) and PB (11.7 g) were added to CE-2 (1.70 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (4) (14.2 g), S1 (0.170 g) and M2 (0.170 g) obtained in Synthesis Example 4 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (12) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 15 PGME (22.2 g) and BCS (14.3 g) were added to CE-1 (0.50 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (4) (23.6 g) and M3 (0.666 g) obtained in Synthesis Example 4 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal alignment treatment agent (13). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Examples 1, 2, 4, 6, 7, 9, 10, 11, 12, and 14 are performed using both glass substrate elements and plastic substrate elements, and Examples 3, 5, 8, 13, 15 , And Comparative Examples 1 to 5 were conducted using glass substrate elements.
- the results of these evaluations are summarized in Table 5, Table 6, Table 7, Table 8, Table 9, and Table 10.
- the liquid crystal display element of the example has higher adhesion between the liquid crystal layer and the liquid crystal alignment film than the liquid crystal display element of the comparative example, and further, the vertical alignment property of the liquid crystal is high and good. Excellent optical characteristics, that is, transparency when no voltage was applied and scattering characteristics when a voltage was applied were good.
- the liquid crystal display element of the comparative example has poor adhesion between the liquid crystal layer and the liquid crystal alignment film, and bubbles are observed in the element after being stored in a high-temperature and high-humidity tank, or the liquid crystal layer and the vertical alignment film peel off. To be observed.
- liquid crystal display element of the comparative example disordered liquid crystal alignment due to insufficient vertical alignment of liquid crystal was observed after storage in a high temperature bath.
- Comparative Example 1 using a polysiloxane polymer that does not contain a specific side chain the liquid crystal was not vertically aligned.
- the liquid crystal display element of the present invention can be suitably used for a reverse type element that is in a transmission state when a voltage is applied and is in a scattering state when a voltage is applied. It is useful for light control windows and optical shutter elements that control the interruption.
- the liquid crystal display element of the present invention when it is made of a plastic substrate such as a film substrate, it can be used by being attached to a glass substrate or window glass used as a support.
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Abstract
Description
偏光板を用いずに光の利用効率の高い液晶表示素子として、液晶の透過状態(透明状態ともいう)と散乱状態との間でスイッチングを行う液晶表示素子があり、一般的には、高分子分散型液晶(PDLC(Polymer Dispersed Liquid Crystal))や高分子ネットワーク型液晶(PNLC(Polymer Network Liquid Crystal))を用いたものが知られている。
従来のPDLCやPNLCを用いた液晶表示素子としては、電圧無印加時に液晶分子がランダムな方向を向いているため、白濁(散乱)状態となり、電圧印加時には液晶が電界方向に配列し、光を透過して透過状態となるノーマル型素子が知られている。しかし、ノーマル型素子においては、透過状態を得るために常時電圧を印加しておく必要があるため、透明状態で使用される場合が多い用途、例えば窓ガラスで使用する場合には、消費電力が大きい。
ノーマル型素子に対して、電圧無印加時に透過状態となり、電圧印加時には、散乱状態になるリバース型素子が報告されている(特許文献1、2参照)。
そこで、本発明は、上記した特性を兼ね備えた液晶表示素子の提供を目的とする。すなわち、本発明の目的は、液晶の垂直配向性が高く、良好な光学特性、すなわち、電圧無印加時の透明性と電圧印加時の散乱特性が良好で、液晶層と垂直液晶配向膜との密着性が高い液晶表示素子を提供することである。さらに、本発明では、上記液晶表示素子のための液晶配向膜、及び該液晶配向膜の形成に用いる液晶配向処理剤を提供する。
(1)液晶と、活性エネルギー線又は熱により重合する重合性化合物とを含む液晶組成物が、電極を備えた2枚の基板の間に配置され、該基板の少なくとも一方に液晶配向膜を有し、前記液晶組成物の一部又は全体が液晶性を表す状態で硬化させることにより液晶と重合性化合物の硬化物複合体を形成させてなる液晶表示素子であり、前記液晶配向膜が、下記の成分(A)及び成分(B)を含有する液晶配向処理剤から形成されることを特徴とする液晶表示素子。
成分(A):下記の式[1]で表わされる構造を有するセルロース系重合体。
(3)前記成分(B)の式[2b]で示されるアルコキシシランが、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、ジメトキシメチルビニルシラン、トリエトキシビニルシラン、ビニルトリメトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、3-(トリエトキシシリル)プロピルメタクリレート、3-(トリメトキシシリル)プロピルアクリレート及び3-(トリメトキシシリル)プロピルメタクリレートからなる群から選ばれる少なくとも1種である上記(1)又は(2)に記載の液晶表示素子。
(5)前記成分(B)が、式[2a]で示されるアルコキシシランを重縮合させて得られるポリシロキサン、又は、式[2a]と、式[2b]若しくは式[2c]で示されるアルコキシシランとを重縮合させて得られるポリシロキサンである、上記(1)~(4)のいずれかに記載の液晶表示素子。
(7)前記溶媒として、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、4-ヒドロキシ-4-メチル-2-ペンタノン、1-ヘキサノール、シクロヘキサノール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールジメチルエーテル、フルフリルアルコール及び下記の式[A1]~式[A3]で示される溶媒からなる群から選ばれる少なくとも1つの溶媒を含有する上記(6)に記載の液晶表示素子。
(10)前記基板が、ガラス基板又はプラスチック基板である上記(1)~(9)のいずれかに記載の液晶表示素子。
(11)上記(1)~(10)のいずれかに記載の液晶表示素子に用いる液晶配向膜であり、前記成分(A)及び成分(B)を含有する液晶配向処理剤から形成される液晶配向膜。
(12)膜厚が、5~300nmである上記(11)に記載の液晶配向膜。
(13)前記の成分(A)及び成分(B)を含有する、上記(11)又は(12)に記載の液晶配向膜を形成するための液晶配向処理剤。
この特定セルロース系重合体は透明性が高い。そのため、液晶配向処理剤から得られる垂直液晶配向膜は、紫外線などの光を吸収しにくく、液晶表示素子を作製する際の活性エネルギー線の照射による液晶組成物中の重合性化合物の反応を促進することができる。
また、特定ポリシロキサン系重合体に含まれる特定側鎖構造の中で、式[2-1]で示される構造は、側鎖部位にベンゼン環、シクロヘキシル環及び複素環からなる群から選ばれる少なくとも1種の環状基、又はステロイド骨格を有する炭素数17~51の2価の有機基を有する。これらの環状基及び有機基の側鎖構造は、剛直な構造を示すことから、式[2-1]で示される特定側鎖構造を有する垂直液晶配向膜を用いた液晶表示素子は、高くて安定な液晶の垂直配向性を得ることができる。さらに、上記の理由で、式[2-1]で示される特定側鎖構造は、側鎖構造の導入量が少なくても高い垂直配向性を得ることができる。そのため、式[2-1]で示される特定側鎖構造を有する垂直液晶配向膜を用いた液晶表示素子は、液晶層と垂直液晶配向膜との密着性がより高いものとなる。
本発明の液晶表示素子は、特定セルロース系重合体及び特定側鎖構造を有する特定ポリシロキサン系重合体を含む液晶配向処理剤から得られる垂直液晶配向膜を用いており、液晶の垂直配向性が高く、良好な光学特性、すなわち、電圧無印加時の透明性と電圧印加時の散乱特性が良好で、さらには液晶層と垂直液晶配向膜との密着性が高い。
また、本発明の液晶表示素子は、電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に液晶及び紫外線により重合する重合性化合物を含む液晶組成物を配置し、さらに、基板の少なくとも一方が液晶を垂直に配向させるような液晶配向膜を有し、液晶組成物の一部又は全体が液晶性を示す状態で、紫外線を照射することで前記液晶組成物の硬化を行い、液晶と重合性化合物の硬化物複合体を形成させる工程を経て製造され、電圧無印加時に透過状態となり、電圧印加時には散乱状態になるリバース型素子として、好適に用いることができる。
特定セルロース系重合体は、下記の式[1]で示される構造の重合体である。
nは100~1000000の整数を示す。なかでも、特定セルロース系重合体の溶媒への溶解性や、液晶配向処理剤として調製した際の取り扱い性の点から、nは100~500,000が好ましい。より好ましいのは100~100,000である。
mは0~3の整数を示す。なかでも、0又は1の整数が好ましい。
X1、X2、X3、X4、X5及びX6は、それぞれ独立して、式[1a]~[1m]からなる群から選ばれる少なくとも1種の基を示すが、これらの基は、1種類であっても2種類以上であっても良い。特に、特定セルロース系重合体の溶媒への溶解性や液晶配向処理剤の塗布性の点から、2種類以上の複数種類を用いることが好ましい。
特に好ましくは、式[1a]と式[1b]~[1m]を用いることである。さらには、式[1a]と式[1c]、式[1d]、式[1e]、式[1h]又は式[1i]を用いることが好ましい。
例えば、セルロース、メチルセルロース、エチルセルロース、プロピルセルロース、ブチルセルロース、メチルエチルセルロース、アセチルセルロース、セルロースプロピオネート、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシブチルメチルセルロース、ヒドロキシプロピルメチルセルロースフタレート、メチルアミノセルロース、エチルアミノセルロース、プロピルアミノセルロース、ベンジルセルロース、トリベンゾイルセルロース、セルロースアセテートブチレート、セルロースアセテートプロピオネート、カルボキシメチルセルロース、カルボキシメチルエチルセルロース又はカルボキシメチルヒドロキシエチルセルロースなどが挙げられる。なかでも、メチルセルロース、エチルセルロース、プロピルセルロース、アセチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロースフタレート、ベンジルセルロース、セルロースアセテートプロピオネート、カルボキシメチルエチルセルロース又はカルボキシメチルヒドロキシエチルセルロースが好ましい。より好ましくは、メチルセルロース、エチルセルロース、アセチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロースフタレート又はカルボキシメチルエチルセルロースである。特に好ましくは、メチルセルロース、エチルセルロース、アセチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、エチルヒドロキシエチルセルロース又はヒドロキシプロピルメチルセルロースフタレートである。
例えば、式[1b]を導入する場合は、セルロースとベンジルクロリドとをアルカリ存在下で反応させる方法、
式[1c]を導入する場合は、セルロースとX7を有するハロゲン化合物とをアルカリ存在下で反応させる方法、
式[1d]を導入する場合は、セルロースとX8を有する酸クロリド化合物とをアルカリ存在下で反応させる方法やセルロースと無水酢酸とを反応させる方法、
式[1e]を導入する場合は、セルロースとX9-OHを有するハロゲン化合物とをアルカリ存在下で反応させる方法、
式[1f]を導入する場合は、セルロースとX10-COOHを有するハロゲン化合物とをアルカリ存在下で反応させる方法、
式[1g]を導入する場合は、セルロースとX11-NH2を有するハロゲン化合物とをアルカリ存在下で反応させる方法、
式[1h]を導入する場合は、セルロースとフタル酸とを反応させる方法、
式[1i]を導入する場合は、セルロースとX12とフタル酸骨格を有するハロゲン化合物とをアルカリ存在下で反応させる方法、
式[1k]を導入する場合は、セルロースと無水マレイン酸とを反応させる方法が挙げられる。
特定セルロース系重合体は、特定セルロース系重合体の溶媒への溶解性や液晶配向処理剤の塗布性、さらには、液晶表示素子の光学特性や液晶層と垂直液晶配向膜との密着性の特性に応じて、1種類又は2種類以上を混合して使用することができる。
ポリシロキサン系重合体は、下記の式[2a]で示されるアルコキシシラン、下記の式[2b]で示されるアルコキシシラン、及び下記の式[2c]で示されるアルコキシシランからなる群から選ばれる少なくとも1種を重縮合させて得られるポリシロキサンである。
A2は、水素原子又は炭素数1~5のアルキル基を示す。なかでも、水素原子又は炭素数1~3のアルキル基が好ましい。
A3は、炭素数1~5のアルキル基を示す。なかでも、重縮合の反応性の観点から、炭素数1~3のアルキル基が好ましい。
mは1又は2の整数を示す。なかでも、合成の観点から、1が好ましい。
nは0~2の整数を示す。
pは0~3の整数を示す。なかでも、重縮合の反応性の観点から、1~3の整数が好ましい。より好ましくは、2又は3である。
なお、m+n+pは4である。
Y3は、単結合、-(CH2)c-(cは1~15の整数である)、-O-、-CH2O-、-COO-及び-OCO-からなる群から選ばれる少なくとも1種の結合基を示す。なかでも、合成の容易さの点から、単結合、-(CH2)c-(cは1~15の整数である)、-O-、-CH2O-又は-COO-が好ましい。より好ましいのは、単結合、-(CH2)c-(cは1~10の整数である)、-O-、-CH2O-又は-COO-である。
Y5は、ベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも1種の2価の環状基を示し、これらの環状基上の任意の水素原子は、炭素数1~3のアルキル基、炭素数1~3のアルコキシル基、炭素数1~3のフッ素含有アルキル基、炭素数1~3のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。なかでも、ベンゼン環又はシクロへキサン環が好ましい。
nは0~4の整数を示す。なかでも、原料の入手性や合成の容易さの点から、0~3が好ましい。より好ましいのは、0~2である。
また、国際公開公報の各表に掲載される(2-605)~(2-629)における、ステロイド骨格を有する炭素数12~25の有機基は、いずれも、本発明のステロイド骨格を有する炭素数17~51の有機基に読み替えるものとする。
なかでも、(2-25)~(2-96)、(2-145)~(2-168)、(2-217)~(2-240)、(2-268)~(2-315)、(2-364)~(2-387)、(2-436)~(2-483)又は(2-603)~(2-615)の組み合わせが好ましい。特に好ましい組み合わせは、(2-49)~(2-96)、(2-145)~(2-168)、(2-217)~(2-240)、(2-603)~(2-606)、(2-607)~(2-609)、(2-611)、(2-612)又は(2-624)である。
Y8は、炭素数8~22のアルキル基又は炭素数6~18のフッ素含有アルキル基を示す。なかでも、炭素数8~18のアルキル基が好ましい。
本発明における特定側鎖構造としては、前記の通り、高くて安定な液晶の垂直配向性を得ることができる点から、式[2-1]で示される特定側鎖構造を用いることが好ましい。
上記の式[2a]で示されるアルコキシシランは、特定ポリシロキサン系重合体の溶媒への溶解性、液晶配向膜にした際の液晶の垂直配向性、さらには、液晶表示素子の光学特性などの特性に応じて、1種類又は2種類以上を混合して使用することができる。
B2は、水素原子又は炭素数1~5のアルキル基を示す。なかでも、水素原子又は炭素数1~3のアルキル基が好ましい。
mは1又は2の整数を示す。なかでも、合成の観点から、1が好ましい。
nは0~2の整数を示す。なかでも、0又は1が好ましい。
pは0~3の整数を示す。なかでも、重縮合の反応性の観点から、1~3の整数が好ましい。より好ましくは、2又は3である。
式[2b]中、m+n+pは4である。
さらに、熱により架橋反応が起こる3-グリシジルオキシプロピル(ジメトキシ)メチルシラン、3-グリシジルオキシプロピル(ジエトキシ)メチルシラン、3-グリシジルオキシプロピルトリメトキシシラン又は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が好ましい。
式[2b]で表わされるアルコキシシランは、特定ポリシロキサン系重合体の溶媒への溶解性、液晶配向膜にした際の液晶の垂直配向性、さらには、液晶表示素子の光学特性などの特性に応じて、1種類又は2種類以上を混合して使用することができる。
D2は、炭素数1~5のアルキル基を示す。なかでも、重縮合の反応性の観点から、炭素数1~3のアルキル基が好ましい。
nは0~3の整数を示す。なかでも、0又は1が好ましい。
式[2c]で表わされるアルコキシシランは、特定ポリシロキサン系重合体の溶媒への溶解性、液晶配向膜にした際の液晶の垂直配向性、さらには、液晶表示素子の光学特性などの特性に応じて、1種類又は2種類以上を混合して使用できる。
また、式[2b]で表わされるアルコキシシランは、すべてのアルコキシシラン中、1~70モル%であることが好ましい。なかでも、1~60モル%が好ましい。
さらに、式[2c]で表わされるアルコキシシランは、すべてのアルコキシシラン中、1~99モル%であることが好ましい。なかでも、1~80モル%が好ましい。
また、特定ポリシロキサン系重合体を重縮合する方法は特に限定されない。例えば、アルコキシシランをアルコール系溶媒やグリコール系溶媒中で、加水分解・重縮合反応させる方法が挙げられる。その際、加水分解・重縮合反応は、部分的に加水分解させても、完全に加水分解させてもよい。完全に加水分解する場合は、理論上、アルコキシシラン中のすべてのアルコキシ基の0.5倍モル量の水を加えれば良いが、0.5倍モル量よりも過剰量の水を加えることが好ましい。特定ポリシロキサン系重合体を得るためには、上記加水分解・重縮合反応に用いる水の量は、目的に応じて適宜選択することができるが、アルコキシシラン中のすべてのアルコキシ基の0.5~2.5倍モル量であることが好ましい。
さらに、アルコキシシランが溶解した溶液を加熱することでも、加水分解・重縮合反応を促進させることもできる。その際の加熱温度及び加熱時間は、目的に応じて適宜選択することができる。例えば、50℃で24時間加熱攪拌して、その後、還流条件下で1時間攪拌するなどの条件が挙げられる。
上記反応に用いる蓚酸の量は、アルコキシシラン中のすべてのアルコキシ基の1モルに対して、0.2~2.0モルとすることが好ましい。また、この反応は、溶液の温度が50~180℃で行うことができるが、溶媒の蒸発や揮散が起こらないように、還流下で数十分から数十時間で行うことが好ましい。
特定ポリシロキサン系重合体を調製する重縮合反応において、式[2a]、式[2b]及び式[2c]で示されるアルコキシシランを複数種用いる場合は、複数種のアルコキシシランを、あらかじめ混合した混合物を用いて反応しても、複数種のアルコキシシランを順次添加しながら反応してもよい。
本発明においては、前記方法で得られたポリシロキサン系重合体の溶液を、そのまま特定ポリシロキサン系重合体として用いても良いし、必要に応じて、前記方法で得られたポリシロキサン系重合体の溶液を濃縮したり、溶媒を加えて希釈したり、他の溶媒に置換して、特定ポリシロキサン系重合体として用いることもできる。
さらに、本発明においては、特定ポリシロキサン系重合体にポリシロキサン系重合体とそれ以外の重合体を用いる場合、ポリシロキサン系重合体にそれ以外の重合体を混合する前に、ポリシロキサン系重合体の重縮合反応の際に発生するアルコールを常圧又は減圧で留去しておくことが好ましい。
本発明における液晶配向処理剤は、液晶配向膜を形成するための塗布溶液であり、成分(A)である特定セルロース系重合体、成分(B)である前記式[2-1]及び式[2-2]で示される構造からなる群から選ばれる少なくとも1種の特定側鎖構造を有する特定ポリシロキサン系重合体及び溶媒を含有する塗布溶液である。
液晶配向処理剤における特定セルロース系重合体と特定ポリシロキサン系重合体の割合は、特定ポリシロキサン系重合体の1質量部に対して、特定セルロース系重合体の割合は、0.01~99質量部が好ましい。なかでも、0.1~9質量部がより好ましく、より好ましいのは、0.1~3質量部である。
それ以外の他の重合体の含有量は、特定セルロース系重合体及び特定ポリシロキサン系重合体を合わせたすべての重合体100質量部に対して、0.5~15質量部が好ましい。なかでも、1~10質量部が好ましい。
液晶配向処理剤に用いる溶媒は、特定セルロース系重合体及び特定ポリシロキサン系重合体を溶解させる溶媒であれば特に限定されない。
また、液晶配向処理剤に用いる溶媒は、特定ポリシロキサン系重合体の重縮合溶液をそのまま用いても良いし、特定ポリシロキサン系重合体の重縮合溶液に新たな溶媒を添加しても良く、さらには、特定ポリシロキサン系重合体の重縮合溶液を新たな溶媒に置換しても良い。新たな溶媒としては、特定セルロース系重合体及び特定ポリシロキサン系重合体を溶解させる溶媒であれば特に限定されない。下記に、その具体例を挙げるが、これらの例に限定されるものではない。
上記の溶媒は、特定セルロース系重合体及び特定ポリシロキサンの溶解性や、液晶配向処理剤を塗布した際の液晶配向膜の塗膜性や表面平滑性の特性に応じて、1種類又は2種類以上を混合して用いることができる。
これら式[B1]~[B8]で表わされる構造は、密着性化合物中に2個以上有することが好ましい。
式[a-3]中、A2は、水素原子又は炭素数1~3のアルキル基を示す。なかでも、密着性化合物の製造の容易さの点から、水素原子又は炭素数1~2のアルキル基が好ましい。より好ましくは、水素原子又はメチル基である。
式[a-5]、及び式[a-6]中、A3、A5、A6及びA9は、それぞれ独立して、水素原子又は炭素数1~3のアルキル基を示す。なかでも、密着性化合物の製造の容易さの点から、水素原子又は炭素数1~2のアルキル基が好ましい。より好ましくは、水素原子又はメチル基である。
式[a-5]、及び式[a-6]中、A4、A7及びA8は、それぞれ独立して、炭素数1~3のアルキレン基を示す。なかでも、密着性化合物の製造の容易さの点から、炭素数1~2のアルキレン基が好ましい。
式[6]中、M5は、前記式[b-1]~[b-8]で示される構造からなる群から選ばれる少なくとも1種の構造を示す。なかでも、密着性化合物の合成の容易さの点から、式[b-1]、式[b-2]又は式[b-6]で示される構造が好ましい。より好ましくは、式[b-1]又は式[b-2]で示される構造である。
式[6]中、nは1~3の整数を示す。なかでも、密着性化合物の合成の容易さの点から、1又は2が好ましい。より好ましいのは、1である。
式[6]中、mは1~3の整数を示す。なかでも、密着性化合物の合成の容易さの点から、1又は2が好ましい。
特定密着性化合物は、垂直液晶配向膜にした際の液晶の垂直配向性、さらには、液晶表示素子の光学特性などの特性に応じて、1種類又は2種類以上を混合して使用することができる。
光ラジカル発生剤としては、紫外線によりラジカルを発生するものであれば特に制限は無く、例えば、tert-ブチルペルオキシ-iso-ブタレート、2,5-ジメチル-2,5-ビス(ベンゾイルジオキシ)へキサン、1,4-ビス[α-(tert-ブチルジオキシ)-iso-プロポキシ]ベンゼン、ジ-tert-ブチルペルオキシド、2,5-ジメチル-2,5-ビス(tert-ブチルジオキシ)へキセンヒドロペルオキシド、α-(iso-プロピルフェニル)-iso-プロピルヒドロペルオキシド、2,5-ジメチルへキサン、tert-ブチルヒドロペルオキシド、1,1-ビス(tert-ブチルジオキシ)-3,3,5-トリメチルシクロへキサン、ブチル-4,4-ビス(tert-ブチルジオキシ)バレレート、シクロへキサノンペルオキシド、2,2’,5,5’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-アミルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ヘキシルペルオキシカルボニル)ベンゾフェノン、3,3’-ビス(tert-ブチルペルオキシカルボニル)-4,4’-ジカルボキシベンゾフェノン、tert-ブチルペルオキシベンゾエート、ジ-tert-ブチルジペルオキシイソフタレートなどの有機過酸化物;9,10-アントラキノン、1-クロロアントラキノン、2-クロロアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノンなどのキノン類;ベンゾインメチル、ベンゾインエチルエーテル、α-メチルベンゾイン、α-フェニルベンゾインなどのベンゾイン誘導体;などが挙げられる。
液晶配向処理剤における特定発生剤の含有量は、すべての重合体成分100質量部に対して、0.01~50質量部であることが好ましい。なかでも、架橋反応が進行し、目的の効果を発現させるためには、すべての重合体成分100質量部に対して0.01~30質量部がより好ましく、より好ましいのは、0.1~20質量部である。
特定発生剤は、垂直液晶配向膜にした際の液晶の垂直配向性、さらには、液晶表示素子の光学特性などの特性に応じて、1種類又は2種類以上を混合して使用することができる。
より具体的には、国際公開公報WO2011/132751の62頁~66頁に掲載される、式[6-1]~[6-48]で表わされる架橋性化合物が挙げられる。
垂直液晶配向膜の膜厚の均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤などが挙げられる。より具体的には、例えば、エフトップEF301、EF303、EF352(以上、トーケムプロダクツ社製)、メガファックF171、F173、R-30(以上、大日本インキ社製)、フロラードFC430、FC431(以上、住友スリーエム社製)、アサヒガードAG710、サーフロンS-382、SC101、SC102、SC103、SC104、SC105、SC106(以上、旭硝子社製)などが挙げられる。
これらの界面活性剤の使用割合は、液晶配向処理剤に含有されるすべての重合体成分100質量部に対して、好ましくは0.01~2質量部、より好ましくは0.01~1質量部である。
液晶配向処理剤には、上記以外の化合物の他に、本発明の効果が損なわれない範囲であれば、垂直液晶配向膜の誘電率や導電性などの電気特性を変化させる目的の誘電体や導電物質を添加してもよい。
本発明における液晶組成物は、少なくとも液晶及び紫外線により重合反応する重合性化合物が含まれる液晶組成物である。
液晶には、ネマチック液晶、スメクチック液晶又はコレステリック液晶を用いることができる。なかでも、負の誘電異方性を有するものが好ましい。また、低電圧駆動及び散乱特性の点からは、誘電率の異方性が大きく、屈折率の異方性が大きいものが好ましい。また、前記の相転移温度、誘電率異方性及び屈折率異方性の各物性値に応じて、2種類以上の液晶を混合して用いることができる。
さらに、液晶表示素子は、液晶組成物中に二色性染料を溶解させてゲストホスト型の素子とすることもできる。この場合には、電圧無印加時は透明で、電圧印加時に吸収(散乱)となる素子が得られる。また、この液晶表示素子では、液晶のダイレクターの方向(配向の方向)は、電圧印加の有無により90度変化する。そのため、この液晶表示素子は、二色性染料の吸光特性の違いを利用することで、ランダム配向と垂直配向でスイッチングを行う従来のゲストホスト型の素子に比べて、高いコントラストが得られる。また、二色性染料を溶解させたゲストホスト型の素子では、液晶が水平方向に配向した場合に有色となり、散乱状態においてのみ不透明となる。そのため、電圧を印加するにつれ、電圧無印加時の無色透明から有色不透明、有色透明の状態に切り替わる素子を得ることもできる。
また、重合性化合物は、液晶に溶解すれば、どのような化合物であってもよい。ただし、重合性化合物を液晶に溶解した際に、液晶組成物の一部又は全体が液晶相を示す温度が存在することが必要となる。液晶組成物の一部が液晶相を示す場合であっても、液晶表示素子を肉眼で確認して、素子内全体が、ほぼ一様な透明性と散乱特性が得られていれば良い。
なかでも、重合性化合物の反応形式は、ラジカル重合であることが好ましい。その際、重合性化合物としては、下記のラジカル型の重合性化合物(モノマー)及びそのオリゴマーを用いることができる。また、前記の通り、これらのモノマーを重合反応させたポリマーを用いることもできる。
上記のラジカル型の重合性化合物は、液晶表示素子の光学特性や液晶層と垂直液晶配向膜との密着性の特性に応じて、1種類又は2種類以上を混合して使用することもできる。
これらのラジカル開始剤は、液晶表示素子の光学特性や液晶層と垂直液晶配向膜との密着性の特性に応じて、1種類又は2種類以上を混合して使用することもできる。
より具体的には、アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換されたメラミン誘導体、ベンゾグアナミン誘導体、グリコールウリルなどが挙げられる。これらメラミン誘導体やベンゾグアナミン誘導体はオリゴマーであっても良い。また、これらはトリアジン環1個当たり、メチルール基又はアルコキシメチル基を平均3個以上6個未満有するものが好ましい。
また、イオン型の重合性化合物としては、エポキシ基やイソシアネート基を含有し、架橋形成基を有する化合物を用いることもできる。
より具体的には、例えば、ジフェニルヨードニウムクロライド、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムメシレート、ジフェニルヨードニウムトシレート、ジフェニルヨードニウムブロミド、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムヘキサフルオロアルセネート、ビス(p-tert-ブチルフェニル)ヨードニウムヘキサフルオロホスフェート、ビス(p-tert-ブチルフェニル)ヨードニウムメシレート、ビス(p-tert-ブチルフェニル)ヨードニウムトシレート、ビス(p-tert-ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート、ビス(p-tert-ブチルフェニル)ヨードニウムテトラフルオロボレート、ビス(p-tert-ブチルフェニル)ヨードニウムクロリド、ビス(p-クロロフェニル)ヨードニウムクロライド、ビス(p-クロロフェニル)ヨードニウムテトラフルオロボレート、トリフェニルスルホニウムクロリド、トリフェニルスルホニウムブロミド、トリ(p-メトキシフェニル)スルホニウムテトラフルオロボレート、トリ(p-メトキシフェニル)スルホニウムヘキサフルオロホスホネート、トリ(p-エトキシフェニル)スルホニウムテトラフルオロボレート、トリフェニルホスホニウムクロリド、トリフェニルホスホニウムブロミド、トリ(p-メトキシフェニル)ホスホニウムテトラフルオロボレート、トリ(p-メトキシフェニル)ホスホニウムヘキサフルオロホスホネート、トリ(p-エトキシフェニル)ホスホニウムテトラフルオロボレート、ビス[[(2-ニトロベンジル)オキシ]カルボニルへキサン-1,6-ジアミン]、ニトロベンジルシクロへキシルカルバメート、ジ(メトキシベンジル)ヘキサメチレンジカルバメート、ビス[[(2-ニトロベンジル)オキシ]カルボニルへキサン-1,6-ジアミン]、ニトロベンジルシクロへキシルカルバメート、ジ(メトキシベンジル)ヘキサメチレンジカルバメートなどが挙げられる。
本発明の液晶表示素子においては、光学特性の点から、上記の重合性化合物の中でラジカル型の重合性化合物を用いることが好ましい。
また、重合性化合物の反応を促進するラジカル開始剤又はイオン開始剤の導入量には特に制限は無いが、液晶100質量部に対して、0.01~10質量部であることが好ましく、0.05~5質量部がより好ましい。特に好ましくは、0.05~3質量部である
本発明の液晶表示素子に用いる基板としては、透明性の高い基板であれば特に限定されず、ガラス基板の他、アクリル基板、ポリカーボネート基板、PET(ポリエチレンテレフタレート)基板などのプラスチック基板、さらにはそれらのフィルムを用いることができる。液晶表示素子をリバース型素子として、調光窓などに用いる場合には、プラスチック基板やフィルムであることが好ましい。また、プロセスの簡素化の観点からは、液晶駆動のためのITO(Indium Tin Oxide)電極、IZO(Indium Zinc Oxide)電極、IGZO(Indium Gallium Zinc Oxide)電極、有機導電膜などが形成された基板を用いることが好ましい。また、反射型のリバース型素子とする場合には、片側の基板のみにならば、シリコンウエハやアルミニウムなどの金属や誘電体多層膜が形成された基板を使用することができる。
液晶配向処理剤の塗布方法は、特に限定されないが、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷、インクジェット法、ディップ法、ロールコータ法、スリットコータ法、スピンナー法、スプレー法などがあり、基板の種類や目的とする垂直液晶配向膜の膜厚に応じて、適宜選択することができる。
焼成後の垂直液晶配向膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると素子の信頼性が低下する場合があるので、好ましくは5~500nmである。より好ましくは10~300nmであり、特に好ましいのは、10~250nmである。
本発明の液晶表示素子に用いる液晶組成物は、前記の通りの液晶組成物であるが、そのなかに、液晶表示素子の電極間隙(ギャップともいう)を制御するためのスペーサーを導入することもできる。
本発明の液晶表示素子では、液晶層と垂直液晶配向膜との密着性が高いため、基板の4片にシール剤を塗布しなくても良い。
液晶表示素子のギャップの大きさは、1~100μmが好ましく、より好ましくは、2~50μmである。特に好ましくは、5~20μmである。ギャップが小さすぎると、液晶表示素子のコントラストが低下し、大きすぎると、素子の駆動電圧が高くなる。
その際に用いる紫外線照射装置の光源としては、例えば、メタルハライドランプ又は高圧水銀ランプが挙げられる。また、紫外線の波長は、250~400nmが好ましい。なかでも、310~370nmが好ましい。また、加熱処理の場合、その温度は、40~120℃、好ましくは60~80℃である。さらに、紫外線処理と加熱処理とを両方同時に行っても、紫外線処理をした後に加熱処理を行っても良い。本発明においては、液晶組成物の硬化は、紫外線処理のみが好ましい。
また、本発明の液晶表示素子は、自動車、鉄道、航空機などの輸送機器や輸送機械に用いる液晶表示素子、具体的には、光の透過と遮断を制御する調光窓やルームミラーに用いる光シャッター素子などに好適に用いることができる。特に、本素子は、電圧無印加時の透明性と電圧印加時の散乱特性が良好であることから、乗り物のガラス窓に使用した場合は、従来のリバース型素子を使用した場合に比べて、夜間時における光の取り入れ効率が高く、外光からの眩しさを防ぐ効果も高くなる。そのため、乗り物を運転する際の安全性や乗車時の快適性を、より改善することが可能となる。また、本素子をフィルムで作製して、乗り物のガラス窓に貼って使用する場合は、液晶層と垂直液晶配向膜との低密着性が要因の不良や劣化が起こりにくく、従来のリバース型素子に比べて信頼性が高くなる。
<液晶組成物>
(液晶) L1:MLC-6608(メルク社製)
(重合性化合物) R1:下記の式[R1]で示される化合物
(光開始剤) P1:下記の式[P1] で示される化合物
CE-1:ヒドロキシエチルセルロース(WAKO社製)
CE-2:ヒドロキシプロピルメチルセルロースフタレート(ACROS社製)
(アルコキシシランモノマー)
E1:下記の式[E1]で表わされるアルコキシシラン
E2:オクタデシルトリエトキシシラン
E3:3-メタクリロキシプロピルトリメトキシシラン
E4:3-ウレイドプロピルトリエトキシシラン
E5:テトラエトキシシラン
S1:下記の式[S1]で表わされる光ラジカル発生剤
S2:下記の式[S2]で表わされる光ラジカル発生剤
M1:下記の式[M1]で示される化合物
M2:下記の式[M2]で示される化合物
M3:下記の式[M3]で示される化合物
PGME:プロピレングリコールモノメチルエーテル
ECS:エチレングリコールモノエチルエーテル
BCS:エチレングリコールモノブチルエーテル
PB:プロピレングリコールモノブチルエーテル
EC:ジエチレングリコールモノエチルエーテル
<合成例1>
温度計及び還流管を備え付けた200mlの四つ口反応フラスコ中で、ECS(28.3g)、E1(4.10g)、E3(7.45g)及びE5(32.5g)を混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、あらかじめECS(14.2g)、水(10.8g)、触媒として蓚酸(0.70g)を混合して調製しておいた溶液を、25℃にて30分かけて滴下し、さらに25℃にて30分間撹拌した。その後、オイルバスを用いて加熱して30分間還流させた後、あらかじめ調製しておいたE4の含有量が92質量%のメタノール溶液(1.20g)とECS(0.90g)の混合溶液を加えた。さらに30分間還流させた後、放冷してSiO2換算濃度が12質量%のポリシロキサン溶液(1)を得た。
温度計及び還流管を備え付けた200mlの四つ口反応フラスコ中で、PGME(28.3g)、E1(8.20g)、E3(19.9g)及びE5(20.0g)を混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、あらかじめPGME(19.1g)、水(10.8g)、触媒として蓚酸(1.10g)を混合して調製しておいた溶液を、25℃にて30分かけて滴下し、さらに25℃にて30分間撹拌した。その後、オイルバスを用いて加熱して30分間還流させた後、あらかじめ調製しておいたE4の含有量92質量%のメタノール溶液(1.20g)とPGME(0.90g)の混合溶液を加えた。さらに30分間還流させた後、放冷してSiO2換算濃度が12質量%のポリシロキサン溶液(2)を得た。
温度計及び還流管を備え付けた200mlの四つ口反応フラスコ中で、ECS(29.2g)、E1(4.10g)及びE5(38.8g)を混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、あらかじめECS(12.1g)、水(10.8g)、触媒として蓚酸(0.50g)を混合して調製しておいた溶液を、25℃にて30分かけて滴下し、さらに25℃にて30分間撹拌した。その後、オイルバスを用いて加熱して30分間還流させた後、あらかじめ調製しておいたE4の含有量92質量%のメタノール溶液(1.20g)とECS(0.90g)の混合溶液を加えた。さらに30分間還流させた後、放冷してSiO2換算濃度が12質量%のポリシロキサン溶液(3)を得た。
温度計及び還流管を備え付けた200mlの四つ口反応フラスコ中で、PGME(28.3g)、E2(4.07g)、E3(7.45g)及びE5(32.5g)を混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、あらかじめPGME(14.2g)、水(10.8g)、触媒として蓚酸(0.70g)を混合して調製しておいた溶液を、25℃にて30分かけて滴下し、さらに25℃にて30分間撹拌した。その後、オイルバスを用いて加熱して30分間還流させた後、あらかじめ調製しておいたE4の含有量が92質量%のメタノール溶液(1.20g)とPGME(0.90g)の混合溶液を加えた。さらに30分間還流させた後、放冷してSiO2換算濃度が12質量%のポリシロキサン溶液(4)を得た。
温度計及び還流管を備え付けた200mlの四つ口反応フラスコ中で、ECS(27.7g)、E3(7.45g)及びE5(32.5g)を混合して、アルコキシシランモノマーの溶液を調製した。この溶液に、あらかじめECS(10.0g)、水(10.8g)及び触媒として蓚酸(0.70g)を混合して調製しておいた溶液を、25℃にて30分かけて滴下し、さらに25℃にて30分間撹拌した。その後、オイルバスを用いて加熱して30分間還流させた後、あらかじめ調製しておいたE4の含有量が92質量%のメタノール溶液(1.20g)とECS(0.90g)の混合溶液を加えた。さらに30分間還流させた後、放冷してSiO2換算濃度が12質量%のポリシロキサン溶液(5)を得た。
各合成例で得られたポリシロキサン系重合体(ポリシロキサン溶液)、及び用いたアルコキシシランモノマーの組成を表1に示す。
(液晶組成物(1)の作製)
L1(11.5g)、R1(1.73g)及びP1(0.12g)を混合し、80℃まで加熱し、その後25℃まで冷却して液晶組成物(1)を得た。
(液晶組成物(2)の作製)
L1(12.0g)、R1(2.40g)及びP1(0.12g)を混合し、80℃まで加熱し、その後25℃まで冷却して液晶組成物(2)を得た。
実施例1~15及び比較例1~5は、液晶配向処理剤の製造例であるが、この液晶配向処理剤は、液晶表示素子の作製及びその評価のためにも使用した。
実施例及び比較例で得られた液晶配向処理剤、組成物含有割合等をまとめて表2~4に示す。
実施例及び比較例で得られた液晶配向処理剤を、細孔径1μmのメンブランフィルタで加圧濾過し、液晶表示素子の作製を行った。具体的には、この液晶配向処理剤を、純水及びIPA(イソプロピルアルコール)で洗浄した100×100mmのITO電極付きガラス基板(縦:100mm、横:100mm、厚さ:0.7mm)のITO面上にスピンコートし、ホットプレート上にて100℃で5分間、熱循環型クリーンオーブンにて200℃で15分間加熱処理をして、膜厚が100nmの液晶配向膜付きのITO基板を得た。得られた液晶配向膜付きのITO基板を2枚用意し、その一方の基板の液晶配向膜面に、6μmのスペーサーを塗布した。その後、その基板のスペーサーを塗布した液晶配向膜面に、ODF(One Drop Filling)法にて前記液晶組成物を滴下し、次いで、他方の基板の液晶配向膜界面が向き合うように貼り合わせを行い、処理前の液晶表示素子を得た。
この処理前の液晶表示素子に、照度60mWのメタルハライドランプを用いて、350nm以下の波長をカットし、365nm換算で7J/cm2の紫外線照射を行った。この際、液晶セルに紫外線を照射している際の照射装置内の温度は、25℃に制御した。これにより、液晶表示素子(リバース型素子)を得た。
実施例及び比較例で得られた液晶配向処理剤を、細孔径1μmのメンブランフィルタで加圧濾過し、液晶表示素子の作製を行った。具体的には、この液晶配向処理剤を、純水で洗浄した150×150mmのITO電極付きPET(ポリエチレンテレフタレート)基板(縦:150mm、横:150mm、厚さ:0.2mm)のITO面上にバーコーターにて塗布をし、ホットプレート上にて100℃で5分間、熱循環型クリーンオーブンにて150℃で1分間加熱処理をして、膜厚が100nmの液晶配向膜付きのITO基板を得た。得られた液晶配向膜付きのITO基板を2枚用意し、その一方の基板の液晶配向膜面に、6μmのスペーサーを塗布した。その後、その基板のスペーサーを塗布した液晶配向膜面に、ODF法にて前記液晶組成物を滴下し、次いで、他方の基板の液晶配向膜界面が向き合うように貼り合わせを行い、処理前の液晶表示素子を得た。
この処理前の液晶表示素子に、照度60mWのメタルハライドランプを用いて、350nm以下の波長をカットし、365nm換算で7J/cm2の紫外線照射を行った。この際、液晶セルに紫外線を照射している際の照射装置内の温度は、25℃に制御した。これにより、液晶表示素子(リバース型素子)を得た。
上記手法で得られた液晶表示素子(ガラス基板)を用いて、液晶配向性の評価を行った。液晶配向性は、本素子を偏光顕微鏡(ECLIPSE E600WPOL、ニコン社製)で観察し、液晶が垂直に配向しているかどうかを確認した。具体的には、液晶が垂直に配向しているものを、本評価に優れるとした(表5~表7中の良好表示)。
その後、液晶配向性の評価が終了した液晶表示素子(ガラス基板)を、温度100℃の高温槽内に336時間保管した。その後、上記と同様の条件で、液晶配向性の評価を行った。具体的には、液晶配向性に乱れが見られず、均一に液晶が配向しているものを、本評価に優れるとした(表5~表7中の良好表示)
上記手法で得られた液晶表示素子(プラスチック基板)を用いて、液晶配向性の評価を行った。液晶配向性は、本素子を偏光顕微鏡(ECLIPSE E600WPOL、ニコン社製)で観察し、液晶が垂直に配向しているかどうかを確認した。具体的には、液晶が垂直に配向しているものを、本評価に優れるとした(表5及び表6中の良好表示)。
その後、液晶配向性の評価が終了した液晶表示素子(プラスチック基板)を、温度100℃の高温槽内に336時間保管した。その後、上記と同様の条件で、液晶配向性の評価を行った。具体的には、液晶配向性に乱れが見られず、均一に液晶が配向しているものを、本評価に優れるとした(表5及び表6中の良好表示)
上記手法で得られた液晶表示素子(ガラス基板)を用いて、光学特性(透明性と散乱特性)の評価を行った。
電圧無印加時の透明性は、電圧無印加状態での液晶表示素子の透過率を測定することで行った。具体的には、測定装置にUV-3600(島津製作所社製)、リファレンスに上記ITO電極付きガラス基板を用い、温度25℃、スキャン波長300~800nmの条件で透過率を測定した。評価は、450nmの波長の透過率で行い、透過率が高いものほど、本評価に優れるとした(表8~表10中に透過率の値を示した)。
電圧印加時の散乱特性は、液晶表示素子に、交流駆動で40Vを印加し、液晶の配向状態を目視観察することで行った。具体的には、本素子が白濁したもの、すなわち、散乱特性が得られたものを、本評価に優れるとした(表8~表10中の良好表示)。
上記手法で得られた液晶表示素子(プラスチック基板)を用いて、光学特性(透明性と散乱特性)の評価を行った。
電圧無印加時の透明性は、電圧無印加状態での液晶表示素子の透過率を測定することで行った。具体的には、測定装置にUV-3600(島津製作所社製)、リファレンスに上記ITO電極付きPET基板を用い、温度25℃、スキャン波長300~800nmの条件で透過率を測定した。評価は、450nmの波長の透過率で行い、透過率が高いものほど、本評価に優れるとした(表8及び表9中に透過率の値を示した)。
電圧印加時の散乱特性は、液晶表示素子に、交流駆動で40Vを印加し、液晶の配向状態を目視観察することで行った。具体的には、本素子が白濁したもの、すなわち、散乱特性が得られたものを、本評価に優れるとした(表8及び表9中の良好表示)。
上記光学特性の評価を行った液晶表示素子を用いて、液晶層と液晶配向膜との密着性の評価を行った。具体的には、液晶表示素子を、温度80℃、湿度90%RHの高温高湿槽内に96時間保管し、本素子内の気泡の有無及び素子の剥離を確認した。その際、本素子内に気泡が見られずに素子の剥離(液晶層と液晶配向膜とが剥がれている状態)が起こっていないものを、本評価に優れるとした(表8~表10中の良好表示)。
上記光学特性の評価を行った液晶表示素子を用いて、液晶層と液晶配向膜との密着性の評価を行った。具体的には、液晶表示素子を、温度80℃、湿度90%RHの高温高湿槽内に96時間保管し、本素子内の気泡の有無及び素子の剥離を確認した。その際、本素子内に気泡が見られずに素子の剥離(液晶層と液晶配向膜とが剥がれている状態)が起こっていないものを、本評価に優れるとした(表8及び表9中の良好表示)。
CE-2(1.10g)に、ECS(21.0g)及びPB(14.2g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例1で得られたポリシロキサン溶液(1)(13.8g)を加え、25℃で5時間攪拌して、液晶配向処理剤(1)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
実施例1で得られた液晶配向処理剤(1)と液晶組成物(2)を用いて、液晶表示素子(ガラス基板、プラスチック基板)を作製して評価した。
<実施例3>
CE-2(1.40g)に、ECS(15.1g)、PGME(15.1g)及びBCS(10.7g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例1で得られたポリシロキサン溶液(1)(14.3g)、S2(0.156g)及びM2(0.467g)を加え、25℃で5時間攪拌して、液晶配向処理剤(2)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(1.65g)に、ECS(33.3g)、BCS(6.00g)及びEC(5.30g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例1で得られたポリシロキサン溶液(1)(13.8g)、S1(0.165g)及びM2(0.165g)を加え、25℃で5時間攪拌して、液晶配向処理剤(3)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(1.00g)に、PGME(28.7g)、BCS(5.70g)及びEC(5.70g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例2で得られたポリシロキサン溶液(2)(19.4g)を加え、25℃で5時間攪拌して、液晶配向処理剤(4)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(0.95g)に、PGME(21.8g)、ECS(10.9g)及びEC(5.40g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例2で得られたポリシロキサン溶液(2)(18.5g)、S2(0.159g)及びM1(0.634g)を加え、25℃で5時間攪拌して、液晶配向処理剤(5)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-1(0.50g)に、PGME(27.9g)及びBCS(8.60g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例2で得られたポリシロキサン溶液(2)(23.6g)、S2(0.233g)及びM3(0.500g)を加え、25℃で5時間攪拌して、液晶配向処理剤(6)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-1(0.65g)に、PGME(28.4g)及びPB(8.40g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例2で得られたポリシロキサン溶液(2)(21.7g)、S2(0.033g)、M2(0.975g)及びK1(0.163g)を加え、25℃で5時間攪拌して、液晶配向処理剤(7)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(1.10g)に、ECS(21.0g)及びPB(14.2g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例3で得られたポリシロキサン溶液(3)(13.8g)を加え、25℃で5時間攪拌して、液晶配向処理剤(8)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
実施例9で得られた液晶配向処理剤(8)と液晶組成物(2)を用いて、液晶表示素子子(ガラス基板、プラスチック基板)を作製して評価した。
<実施例11>
CE-2(1.40g)に、ECS(35.6g)及びEC(5.30g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例3で得られたポリシロキサン溶液(3)(14.3g)、S2(0.311g)、M2(0.778g)及びK1(0.062g)を加え、25℃で5時間攪拌して、液晶配向処理剤(9)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(1.65g)に、ECS(17.8g)、PGME(17.8g)及びEC(5.30g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例3で得られたポリシロキサン溶液(3)(11.3g)を加え、25℃で5時間攪拌して、液晶配向処理剤(10)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(0.65g)に、PGME(25.6g)及びBCS(11.2g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例4で得られたポリシロキサン溶液(4)(21.7g)を加え、25℃で5時間攪拌して、液晶配向処理剤(11)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-2(1.70g)に、PGME(34.3g)及びPB(11.7g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例4で得られたポリシロキサン溶液(4)(14.2g)、S1(0.170g)及びM2(0.170g)を加え、25℃で5時間攪拌して、液晶配向処理剤(12)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
CE-1(0.50g)に、PGME(22.2g)及びBCS(14.3g)を加え、50℃で5時間攪拌した。その後、この溶液に、合成例4で得られたポリシロキサン溶液(4)(23.6g)及びM3(0.666g)を加え、25℃で5時間攪拌して、液晶配向処理剤(13)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリシロキサン溶液(5)(15.0g)に、ECS(6.50g)及びPB(8.50g)を加え、25℃で5時間攪拌して、液晶配向処理剤(14)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例1で得られたポリシロキサン溶液(1)(15.5g)に、ECS(6.80g)及びPB(8.70g)を加え、25℃で5時間攪拌して、液晶配向処理剤(15)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
比較例2で得られた液晶配向処理剤(15)と液晶組成物(2)を用いて、液晶表示素子の作製(ガラス基板)、液晶配向性の評価(ガラス基板)、光学特性(透過率と散乱特性)の評価(ガラス基板)、及び液晶層と液晶配向膜との密着性の評価(ガラス基板)を行った。
合成例3で得られたポリシロキサン溶液(3)(15.0g)に、ECS(6.50g)及びPB(8.50g)を加え、25℃で5時間攪拌して、液晶配向処理剤(16)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
比較例4で得られた液晶配向処理剤(16)と液晶組成物(2)を用いて、液晶表示素子(ガラス基板)を作製して評価した。
下記の表5、表6、表7、表8、表9及び表10に示すように、上記実施例でそれぞれ得られた液晶配向処理剤(1)~(13)又は比較例でそれぞれ得られた液晶配向処理剤(14)~(16)のいずれかと、前記の液晶組成物(1)又は(2)を用いて、前記した液晶表示素子の作製及び液晶配向性の評価、光学特性(透明性と散乱特性)の評価、及び液晶層と垂直液晶配向膜との密着性の評価を行った。
なお、実施例1、2、4、6、7、9、10、11、12及び14は、ガラス基板の素子とプラスチック基板の素子の両方で行い、実施例3、5、8、13、15、及び比較例1~5は、ガラス基板の素子で行った。これらの評価の結果を表5、表6、表7、表8、表9及び表10にまとめて示した。
*2:液晶配向性に乱れが見られた。
*3:液晶が垂直に配向していないため、測定できなかった。
*4:素子が、液晶層と液晶配向膜との間で剥離した。
*5:素子内に、気泡が見られた。
一方で、比較例の液晶表示素子は、液晶層と液晶配向膜との密着性が悪く、高温高湿槽に保管した後に素子内に気泡が見られたり、液晶層と垂直配向膜とが剥離することが観察された。また、比較例の液晶表示素子では、高温槽に保管した後に、液晶の垂直配向性不足に伴う液晶配向性の乱れが見られた。
具体的には、同一の特定ポリシロキサン系重合体を含み、成分(A)である特定セルロース系重合体を含む実施例と含まない比較例、すなわち、実施例1と比較例2、実施例2と比較例3、実施例9と比較例4、及び実施例10と比較例5との比較では、明確な差が認められた。
また、特定側鎖を含まないポリシロキサン系重合体を用いた比較例1では、液晶が垂直配向しなかった。
さらに、液晶配向処理剤に、特定発生剤、特定密着性化合物及び特定架橋性化合物を導入した場合、形成された液晶表示素子において、液晶層と垂直液晶配向膜との密着性が、より良好であった。具体的には、実施例2と実施例3及び実施例9と実施例11との比較で、明確な差が認められた。
なお、2013年7月19日に出願された日本特許出願2013-150498号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (13)
- 液晶と、活性エネルギー線又は熱により重合する重合性化合物とを含む液晶組成物が、電極を備えた2枚の基板の間に配置され、該基板の少なくとも一方に液晶配向膜を有し、前記液晶組成物の一部又は全体が液晶性を表す状態で硬化させることにより液晶と重合性化合物の硬化物複合体を形成させてなる液晶表示素子であり、前記液晶配向膜が下記の成分(A)及び成分(B)を含有する液晶配向処理剤から形成されることを特徴とする液晶表示素子。
成分(A):下記の式[1]で表わされる構造を有するセルロース系重合体。
(X1、X2、X3、X4、X5及びX6は、それぞれ独立して、下記の式[1a]~[1m]からなる群から選ばれる少なくとも1種の基を示す。nは100~1000000の整数を示す。)
(X7、X8、X9、X10、X11、X12、X13、及びX14は、それぞれ独立して、ベンゼン環、メチル基、エチル基、n-プロピル基、イソプロピル基及びブチル基からなる群から選ばれる少なくとも1種を示す。nは0~3の整数を示す。mは0~3の整数を示す。)
成分(B):下記の式[2a]で示されるアルコキシシラン、下記の式[2b]で示されるアルコキシシラン、及び下記の式[2c]で示されるアルコキシシランからなる群から選ばれる少なくとも1種を重縮合させて得られるポリシロキサン系重合体。
(A1は、下記の式[2-1]及び式[2-2]で示される構造からなる群から選ばれる少なくとも1種の構造を示す。A2は、水素原子又は炭素数1~5のアルキル基を示す。A3は、炭素数1~5のアルキル基を示す。mは1又は2の整数を示す。nは0~2の整数を示す。pは0~3の整数を示す。ただし、m+n+pは4である。)
(Y1は、単結合、-(CH2)a-(aは1~15の整数である)、-O-、-CH2O-、-COO-及び-OCO-からなる群から選ばれる少なくとも1種を示す。Y2は、単結合又は-(CH2)b-(bは1~15の整数である)を示す。Y3は、単結合、-(CH2)c-(cは1~15の整数である)、-O-、-CH2O-、-COO-及び-OCO-からなる群から選ばれる少なくとも1種を示す。Y4は、ベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも1種の2価の環状基、又はステロイド骨格を有する炭素数17~51の2価の有機基を示し、前記環状基上の任意の水素原子は、炭素数1~3のアルキル基、炭素数1~3のアルコキシル基、炭素数1~3のフッ素含有アルキル基、炭素数1~3のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。Y5は、ベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも1種の環状基を示し、これらの環状基上の任意の水素原子は、炭素数1~3のアルキル基、炭素数1~3のアルコキシル基、炭素数1~3のフッ素含有アルキル基、炭素数1~3のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。nは0~4の整数を示す。Y6は、炭素数1~18のアルキル基、炭素数1~18のフッ素含有アルキル基、炭素数1~18のアルコキシル基及び炭素数1~18のフッ素含有アルコキシル基からなる群から選ばれる少なくとも1種を示す。nは0~4の整数を示す。)
(Y7は、単結合、-O-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3)CO-、-COO-及び-OCO-からなる群から選ばれる少なくとも1種の結合基を示す、Y8は、炭素数8~22のアルキル基又は炭素数6~18のフッ素含有アルキル基を示す。)
(B1は、ビニル基、エポキシ基、アミノ基、メルカプト基、イソシアネート基、メタクリル基、アクリル基、ウレイド基及びシンナモイル基からなる群から選ばれる少なくとも1種を有する炭素数2~12の有機基を示す。B2は、水素原子又は炭素数1~5のアルキル基を示す。B3は、炭素数1~5のアルキル基を示す。mは1又は2の整数を示す。nは0~2の整数を示す。pは0~3の整数を示す。ただし、m+n+pは4である。)
(D1は、水素原子又は炭素数1~5のアルキル基を示す。D2は、炭素数1~5のアルキル基を示す。nは0~3の整数を示す。) - 成分(A)と成分(B)の割合が、成分(B)の1質量部に対して、成分(A)が0.1~9質量部である請求項1に記載の液晶表示素子。
- 前記成分(B)の式[2b]で示されるアルコキシシランが、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、ジメトキシメチルビニルシラン、トリエトキシビニルシラン、ビニルトリメトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、3-(トリエトキシシリル)プロピルメタクリレート、3-(トリメトキシシリル)プロピルアクリレート及び3-(トリメトキシシリル)プロピルメタクリレートからなる群から選ばれる少なくとも1種である請求項1又は2に記載の液晶表示素子。
- 前記成分(B)の式[2b]で示されるアルコキシシランが、3-グリシジルオキシプロピル(ジメトキシ)メチルシラン、3-グリシジルオキシプロピル(ジエトキシ)メチルシラン、3-グリシジルオキシプロピルトリメトキシシラン及び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からなる群から選ばれる少なくとも1種である請求項1又は2に記載の液晶表示素子。
- 前記成分(B)が、式[2a]で示されるアルコキシシランを重縮合させて得られるポリシロキサン、又は、式[2a]と、式[2b]若しくは式[2c]で示されるアルコキシシランとを重縮合させて得られるポリシロキサンである、請求項1~4のいずれか1項に記載の液晶表示素子。
- さらに、前記液晶配向処理剤中に溶媒を含有する請求項1~5のいずれか1項に記載の液晶表示素子。
- 前記溶媒として、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、4-ヒドロキシ-4-メチル-2-ペンタノン、1-ヘキサノール、シクロヘキサノール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールジメチルエーテル、フルフリルアルコール及び下記の式[A1]~式[A3]で示される溶媒からなる群から選ばれる少なくとも1つの溶媒を含有する請求項6に記載の液晶表示素子。
(A1は、炭素数1~3のアルキル基を示す。A2は、炭素数1~3のアルキル基を示す。A3は、炭素数1~4のアルキル基を示す。) - さらに、前記液晶配向処理剤中に、光ラジカル発生剤、光酸発生剤及び光塩基発生剤からなる群から選ばれる少なくとも1つの発生剤を含有する請求項1~8のいずれか1項に記載の液晶表示素子。
- 前記基板が、ガラス基板又はプラスチック基板である請求項1~9のいずれか1項に記載の液晶表示素子。
- 請求項1~10のいずれか1項に記載の液晶表示素子に用いる液晶配向膜であり、前記の成分(A)及び成分(B)を含有する液晶配向処理剤から形成される液晶配向膜。
- 膜厚が5~500nmである請求項11に記載の液晶配向膜。
- 前記の成分(A)及び成分(B)を含有する、請求項11又は12に記載の液晶配向膜を形成するための液晶配向処理剤。
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| JP7509286B2 (ja) | 2015-04-14 | 2024-07-02 | Jsr株式会社 | 液晶配向剤 |
| WO2025216191A1 (ja) * | 2024-04-09 | 2025-10-16 | 日産化学株式会社 | 液晶調光素子 |
| WO2025216187A1 (ja) * | 2024-04-09 | 2025-10-16 | 日産化学株式会社 | 液晶調光素子 |
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| JP2012234146A (ja) * | 2011-04-21 | 2012-11-29 | Jsr Corp | 位相差フィルム用液晶配向剤、位相差フィルム用液晶配向膜、位相差フィルム及びその製造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPWO2015012368A1 (ja) * | 2013-07-25 | 2017-03-02 | 日産化学工業株式会社 | 液晶表示素子、液晶配向処理剤、及び液晶配向膜 |
| JP7509286B2 (ja) | 2015-04-14 | 2024-07-02 | Jsr株式会社 | 液晶配向剤 |
| TWI896229B (zh) * | 2015-04-14 | 2025-09-01 | 日商Jsr股份有限公司 | 液晶配向劑、液晶配向膜及液晶元件 |
| WO2025216191A1 (ja) * | 2024-04-09 | 2025-10-16 | 日産化学株式会社 | 液晶調光素子 |
| WO2025216187A1 (ja) * | 2024-04-09 | 2025-10-16 | 日産化学株式会社 | 液晶調光素子 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105556381A (zh) | 2016-05-04 |
| TWI623796B (zh) | 2018-05-11 |
| JPWO2015008846A1 (ja) | 2017-03-02 |
| CN105556381B (zh) | 2019-03-15 |
| TW201516526A (zh) | 2015-05-01 |
| KR20160032220A (ko) | 2016-03-23 |
| JP6390619B2 (ja) | 2018-09-19 |
| KR102237637B1 (ko) | 2021-04-07 |
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