CN105556381A - Liquid crystal display element, liquid crystal alignment treatment agent, and liquid crystal alignment film - Google Patents

Liquid crystal display element, liquid crystal alignment treatment agent, and liquid crystal alignment film Download PDF

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Publication number
CN105556381A
CN105556381A CN201480051792.3A CN201480051792A CN105556381A CN 105556381 A CN105556381 A CN 105556381A CN 201480051792 A CN201480051792 A CN 201480051792A CN 105556381 A CN105556381 A CN 105556381A
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liquid crystal
carbon number
group
represent
composition
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CN105556381B (en
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三木徳俊
片山雅章
巴幸司
菊池奈穂
保坂和義
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133719Surface-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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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/26Cellulose ethers
    • C08L1/28Alkyl ethers
    • C08L1/284Alkyl ethers with hydroxylated hydrocarbon radicals
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/32Cellulose ether-esters
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/0422Sugars
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    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/40Liquid 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
    • C09K19/406Liquid 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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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56Aligning agents
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1334Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444Liquid 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
    • C09K2019/0448Liquid 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
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1334Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • G02F1/13347Constructional 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

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  • Polymers & Plastics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Dispersion Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Manufacturing & Machinery (AREA)
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  • Silicon Polymers (AREA)

Abstract

A liquid crystal display element obtained by disposing a liquid crystal composition containing a liquid crystal and a polymerizable compound that is polymerized by an active energy ray or heat between two substrates provided with an electrode, providing a liquid crystal alignment film to at least one of the substrates, performing curing in a state in which all or some of the liquid crystal composition is exhibiting liquid crystallinity, and forming a cured product composite of the liquid crystal and the polymerizable compound, the liquid crystal alignment film being formed of a liquid crystal alignment treatment agent containing the following component (A) and component (B). Component (A): a cellulose-based polymer having a specific structure. Component (B): a polysiloxane-based polymer having a specific structure.

Description

Liquid crystal represents element, aligning agent for liquid crystal and liquid crystal orientation film
Technical field
The present invention relates to the transmission scattering type liquid crystal presenting scattering state when presenting pellucidity when not applying voltage and apply voltage and represent element, for the aligning agent for liquid crystal of this element and liquid crystal orientation film.
Background technology
Represent element as the liquid crystal employing liquid crystal material, in fact use TN (twisted nematic, TwistedNematic) pattern.This pattern utilizes the optically-active characteristic of liquid crystal to carry out the conversion of light, needs to use polaroid when representing element as liquid crystal.However, it is known that cause the utilization ratio step-down of light owing to using polaroid.
Utilization ratio as light is high and do not use the liquid crystal of polaroid to represent element, the liquid crystal carrying out changing between the transmissive state (also referred to as pellucidity) and scattering state of liquid crystal is had to represent element, in general, there will be a known use polymer dispersion type liquid crystal (PDLC (PolymerDispersedLiquidCrystal)), macromolecule network type liquid crystal (PNLC (PolymerNetworkLiquidCrystal)) liquid crystal represent element.
The liquid crystal employing them represents that element between a pair substrate possessing electrode, has liquid crystal layer and the liquid crystal manufactured via following operation represents element, described operation is: between aforementioned a pair substrate, configure liquid-crystal composition, described liquid-crystal composition comprises the polymerizable compound be polymerized because of active energy beam and at least one of hankering, under a part for liquid-crystal composition or the state of overall display liquid crystal liquid crystal property, carry out the solidification of foregoing liquid crystal composition, form the solidfied material compound of liquid crystal and polymerizable compound.Further, this liquid crystal represents that element controls transmissive state and the scattering state of liquid crystal by applying voltage.
Liquid crystal as the existing PDLC of employing, PNLC represents element, known following standard form element: wherein, liquid crystal molecule when not applying voltage towards random direction, therefore gonorrhoea (scattering) state is presented, liquid crystal arranges along direction of an electric field when applying voltage, thus transmitted light and present transmissive state.But standard form element needs to apply voltage to obtain transmissive state always, therefore in the purposes that the situation for pellucidity is more, such as, time for glass pane, its power consumption is large.
As standard form element, report has the flyback type element (with reference to patent documentation 1,2) presenting transmissive state when not applying voltage, presenting scattering state when applying voltage.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 2885116 publications
Patent documentation 2: Japanese Patent No. 4132424 publications
Summary of the invention
the problem that invention will solve
In flyback type element, must liquid crystal vertical-tropism be made, therefore can use the liquid crystal orientation film (also referred to as vertical liquid crystal tropism film) of liquid crystal vertical-tropism.Now, vertical liquid crystal tropism film is the film that hydrophobicity is high, therefore the adaptation step-down of liquid crystal layer and liquid crystal orientation film.Therefore, in the liquid-crystal composition for flyback type element, the polymerizable compound (also referred to as hardening agent) of the adaptation for improving liquid crystal layer and liquid crystal orientation film must be imported in a large number.But the problem that a large amount of when importing polymerizable compound, the vertical orientated property that there is liquid crystal is subject to hindering, transparency when not applying voltage significantly reduces with scattering properties when applying voltage.Therefore, the liquid crystal orientation film for flyback type element needs higher liquid crystal vertical-tropism.
Thus, the object of the invention is to, provide the liquid crystal having above-mentioned characteristic concurrently to represent element.That is, the object of the invention is to, provide that the vertical orientated property of liquid crystal is high, the transparency of optical characteristics when well namely not applying voltage is good with scattering properties when applying voltage, liquid crystal that the adaptation of liquid crystal layer and vertical liquid crystal tropism film is high represents element.And then, the invention provides and represent the liquid crystal orientation film of element and the aligning agent for liquid crystal for the formation of this liquid crystal orientation film for above-mentioned liquid crystal.
for the scheme of dealing with problems
Present inventor has performed further investigation, found that: by having the liquid crystal orientation film obtained by aligning agent for liquid crystal, the transparency when adaptation that can obtain liquid crystal layer and liquid crystal orientation film is high and the vertical orientated property of liquid crystal is high, namely optical characteristics does not well the apply voltage liquid crystal good with scattering properties when applying voltage represents element, and described aligning agent for liquid crystal comprises: the cellulose-based polymkeric substance of ad hoc structure and have the polysiloxane based polymer of side chain of ad hoc structure.
The present invention is based on described opinion, there is following purport.
(1) a kind of liquid crystal represents element, it is characterized in that, it is following acquisition: comprise liquid crystal and the liquid-crystal composition of polymerizable compound that is polymerized because of active energy beam or heat be configured in possess electrode two plate bases between, at least one in this substrate has liquid crystal orientation film, be cured under a part for foregoing liquid crystal composition or the state of overall display liquid crystal liquid crystal property, thus forming the solidfied material compound of liquid crystal and polymerizable compound, foregoing liquid crystal alignment films is formed by the aligning agent for liquid crystal containing following compositions (A) and composition (B).
Composition (A): the cellulose-based polymkeric substance with structure shown in following formula [1].
(X 1, X 2, X 3, X 4, X 5and X 6represent at least a kind of group be selected from the group be made up of following formula [1a] ~ [1m] independently of one another.N represents the integer of 100 ~ 1000000.)
(X 7, X 8, X 9, X 10, X 11, X 12, X 13and X 14represent at least a kind that is selected from the group be made up of phenyl ring, methyl, ethyl, n-pro-pyl, isopropyl and butyl independently of one another.N represents the integer of 0 ~ 3.M represents the integer of 0 ~ 3.)
Composition (B): make to be selected from least a kind of polycondensation in the group be made up of the alkoxy silane shown in the alkoxy silane shown in following formula [2a], following formula [2b] and the alkoxy silane shown in following formula [2c] and the polysiloxane based polymer obtained.
(A 1) mSi(A 2) n(OA 3) p[2a]
(A 1represent at least a kind of structure in the group being selected from and being made up of structure shown in following formula [2-1] and formula [2-2].A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5.A 3represent the alkyl of carbon number 1 ~ 5.M represents the integer of 1 or 2.N represents the integer of 0 ~ 2.P represents the integer of 0 ~ 3.Wherein, m+n+p is 4.)
(Y 1represent and be selected from by singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2at least a kind in the group of O-,-COO-and-OCO-composition.Y 2represent singly-bound or-(CH 2) b-(b is the integer of 1 ~ 15).Y 3represent and be selected from by singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2at least a kind in the group of O-,-COO-and-OCO-composition.Y 4represent the divalent organic group of at least a kind of divalent cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle or the carbon number 17 ~ 51 with steroid skeleton, any hydrogen atom on aforementioned cyclic group is optionally replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom.Y 5represent at least a kind of cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom.N represents the integer of 0 ~ 4.Y 6represent at least a kind that is selected from by the group formed containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18 of the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18.N represents the integer of 0 ~ 4.)
—--Y 7—Y 8[2-2]
(Y 7represent and be selected from by singly-bound ,-O-,-CH 2o-,-CONH-,-NHCO-,-CON (CH 3)-,-N (CH 3) CO-,-COO-and-OCO-composition group at least a kind of binding groups, Y 8represent the alkyl of carbon number 8 ~ 22 or carbon number 6 ~ 18 containing fluoroalkyl.)
(B 1) mSi(B 2) n(OB 3) p[2b]
(B 1represent have in the group being selected from and being made up of vinyl, epoxy radicals, amino, sulfydryl, isocyanate group, methacryl, acryloyl group, urea groups and cinnamoyl at least a kind and carbon number is the organic group of 2 ~ 12.B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5.B 3represent the alkyl of carbon number 1 ~ 5.M represents the integer of 1 or 2.N represents the integer of 0 ~ 2.P represents the integer of 0 ~ 3.Wherein, m+n+p is 4.)
(D 1) nSi(OD 2) 4-n[2c]
(D 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5.D 2represent the alkyl of carbon number 1 ~ 5.N represents the integer of 0 ~ 3.)
(2) liquid crystal according to above-mentioned (1) represents element, and wherein, composition (A) with the ratio of composition (B) is: relative to composition (B) 1 mass parts, composition (A) is 0.1 ~ 9 mass parts.
(3) liquid crystal according to above-mentioned (1) or (2) represents element, wherein, the alkoxy silane shown in formula [2b] in aforesaid ingredients (B) is for being selected from by allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl ester, at least a kind in the group of acrylic acid 3-(trimethoxysilyl) propyl ester and methacrylic acid 3-(trimethoxysilyl) propyl ester composition.
(4) liquid crystal according to above-mentioned (1) or (2) represents element, wherein, the alkoxy silane shown in formula [2b] in aforesaid ingredients (B) is for being selected from by least a kind in the group of 3-glycidoxypropyl group (dimethoxy) methyl-monosilane, 3-glycidoxypropyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane and 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane composition.
(5) liquid crystal according to any one of above-mentioned (1) ~ (4) represents element, wherein, aforesaid ingredients (B) makes the alkoxy silane polycondensation shown in formula [2a] and the polysiloxane obtained or the polysiloxane making the alkoxy silane shown in formula [2a] and formula [2b] or the alkoxy silane polycondensation shown in formula [2c] and obtain.
(6) liquid crystal according to any one of above-mentioned (1) ~ (5) represents element, wherein, also containing solvent in foregoing liquid crystal aligning agent.
(7) liquid crystal according to above-mentioned (6) represents element, wherein, as aforementioned solvents, containing being selected from by MEK, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1, ammediol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol list propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, at least one solvent in the group of the solvent composition shown in furfuryl alcohol and following formula [A1] ~ formula [A3].
(A 1represent the alkyl of carbon number 1 ~ 3.A 2represent the alkyl of carbon number 1 ~ 3.A 3represent the alkyl of carbon number 1 ~ 4.)
(8) liquid crystal according to any one of above-mentioned (1) ~ (7) represents element, wherein, also containing adaptation compound in foregoing liquid crystal aligning agent, described adaptation compound has at least a kind in the group being selected from and being made up of structure following formula [B1] ~ [B8] Suo Shi.
(B 1represent hydrogen atom or phenyl ring.B 2represent at least a kind of cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle.B 3represent at least a kind that is selected from by the group formed containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18 of the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18.)
(9) liquid crystal according to any one of above-mentioned (1) ~ (8) represents element, wherein, also produce agent containing being selected from by optical free radical in foregoing liquid crystal aligning agent, light acid producing agent and light alkali produce at least a kind of generation agent in the group that agent form.
(10) liquid crystal according to any one of above-mentioned (1) ~ (9) represents element, and wherein, aforesaid base plate is glass substrate or plastic base.
(11) a kind of liquid crystal orientation film, it, for representing the liquid crystal orientation film of element for the liquid crystal according to any one of above-mentioned (1) ~ (10), is formed by the aligning agent for liquid crystal containing aforesaid ingredients (A) and composition (B).
(12) liquid crystal orientation film according to above-mentioned (11), wherein, thickness is 5 ~ 300nm.
(13) aligning agent for liquid crystal, it contains aforesaid ingredients (A) and composition (B), for the formation of the liquid crystal orientation film described in above-mentioned (11) or (12).
the effect of invention
According to the present invention, by using the vertical liquid crystal tropism film obtained by aligning agent for liquid crystal, can provide that the adaptation of liquid crystal layer and vertical liquid crystal tropism film vertical orientated property that is high and then liquid crystal is high, liquid crystal that the transparency of optical characteristics when well namely not applying voltage is good with scattering properties when applying voltage represents element, described aligning agent for liquid crystal comprises: the cellulose-based polymkeric substance of ad hoc structure and have the polysiloxane based polymer of side chain of ad hoc structure.Especially, liquid crystal of the present invention represents that element can compatibly for presenting transmissive state, presenting the flyback type element of scattering state when applying voltage when not applying voltage, can be used as being expressed as object liquid crystal display, light-regulating window, shutter element etc. for the transmission and blocking that control light.
Embodiment
Liquid crystal of the present invention represents that the aligning agent for liquid crystal used in element contains: as composition (A) cellulose-based polymkeric substance (also referred to as special fiber prime system polymkeric substance) and, as the polysiloxane based polymer (also referred to as specific polysiloxane based polymer) of composition (B).
The transparency of this special fiber prime system polymkeric substance is high.Therefore, the vertical liquid crystal tropism film obtained by aligning agent for liquid crystal is not easy to absorb the light such as ultraviolet, can promote when making liquid crystal represents element by irradiating the reaction of the polymerizable compound in the liquid-crystal composition of active energy beam.
In addition, among the particular side chain structure that specific polysiloxane based polymer comprises, the structure shown in formula [2-1] has at side chain position: be selected from least a kind of cyclic group in the group be made up of phenyl ring, cyclohexyl ring and heterocycle; Or there is the divalent organic group of the carbon number 17 ~ 51 of steroid skeleton.The side-chain structure of these cyclic groups and organic group shows upright and outspoken structure, and therefore, the liquid crystal employing the vertical liquid crystal tropism film with particular side chain structure shown in formula [2-1] represents that element can obtain high and stable liquid crystal vertical-tropism.And then, for the above reasons, formula [2-1] even if shown in the import volume of particular side chain structure side-chain structure also can obtain high vertical orientated property less.Therefore, the liquid crystal employing the vertical liquid crystal tropism film with particular side chain structure shown in formula [2-1] represents that the liquid crystal layer of element and the adaptation of vertical liquid crystal tropism film become higher.
< liquid crystal represents element >
Liquid crystal of the present invention represents that element uses the vertical liquid crystal tropism film obtained by aligning agent for liquid crystal, described aligning agent for liquid crystal comprises special fiber prime system polymkeric substance and has the specific polysiloxane based polymer of particular side chain structure, the vertical orientated property of liquid crystal is high, transparency when namely optical characteristics does not well apply voltage is good with scattering properties when applying voltage, and then the adaptation of liquid crystal layer and vertical liquid crystal tropism film is high.
In addition, liquid crystal of the present invention represents that element between a pair substrate possessing electrode, has liquid crystal layer and the following liquid crystal formed represents element: between aforementioned a pair substrate, configure liquid-crystal composition, the polymerizable compound that described liquid-crystal composition comprises liquid crystal and is polymerized because of ultraviolet, and then, at least one substrate has the liquid crystal orientation film making liquid crystal vertical-tropism such, by irradiation ultraviolet radiation under a part for liquid-crystal composition or the state of overall display liquid crystal liquid crystal property, carry out the solidification of foregoing liquid crystal composition, thus form the solidfied material compound of liquid crystal and polymerizable compound, described liquid crystal represents that element can be suitably used as and does not present transmissive state when applying voltage, the flyback type element of scattering state is presented when applying voltage.
< special fiber prime system polymkeric substance >
Special fiber prime system polymkeric substance is the polymkeric substance of structure shown in following formula [1].
In formula [1], X 1, X 2, X 3, X 4, X 5and X 6represent at least a kind of group be selected from the group be made up of following formula [1a] ~ [1m] independently of one another.
N represents the integer of 100 ~ 1000000.Wherein, from the view point of special fiber prime system polymkeric substance dissolubility in a solvent, be prepared into aligning agent for liquid crystal time treatability, n is preferably 100 ~ 500,000.Be more preferably 100 ~ 100,000.
X 7, X 8, X 9, X 10, X 11, X 12, X 13and X 14represent at least a kind that is selected from the group be made up of phenyl ring, methyl, ethyl, n-pro-pyl, isopropyl and butyl independently of one another.
N represents the integer of 0 ~ 3.Wherein, the integer of 0 or 1 is preferably.
M represents the integer of 0 ~ 3.Wherein, the integer of 0 or 1 is preferably.
X 1, X 2, X 3, X 4, X 5and X 6represent at least a kind of group in the group selecting free style [1a] ~ [1m] to form independently of one another, these groups can be a kind also can be two or more.Especially, from the view point of special fiber prime system polymkeric substance dissolubility in a solvent, the coating of aligning agent for liquid crystal, preferably use of more than two kinds multiple.
Particularly preferably use formula [1a] and formula [1b] ~ [1m].Preferably use formula [1a] and formula [1c], formula [1d], formula [1e], formula [1h] or formula [1i] further.
As the concrete example of special fiber prime system polymkeric substance, following polymkeric substance can be listed, be not limited to these examples.
Include, for example out cellulose, methylcellulose, ethyl cellulose, propyl cellulose, butyl cellulose, methylethylcellulose, acetylcellulose, cellulose propionate, Carboxymethyl Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylhydroxyethylcellulose, hydroxy butyl methyl cellulose, hydroxypropylmethyl cellulose phthalate, methylamino cellulose, ethylamino cellulose, third aminocellulose, benzylcellulose, tri-benzoyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, carboxymethyl cellulose, carboxymethylethylcellulose or carboxymethyl hydroxyethyl cellulose etc.Wherein, methylcellulose, ethyl cellulose, propyl cellulose, acetylcellulose, Carboxymethyl Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethyl cellulose phthalate, benzylcellulose, cellulose acetate propionate, carboxymethylethylcellulose or carboxymethyl hydroxyethyl cellulose is preferably.Be more preferably methylcellulose, ethyl cellulose, acetylcellulose, Carboxymethyl Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethyl cellulose phthalate or carboxymethylethylcellulose.Be particularly preferably methylcellulose, ethyl cellulose, acetylcellulose, Carboxymethyl Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethylcellulose or hydroxypropylmethyl cellulose phthalate.
These cellulose derivatives can easyly obtain.In addition, shown in introducing-type [1b] ~ [1m], the method for structure is not particularly limited, and can use existing method.
Include, for example out following method:
When introducing-type [1b], make the method that cellulose and benzyl chloride react in the presence of base;
When introducing-type [1c], make cellulose and there is X 7the method that reacts in the presence of base of halogen compounds;
When introducing-type [1d], make cellulose and there is X 8the method that reacts in the presence of base of chloride compounds, make the method that cellulose and acetic anhydride react;
When introducing-type [1e], make cellulose and there is X 9the method that the halogen compounds of-OH reacts in the presence of base;
When introducing-type [1f], make cellulose and there is X 10the method that the halogen compounds of-COOH reacts in the presence of base;
When introducing-type [1g], make cellulose and there is X 11-NH 2the method that reacts in the presence of base of halogen compounds;
When introducing-type [1h], make the method that cellulose and phthalic acid react;
When introducing-type [1i], make cellulose and there is X 12the method reacted in the presence of base with the halogen compounds of phthalic acid skeleton,
When introducing-type [1k], make the method that cellulose and maleic anhydride react.
Special fiber prime system polymkeric substance can represent the characteristic of the adaptation of the optical characteristics of element, liquid crystal layer and vertical liquid crystal tropism film according to the coating of special fiber prime system polymkeric substance dissolubility in a solvent, aligning agent for liquid crystal and liquid crystal and use a kind or be mixed with two or more.
< polysiloxane based polymer >
Polysiloxane based polymer makes to be selected from least a kind of polycondensation in the group that is made up of the alkoxy silane shown in the alkoxy silane shown in following formula [2a], following formula [2b] and the alkoxy silane shown in following formula [2c] and the polysiloxane obtained.
(A 1) mSi(A 2) n(OA 3) p[2a]
In formula [2a], A 1represent at least a kind of structure in the group being selected from and being made up of structure shown in following formula [2-1] or formula [2-2].Wherein, from high and stable liquid crystal vertical-tropism this point can be obtained, the structure shown in formula [2-1] is preferably.
A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5.Wherein, the alkyl of hydrogen atom or carbon number 1 ~ 3 is preferably.
A 3represent the alkyl of carbon number 1 ~ 5.Wherein, from the view point of polycondensation reaction, be preferably the alkyl of carbon number 1 ~ 3.
M represents the integer of 1 or 2.Wherein, from the view point of synthesis, be preferably 1.
N represents the integer of 0 ~ 2.
P represents the integer of 0 ~ 3.Wherein, from the view point of polycondensation reaction, be preferably the integer of 1 ~ 3.Be more preferably 2 or 3.
It should be noted that, m+n+p is 4.
In formula [2-1], Y 1represent and be selected from by singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2at least a kind of binding groups in the group of O-,-COO-and-OCO-composition.Wherein, from the view point of raw material availability, synthesis easness, singly-bound ,-(CH is preferably 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2o-or-COO-.Be more preferably singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 10) ,-O-,-CH 2o-or-COO-.
Y 2represent singly-bound or-(CH 2) b-(b is the integer of 1 ~ 15).Wherein, singly-bound or-(CH is preferably 2) b-(b is the integer of 1 ~ 10).
Y 3represent and be selected from by singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2at least a kind of binding groups in the group of O-,-COO-and-OCO-composition.Wherein, from the view point of synthesis easness, singly-bound ,-(CH is preferably 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2o-or-COO-.Be more preferably singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 10) ,-O-,-CH 2o-or-COO-.
Y 4for being selected from least a kind of divalent cyclic group in the group that is made up of phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom.And then, X 4can be selected from the organic group in the organic group of the carbon number 17 ~ 51 with steroid skeleton.Wherein, from the view point of synthesis easness, be preferably phenyl ring, cyclohexane ring or there is the organic group of carbon number 17 ~ 51 of steroid skeleton.
Y 5represent at least a kind of divalent cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom.Wherein, phenyl ring or cyclohexane ring is preferably.
Y 6represent at least a kind that is selected from by the group formed containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18 of the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18.Wherein, be preferably the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 10 containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 10.Be more preferably the alkyl of carbon number 1 ~ 12 or the alkoxy of carbon number 1 ~ 12.Be particularly preferably the alkyl of carbon number 1 ~ 9 or the alkoxy of carbon number 1 ~ 9.
N represents the integer of 0 ~ 4.Wherein, from the view point of raw material availability, synthesis easness, 0 ~ 3 is preferably.Be more preferably 0 ~ 2.
As Y 1, Y 2, Y 3, Y 4, Y 5, Y 6with the preferred compositions of n, the combination that (2-1) ~ (2-629) is identical recorded with the table 6 ~ table 47 of 13 pages of International Publication publication WO2011/132751 (2011.10.27 is open) ~ 34 pages can be listed.It should be noted that, the Y1 ~ Y6 in each table of International Publication publication can be regarded as Y of the present invention 1~ Y 6.
In addition, the organic group of the carbon number 12 ~ 25 with steroid skeleton in (2-605) ~ (2-629) that carry of each token of International Publication publication is all interpreted as the organic group with the carbon number 17 ~ 51 of steroid skeleton of the present invention.
Wherein, the combination of (2-25) ~ (2-96), (2-145) ~ (2-168), (2-217) ~ (2-240), (2-268) ~ (2-315), (2-364) ~ (2-387), (2-436) ~ (2-483) or (2-603) ~ (2-615) is preferably.Particularly preferably be combined as (2-49) ~ (2-96), (2-145) ~ (2-168), (2-217) ~ (2-240), (2-603) ~ (2-606), (2-607) ~ (2-609), (2-611), (2-612) or (2-624).
—--Y 7-—Y 8[2-2]
In formula [2-2], Y 7represent and be selected from by singly-bound ,-O-,-CH 2o-,-CONH-,-NHCO-,-CON (CH 3)-,-N (CH 3) CO-,-COO-and-OCO-composition group at least a kind of binding groups.Wherein, singly-bound ,-O-,-CH is preferably 2o-,-CONH-,-CON (CH 3)-or-COO-.Be more preferably singly-bound ,-O-,-CONH-or-COO-.
Y 8represent the alkyl of carbon number 8 ~ 22 or carbon number 6 ~ 18 containing fluoroalkyl.Wherein, the alkyl of carbon number 8 ~ 18 is preferably.
As the particular side chain structure in the present invention, as implied above, from the view point of high and stable liquid crystal vertical-tropism can be obtained, preferably use the particular side chain structure shown in formula [2-1].
As the concrete example of the alkoxy silane shown in formula [2a], the alkoxy silane shown in following formula [2a-1] ~ [2a-32] can be listed.
(R 1represent the alkyl of carbon number 1 ~ 3.R 2represent the alkyl of carbon number 1 ~ 3.M represents the integer of 2 or 3.N represents the integer of 0 or 1.)
(R 1represent the alkyl of carbon number 1 ~ 3.R 2represent the alkyl of carbon number 1 ~ 3.R 3represent and be selected from by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH 3)-,-N (CH 3) CO-,-OCH 2-,-CH 2o-,-COOCH 2-and-CH 2at least a kind of binding groups in the group of OCO-composition.R 4represent at least a kind that is selected from by the alkyl of carbon number 1 ~ 12, alkoxy, the group that forms containing fluoroalkyl and fluoroalkoxy.M represents the integer of 2 or 3.N represents the integer of 0 or 1.)
(R 1represent the alkyl of carbon number 1 ~ 3.R 2represent the alkyl of carbon number 1 ~ 3.R 3represent and be selected from by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH 3)-,-N (CH 3) CO-,-OCH 2-,-CH 2o-,-COOCH 2-and-CH 2at least a kind of binding groups in the group of OCO-composition.R 4represent at least a kind that is selected from by the alkyl of carbon number 1 ~ 12, alkoxy, the group that forms containing fluoroalkyl, fluoroalkoxy, fluorine-based, cyano group, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group and hydroxyl.M represents the integer of 2 or 3.N represents the integer of 0 or 1.)
(in formula [2a-25] ~ [2a-31], R 1represent the alkyl of carbon number 1 ~ 3.R 2represent the alkyl of carbon number 1 ~ 3.R 3represent and be selected from by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH 3)-,-N (CH 3) CO-,-OCH 2-,-CH 2o-,-COOCH 2-and-CH 2at least a kind in the group of OCO-composition.R 4represent at least a kind that is selected from by the alkyl of carbon number 1 ~ 12, alkoxy, the group that forms containing fluoroalkyl and fluoroalkoxy.M represents the integer of 2 or 3.N represents the integer of 0 or 1.)
(R 1represent the alkyl of carbon number 1 ~ 3.R 2represent the alkyl of carbon number 1 ~ 3.M represents the integer of 2 or 3.N represents the integer of 0 or 1.B 4represent the alkyl of the carbon number 3 ~ 20 be optionally replaced by fluorine atoms.B 3represent Isosorbide-5-Nitrae-cyclohexylene or Isosorbide-5-Nitrae-phenylene.B 2represent that oxygen atom or-COO-* (wherein, attach key and the B of " * " 3carry out bonding.)。B 1represent that oxygen atom or-COO-* (wherein, attach the key of " * " and (CH 2) a 2) carry out bonding.)。A 1represent the integer of 0 or 1.A 2represent the integer of 2 ~ 10.A 3represent the integer of 0 or 1.)
Alkoxy silane shown in above-mentioned formula [2a] can according to specific polysiloxane based polymer dissolubility in a solvent, make liquid crystal orientation film time liquid crystal vertical-tropism and liquid crystal represent the characteristic of the optical characteristics of element etc. and use a kind or be mixed with two or more.
(B 1) mSi(B 2) n(OB 3) p[2b]
In formula [2b], B 1represent the organic group with the carbon number 2 ~ 12 of vinyl, epoxy radicals, amino, sulfydryl, isocyanate group, methacryl, acryloyl group, urea groups or cinnamoyl.Wherein, from the view point of acquisition easness, alternatively base, vinyl, epoxy radicals, amino, methacryl, acryloyl group or urea groups is preferably.Be more preferably methacryl, acryloyl group or urea groups.
B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5.Wherein, the alkyl of hydrogen atom or carbon number 1 ~ 3 is preferably.
B 3represent the alkyl of carbon number 1 ~ 5.Wherein, from the view point of polycondensation reaction, be preferably the alkyl of carbon number 1 ~ 3.
M represents the integer of 1 or 2.Wherein, from the view point of synthesis, be preferably 1.
N represents the integer of 0 ~ 2.Wherein, 0 or 1 is preferably.
P represents the integer of 0 ~ 3.Wherein, from the view point of polycondensation reaction, be preferably the integer of 1 ~ 3.Be more preferably 2 or 3.
In formula [2b], m+n+p is 4.
As the concrete example of the alkoxy silane shown in formula [2b], include, for example out allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, between styryl ethyl triethoxysilane, to styryl ethyl triethoxysilane, between styrylmethyl triethoxysilane, to styrylmethyl triethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino) propyl trimethoxy silicane, diethoxy (3-glycidoxypropyl group) methyl-monosilane, 3-glycidoxypropyl group (dimethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-(2-aminoethylamino) dimethylamine oxygen butyldimethylsilyl, 3-(2-aminoethylamino) propyl-triethoxysilicane, 3-(2-aminoethylamino) propyl trimethoxy silicane, 3-aminopropyl diethoxymethylsilane, APTES, 3-TSL 8330, trimethoxy [3-(phenyl amino) propyl group] silane, 3-mercaptopropyi (dimethoxy) methyl-monosilane, (3-mercaptopropyi) triethoxysilane, (3-mercaptopropyi) trimethoxy silane, 3-(triethoxysilyl) propylisocyanate, methacrylic acid 3-(triethoxysilyl) propyl ester, methacrylic acid 3-(trimethoxysilyl) propyl ester, acrylic acid 3-(triethoxysilyl) propyl ester, acrylic acid 3-(trimethoxysilyl) propyl ester, methacrylic acid 3-(triethoxysilyl) ethyl ester, methacrylic acid 3-(trimethoxysilyl) ethyl ester, acrylic acid 3-(triethoxysilyl) ethyl ester, acrylic acid 3-(trimethoxysilyl) ethyl ester, methacrylic acid 3-(triethoxysilyl) methyl esters, methacrylic acid 3-(trimethoxysilyl) methyl esters, acrylic acid 3-(triethoxysilyl) methyl esters, acrylic acid 3-(trimethoxysilyl) methyl esters, γ-urea propyl-triethoxysilicane, γ-urea propyl trimethoxy silicane, γ-urea propyl group tripropoxy silane, (R)-N-1-phenylethyl-N '-triethoxysilylpropyltetrasulfide urea, (R)-N-1-phenylethyl-N '-trimethoxy-silylpropyl urea, two [3-(trimethoxysilyl) propyl group] urea, two [3-(tripropoxy-silicane base) propyl group] urea, 1-[3-(trimethoxysilyl) propyl group] urea etc.
Wherein, preferably, the allyltriethoxysilane of free radical reaction, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl ester, acrylic acid 3-(trimethoxysilyl) propyl ester or methacrylic acid 3-(trimethoxysilyl) propyl ester is there is because of light.
Further preferably, 3-glycidoxypropyl group (dimethoxy) methyl-monosilane of cross-linking reaction, 3-glycidoxypropyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane or 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane is there is because of heat.
Alkoxy silane shown in formula [2b] can according to specific polysiloxane based polymer dissolubility in a solvent, make liquid crystal orientation film time liquid crystal vertical-tropism and liquid crystal represent the characteristic of the optical characteristics of element etc. and use a kind or be mixed with two or more.
(D 1) nSi(OD 2) 4-n[2c]
In formula [2c], D 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5.The hydrogen atom of these alkyl is optionally replaced by halogen atom, nitrogen-atoms, oxygen atom or sulphur atom.Wherein, the alkyl of hydrogen atom or carbon number 1 ~ 3 is preferably.
D 2represent the alkyl of carbon number 1 ~ 5.Wherein, from the view point of polycondensation reaction, be preferably the alkyl of carbon number 1 ~ 3.
N represents the integer of 0 ~ 3.Wherein, 0 or 1 is preferably.
As the concrete example of the alkoxy silane shown in formula [2c], include, for example out tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl tripropoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethoxy diethylsilane, dibutoxy dimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyl dimethoxymethylsilane, 3-chloropropyl triethoxysilane, 2-cyano ethyl triethoxysilane, trimethoxy (3, 3, 3-trifluoro propyl) silane, hexyl trimethoxy silane, 3-trimethoxy-silylpropyl chloride etc.
Be the alkoxy silane of 0 as the n in formula [2c], tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc. can be listed, as the alkoxy silane shown in formula [2c], preferably use these alkoxy silanes.
Alkoxy silane shown in formula [2c] can according to specific polysiloxane based polymer dissolubility in a solvent, make liquid crystal orientation film time liquid crystal vertical-tropism and liquid crystal represent the characteristic of the optical characteristics of element etc. and use a kind or be mixed with two or more.
Specific polysiloxane based polymer makes to be selected from least a kind of polycondensation in the group that is made up of the alkoxy silane shown in the alkoxy silane shown in previously described formula [2a], formula [2b] and the alkoxy silane shown in formula [2c] and the polysiloxane obtained.Specifically, it is the polysiloxane making a kind of alkoxy silane polycondensation shown in formula [2a] and obtain, make 2 kinds of alkoxy silane polycondensations shown in formula [2a] and formula [2b] and the polysiloxane obtained, make 2 kinds of alkoxy silane polycondensations shown in formula [2a] and formula [2c] and the polysiloxane obtained, and make formula [2a], 3 kinds of alkoxy silane polycondensations shown in formula [2b] and formula [2c] and the polysiloxane obtained.
Wherein, from the reactivity of polycondensation, specific polysiloxane based polymer deliquescent viewpoint in a solvent, preferably make multiple alkoxy silane polycondensation and the polysiloxane obtained.That is, preferably, 2 kinds of alkoxy silane polycondensations shown in formula [2a] and formula [2b] are made and the polysiloxane obtained; Make 2 kinds of alkoxy silane polycondensations shown in formula [2a] and formula [2c] and the polysiloxane obtained; Or, make formula [2a], 3 kinds of alkoxy silane polycondensations shown in formula [2b] and formula [2c] and the polysiloxane obtained.Wherein, formula [2a], 3 kinds of alkoxy silane polycondensations shown in formula [2b] and formula [2c] and the polysiloxane obtained preferably is made.
When making specific polysiloxane based polymer, when using multiple alkoxy silane, the alkoxy silane shown in formula [2a] is preferably 1 ~ 40 % by mole in all alkoxy silanes.Wherein, 1 ~ 30 % by mole is preferably.
In addition, the alkoxy silane shown in formula [2b] is preferably 1 ~ 70 % by mole in all alkoxy silanes.Wherein, 1 ~ 60 % by mole is preferably.
And then the alkoxy silane shown in formula [2c] is preferably 1 ~ 99 % by mole in all alkoxy silanes.Wherein, 1 ~ 80 % by mole is preferably.
The method making specific polysiloxane based polymer is not particularly limited.Include, for example out: make polycondensation and the method obtained in a solvent of the alkoxy silane shown in formula [2a]; Make polycondensation and the method obtained in a solvent of 2 kinds of alkoxy silanes shown in formula [2a] and formula [2b]; Make polycondensation and the method obtained in a solvent of 2 kinds of alkoxy silanes shown in formula [2a] Yu formula [2c]; And, make formula [2a], 3 kinds of alkoxy silanes shown in formula [2b] and formula [2c] polycondensation and the method obtained in a solvent.In addition, these alkoxy silanes are carried out polycondensation and obtain with the form of the solution being evenly dissolved in solvent by specific polysiloxane based polymer of the present invention.
In addition, the method that specific polysiloxane based polymer carries out polycondensation is not particularly limited.Include, for example the method that hydrolysis/condensation reaction occurs alkoxy silane of sening as an envoy in alcohol series solvent, glycol series solvent.Now, hydrolysis/condensation reaction can be partial hydrolysis, also can complete hydrolysis.During complete hydrolysis, the water of 0.5 times of molar weight of all alkoxys in alkoxy silane can be added in theory, preferably add being in a ratio of excessive water with 0.5 times of molar weight.In order to obtain specific polysiloxane based polymer, the water yield used in said hydrolyzed/polycondensation reaction suitably can be selected according to object, is preferably 0.5 ~ 2.5 times of molar weight of all alkoxys in alkoxy silane.
In addition, in order to facilitation of hydrolysis/polycondensation reaction, the acid compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid can be used; The alkali compounds such as ammonia, methylamine, ethamine, monoethanolamine, triethylamine; The catalyzer such as the slaine of hydrochloric acid, nitric acid, oxalic acid etc.
And then, by will the solution heating of alkoxy silane be dissolved with, also can facilitation of hydrolysis/polycondensation reaction.Heating-up temperature now and heat time suitably can be selected according to object.Include, for example out: add thermal agitation 24 hours with 50 DEG C, under reflux conditions stir thereafter the condition waited for 1 hour.
As other polycondensation method, can list: the method heating the potpourri of alkoxy silane, solvent and oxalic acid to carry out polycondensation reaction.Specifically, be in solvent, add oxalic acid in advance and after making oxalic acid solution, the method for mixed oxyalkyl silane under the state that heated this solution.
Relative to all alkoxys in alkoxy silane 1 mole, the oxalic acid amount used in above-mentioned reaction is preferably set to 0.2 ~ 2.0 mole.In addition, this reaction can be carried out under the solution temperature of 50 ~ 180 DEG C, in order to not make solvent evaporate, be vaporized, preferably carries out several tens minutes ~ tens of hours under reflux.
Prepare in the polycondensation reaction of specific polysiloxane based polymer, during multiple in alkoxy silane shown in use formula [2a], formula [2b] and formula [2c], use and the potpourri that multiple alkoxy silane is pre-mixed is reacted, also can add multiple alkoxy silane successively while react.
As the solvent used in the polycondensation reaction of alkoxy silane, as long as the solvent of dissolvane TMOS, be just not particularly limited.In addition, even do not dissolve the solvent of alkoxy silane, as long as dissolve along with the propelling of the polycondensation reaction of alkoxy silane.As the solvent now used, in general, produce alcohol due to the polycondensation reaction of alkoxy silane, therefore, alcohol series solvent, glycol series solvent, glycol ethers series solvent, the solvent etc. good with the compatibility of alcohol can be used.
As the concrete example of the solvent used in this polycondensation reaction, the alcohol series solvents such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol can be listed, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, 1,3-PD, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-PD, 2,4-pentanediols, 2, the glycol series solvents such as 3-pentanediol, 1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol dipropyl ether, the glycol ethers series solvents such as propylene glycol dibutyl ethers, the solvent etc. that METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolacton, DMF, DMA, dimethyl sulfoxide (DMSO), tetramethylurea, hexamethylphosphorictriamide, metacresol etc. are good with the intermiscibility of alcohol.In addition, when carrying out polycondensation reaction, above-mentioned solvent can use a kind or be mixed with two or more.
About the solution of the polysiloxane based polymer obtained by preceding method, the silicon atom had in all alkoxy silanes dropped into as raw material is converted into SiO 2concentration (also referred to as SiO 2converted score) be preferably below 20 quality %.Wherein, 5 ~ 15 quality % are preferably.By selecting any concentration in this concentration range, can suppress to produce gel in solution, the solution of uniform polysiloxane based polymer can be obtained.
In the present invention, the solution of the polysiloxane based polymer obtained by preceding method directly can be used as specific polysiloxane based polymer, as required, also the solution of the polysiloxane based polymer utilizing preceding method to obtain can be concentrated or add solvent and carry out diluting or be replaced as other solvent, thus also can be used as specific polysiloxane based polymer.
As the solvent used during dilution (also referred to as interpolation solvent), can be solvent, other solvent of using in polycondensation reaction.As long as this interpolation solvent is just not particularly limited in the scope that polysiloxane series polymer uniform dissolves, can selects arbitrarily and use one kind or two or more.As this interpolation solvent, except the solvent used in aforementioned polycondensation reaction, also can list the ketone series solvents such as acetone, MEK, methyl isobutyl ketone; The ester series solvents etc. such as methyl acetate, ethyl acetate, ethyl lactate.
And then, in the present invention, when specific polysiloxane based polymer use polysiloxane based polymer and polymkeric substance in addition, preferably, mix polymkeric substance in addition in polysiloxane based polymer before, the alcohol produced during polycondensation reaction under normal or reduced pressure to polysiloxane based polymer carries out distillation and removes.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention is the coating solution for the formation of liquid crystal orientation film, be the coating solution containing the special fiber prime system polymkeric substance as composition (A), the specific polysiloxane based polymer as composition (B) and solvent, described specific polysiloxane based polymer has at least a kind of particular side chain structure in the group being selected from and being made up of structure shown in previously described formula [2-1] and formula [2-2].
About the ratio of the special fiber prime system polymkeric substance in aligning agent for liquid crystal and specific polysiloxane based polymer, relative to specific polysiloxane based polymer 1 mass parts, the ratio of special fiber prime system polymkeric substance is preferably 0.01 ~ 99 mass parts.Wherein, 0.1 ~ 9 mass parts, more preferably 0.1 ~ 3 mass parts is more preferably.
All component of polymer in aligning agent for liquid crystal can be all special fiber prime system polymkeric substance and specific polysiloxane based polymer, also can be mixed with other polymkeric substance in addition.As polymkeric substance in addition, the polysiloxane based polymer without specific side chain shown in previously described formula [2-1] or formula [2-2] can be listed.In addition, at least a kind of polymkeric substance in the group being selected from and being made up of acrylic polymers, methacrylic polymer, novolac resin, polycarboxylated styrene, polyamide, polyester, polyamic acid and polyimide can also be mixed.
Add up to relative to by special fiber prime system polymkeric substance and specific polysiloxane based polymer all polymkeric substance 100 mass parts obtained, the content of other polymkeric substance is in addition preferably 0.5 ~ 15 mass parts.Wherein, 1 ~ 10 mass parts is preferably.
From the view point of the coating process of aligning agent for liquid crystal, obtain target film thickness, the content of the solvent in aligning agent for liquid crystal can suitably be selected.Wherein, from the view point of forming uniform liquid crystal orientation film by being coated with, the solvent in aligning agent for liquid crystal is preferably 50 ~ 99.9 quality %.Wherein, be preferably 60 ~ 99 quality %, be more preferably 65 ~ 99 quality %.
As long as the solvent that the solvent used in aligning agent for liquid crystal dissolves special fiber prime system polymkeric substance and specific polysiloxane based polymer is just not particularly limited.
In addition, the solvent used in aligning agent for liquid crystal directly can use the polycondensation solution of specific polysiloxane based polymer, also new solvent can be added in the polycondensation solution of specific polysiloxane based polymer, and then, can also by the solvent of the polycondensation solution replacement Cheng Xin of specific polysiloxane based polymer.As new solvent, as long as the solvent dissolving special fiber prime system polymkeric substance and specific polysiloxane based polymer is just not particularly limited.Below enumerate its concrete example, but be not limited to these examples.
Include, for example out DMF, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 1,3-dimethyl-imidazolinone, MEK, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, ethanol, isopropyl alcohol, n-butyl alcohol, 2-butanols, isobutyl alcohol, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, isoamylol, tert-pentyl alcohol, 3-methyl-2-butanols, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, cyclohexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2-ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butylene glycol, 1,3-BDO, BDO, 2,3-butanediol, 1,5-PD, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ethers, hexyl ether, diox, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate butyl ether, 1,2-butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4-heptanone, 3-ethoxybutyl acetate, 1-methyl amyl acetate, 2-ethyl-butyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol mono hexyl ether, 2-(own oxygen base) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, propylene glycol, glycol monobutyl ether, 1-(Butoxyethoxy) propyl alcohol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol dimethyl ether, DPGME, dihydroxypropane single-ethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol monoacetate, ethylene diacetate, TC acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxy ethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol monoethyl, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.And then, also can list the solvent shown in following formula [A1] ~ formula [A3].
(A 1represent the alkyl of carbon number 1 ~ 3.A 2represent the alkyl of carbon number 1 ~ 3.A 3represent the alkyl of carbon number 1 ~ 4.)
Wherein, be preferably 1, 3-dimethyl-imidazolinone, MEK, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 2-methyl-1-butene alcohol, 1-hexanol, cyclohexanol, 1, ammediol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol list propyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol list propyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol, or the solvent etc. shown in formula [A1] ~ formula [A3].
Be more preferably MEK, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1, ammediol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol list propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol, or the solvent etc. shown in formula [A1] ~ formula [A3].
Above-mentioned solvent can dissolubility, coating of liquid crystalline aligning agent according to special fiber prime system polymkeric substance and specific polysiloxane time the film of liquid crystal orientation film, the characteristic of surface smoothness and use a kind or be mixed with two or more.
In order to improve the adaptation of liquid crystal layer and vertical liquid crystal tropism film, preferably, in aligning agent for liquid crystal of the present invention, import the compound (also referred to as specific adaptation compound) of at least a kind had in the group being selected from and being made up of structure following formula [B1] ~ [B8] Suo Shi.
Preferably there is in adaptation compound the structure shown in more than 2 these formulas [B1] ~ [B8].
(B 1represent hydrogen atom or phenyl ring.B 2represent at least a kind of cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle.B 3represent at least a kind that is selected from by the group formed containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18 of the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18.)
As specific adaptation compound more specifically, preferably use the compound shown in following formula [6].
In formula [6], M 1represent at least a kind of structure be selected from the group be made up of structure following formula [a-1] ~ [a-7] Suo Shi.Wherein, from the view point of the ease of manufacture of adaptation compound of the present invention, be preferably formula [a-1], formula [a-2], formula [a-3], formula [a-5] or the structure shown in formula [a-6].Be more preferably formula [a-1], formula [a-3], formula [a-5] or the structure shown in formula [a-6].
In formula [a-2], A 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5.Wherein, from the view point of the ease of manufacture of adaptation compound, be preferably the alkyl of hydrogen atom or carbon number 1 ~ 2.Be more preferably hydrogen atom or methyl.
In formula [a-3], A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 3.Wherein, from the view point of the ease of manufacture of adaptation compound, be preferably the alkyl of hydrogen atom or carbon number 1 ~ 2.Be more preferably hydrogen atom or methyl.
In formula [a-5] and formula [a-6], A 3, A 5, A 6and A 9represent the alkyl of hydrogen atom or carbon number 1 ~ 3 independently of one another.Wherein, from the view point of the ease of manufacture of adaptation compound, be preferably the alkyl of hydrogen atom or carbon number 1 ~ 2.Be more preferably hydrogen atom or methyl.
In formula [a-5] and formula [a-6], A 4, A 7and A 8represent the alkylidene of carbon number 1 ~ 3 independently of one another.Wherein, from the view point of the ease of manufacture of adaptation compound, be preferably the alkylidene of carbon number 1 ~ 2.
In formula [6], M 2represent and be selected from by singly-bound ,-CH 2-,-O-,-NH-,-N (CH 3)-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-,-OCO-,-CON (CH 3)-and-N (CH 3) CO-composition group at least a kind of binding groups.Wherein, from the view point of the synthesis easness of adaptation compound, be preferably singly-bound ,-CH 2-,-O-,-NH-,-CONH-,-NHCO-,-CH 2o-,-OCH 2-,-COO-,-OCO-,-CON (CH 3)-or-N (CH 3) CO-.Be more preferably singly-bound ,-CH 2-,-O-,-NH-,-CONH-,-CH 2o-,-OCH 2-,-COO-or-OCO-.Be particularly preferably singly-bound ,-O-,-CONH-,-OCH 2-,-COO-or-OCO-.
In formula [6], M 3represent and be selected from by the alkylidene of carbon number 1 ~ 20 ,-(CH 2-CH 2-O) p-(p represents the integer of 1 ~ 10) ,-(CH 2-O-) q-(q represents the integer of 1 ~ 10) and carbon number 6 ~ 20 at least a kind that has in the group of the organic group composition of phenyl ring or cyclohexane ring.Now, any-CH in aforementioned alkylidene 2-Ji is optionally by-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) 2o-replaces, and the hydrogen atom being bonded to any carbon atom is optionally replaced by hydroxyl (OH yl), carboxyl (COOH yl) or halogen atom.
Wherein, from the view point of the ease of manufacture of adaptation compound, be preferably alkylidene, the-(CH of carbon number 1 ~ 20 2-CH 2-O) p-(p represents the integer of 1 ~ 10) ,-(CH 2-O-) q-(q represents the integer of 1 ~ 10) or the structure shown in following formula [c-1] ~ formula [c-5].Be more preferably the alkylidene of carbon number 1 ~ 15 ,-(CH 2-CH 2-O) p-(p represents the integer of 1 ~ 10) ,-(CH 2-O-) q-(q represents the integer of 1 ~ 10), following formula [c-1], formula [c-3], formula [c-4] or the structure shown in formula [c-5].Be particularly preferably the alkylidene of carbon number 1 ~ 15 ,-(CH 2-CH 2-O) p-(p represents the integer of 1 ~ 10), formula [c-1], formula [c-4] or the structure shown in formula [c-5].
In formula [6], M 4represent and be selected from by singly-bound ,-CH 2-,-OCH 2-and O-CH 2-CH 2at least a kind of binding groups in the group of-composition.Wherein, from the view point of the synthesis easness of adaptation compound, be preferably singly-bound ,-CH 2-or-OCH 2-shown structure.
In formula [6], M 5represent at least a kind of structure be selected from the group be made up of structure previously described formula [b-1] ~ [b-8] Suo Shi.Wherein, from the view point of the synthesis easness of adaptation compound, be preferably formula [b-1], formula [b-2] or the structure shown in formula [b-6].Be more preferably formula [b-1] or the structure shown in formula [b-2].
In formula [6], n represents the integer of 1 ~ 3.Wherein, from the view point of the synthesis easness of adaptation compound, be preferably 1 or 2.Be more preferably 1.
In formula [6], m represents the integer of 1 ~ 3.Wherein, from the view point of the synthesis easness of adaptation compound, be preferably 1 or 2.
As specific adaptation compound, preferably use at least a kind of compound in the group being selected from and being made up of compound shown in following formula [6-1] and formula [6-5].
(n represents the integer of 1 ~ 10.M represents the integer of 1 ~ 10.)
And then, as specific adaptation compound, the following compound illustrated can be listed.Include, for example out the compound in trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyloxyethoxy trimethylolpropane, poly-(methyl) acrylate equimolecular of glycerine polyglycidyl ether with 3 polymerism unsaturated groups, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane bisphenol A-type two (methyl) acrylate, epoxypropane bisphenol type two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, there is in 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate equimolecular the compound of 2 polymerism unsaturated groups, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 2-phenoxy group-2-hydroxy propyl ester, 2-(methyl) acryloxy-2-hydroxypropyl phthalate, (methyl) acrylic acid 3-chlorine-2-hydroxyl propyl ester, glycerine list (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl phosphate, there is in N-methylol (methyl) acrylamide equimolecular the compound etc. of 1 polymerism unsaturated group.
The content of the specific adaptation compound in aligning agent for liquid crystal is preferably 0.1 ~ 150 mass parts relative to all component of polymer 100 mass parts.In order to advance cross-linking reaction to show target effect, relative to all component of polymer 100 mass parts, being more preferably 0.1 ~ 100 mass parts, most especially preferably being 1 ~ 50 mass parts.
Specific adaptation compound can represent the characteristic of the optical characteristics of element etc. according to liquid crystal vertical-tropism when making vertical liquid crystal tropism film and liquid crystal and use a kind or be mixed with two or more.
In order to improve the adaptation of liquid crystal layer and vertical liquid crystal tropism film, preferably import in the aligning agent for liquid crystal in the present invention be selected from produce agent by optical free radical, light acid producing agent and light alkali produce at least a kind of specific generation agent in the group that agent forms.
Produce agent as optical free radical, as long as the generation agent producing free radical because of ultraviolet is just not particularly limited, include, for example out tert-butyl hydroperoxide isobutyrate, two (benzoyl titanium dioxide) hexane of 2,5-dimethyl-2,5-, Isosorbide-5-Nitrae-bis-[α-(tert-butyl group titanium dioxide) isopropoxy] benzene, di-tert-butyl peroxide, two (tert-butyl group titanium dioxide) the hexene hydrogen peroxide of 2,5-dimethyl-2,5-, α-(isopropyl phenyl) hyperis, 2,5-dimethylhexane, tert-butyl hydroperoxide, two (tert-butyl group titanium dioxide)-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two (tert-butyl group titanium dioxide) valerate of butyl-4,4-, Cyclohexanone peroxides, 2,2 ', 5,5 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (t-amyl peroxy carbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxidating carbonyl) benzophenone, 3,3 '-bis-(tert-butyl hydroperoxide carbonyl)-4,4 '-benzophenonedicarboxylic acid, tert butyl peroxy benzoate, the organic peroxides such as di-t-butyl diperoxy isophthalic acid ester, the quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, prestox anthraquinone, 1,2-benzo anthraquinone, the benzoin derivatives etc. such as benzoin methylether, benzoin ethyl ether, Alpha-Methyl benzoin, α-phenylbenzoin.
Agent is produced as light acid producing agent and light alkali, as long as the generation agent producing acid or alkali because of ultraviolet is just not particularly limited, include, for example out triazine based compound, acetophenone derivs compound, two sulfone based compounds, bisdiazo methane series compound, sulfonic acid compound, diaryl group iodized salt, triarylsulfonium salt, San Fang Ji phosphonium salt, iron-arene complexes etc.More specifically, include, for example out diphenyliodonium chloride, diphenylsulfonium Loprazolam iodine, diphenylmethyl sulfonic acid iodine, diphenylmethyl benzene sulfonic acid iodine, diphenyl IBr, diphenyl tetrafluoro boric acid iodine, diphenyl hexafluoro-iodide antimonate, diphenyl hexafluoroarsenate iodine, two (to tert-butyl-phenyl) iodonium hexafluorophosphate, two (to tert-butyl-phenyl) methane-sulforic acid iodine, two (to tert-butyl-phenyl) toluenesulfonic acid iodine, two (to tert-butyl-phenyl) trifluoromethayl sulfonic acid iodine, two (to tert-butyl-phenyl) tetrafluoro boric acid iodine, two (to tert-butyl-phenyl) lodine chloride, two (rubigan) lodine chloride, two (rubigan) tetrafluoro boric acid iodine, benzyltriphenylphosphonium chloride sulfonium, triphenyl phosphonium bromide sulfonium, three (p-methoxyphenyl) tetrafluoro boric acid sulfonium, three (p-methoxyphenyl) hexafluoro phosphonic acids sulfonium, three (to ethoxyl phenenyl) tetrafluoro boric acid sulfonium, triphenyl phosphonium chloride, triphenyl phosphonium bromide, three (p-methoxyphenyl) Si Fu Peng Suan Phosphonium, three (p-methoxyphenyl) six Fu Lin Suan Phosphonium, three (to ethoxyl phenenyl) Si Fu Peng Suan Phosphonium, two [[(2-nitrobenzyl) oxygen base] carbonyl hexane-1,6-diamines], nitrobenzyl cyclohexylcarbamate, two (methoxy-benzyl) hexa-methylene diamino formic ether, two [[(2-nitrobenzyl) oxygen base] carbonyl hexane-1,6-diamines], nitrobenzyl cyclohexylcarbamate, two (methoxy-benzyl) hexa-methylene diamino formic ether etc.
Wherein, from the view point of the adaptation that effectively can improve liquid crystal layer and liquid crystal orientation film, specific generation agent preferably uses optical free radical to produce agent.
The content of the specific generation agent in aligning agent for liquid crystal is preferably 0.01 ~ 50 mass parts relative to all component of polymer 100 mass parts.Wherein, in order to advance cross-linking reaction to show target effect, relative to all component of polymer 100 mass parts, being more preferably 0.01 ~ 30 mass parts, being more preferably 0.1 ~ 20 mass parts.
Specific generation agent can represent the characteristic of the optical characteristics of element etc. according to liquid crystal vertical-tropism when making vertical liquid crystal tropism film and liquid crystal and use a kind or be mixed with two or more.
From the view point of the film hardness improving vertical liquid crystal tropism film, in aligning agent for liquid crystal of the present invention, preferably import at least a kind of substituent compound (being also referred to as specific cross-linked compound) etc. had in the group being selected from and being made up of epoxy radicals, isocyanate group, oxetanyl, cyclocarbonate radical, hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl.These substituting groups need there are more than 2 in cross-linked compound.
As the cross-linked compound with epoxy radicals or isocyanate group, include, for example out bisphenol acetone glycidol ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four glycidyl group aminobphenyl, four glycidyl group m-xylene diamine, two (amino-ethyl) cyclohexane of four glycidyl group-1,3-, tetraphenyl glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, two (1-(2,3-glycidoxy)-1-trifluoromethyl-2,2, the 2-trifluoromethyl) benzene of 1,3-, two (2, the 3-glycidoxy) octafluorobiphenyl of 4,4-, triglycidyl group para-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-glycidoxy) phenyl)-2-(4-(two (4-(2, the 3-glycidoxy) phenyl) ethyl of 1,1-) phenyl) propane, 1, two (4-(1-(the 4-(2 of 3-, 3-glycidoxy) phenyl)-1-(4-(1-(4-(2,3-glycidoxy) phenyl)-1-Methylethyl) phenyl) ethyl) phenoxy group)-2-propyl alcohol etc.
The cross-linked compound with oxetanyl is the cross-linked compound with the oxetanyl shown at least 2 following formula [4].
Specifically, 58 pages ~ 59 pages cross-linked compounds shown in formula [4a] ~ [4k] recorded of International Publication publication WO2011/132751 (2011.10.27 is open) can be listed.
The cross-linked compound with cyclocarbonate radical is the cross-linked compound with the cyclocarbonate radical shown at least 2 following formula [5].
Specifically, 76 pages ~ 82 pages cross-linked compounds shown in formula [5-1] ~ [5-42] recorded of International Publication publication WO2012/014898 (2012.2.2 is open) can be listed.
As at least a kind of substituent cross-linked compound had in the group selecting free hydroxyl and alkoxy composition, include, for example out the amino resins with hydroxyl or alkoxy, such as melmac, carbamide resin, guanamine resin, glycolurilformaldehyde resins, succinamide-formaldehyde resin, ethylene urea-formaldehyde resins etc.Specifically, melamine derivative, benzoguanamine derivant, glycoluril etc. that amino hydrogen atom is replaced by methylol and/or alkoxy methyl can be used.This melamine derivative or benzoguanamine derivant also can exist with dimer or trimerical form.They preferably every 1 triazine ring there is average more than 3 and the methylol of less than 6 or alkoxy methyl.
As the example of this melamine derivative or benzoguanamine derivant, every 1 triazine ring that can list commercially available product replaces the MX-750 of average 3.7 methoxies, every 1 triazine ring replaces the MW-30 (being Sanwa Chemical Co., Ltd above) having average 5.8 methoxies, CYMEL300,301,303,350,370,771,325,327,703, the methoxymethylated melamines such as 712; CYMEL235,236,238,212,253, the methoxymethylated butoxymethyl melamines such as 254; CYMEL506, the butoxymethyl melamines such as 508; The carboxylic methoxymethylated isobutoxymethyl melamine of CYMEL1141 and so on; The methoxymethylated ethoxyl methyl benzoguanamine of CYMEL1123 and so on; The methoxymethylated butoxymethyl benzoguanamine of CYMEL1123-10 and so on; The butoxymethyl benzoguanamine of CYMEL1128 and so on; The carboxylic methoxymethylated ethoxyl methyl benzoguanamine (being Mitsui サ イ ア Na ミ De Inc. above) etc. of CYMEL1125-80 and so on.In addition, as the example of glycoluril, the butoxymethyl glycoluril of CYMEL1170 and so on can be listed; The methylolation glycoluril of CYMEL1172 and so on; The methoxyl methylolation glycoluril etc. of Powderlink1174 and so on.
As benzene or the benzene phenoloid with hydroxyl or alkoxy, include, for example out 1,3,5-tri-(methoxy) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, Isosorbide-5-Nitrae-bis-(sec-butoxymethyl) benzene, 2,6-bishydroxymethyl p-t-butyl phenols etc.
More specifically, 62 pages ~ 66 pages cross-linked compounds shown in formula [6-1] ~ [6-48] recorded of International Publication publication WO2011/132751 can be listed.
The content of the cross-linked compound in aligning agent for liquid crystal is preferably 0.1 ~ 100 mass parts relative to all component of polymer 100 mass parts.In order to advance cross-linking reaction to show target effect, relative to all component of polymer 100 mass parts, being more preferably 0.1 ~ 50 mass parts, most especially preferably being 1 ~ 30 mass parts.
In the present invention, move as the electric charge promoted in vertical liquid crystal tropism film, promote that element takes off the compound of electric charge, also can add 69 pages ~ 73 pages nitrogen heterocyclic ring amines shown in formula [M1] ~ [M156] recorded of International Publication publication WO2011/132751 (2011.10.27 is open) in aligning agent for liquid crystal.This amines can be added directly in aligning agent for liquid crystal, and preferably making concentration with suitable solvent is add after 0.1 ~ 10 quality %, the solution preferably making 1 ~ 7 quality % again.As this solvent, as long as dissolve the organic solvent of above-mentioned special fiber prime system polymkeric substance and specific polysiloxane based polymer, be just not particularly limited.
In addition, in the scope not damaging effect of the present invention, aligning agent for liquid crystal can use the film thickness uniformity of liquid crystal orientation film, the compound of surface smoothness raising during coating of liquid crystalline aligning agent.And then, also can use the compound etc. that the adaptation of vertical liquid crystal tropism film and substrate improves.
As the compound making the film thickness uniformity of vertical liquid crystal tropism film, surface smoothness improves, fluorine system surfactant, silicone based surfactants, nonionic system surfactant etc. can be listed.More specifically, include, for example out EftopEF301, EF303, EF352 (being TohkemproductsCorporation system above); MegafacF171, F173, R-30 (being large Japanese ink Co., Ltd. system above); FluoradFC430, FC431 (being Sumitomo3MLimited system above); AsahiGuardAG710, SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (being Asahi Glass Co., Ltd's system above) etc.
The usage ratio of these surfactants is preferably 0.01 ~ 2 mass parts relative to all component of polymer 100 mass parts contained in aligning agent for liquid crystal, is more preferably 0.01 ~ 1 mass parts.
As the concrete example of the compound making the adaptation of vertical liquid crystal tropism film and substrate improve, can list following illustrate containing the compound of functional silanes, the compound containing epoxy radicals.Include, for example out 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide triethylene triamine, N-trimethoxy-silylpropyl triethylene triamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the ethoxy ethylene)-3-TSL 8330 of N-, two (the ethoxy ethylene)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N ' ,-four glycidyl group m-xylene diamine, two (N, the N-diglycidyl amino methyl) cyclohexane of 1,3-, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
When using these to make liquid crystal orientation film and the closely sealed compound of substrate, relative to all component of polymer 100 mass parts contained in aligning agent for liquid crystal, be preferably 0.1 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts.During less than 0.1 mass parts, cannot expect the effect improving adaptation, during more than 30 mass parts, the storage stability of aligning agent for liquid crystal is deteriorated sometimes.
In aligning agent for liquid crystal, outside compound in addition to the foregoing, as long as in the scope not damaging effect of the present invention, then also can add dielectric, the conductive materials of the electrical characteristics such as specific inductive capacity, electric conductivity for changing vertical liquid crystal tropism film.
< liquid-crystal composition >
Liquid-crystal composition in the present invention at least comprises liquid crystal and the liquid-crystal composition of the polymerizable compound of polymerization reaction take place because of ultraviolet.
Liquid crystal can use nematic liquid crystal, smectic liquid crystal or cholesteric liquid crystal.Wherein, preferably there is negative dielectric anisotropy.In addition, from the view point of low voltage drive and scattering properties, preferably, the anisotropy of specific inductive capacity anisotropy that is large, refractive index is large.In addition, according to each physics value of aforementioned phase transition temperature, dielectric constant anisotropy and refractive anisotrop, the liquid crystal that can be mixed with two or more.
In order to drive liquid crystal to represent element with active elements such as TFT (thin film transistor (TFT), ThinFilmTransistor), require that the resistance of liquid crystal is high, voltage retention (also referred to as VHR) high.Therefore, as liquid crystal, the fluorine system that preferred use resistance is high, VHR does not reduce because of ultraviolet isoreactivity energy-ray, chlorine system liquid crystal.
And then, represent element about liquid crystal, bitintability dyestuff also can be made to be dissolved in liquid-crystal composition and make guest-host type element.Now, be transparent when can not applied voltage and the element of appearance absorption (scattering) when applying voltage.In addition, this liquid crystal represents in element, and whether the direction (direction of orientation) of the director of liquid crystal is because applying voltage and occur 90 degree of changes.Therefore, compare with the vertical orientated existing guest-host type element carrying out changing with by random orientation, this liquid crystal represents that element passes through to utilize the extinction characteristic difference of bitintability dyestuff and can obtain high-contrast.In addition, be dissolved with in the guest-host type element of bitintability dyestuff, liquid crystal becomes coloured along during horizontal direction orientation, only becomes opaque in the scattering state.Therefore, the water white transparency that also can obtain when never applying voltage along with the applying of voltage switches to the element of coloured opaque, colored transparent state.
As polymerizable compound, as long as the compound of the solidfied material (being such as polymer network and so on) of liquid-crystal composition can be formed because of ultraviolet polymerization reaction take place.Now, the monomer of polymerizable compound can be directed in liquid-crystal composition, or the polymkeric substance that also can obtain making this monomer polymerization reaction take place is in advance directed in liquid-crystal composition.Wherein, even if when making polymkeric substance, also need the position with the polymerization reaction take place because of ultraviolet.More preferably, namely suppress the high viscosity of liquid-crystal composition, deliquescent viewpoint in liquid crystal from the process of liquid-crystal composition, preferably in liquid-crystal composition, import monomer and make its polymerization reaction take place making irradiation ultraviolet radiation when liquid crystal represents element thus form the method for solidfied material.
In addition, if polymerizable compound is dissolved in liquid crystal, then it can be any compound.Wherein, when polymerizable compound is dissolved in liquid crystal, need to exist the temperature that the part of liquid-crystal composition or entirety are shown as liquid crystal phase.Even a part for liquid-crystal composition is shown as the situation of liquid crystal phase, with the naked eye confirm liquid crystal represent element and in element entirety can obtain the basically identical transparency and scattering properties.
As long as the compound of polymerizable compound polymerization reaction take place because of ultraviolet, now, advance polymerization with which kind of reaction formation, form the solidfied material (solidfied material compound) of liquid-crystal composition.As concrete reaction formation, free radical polymerization, cationic polymerization, anionic polymerisation or addition polymerization can be listed.
Wherein, the reaction formation of polymerizable compound is preferably free radical polymerization.Now, as polymerizable compound, following radical-type polymerization compound (monomer) and oligomer thereof can be used.In addition, as implied above, also can use the polymkeric substance of these monomer polymerization reaction take places.
As simple function polymerizable compound (also referred to as monofunctional monomer), include, for example out 2-EHA, acrylic acid butyl ethyl ester, acrylate, butoxy ethyl, 2 cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, Hydroxyethyl Acrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid N, N-lignocaine ethyl ester, acrylic acid N, N-dimethylaminoethyl, acrylic acid two ring pentyl ester, acrylic acid dicyclopentenyl ester, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, acrylic acid morpholine ester, acrylate, phenoxy group diethylene glycol acrylate, acrylic acid 2,2,2-trifluoro ethyl ester, acrylic acid 2,2,3,3,3-five fluorine propyl ester, acrylic acid 2,2,3,3-tetrafluoro propyl ester, acrylic acid 2,2,3,4,4,4-hexafluoro butyl ester, 2-Ethylhexyl Methacrylate, butylethylmethacrylate, methacrylic acid butoxyethyl, methacrylic acid 2-cyanaoethyl methacrylate, acrylic acid benzyl methyl esters, cyclohexyl methacrylate, hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, acrylic acid 2-ethoxy ethyl ester, methacrylic acid N, N-lignocaine ethyl ester, methacrylic acid N, N-dimethylaminoethyl, methacrylic acid two ring pentyl ester, methacrylic acid dicyclopentenyl ester, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, methacrylic acid morpholine ester, phenoxyethyl methacrylate, phenoxy group diethylene glycol methacrylate, methacrylic acid 2,2,2-trifluoro ethyl ester, methacrylic acid 2,2,3,3-tetrafluoro propyl ester, the monomers such as methacrylic acid 2,2,3,4,4,4-hexafluroprobutyl alcohol and their oligomer.
As two sense polymerizable compounds (also referred to as two functional monomers), include, for example out 4,4 '-two acryloxy Stilbene, 4,4 '-two acryloxy dimethyl Stilbene, 4,4 '-two acryloxy diethyl Stilbene, 4,4 '-two acryloxy dipropyl Stilbene, 4,4 '-two acryloxy dibutyl Stilbene, 4,4 '-two acryloxy diamyl Stilbene, 4,4 '-two acryloxy dihexyl Stilbene, 4,4 '-two acryloxy difluoro Stilbene, 2,2,3,3,4,4-hexafluoro pentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoro propyl group-1,3-diacrylate, dimethacrylate, BDO dimethylacrylate, 1,3-BDO dimethylacrylate, HDDMA, neopentylglycol dimethacrylate, TEG dimethylacrylate, 4,4 '-biphenyl diacrylate, diethylstilbestrol diacrylate, Isosorbide-5-Nitrae-bis-acryloxy benzene, 4,4 '-bis-acryloxy diphenyl ether, 4,4 '-bis-acryloxy diphenyl methane, 3,9-[1,1-dimethyl-2-acryloyl-oxyethyl]-2,4,8,10-tetra-oxaspiro [5,5] undecane, α, α '-bis-[4-acryloxy phenyl]-Isosorbide-5-Nitrae-diisopropyl benzene, Isosorbide-5-Nitrae-bis-acryloxy phenyl tetrafluoride, 4,4 '-bis-acryloxy octafluorobiphenyl, diethylene glycol acrylate, BDO diacrylate, 1,3-BDO diacrylate, bicyclopentyl diacrylate, glycerol diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate, tetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, 1,9-nonanediol dimethylacrylate, polyethylene glycol dimethacrylate or polypropylene glycol dimethacrylate, or their oligomer etc.
As multifunctional polymerizable compound (also referred to as polyfunctional monomer), include, for example out trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, double trimethylolpropane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol monohydroxypentaacrylate, trimethylol-propane trimethacrylate, pentaerythritol tetramethylacrylate, pentaerythritol acrylate trimethyl, double trimethylolpropane tetramethyl acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxy pentamethacrylates, or 2, 2, 3, 3, 4, 4-hexafluoro pentanediol-1, 5-dimethylacrylate, or their oligomer etc.
Above-mentioned radical-type polymerization compound also can represent the characteristic of the adaptation of the optical characteristics of element, liquid crystal layer and vertical liquid crystal tropism film according to liquid crystal and use a kind or be mixed with two or more.
In order to promote that liquid-crystal composition forms solidfied material, for the object of the polymerizable compound generation free radical polymerization promoted in liquid-crystal composition, preferably import the radical initiator (polymerization initiator) producing free radical because of ultraviolet.Include, for example out tert-butyl hydroperoxide isobutyrate, two (benzoyl titanium dioxide) hexane of 2,5-dimethyl-2,5-, Isosorbide-5-Nitrae-bis-[α-(tert-butyl group titanium dioxide) isopropoxy] benzene, di-tert-butyl peroxide, two (tert-butyl group titanium dioxide) the hexene hydrogen peroxide of 2,5-dimethyl-2,5-, α-(isopropyl phenyl) hyperis, 2,5-dimethylhexane, tert-butyl hydroperoxide, two (tert-butyl group titanium dioxide)-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two (tert-butyl group titanium dioxide) valerate of butyl-4,4-, Cyclohexanone peroxides, 2,2 ', 5,5 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (t-amyl peroxy carbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxidating carbonyl) benzophenone, 3,3 '-bis-(tert-butyl hydroperoxide carbonyl)-4,4 '-benzophenonedicarboxylic acid, tert butyl peroxy benzoate, the organic peroxides such as di-t-butyl diperoxy isophthalic acid ester, the quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, prestox anthraquinone, 1,2-benzo anthraquinone, the benzoin derivatives etc. such as benzoin methylether, benzoin ethyl ether, Alpha-Methyl benzoin, α-phenylbenzoin.
These radical initiators also can represent the characteristic of the adaptation of the optical characteristics of element, liquid crystal layer and vertical liquid crystal tropism film according to liquid crystal and use a kind or be mixed with two or more.
As polymerizable compound, following ionic polymerization compound also can be used.Specifically, for have select free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl to form group at least a kind of compound being cross-linked to form group.
More specifically, amino hydrogen atom can be listed by methylol, alkoxy methyl or melamine derivative, benzoguanamine derivant, glycoluril etc. that both replaces.These melamine derivative, benzoguanamine derivant can be oligomer.In addition, they preferably every 1 triazine ring there are average more than 3 and less than 6 methylols or alkoxy methyl.
As the concrete example of this melamine derivative, benzoguanamine derivant, every 1 triazine ring that include, for example out commercially available product replaces the MX-750 having average 3.7 methoxies; Every 1 triazine ring replaces the MW-30 (being Sanwa Chemical Co., Ltd above) having average 5.8 methoxies; CYMEL300,301,303,350,370,771,325,327,703, the methoxymethylated melamines such as 712; CYMEL235,236,238,212,253, the methoxymethylated butoxymethyl melamines such as 254; CYMEL506, the butoxymethyl melamines such as 508; The carboxylic methoxymethylated isobutoxymethyl melamine of CYMEL1141 and so on; The methoxymethylated ethoxyl methyl benzoguanamine of CYMEL1123 and so on; The butoxymethyl benzoguanamine of the methoxymethylated butoxymethyl benzoguanamine, CYMEL1128 and so on of CYMEL1123-10 and so on; The carboxylic methoxymethylated ethoxyl methyl benzoguanamine (being Mitsui サ イ テ ッ Network Inc. above) of CYMEL1125-80 and so on.In addition, as the example of glycoluril, the methylolation glycoluril etc. of the butoxymethyl glycoluril, CYMEL1172 and so on of CYMEL1170 and so on can be listed.
As benzene or the benzene phenoloid with hydroxyl or alkoxy, include, for example out 1,3,5-tri-(methoxymethoxy) benzene, 1,2,4-tri-(isopropoxy methoxyl) benzene, Isosorbide-5-Nitrae-bis-(sec-butoxy methoxyl) benzene, 2,6-bishydroxymethyl p-t-butyl phenols etc.
In addition, as ionic polymerization compound, also can use and comprise epoxy radicals, isocyanate group and there is the compound being cross-linked to form group.
Specifically, include, for example out bisphenol acetone glycidol ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four glycidyl group aminobphenyl, four glycidyl group m-xylene diamine, two (amino-ethyl) cyclohexane of four glycidyl group-1,3-, tetraphenyl glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, two (1-(2,3-glycidoxy)-1-trifluoromethyl-2,2, the 2-trifluoromethyl) benzene of 1,3-, two (2, the 3-glycidoxy) octafluorobiphenyl of 4,4-, triglycidyl group para-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-glycidoxy) phenyl)-2-(4-(two (4-(2, the 3-glycidoxy) phenyl) ethyl of 1,1-) phenyl) propane, 1, two (4-(1-(the 4-(2 of 3-, 3-glycidoxy) phenyl)-1-(4-(1-(4-(2,3-glycidoxy phenyl)-1-Methylethyl) phenyl) ethyl) phenoxy group)-2-propyl alcohol etc.
When using ionic polymerization compound, in order to promote its polyreaction, also can import the following ionic initiator producing acid or alkali because of ultraviolet.Specifically, such as can use triazine based compound, acetophenone derivs compound, two sulfone based compounds, bisdiazo methane series compound, sulfonic acid compound, diaryl group iodized salt, triarylsulfonium salt, San Fang Ji phosphonium salt, iron-arene complexes etc., but be not limited to them.
More specifically, include, for example out diphenyliodonium chloride, diphenylsulfonium Loprazolam iodine, diphenylmethyl sulfonic acid iodine, diphenylmethyl benzene sulfonic acid iodine, diphenyl IBr, diphenyl tetrafluoro boric acid iodine, diphenyl hexafluoro-iodide antimonate, diphenyl hexafluoroarsenate iodine, two (to tert-butyl-phenyl) iodonium hexafluorophosphate, two (to tert-butyl-phenyl) methane-sulforic acid iodine, two (to tert-butyl-phenyl) toluenesulfonic acid iodine, two (to tert-butyl-phenyl) trifluoromethayl sulfonic acid iodine, two (to tert-butyl-phenyl) tetrafluoro boric acid iodine, two (to tert-butyl-phenyl) lodine chloride, two (rubigan) lodine chloride, two (rubigan) tetrafluoro boric acid iodine, benzyltriphenylphosphonium chloride sulfonium, triphenyl phosphonium bromide sulfonium, three (p-methoxyphenyl) tetrafluoro boric acid sulfonium, three (p-methoxyphenyl) hexafluoro phosphonic acids sulfonium, three (to ethoxyl phenenyl) tetrafluoro boric acid sulfonium, triphenyl phosphonium chloride, triphenyl phosphonium bromide, three (p-methoxyphenyl) Si Fu Peng Suan Phosphonium, three (p-methoxyphenyl) six Fu Lin Suan Phosphonium, three (to ethoxyl phenenyl) Si Fu Peng Suan Phosphonium, two [[(2-nitrobenzyl) oxygen base] carbonyl hexane-1,6-diamines], nitrobenzyl cyclohexylcarbamate, two (methoxy-benzyl) hexa-methylene diamino formic ether, two [[(2-nitrobenzyl) oxygen base] carbonyl hexane-1,6-diamines], nitrobenzyl cyclohexylcarbamate, two (methoxy-benzyl) hexa-methylene diamino formic ether etc.
Liquid crystal of the present invention represents in element, from the view point of optical characteristics, among above-mentioned polymerizable compound, preferably uses the polymerizable compound of free radical type.
The import volume of the polymerizable compound in liquid-crystal composition is not particularly limited, when the import volume of polymerizable compound is many, polymerizable compound can not be dissolved in liquid crystal or there is not the change that liquid-crystal composition is shown as the temperature of liquid crystal phase or the pellucidity of element and scattering state and diminish, and optical characteristics is deteriorated.In addition, when the import volume of polymerizable compound is few, the adaptation of the curability step-down of liquid crystal layer and then liquid crystal layer and liquid crystal orientation film reduces, and liquid crystal aligning easily becomes disorderly relative to mechanical external pressure.Therefore, the import volume of polymerizable compound is preferably 1 ~ 50 mass parts relative to liquid crystal 100 mass parts, is more preferably 5 ~ 40 mass parts.Be particularly preferably 11 ~ 30 mass parts.
In addition, the import volume for the radical initiator or ionic initiator that promote the reaction of polymerizable compound is not particularly limited, and relative to liquid crystal 100 mass parts, is preferably 0.01 ~ 10 mass parts, is more preferably 0.05 ~ 5 mass parts.Be particularly preferably 0.05 ~ 3 mass parts.
< vertical liquid crystal tropism film and liquid crystal represent the method for making > of element
The substrate used in element is represented as liquid crystal of the present invention, as long as the high substrate of the transparency is just not particularly limited, except glass substrate, plastic base and their films such as acrylic compounds substrate, polycarbonate substrate, PET (polyethylene terephthalate) substrate can also be used.When liquid crystal being represented element is made flyback type element and is used for light-regulating window etc., be preferably plastic base, film.In addition, from the view point of Simplified flowsheet, preferred use is formed with the ITO (tin indium oxide for driving liquid crystal, IndiumTinOxide) electrode, IZO (indium zinc oxide, IndiumZincOxide) substrate of electrode, IGZO (indium oxide gallium zinc, IndiumGalliumZincOxide) electrode, Organic Conductive Films etc.In addition, when making the flyback type element of reflection-type, if be only single sided substrate, then also can use the metal such as silicon wafer, aluminium, be formed with the substrate of dielectric multilayer film.
Liquid crystal of the present invention represents that at least one substrate of element has the vertical liquid crystal tropism film making liquid crystal molecule vertical orientated.Aligning agent for liquid crystal can be coated on substrate and after burning till by this vertical liquid crystal tropism film, to be penetrated etc. carry out orientation process and obtain by brushing process, illumination.Wherein, when vertical liquid crystal tropism film of the present invention, do not carry out these orientation process and can be used as vertical liquid crystal tropism film yet.
The coating process of aligning agent for liquid crystal is not particularly limited, industrial have serigraphy, hectographic printing, flexible printing, ink-jet method, dip coating, rolling method, slot coated method, spin coater method, spraying process etc., suitably can select according to the target film thickness of the kind of substrate, vertical liquid crystal tropism film.
Aligning agent for liquid crystal is coated on after on substrate, utilize the heater means of hot plate, thermal cycle type baking oven, IR (infrared ray) type baking oven etc., according to the solvent used in the kind of substrate, aligning agent for liquid crystal, with 30 ~ 300 DEG C, preferably with the temperature of 30 ~ 250 DEG C, solvent is evaporated, thus vertical liquid crystal tropism film can be made.Especially, during substrate use plastic base, preferably process with the temperature of 30 ~ 150 DEG C.
When the thickness of the vertical liquid crystal tropism film after burning till is blocked up, be disadvantageous in the power consumption representing element at liquid crystal, when thickness is crossed thin, the reliability of element reduces sometimes, is therefore preferably 5 ~ 500nm.Be more preferably 10 ~ 300nm, be particularly preferably 10 ~ 250nm.
Liquid crystal of the present invention represents that the liquid-crystal composition used in element is liquid-crystal composition as described above, wherein, also can import the sept of the electrode gap (also referred to as gap) representing element for controlling liquid crystal.
The method for implanting of liquid-crystal composition is not particularly limited, and include, for example out following method.Namely, during substrate use glass substrate, following method can be listed: a pair substrate preparing to be formed with vertical liquid crystal tropism film, one-sided substrate 4 pieces is all coated with sealant except a part, thereafter, be pasted on the substrate of opposite side with the surface of vertical liquid crystal tropism film towards the mode of inner side, make dummy cell thus.Further, from the position decompression injection liquid crystal composite of uncoated sealant, thus the unit being injected with liquid-crystal composition is obtained.And then, when substrate use plastic base, film, following method can be listed: a pair substrate preparing to be formed with vertical liquid crystal tropism film, one-sided substrate utilizes ODF, and (liquid crystal drop following formula injects, OneDropFilling) dropping liquid such as method, ink-jet method crystal composite, thereafter paste the substrate of opposite side, thus obtain the unit being injected with liquid-crystal composition.
Liquid crystal of the present invention represents in element, because the adaptation of liquid crystal layer and vertical liquid crystal tropism film is high, therefore, 4 pieces of substrates also can not be coated with sealant.
Liquid crystal represents that the gap of element can with controls such as aforementioned septs.The method can list: in liquid-crystal composition, import the method for the sept of target sizes as described above, use the method etc. with the substrate of the intercolumniation parting of target sizes.In addition, substrate uses plastics, film substrate and when carrying out the laminating of substrate by lamination, can not import sept ground control gap.
Liquid crystal represents that the gap length of element is preferably 1 ~ 100 μm, is more preferably 2 ~ 50 μm.Be particularly preferably 5 ~ 20 μm.When gap is too small, liquid crystal represents that the contrast of element reduces, and during excesssive gap, the driving voltage of element uprises.
Liquid crystal of the present invention represents that element is by carrying out the solidification of liquid-crystal composition under the state that is shown as liquid crystal liquid crystal property in a part or the entirety of liquid-crystal composition, thus the solidfied material compound forming liquid crystal and polymerizable compound obtains.The solidification of this liquid-crystal composition is undertaken by carrying out Ultraviolet radiation to foregoing liquid crystal composition injection unit and adding at least one process hankered.
As the light source of the ultraviolet lamp now used, include, for example out metal halide lamp or high-pressure sodium lamp.In addition, ultraviolet wavelength is preferably 250 ~ 400nm.Wherein, 310 ~ 370nm is preferably.In addition, when heating, its temperature is 40 ~ 120 DEG C, is preferably 60 ~ 80 DEG C.And then, also can carry out both UV treatment and heating simultaneously, can also heat after UV treatment.In the present invention, the solidification of liquid-crystal composition preferably only carries out UV treatment.
As mentioned above, the transparency when liquid crystal employing the vertical liquid crystal tropism film obtained by aligning agent for liquid crystal of the present invention represents that element can become that the adaptation vertical orientated property that is high and then liquid crystal of liquid crystal layer and vertical liquid crystal tropism film is high, namely optical characteristics does not well the apply voltage liquid crystal good with scattering properties when applying voltage represents element, and described aligning agent for liquid crystal comprises the cellulose-based polymkeric substance of ad hoc structure and has the polysiloxane based polymer of side chain of ad hoc structure.Especially, this element can compatibly for presenting transmissive state when not applying voltage and presenting the flyback type element of scattering state when applying voltage, as with the liquid crystal display being expressed as object, control the transmission of light and the light-regulating window, shutter element etc. of blocking is useful.As substrate now, preferably use plastic base, film.
In addition, liquid crystal of the present invention represents that element can represent element by the liquid crystal compatibly for using in the transportation machines such as automobile, train, aircraft and Transport Machinery, specifically, the shutter element etc. for using in the light-regulating window of the transmission and blocking that control light, rearview mirror.Especially, because transparency when not applying voltage is good with scattering properties when applying voltage, when therefore this element being used for the windowpane of the vehicles, compared with employing the situation of existing flyback type element, the acquisition efficiency of the light at night is high, and the effect preventing extraneous light dazzling also uprises.Therefore, it is possible to improve further security when driving a conveyance, by bus time comfortableness.In addition, when utilizing film to make this element and be pasted on the windowpane of the vehicles and use, be less likely to occur low by the adaptation of liquid crystal layer and vertical liquid crystal tropism film and cause bad, deteriorated, compared with existing flyback type element, reliability uprises.
And then, liquid crystal of the present invention represents that element also may be used for LCD (liquid crystal display, LiquidCrystalDisplay), the display equipment such as OLED (Organic Light Emitting Diode, OrganicLight-emittingDiode) display light guide plate, employ the backboard of the transparent display of these displays.Specifically, composition transparent display and this element and on transparent display, carry out picture when representing, this element can suppress light to enter from the back side.Now, this element carries out picture when representing on transparent display, applies voltage and presents scattering state, picture can be made to represent clear, after end picture represents, present and do not execute alive pellucidity.
Embodiment
Below list embodiment to illustrate in greater detail the present invention, but not by their limited explanation.It should be noted that, the abbreviation of the compound used in synthesis example, embodiment and comparative example is as follows.
< liquid-crystal composition >
(liquid crystal) L1:MLC-6608 (MERCKCORPORATION system)
(polymerizable compound) R1: the compound shown in following formula [R1]
(light trigger) P1: the compound shown in following formula [P1]
(special fiber prime system polymkeric substance)
CE-1: hydroxyethyl cellulose (Wako Pure Chemical Industries, Ltd.'s system)
CE-2: hydroxypropylmethyl cellulose phthalate (ACROS Inc.)
(alkoxy silane monomer)
E1: the alkoxy silane shown in following formula [E1]
E2: octadecyltriethoxy silane
E3:3-methacryloxypropyl trimethoxy silane
E4:3-urea propyl-triethoxysilicane
E5: tetraethoxysilane
(specific generation agent)
S1: the optical free radical shown in following formula [S1] produces agent
S2: the optical free radical shown in following formula [S2] produces agent
(specific adaptation compound)
M1: the compound shown in following formula [M1]
M2: the compound shown in following formula [M2]
M3: the compound shown in following formula [M3]
(specific cross-linked compound)
K1: the compound shown in following formula [K1]
(solvent)
PGME: propylene glycol monomethyl ether
ECS: ethylene glycol monomethyl ether
BCS: ethylene glycol monobutyl ether
PB: glycol monobutyl ether
EC: TC
" synthesis of polysiloxane based polymer "
< synthesis example 1>
In the 200ml tetra-neck reaction flask possessing thermometer and recirculatory pipe, mixing ECS (28.3g), E1 (4.10g), E3 (7.45g) and E5 (32.5g), thus prepare the solution of alkoxy silane monomer.Expend at 25 DEG C in 30 points of these solution of clockwise and drip in advance using ECS (14.2g), water (10.8g), the solution prepare as oxalic acid (0.70g) mixing of catalyzer, and then stirring 30 minutes at 25 DEG C.Thereafter, oil bath is used to carry out heating and after refluxing 30 minutes, the content adding previously prepared E4 is the methanol solution (1.20g) of 92 quality % and the mixed solution of ECS (0.90g).Further backflow, after 30 minutes, naturally cools, thus obtains SiO 2converted score is the polysiloxane solution (1) of 12 quality %.
< synthesis example 2>
In the 200ml tetra-neck reaction flask possessing thermometer and recirculatory pipe, mixing PGME (28.3g), E1 (8.20g), E3 (19.9g) and E5 (20.0g), thus prepare the solution of alkoxy silane monomer.Expend at 25 DEG C in 30 points of these solution of clockwise and drip in advance using PGME (19.1g), water (10.8g), the solution prepare as oxalic acid (1.10g) mixing of catalyzer, and then stirring 30 minutes at 25 DEG C.Thereafter, oil bath is used to carry out heating and after refluxing 30 minutes, the content adding previously prepared E4 is the methanol solution (1.20g) of 92 quality % and the mixed solution of PGME (0.90g).Further backflow, after 30 minutes, naturally cools, thus obtains SiO 2converted score is the polysiloxane solution (2) of 12 quality %.
< synthesis example 3>
In the 200ml tetra-neck reaction flask possessing thermometer and recirculatory pipe, mixing ECS (29.2g), E1 (4.10g) and E5 (38.8g), thus prepare the solution of alkoxy silane monomer.Expend at 25 DEG C in 30 points of these solution of clockwise and drip in advance using ECS (12.1g), water (10.8g), the solution prepare as oxalic acid (0.50g) mixing of catalyzer, and then stirring 30 minutes at 25 DEG C.Thereafter, oil bath is used to carry out heating and after refluxing 30 minutes, the content adding previously prepared E4 is the methanol solution (1.20g) of 92 quality % and the mixed solution of ECS (0.90g).Further backflow, after 30 minutes, naturally cools, thus obtains SiO 2converted score is the polysiloxane solution (3) of 12 quality %.
< synthesis example 4>
In the 200ml tetra-neck reaction flask possessing thermometer and recirculatory pipe, mixing PGME (28.3g), E2 (4.07g), E3 (7.45g) and E5 (32.5g), thus prepare the solution of alkoxy silane monomer.Expend at 25 DEG C in 30 points of these solution of clockwise and drip in advance using PGME (14.2g), water (10.8g), the solution prepare as oxalic acid (0.70g) mixing of catalyzer, and then stirring 30 minutes at 25 DEG C.Thereafter, oil bath is used to carry out heating and after refluxing 30 minutes, the content adding previously prepared E4 is the methanol solution (1.20g) of 92 quality % and the mixed solution of PGME (0.90g).Further backflow, after 30 minutes, naturally cools, thus obtains SiO 2converted score is the polysiloxane solution (4) of 12 quality %.
< synthesis example 5>
In the 200ml tetra-neck reaction flask possessing thermometer and recirculatory pipe, mixing ECS (27.7g), E3 (7.45g) and E5 (32.5g), thus prepare the solution of alkoxy silane monomer.Expend at 25 DEG C in 30 points of these solution of clockwise and drip in advance using the solution that ECS (10.0g), water (10.8g) and the oxalic acid (0.70g) as catalyzer mix and prepares, and then stir 30 minutes at 25 DEG C.Thereafter, oil bath is used to carry out heating and after refluxing 30 minutes, the content adding previously prepared E4 is the methanol solution (1.20g) of 92 quality % and the mixed solution of ECS (0.90g).Further backflow, after 30 minutes, naturally cools, thus obtains SiO 2converted score is the polysiloxane solution (5) of 12 quality %.
The composition of the polysiloxane based polymer (polysiloxane solution) obtained in each synthesis example and the alkoxy silane monomer used is shown in table 1.
[table 1]
" making of liquid-crystal composition "
(making of liquid-crystal composition (1))
L1 (11.5g), R1 (1.73g) and P1 (0.12g) are mixed, is heated to 80 DEG C, is cooled to thereafter 25 DEG C, thus obtain liquid-crystal composition (1).
(making of liquid-crystal composition (2))
L1 (12.0g), R1 (2.40g) and P1 (0.12g) are mixed, is heated to 80 DEG C, is cooled to thereafter 25 DEG C, thus obtain liquid-crystal composition (2).
" manufacture of aligning agent for liquid crystal "
Embodiment 1 ~ 15 and comparative example 1 ~ 5 are Production Examples of aligning agent for liquid crystal, and this aligning agent for liquid crystal also represents making and the evaluation thereof of element for liquid crystal.
The aligning agent for liquid crystal obtained in embodiment and comparative example, composition are shown in table 2 ~ 4 containing proportional etc. summary.
" liquid crystal represents the making (glass substrate) of element "
The membrane filter being 1 μm by the aligning agent for liquid crystal aperture obtained in embodiment and comparative example carries out pressure filtration, carries out the making that liquid crystal represents element.Specifically, this aligning agent for liquid crystal is spun on the ito surface of glass substrate (vertical: 100mm, horizontal stroke: 100mm, thickness: 0.7mm) of the band ITO electrode of 100 × 100mm through cleaning with pure water and IPA (isopropyl alcohol), hot plate heats 5 minutes with 100 DEG C, and clean baking oven with 200 DEG C of heating 15 minutes by thermal cycle type, thus obtain the ito substrate that band thickness is the liquid crystal orientation film of 100nm.Prepare the ito substrate of band liquid crystal orientation film of 2 pieces of gained, the sept of coating 6 μm on the liquid crystal aligning face of one piece of substrate wherein.Thereafter, the liquid crystal aligning face being coated with sept to this substrate utilizes ODF (OneDropFilling) method to drip foregoing liquid crystal composition, then, fit in the mode of the liquid crystal aligning membrane interface towards another substrate, thus obtain liquid crystal before treatment and represent element.
Represent element for this liquid crystal before treatment, use the metal halide lamp that illumination is 60mW, cut out the wavelength of below 350nm, carry out being scaled 7J/cm with 365nm 2ultraviolet radiation.Now, control at 25 DEG C to the temperature in irradiation unit during liquid crystal cells irradiation ultraviolet radiation.Obtain liquid crystal thus and represent element (flyback type element).
" liquid crystal represents the making (plastic base) of element "
The membrane filter being 1 μm by the aligning agent for liquid crystal aperture obtained in embodiment and comparative example carries out pressure filtration, carries out the making that liquid crystal represents element.Specifically, by bar coater, this aligning agent for liquid crystal is coated on the ito surface of PET (polyethylene terephthalate) substrate (vertical: 150mm, horizontal stroke: 150mm, thickness: 0.2mm) of the band ITO electrode of 150 × 150mm through cleaning with pure water, hot plate heats 5 minutes with 100 DEG C, and clean baking oven with 150 DEG C of heating 1 minute by thermal cycle type, thus obtain the ito substrate that band thickness is the liquid crystal orientation film of 100nm.Prepare the ito substrate of band liquid crystal orientation film of 2 pieces of gained, the sept of coating 6 μm on the liquid crystal aligning face of one piece of substrate wherein.Thereafter, on the liquid crystal aligning face being coated with sept of this substrate, utilize ODF method to drip foregoing liquid crystal composition, then, fit in the mode of the liquid crystal aligning membrane interface towards another substrate, thus obtain liquid crystal before treatment and represent element.
Represent element for this liquid crystal before treatment, use the metal halide lamp that illumination is 60mW, cut out the wavelength of below 350nm, carry out being scaled 7J/cm with 365nm 2ultraviolet radiation.Now, control at 25 DEG C to the temperature in irradiation unit during liquid crystal cells irradiation ultraviolet radiation.Obtain liquid crystal thus and represent element (flyback type element).
" evaluation (glass substrate) of liquid crystal aligning "
Use the liquid crystal utilizing said method to obtain to represent element (glass substrate), carry out the evaluation of liquid crystal aligning.About liquid crystal aligning, observe this element with polarization microscope (ECLIPSEE600WPOL, Nikon Corp.'s system), confirm that whether liquid crystal is vertical orientated.Specifically, the sample of liquid crystal vertical-tropism is regarded as this evaluation excellence (being expressed as in table 5 ~ table 7 " well ").
Thereafter, the liquid crystal after the evaluation of liquid crystal aligning being terminated represents that element (glass substrate) is take care of 336 hours in the high temperature groove of 100 DEG C in temperature.Thereafter, condition same as described above is utilized to carry out the evaluation of liquid crystal aligning.Specifically, when not observing the homogeneous orientation of liquid crystal aligning sexual disorder, liquid crystal, this evaluation excellence (being expressed as in table 5 ~ table 7 " well ") is regarded as.
" evaluation (plastic base) of liquid crystal aligning "
Use the liquid crystal utilizing said method to obtain to represent element (plastic base), carry out the evaluation of liquid crystal aligning.About liquid crystal aligning, observe this element with polarization microscope (ECLIPSEE600WPOL, Nikon Corp.'s system), confirm that whether liquid crystal is vertical orientated.Specifically, the sample of liquid crystal vertical-tropism is regarded as this evaluation excellence (being expressed as " well " in table 5 and table 6).
Thereafter, the liquid crystal after the evaluation of liquid crystal aligning being terminated represents that element (plastic base) is take care of 336 hours in the high temperature groove of 100 DEG C in temperature.Thereafter, condition same as described above is utilized to carry out the evaluation of liquid crystal aligning.Specifically, when not observing the homogeneous orientation of liquid crystal aligning sexual disorder, liquid crystal, this evaluation excellence (being expressed as in table 5 ~ table 6 " well ") is regarded as.
" evaluation (glass substrate) of optical characteristics (transparency and scattering properties) "
Use the liquid crystal utilizing said method to obtain to represent element (glass substrate), carry out the evaluation of optical characteristics (transparency and scattering properties).
About transparency when not applying voltage, represent that the transmissivity of element is evaluated by measuring the liquid crystal do not applied under voltage status.Specifically, determinator uses UV-3600 (Shimadzu Seisakusho Ltd.'s system), and contrast uses the glass substrate of above-mentioned band ITO electrode, temperature be 25 DEG C, scanning wavelength measures transmissivity under being the condition of 300 ~ 800nm.Evaluate by the transmissivity of 450nm wavelength, transmissivity is higher, then regard as this evaluation more excellent (value of transmissivity shown in table 8 ~ table 10).
Scattering properties during applying voltage is by representing that to liquid crystal element applies 40V to exchange to drive, and the state of orientation of visualization liquid crystal is carried out.Specifically, this element gonorrhoea, when can access scattering properties, regard as this evaluation excellence (being expressed as in table 8 ~ table 10 " well ").
" evaluation (plastic base) of optical characteristics (transparency and scattering properties) "
Use the liquid crystal utilizing said method to obtain to represent element (plastic base), carry out the evaluation of optical characteristics (transparency and scattering properties).
About transparency when not applying voltage, represent that the transmissivity of element is evaluated by measuring the liquid crystal do not applied under voltage status.Specifically, determinator uses UV-3600 (Shimadzu Seisakusho Ltd.'s system), and contrast uses the pet substrate of above-mentioned band ITO electrode, temperature be 25 DEG C, scanning wavelength measures transmissivity under being the condition of 300 ~ 800nm.Evaluate by the transmissivity of 450nm wavelength, transmissivity is higher, then regard as this evaluation more excellent (value of transmissivity shown in table 8 and table 9).
Scattering properties during applying voltage is by representing that to liquid crystal element applies 40V to exchange to drive, and the state of orientation of visualization liquid crystal is carried out.Specifically, this element gonorrhoea, when can access scattering properties, regard as this evaluation excellence (being expressed as " well " in table 8 and table 9).
The evaluation (glass substrate) of the adaptation of (vertical) liquid crystal orientation film " liquid crystal layer with "
Use the liquid crystal having carried out above-mentioned optical characteristics evaluation to represent element, carry out the adaptation evaluation of liquid crystal layer and liquid crystal orientation film.Specifically, liquid crystal is represented element is taken care of 96 hours in the hot and humid groove of temperature 80 DEG C, humidity 90%RH, confirm in this element, have bubble-free and element whether to peel off.Now, bubble will do not observed in this element and element is peeled off (state that liquid crystal layer and liquid crystal orientation film there occurs stripping) and regarded as this evaluation excellence (being expressed as in table 8 ~ table 10 " well ").
The evaluation (plastic base) of the adaptation of (vertical) liquid crystal orientation film " liquid crystal layer with "
Use the liquid crystal having carried out above-mentioned optical characteristics evaluation to represent element, carry out the adaptation evaluation of liquid crystal layer and liquid crystal orientation film.Specifically, liquid crystal is represented element is taken care of 96 hours in the hot and humid groove of temperature 80 DEG C, humidity 90%RH, confirm in this element, have bubble-free and element whether to peel off.Now, bubble will do not observed in this element and element is peeled off (state that liquid crystal layer and liquid crystal orientation film there occurs stripping) and regarded as this evaluation excellence (being expressed as " well " in table 8 and table 9).
< embodiment 1>
In CE-2 (1.10g), add ECS (21.0g) and PB (14.2g), stir 5 hours with 50 DEG C.Thereafter, add in this solution polysiloxane solution (1) (13.8g) that utilize synthesis example 1 to obtain, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (1).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 2>
Use the aligning agent for liquid crystal (1) and liquid-crystal composition (2) that obtain in embodiment 1, make liquid crystal and represent element (glass substrate, plastic base) and evaluate.
< embodiment 3>
In CE-2 (1.40g), add ECS (15.1g), PGME (15.1g) and BCS (10.7g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (1) (14.3g), the S2 (0.156g) and M2 (0.467g) that utilize synthesis example 1 to obtain is added in this solution, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (2).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 4>
In CE-2 (1.65g), add ECS (33.3g), BCS (6.00g) and EC (5.30g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (1) (13.8g), the S1 (0.165g) and M2 (0.165g) that utilize synthesis example 1 to obtain is added in this solution, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (3).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 5>
In CE-2 (1.00g), add PGME (28.7g), BCS (5.70g) and EC (5.70g), stir 5 hours with 50 DEG C.Thereafter, add in this solution polysiloxane solution (2) (19.4g) that utilize synthesis example 2 to obtain, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (4).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 6>
In CE-2 (0.95g), add PGME (21.8g), ECS (10.9g) and EC (5.40g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (2) (18.5g), the S2 (0.159g) and M1 (0.634g) that utilize synthesis example 2 to obtain is added in this solution, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (5).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 7>
In CE-1 (0.50g), add PGME (27.9g) and BCS (8.60g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (2) (23.6g), the S2 (0.233g) and M3 (0.500g) that utilize synthesis example 2 to obtain is added in this solution, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (6).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 8>
In CE-1 (0.65g), add PGME (28.4g) and PB (8.40g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (2) (21.7g), S2 (0.033g) that in this solution, interpolation utilizes synthesis example 2 to obtain, M2 (0.975g) and K1 (0.163g), stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (7).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 9>
In CE-2 (1.10g), add ECS (21.0g) and PB (14.2g), stir 5 hours with 50 DEG C.Thereafter, add in this solution polysiloxane solution (3) (13.8g) that utilize synthesis example 3 to obtain, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (8).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 10>
Use the aligning agent for liquid crystal (8) and liquid-crystal composition (2) that obtain in embodiment 9, make liquid crystal and represent element (glass substrate, plastic base) and evaluate.
< embodiment 11>
In CE-2 (1.40g), add ECS (35.6g) and EC (5.30g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (3) (14.3g), S2 (0.311g) that in this solution, interpolation utilizes synthesis example 3 to obtain, M2 (0.778g) and K1 (0.062g), stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (9).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 12>
In CE-2 (1.65g), add ECS (17.8g), PGME (17.8g) and EC (5.30g), stir 5 hours with 50 DEG C.Thereafter, add in this solution polysiloxane solution (3) (11.3g) that utilize synthesis example 3 to obtain, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (10).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 13>
In CE-2 (0.65g), add PGME (25.6g) and BCS (11.2g), stir 5 hours with 50 DEG C.Thereafter, add in this solution polysiloxane solution (4) (21.7g) that utilize synthesis example 4 to obtain, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (11).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 14>
In CE-2 (1.70g), add PGME (34.3g) and PB (11.7g), stir 5 hours with 50 DEG C.Thereafter, polysiloxane solution (4) (14.2g), the S1 (0.170g) and M2 (0.170g) that utilize synthesis example 4 to obtain is added in this solution, stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (12).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< embodiment 15>
In CE-1 (0.50g), add PGME (22.2g) and BCS (14.3g), stir 5 hours with 50 DEG C.Thereafter, in this solution, add utilize synthesis example 4 to obtain polysiloxane solution (4) (23.6g) and M3 (0.666g), stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (13).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< comparative example 1>
In the polysiloxane solution utilizing synthesis example 5 to obtain (5) (15.0g), add ECS (6.50g) and PB (8.50g), stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (14).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< comparative example 2>
In the polysiloxane solution utilizing synthesis example 1 to obtain (1) (15.5g), add ECS (6.80g) and PB (8.70g), stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (15).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< comparative example 3>
Use in comparative example 2 aligning agent for liquid crystal (15) and liquid-crystal composition (2) that obtain, carry out the evaluation (glass substrate) that liquid crystal represents the making (glass substrate) of element, the evaluation (glass substrate) of liquid crystal aligning, the evaluation (glass substrate) of optical characteristics (transmissivity and scattering properties) and the adaptation of liquid crystal layer and liquid crystal orientation film.
< comparative example 4>
In the polysiloxane solution utilizing synthesis example 3 to obtain (3) (15.0g), add ECS (6.50g) and PB (8.50g), stir 5 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (16).It is abnormal that this aligning agent for liquid crystal does not observe muddiness, precipitation etc., confirms as uniform solution.
< comparative example 5>
Use the aligning agent for liquid crystal (16) and liquid-crystal composition (2) that obtain in comparative example 4, make liquid crystal and represent element (glass substrate) and evaluate.
The liquid crystal of < embodiment 1 ~ 18, comparative example 1 ~ 5> represents the evaluation of element
As shown in following table 5, table 6, table 7, table 8, table 9 and table 10, use in above-described embodiment any one and the foregoing liquid crystal composition (1) in aligning agent for liquid crystal (14) ~ (16) obtained respectively in aligning agent for liquid crystal (1) ~ (13) or comparative example obtained respectively or (2), carry out the evaluation that foregoing liquid crystal represents the evaluation of the making of element and liquid crystal aligning, the evaluation of optical characteristics (transparency and scattering properties) and the adaptation of liquid crystal layer and vertical liquid crystal tropism film.
It should be noted that, embodiment 1,2,4,6,7,9,10,11,12 and 14 is carried out for the element of glass substrate and both elements of plastic base, and embodiment 3,5,8,13,15 and comparative example 1 ~ 5 carry out for the element of glass substrate.These results evaluated are summed up and is shown in table 5, table 6, table 7, table 8, table 9 and table 10.
In addition, for embodiment 2,3,9,11 and comparative example 3,4, in the evaluation of the adaptation of liquid crystal layer and vertical liquid crystal tropism film, test as aforesaid standards and emphasize test, also having carried out keeping 168 little evaluations (other condition is identical with aforementioned condition) constantly in the hot and humid groove of temperature 80 DEG C, humidity 90%RH.Its result, does not observe bubble in the element of embodiment 3,11, can be observed a small amount of bubble in the element of embodiment 2,9, can be observed a large amount of bubble and a part of position can be observed the stripping of element in the element of comparative example 3,4.
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
[table 10]
* 1: liquid crystal is not vertical orientated.
* 2: can be observed liquid crystal aligning sexual disorder.
* 3: liquid crystal is not vertical orientated, therefore cannot measure.
* 4: element is peeled off between liquid crystal layer and liquid crystal orientation film.
* 5: in element, can be observed bubble.
From the above results: compared with representing element with the liquid crystal of comparative example, the liquid crystal of embodiment represents that the adaptation of the liquid crystal layer of element and liquid crystal orientation film is high, and then the vertical orientated property of liquid crystal is high, transparency when well, namely optical characteristics does not apply voltage is good with scattering properties when applying voltage.
On the other hand, the liquid crystal of comparative example represents that the adaptation of the liquid crystal layer of element and liquid crystal orientation film is poor, in hot and humid groove after keeping, can be observed bubble or can be observed liquid crystal layer and vertical alignment layer is peeled off in element.In addition, the liquid crystal of comparative example represents element in high temperature groove after keeping, can be observed and that cause liquid crystal aligning sexual disorder not enough by the vertical orientated property of liquid crystal.
Specifically, comprise same specific polysiloxane based polymer and comprise as the special fiber prime system polymkeric substance of composition (A) embodiment with do not comprise in the contrast of comparative example of special fiber prime system polymkeric substance, namely embodiment 1 and comparative example 2, embodiment 2 and comparative example 3, embodiment 9 and comparative example 4 and embodiment 10 are with the contrast of comparative example 5, can be observed notable difference.
In addition, employ in the comparative example 1 not containing the polysiloxane based polymer of specific side chain, liquid crystal is not vertical orientated.
And then, aligning agent for liquid crystal imported specific generation agent, specific adaptation compound and specific cross-linked compound time, the liquid crystal formed represents in element, and the adaptation of liquid crystal layer and vertical liquid crystal tropism film is better.Specifically, by embodiment 2 and embodiment 3 and embodiment 9 and the contrast of embodiment 11, can be observed notable difference.
utilizability in industry
Liquid crystal of the present invention represents that element can compatibly for presenting transmissive state when applying voltage and presenting the flyback type element of scattering state when applying voltage, for the liquid crystal display being expressed as object and for the transmission and blocking that control light light-regulating window, shutter element etc. for be useful.In addition, with the plastic bases such as film substrate make liquid crystal of the present invention represent element time, also can fit in and use as the glass substrate of supporting mass, glass pane.
It should be noted that, the full content of the instructions of No. 2013-150498, the Japanese patent application of application on July 19th, 2013, claims and summary is quoted so far, as the disclosure of instructions of the present invention.

Claims (13)

1. a liquid crystal represents element, it is characterized in that, it is following acquisition: comprise liquid crystal and the liquid-crystal composition of polymerizable compound that is polymerized because of active energy beam or heat be configured in possess electrode two plate bases between, at least one in this substrate has liquid crystal orientation film, be cured under a part for described liquid-crystal composition or the state of overall display liquid crystal liquid crystal property, thus form the solidfied material compound of liquid crystal and polymerizable compound
Described liquid crystal orientation film is formed by the aligning agent for liquid crystal containing following compositions (A) and composition (B),
Composition (A): the cellulose-based polymkeric substance with structure shown in following formula [1],
X 1, X 2, X 3, X 4, X 5and X 6represent at least a kind of group be selected from the group be made up of following formula [1a] ~ [1m] independently of one another; N represents the integer of 100 ~ 1000000,
X 7, X 8, X 9, X 10, X 11, X 12, X 13and X 14represent at least a kind that is selected from the group be made up of phenyl ring, methyl, ethyl, n-pro-pyl, isopropyl and butyl independently of one another; N represents the integer of 0 ~ 3; M represents the integer of 0 ~ 3,
Composition (B): make to be selected from least a kind of polycondensation in the group be made up of the alkoxy silane shown in the alkoxy silane shown in following formula [2a], following formula [2b] and the alkoxy silane shown in following formula [2c] and the polysiloxane based polymer obtained
(A 1) mSi(A 2) n(OA 3) p[2a]
A 1represent at least a kind of structure in the group being selected from and being made up of structure shown in following formula [2-1] and formula [2-2]; A 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5; A 3represent the alkyl of carbon number 1 ~ 5; M represents the integer of 1 or 2; N represents the integer of 0 ~ 2; P represents the integer of 0 ~ 3; Wherein, m+n+p is 4,
Y 1represent and be selected from by singly-bound ,-(CH 2) a-,-O-,-CH 2at least a kind in the group of O-,-COO-and-OCO-composition, wherein, a is the integer of 1 ~ 15; Y 2represent singly-bound or-(CH 2) b-, wherein, b is the integer of 1 ~ 15; Y 3represent and be selected from by singly-bound ,-(CH 2) c-,-O-,-CH 2at least a kind in the group of O-,-COO-and-OCO-composition, wherein, c is the integer of 1 ~ 15; Y 4represent the divalent organic group of at least a kind of divalent cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle or the carbon number 17 ~ 51 with steroid skeleton, any hydrogen atom on described cyclic group is optionally replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y 5represent at least a kind of cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxy of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; N represents the integer of 0 ~ 4; Y 6represent at least a kind that is selected from by the group formed containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18 of the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18; N represents the integer of 0 ~ 4,
-Y 7-Y 8[2-2]
Y 7represent and be selected from by singly-bound ,-O-,-CH 2o-,-CONH-,-NHCO-,-CON (CH 3)-,-N (CH 3) CO-,-COO-and-OCO-composition group at least a kind of binding groups; Y 8represent the alkyl of carbon number 8 ~ 22 or carbon number 6 ~ 18 containing fluoroalkyl,
(B 1) mSi(B 2) n(OB 3) p[2b]
B 1represent have in the group being selected from and being made up of vinyl, epoxy radicals, amino, sulfydryl, isocyanate group, methacryl, acryloyl group, urea groups and cinnamoyl at least a kind and carbon number is the organic group of 2 ~ 12; B 2represent the alkyl of hydrogen atom or carbon number 1 ~ 5; B 3represent the alkyl of carbon number 1 ~ 5; M represents the integer of 1 or 2; N represents the integer of 0 ~ 2; P represents the integer of 0 ~ 3; Wherein, m+n+p is 4,
(D 1) nSi(OD 2) 4-n[2c]
D 1represent the alkyl of hydrogen atom or carbon number 1 ~ 5; D 2represent the alkyl of carbon number 1 ~ 5; N represents the integer of 0 ~ 3.
2. liquid crystal according to claim 1 represents element, and wherein, composition (A) with the ratio of composition (B) is: relative to composition (B) 1 mass parts, composition (A) is 0.1 ~ 9 mass parts.
3. liquid crystal according to claim 1 and 2 represents element, wherein, the alkoxy silane shown in formula [2b] in described composition (B) is for being selected from by allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl ester, at least a kind in the group of acrylic acid 3-(trimethoxysilyl) propyl ester and methacrylic acid 3-(trimethoxysilyl) propyl ester composition.
4. liquid crystal according to claim 1 and 2 represents element, wherein, the alkoxy silane shown in formula [2b] in described composition (B) is for being selected from by least a kind in the group of 3-glycidoxypropyl group dimethoxymethylsilane, 3-glycidoxypropyl group diethoxymethylsilane, 3-glycidoxypropyltrime,hoxysilane and 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane composition.
5. the liquid crystal according to any one of Claims 1 to 4 represents element, wherein, described composition (B) makes the alkoxy silane polycondensation shown in formula [2a] and the polysiloxane obtained or the polysiloxane making the alkoxy silane shown in formula [2a] and formula [2b] or the alkoxy silane polycondensation shown in formula [2c] and obtain.
6. the liquid crystal according to any one of Claims 1 to 5 represents element, wherein, also containing solvent in described aligning agent for liquid crystal.
7. liquid crystal according to claim 6 represents element, wherein, as described solvent, containing being selected from by MEK, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1, ammediol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol list propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, at least one solvent in the group of the solvent composition shown in furfuryl alcohol and following formula [A1] ~ formula [A3],
A 1represent the alkyl of carbon number 1 ~ 3; A 2represent the alkyl of carbon number 1 ~ 3; A 3represent the alkyl of carbon number 1 ~ 4.
8. the liquid crystal according to any one of claim 1 ~ 7 represents element, wherein, also containing adaptation compound in described aligning agent for liquid crystal, described adaptation compound has at least a kind in the group being selected from and being made up of structure following formula [B1] ~ [B8] Suo Shi
B 1represent hydrogen atom or phenyl ring; B 2represent at least a kind of cyclic group be selected from the group be made up of phenyl ring, cyclohexane ring and heterocycle; B 3represent at least a kind that is selected from by the group formed containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18 of the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18.
9. the liquid crystal according to any one of claim 1 ~ 8 represents element, wherein, also produces agent containing being selected from by optical free radical in described aligning agent for liquid crystal, light acid producing agent and light alkali produce at least a kind of generation agent in the group that agent form.
10. the liquid crystal according to any one of claim 1 ~ 9 represents element, and wherein, described substrate is glass substrate or plastic base.
11. 1 kinds of liquid crystal orientation films, it represents the liquid crystal orientation film of element for the liquid crystal according to any one of claim 1 ~ 10, is formed by the aligning agent for liquid crystal containing described composition (A) and composition (B).
12. liquid crystal orientation films according to claim 11, wherein, thickness is 5 ~ 500nm.
13. 1 kinds of aligning agent for liquid crystal, it contains described composition (A) and composition (B), for the formation of the liquid crystal orientation film described in claim 11 or 12.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110945416A (en) * 2017-07-27 2020-03-31 日产化学株式会社 Resin composition, resin film, and liquid crystal display element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105593752B (en) * 2013-07-25 2019-01-22 日产化学工业株式会社 Liquid crystal indicates element, aligning agent for liquid crystal and liquid crystal orientation film
JP6672815B2 (en) 2015-04-14 2020-03-25 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07218918A (en) * 1994-02-08 1995-08-18 Shin Etsu Chem Co Ltd Liquid crystal display element
JP2003255315A (en) * 2001-12-28 2003-09-10 Asahi Glass Co Ltd Liquid crystal dimmer element and method for manufacturing the same
US20070218216A1 (en) * 2006-03-17 2007-09-20 Fujifilm Corporation Light modulating material
JP5017963B2 (en) * 2006-08-29 2012-09-05 Dic株式会社 Liquid crystal element
CN102757795A (en) * 2011-04-21 2012-10-31 Jsr株式会社 Liquid crystal aligning agent for retardation film, liquid crystal aligning film for retardation film, retardation film and method for preparing retardation film

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0743726A (en) * 1993-05-28 1995-02-14 Hoechst Japan Ltd Liquid crystal display element
JP2885116B2 (en) 1994-07-05 1999-04-19 日本電気株式会社 Liquid crystal optical element and manufacturing method thereof
JP4132424B2 (en) 1999-06-22 2008-08-13 旭硝子株式会社 Manufacturing method of liquid crystal optical element
JP5498880B2 (en) 2010-07-12 2014-05-21 株式会社構造計画研究所 Simulation apparatus, simulation method, and program
CN103718091B (en) * 2011-05-27 2016-08-31 日产化学工业株式会社 Silicon-containing liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display cells

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07218918A (en) * 1994-02-08 1995-08-18 Shin Etsu Chem Co Ltd Liquid crystal display element
JP2003255315A (en) * 2001-12-28 2003-09-10 Asahi Glass Co Ltd Liquid crystal dimmer element and method for manufacturing the same
US20070218216A1 (en) * 2006-03-17 2007-09-20 Fujifilm Corporation Light modulating material
JP5017963B2 (en) * 2006-08-29 2012-09-05 Dic株式会社 Liquid crystal element
CN102757795A (en) * 2011-04-21 2012-10-31 Jsr株式会社 Liquid crystal aligning agent for retardation film, liquid crystal aligning film for retardation film, retardation film and method for preparing retardation film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110945416A (en) * 2017-07-27 2020-03-31 日产化学株式会社 Resin composition, resin film, and liquid crystal display element

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