CN105659154A - Liquid crystal orienting agent, liquid crystal orientation film, and liquid crystal display element - Google Patents

Liquid crystal orienting agent, liquid crystal orientation film, and liquid crystal display element Download PDF

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CN105659154A
CN105659154A CN201480057984.5A CN201480057984A CN105659154A CN 105659154 A CN105659154 A CN 105659154A CN 201480057984 A CN201480057984 A CN 201480057984A CN 105659154 A CN105659154 A CN 105659154A
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liquid crystal
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represent
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aligning agent
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CN105659154B (en
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桥本淳
若林晓子
三木徳俊
保坂和義
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Nissan Chemical Corp
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

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Abstract

The purpose of the present invention is to provide a liquid crystal orientation film without a reduction in vertical orientation even after exposure to high temperature and light irradiation for a long time. Provided is a liquid crystal orientation film additionally capable of improving adhesiveness between a sealing agent and the liquid crystal orientation film, suppressing the incidence of display anomalies near the contours of liquid crystal display elements under high temperature and humidity, and further suppressing a reduction in the voltage retention rate. Further provided is a liquid crystal orientation agent containing a polysiloxane obtained by polycondensing an alkoxysilane having a side chain for orienting liquid crystals vertically, and a polysiloxane obtained by polycondensing an alkoxysilane having a side chain that includes a photoreactive group in its structure. However, the side chain for orienting liquid crystals vertically and the side chain that includes the photoreactive group in its structure are not present in the same polysiloxane.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
Technical field
The present invention relates to the liquid crystal representing the aligning agent for liquid crystal of element, the liquid crystal orientation film obtained by this aligning agent for liquid crystal for the manufacture of liquid crystal and employing this liquid crystal orientation film and represent element.
Background technology
Liquid crystal represent element now as realize volume thin/the expression equipment of light weight and be widely used. Usually, this liquid crystal represents that element is in order to determine the state of orientation of liquid crystal and use liquid crystal orientation film.
As the characteristic that liquid crystal orientation film requires, have and liquid crystal molecule is remained arbitrary value relative to the orientation pitch angle of real estate, namely control liquid crystal pretilt angle. The size of this tilt angle known is by selecting to change to the structure of the polyimide forming liquid crystal orientation film. Control among the technology of tilt angle by the structure of polyimide, the method that the diamines with side chain is used as part polyimide raw material can be controlled tilt angle according to the use ratio of this diamines, therefore the tilt angle being easier to obtain target is useful (such as with reference to patent documentation 1) as the means increasing tilt angle. In addition, for like this for increasing two amine components of liquid crystal pretilt angle, also carry out for improving the stability of tilt angle, the structural research of process dependency, as the side-chain structure wherein used, it is proposed that comprise the structure (such as with reference to patent documentation 2) of the ring structure such as phenyl, cyclohexyl.
In recent years, the inorganic system resin coating formed by the composition comprising polysiloxane based polymer is used to interlayer dielectric, protective membrane and liquid crystal orientation film. Wherein, represent for element for liquid crystal, in order to improve the orientation of mesomorphic phase for heat, or in order to improve the film hardness of liquid crystal orientation film and improve the printing coating of aligning agent for liquid crystal, it is proposed that use aligning agent for liquid crystal and the liquid crystal orientation film (such as with reference to patent documentation 3 and 4) of polysiloxane based polymer.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2-282726 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-278724 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-27761 publication
Patent documentation 4: No. 2008/044644th, International Publication publication
Summary of the invention
The problem that invention to be solved
Liquid crystal orientation film is also for controlling the tilt angle of mesomorphic phase for the angle of substrate, i.e. liquid crystal.Especially, VA (VerticalAlignment, vertical orientated) pattern, PSA (PolymerSustainedAlignment, polymer stabilizing orientation) pattern etc. needs to make liquid crystal vertical-tropism, therefore, liquid crystal orientation film is required the ability (also referred to as vertical orientated property, high tilt angle) making liquid crystal vertical-tropism. And then, for liquid crystal orientation film, not only requiring high vertical orientated property, its stability is also important. Especially, the liquid crystal employing the backlight that thermal discharge is big, light irradiation dose is many in order to obtain high brightness represents that element such as auto navigation system, large-scale tv are sometimes being exposed to high temperature for a long time and are using under environment that illumination is penetrated or place. Under this kind of critical conditions, when vertical orientated property reduces, can there is to obtain the expression characteristic at initial stage or represent the unequal problem of generation.
In recent years, employ liquid crystal represent element towards the mobile purposes such as smart mobile phone, portable phone. In these purposes, in order to guarantee expression face as much as possible, it is necessary to be used in bonding liquid crystal and represent that the width of the sealing agent between the substrate of element is narrower than in the past. And then, due to above-mentioned reason, also require sealing agent is drawn the top that position is located at position that the end of the liquid crystal orientation film weak with the cementability of sealing agent contacts or liquid crystal orientation film. Now, owing to using under hot and humid condition, the water capacity is easily mixed into, between sealing agent and liquid crystal orientation film, liquid crystal represents that near the frame of element, generation represents uneven.
In addition, liquid crystal represents when being mixed into water in element, liquid crystal represents electrical characteristic and the voltage retention much slower of element, it is easy to one of element represents bad i.e. after image bad (also referred to as line after image) to occur liquid crystal to represent, the liquid crystal that cannot obtain reliability high represents element.
Thus, it is an object of the present invention to provide the aligning agent for liquid crystal having above-mentioned characteristic concurrently. That is, high temperature it is exposed to for a long time and after illumination penetrates even if it is an object of the present invention to provide, the liquid crystal orientation film that vertical orientated property also can not reduce. In addition, its object is to, it is provided that the cementability of sealing agent and liquid crystal orientation film can be improved, suppress liquid crystal to represent the liquid crystal orientation film occurring near the frame of element to represent uneven and then suppress voltage retention to reduce under hot and humid condition.
In addition, it is provided that the liquid crystal with above-mentioned liquid crystal orientation film represents element, can give the aligning agent for liquid crystal of above-mentioned liquid crystal orientation film.
And then, it is an object of the present invention to provide the liquid crystal possessing the liquid crystal orientation film being consistent with above-mentioned requirements and represent element.
For the scheme dealt with problems
Present inventor has performed further investigation, found that: the aligning agent for liquid crystal containing the polysiloxane organoalkoxysilane polycondensation of ad hoc structure obtained is extremely effective for realizing above-mentioned purpose, thus completes the present invention.
That is, the present invention has following purport.
(1) a kind of aligning agent for liquid crystal, it contains the polysiloxane of (A) composition and the polysiloxane of (B) composition,
(A) composition is the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane shown in following formula [1a] and obtain, and wherein, this organoalkoxysilane composition does not contain the organoalkoxysilane shown in following formula [1b],
(A1)m1Si(A2)n1(OA3)p1[1a]
[in formula, A1Represent at least a kind of structure being selected from structure shown in following formula [1-1] and formula [1-2],
A2Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another,
A3Represent the alkyl of carbon number 1��5 independently of one another,
M1 represents the integer of 1 or 2,
N1 represents the integer of 0��2,
P1 represents the integer of 0��3, and wherein, m1+n1+p1 is 4],
-Y7--Y8[1-2]
(in formula, Y1Represent singly-bound ,-(CH2)a-(a is the integer of 1��15) ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-,
Y2Represent singly-bound or-(CH2)b-(b is the integer of 1��15),
Y3Represent singly-bound ,-(CH2)c-(c is the integer of 1��15) ,-O-,-CH2O-,-COO-or-OCO-,
Y4Represent the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle or the 2 valency organic groups with the carbon number 17��51 of steroid skeleton, any hydrogen atom on aforementioned cyclic group is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom
Y5Represent the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom
N represents the integer of 0��4,
Y6Represent the fluoroalkoxy of the alkyl of carbon number 1��18, the fluorine-containing alkyl of carbon number 1��18, the alkoxyl group of carbon number 1��18 or carbon number 1��18,
Y7Represent singly-bound ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-,
Y8Represent the alkyl of carbon number 8��22 or the fluorine-containing alkyl of carbon number 6��18),
(B) composition is the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane shown in following formula [1b] and obtain, and wherein, this organoalkoxysilane composition does not contain the organoalkoxysilane shown in previously described formula [1a],
(B1)m2si(B2)n2(oB3)p2[1b]
(in formula, B1Represent the organic group of the carbon number 2��12 with vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl independently of one another,
B2Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another,
B3Represent the alkyl of carbon number 1��5 or the alkoxyalkyl of carbon number 1��5 independently of one another,
M2 represents the integer of 1 or 2,
N2 represents the integer of 0��2,
P2 represents the integer of 0��3, and wherein, m2+n2+p2 is 4).
(2) aligning agent for liquid crystal according to above-mentioned (1), wherein, organoalkoxysilane shown in formula [1b] is for being selected from by allyl group triethoxyl silane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl ester, in the group of vinylformic acid 3-(trimethoxysilyl) propyl ester and methacrylic acid 3-(trimethoxysilyl) propyl ester composition at least a kind.
(3) aligning agent for liquid crystal according to above-mentioned (1), wherein, in the group that organoalkoxysilane shown in formula [1b] is made up of 3-glycidoxy propyl group (dimethoxy) methyl-monosilane, 3-glycidoxy propyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane and 2-(the own base of 3,4-oxirane ring) ethyl trimethoxy silane for being selected from least a kind.
(4) aligning agent for liquid crystal according to any one of above-mentioned (1)��above-mentioned (3), wherein, as (C) composition, containing the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane shown in following formula [1c] and obtain, wherein, this organoalkoxysilane composition is not containing the organoalkoxysilane shown in previously described formula [1a] and previously described formula [1b]
(D1)n3si(OD2)4-n3[1c]
(in formula, D1Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another,
D2Represent the alkyl of carbon number 1��5 independently of one another,
N3 represents the integer of 0��3).
(5) aligning agent for liquid crystal according to any one of above-mentioned (1)��above-mentioned (4), wherein, containing being selected from by methylethylketone in foregoing liquid crystal aligning agent, pimelinketone, cyclopentanone, 4-hydroxy-4-methyl-2 pentanone, the own alcohol of 1-, hexalin, 1, ammediol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol single-butyl ether, DPGME, dipropylene glycol dimethyl ether, furfuryl alcohol, and following formula [X1], at least one solvent in the group of the composition of solvent shown in formula [X2] and formula [X3],
(in formula, X1Represent the alkyl of carbon number 1��3, X2Represent the alkyl of carbon number 1��3, X3Represent the alkyl of carbon number 1��4).
(6) aligning agent for liquid crystal according to any one of above-mentioned (1)��above-mentioned (5), it contains at least one solvent in the group being selected from and being made up of METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolactone and 1,3-dimethyl-imidazolinone.
(7) a kind of liquid crystal orientation film, the aligning agent for liquid crystal according to any one of its use above-mentioned (1)��above-mentioned (6) obtains.
(8) a kind of liquid crystal orientation film, the aligning agent for liquid crystal according to any one of its use above-mentioned (1)��above-mentioned (6) is obtained by ink jet method.
(9) a kind of liquid crystal represents element, and it has the liquid crystal orientation film described in above-mentioned (7) or above-mentioned (8).
(10) liquid crystal orientation film according to above-mentioned (7) or above-mentioned (8), it is characterized in that, its be used to possess electrode one to substrate between there is liquid crystal layer and the liquid crystal that manufactures via following operation represents element, described operation is: aforementioned one to substrate between configure liquid-crystal composition, described liquid-crystal composition comprises the polymerizable compound being polymerized because of active energy beam and at least one hankered, while make aforementioned polymeric compound polymerization to applying voltage limit between former electrodes.
(11) a kind of liquid crystal represents element, it is characterised in that, it has the liquid crystal orientation film described in above-mentioned (10).
(12) liquid crystal orientation film according to above-mentioned (7) or above-mentioned (8), it is characterized in that, its be used to possess electrode one to substrate between there is liquid crystal layer and the liquid crystal that manufactures via following operation represents element, described operation is: aforementioned one to substrate between configure liquid crystal orientation film, described liquid crystal orientation film comprises the polymerizable group being polymerized because of active energy beam and at least one hankered, while make aforementioned polymeric group be polymerized to applying voltage limit between former electrodes.
(13) a kind of liquid crystal represents element, it is characterised in that, it has the liquid crystal orientation film described in above-mentioned (12).
The effect of invention
The aligning agent for liquid crystal containing the polysiloxane obtained by the organoalkoxysilane of ad hoc structure of the present invention can provide the cementability showing high and stable vertical orientated property and can improving sealing agent and liquid crystal orientation film, suppress liquid crystal to represent the liquid crystal orientation film occurring near the frame of element to represent inequality and then suppress voltage retention to reduce under hot and humid condition. Therefore, the liquid crystal with the liquid crystal orientation film thus obtained represents that element becomes the liquid crystal with high reliability and represents element.
Embodiment
Present inventor has performed further investigation, found that following opinion, thus complete the present invention.
The present invention relates to the aligning agent for liquid crystal of the polysiloxane of the polysiloxane containing following (A) composition and (B) composition, the liquid crystal orientation film using this aligning agent for liquid crystal and obtain and the liquid crystal with this liquid crystal orientation film represents element.
(A) composition: the polysiloxane (also referred to as specific polysiloxane (A)) that the organoalkoxysilane composition polycondensation of the organoalkoxysilane (also referred to as specific alkoxysilane (a)) shown in following formula [1a] will be comprised and obtain. Now, this organoalkoxysilane composition is not containing the organoalkoxysilane shown in following formula [1b].
(A1)m1Si(A2)n1(OA3)p1[1a]
(in formula [1a], A1Represent at least a kind of structure being selected from structure (being also referred to as particular side chain structure) shown in following formula [1-1] and formula [1-2], A2Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another, A3Representing the alkyl of carbon number 1��5 independently of one another, m1 represents the integer of 1 or 2, and n1 represents the integer of 0��2, and p1 represents the integer of 0��3. Wherein, m1+n1+p1 represents integer 4).
(in formula [1-1], Y1Represent singly-bound ,-(CH2)a-(a is the integer of 1��15) ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-, Y2Represent singly-bound or-(CH2)b-(b is the integer of 1��15), Y3Represent singly-bound ,-(CH2)c-(c is the integer of 1��15) ,-O-,-CH2O-,-COO-or-OCO-, Y4Represent the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle or the 2 valency organic groups with the carbon number 17��51 of steroid skeleton, any hydrogen atom on aforementioned cyclic group is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom, Y5Represent the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom, n represents the integer of 0��4, Y6Represent the fluoroalkoxy of the alkyl of carbon number 1��18, the fluorine-containing alkyl of carbon number 1��18, the alkoxyl group of carbon number 1��18 or carbon number 1��18).
-Y7--Y8[1-2]
(in formula [1-2], Y7Represent singly-bound ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-, Y8Represent the alkyl of carbon number 8��22 or the fluorine-containing alkyl of carbon number 6��18).
(B) composition: the polysiloxane (also referred to as specific polysiloxane (B)) that the organoalkoxysilane composition polycondensation of the organoalkoxysilane (also referred to as specific alkoxysilane (b)) shown in following formula [1b] will be comprised and obtain. Now, this organoalkoxysilane composition is not containing the organoalkoxysilane shown in previously described formula [1a].
(B1)m2si(B2)n2(oB3)p2[1b]
(in formula [1b], B1Represent the organic group of the carbon number 2��12 with vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl independently of one another, B2Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another, B3Representing the alkyl of carbon number 1��5 or the alkoxyalkyl of carbon number 1��5 independently of one another, m represents the integer of 1 or 2, and n represents the integer of 0��2, and p represents the integer of 0��3. Wherein, m+n+p is 4).
The ability height making liquid crystal vertical-tropism of the particular side chain structure contained by specific alkoxysilane (a) in (A) composition of the present invention. Wherein, the structure shown in previously described formula [1-1] has phenyl ring, cyclohexyl ring or heterocycle or has 2 valency organic groups of the carbon number 17��25 of steroid skeleton at side chain position. The side-chain structure of these rings and organic group shows upright and outspoken structure, therefore, it may also be useful to the liquid crystal with the vertical liquid crystal tropism film of particular side chain structure shown in formula [1-1] represents that element can obtain high and stable liquid crystal vertical-tropism.
In addition, the specific alkoxysilane (b) in (B) composition of the present invention has vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl. It is known that these organic groups are reacted by hot, uviolizing. Further, the reactive group of the compound comprised in these organic groups and sealing agent by heat, ultraviolet and there is the chemical reaction with chemical bonding. Therefore, when employing the aligning agent for liquid crystal of the present invention, the curing process of sealing agent when representing element by making liquid crystal, uviolizing operation or firing process, the reactive group generation chemical reaction of the compound that above-mentioned organic group in liquid crystal orientation film and sealing agent comprise and make sealing agent and liquid crystal orientation film carry out chemical bonding such that it is able to improve their cementability.
From the view point of above, the aligning agent for liquid crystal of the present invention can form that display is high and stable vertical orientated property and can improve the cementability of sealing agent and liquid crystal orientation film, suppress liquid crystal to represent to occur near the frame of element to represent uneven and then suppress the liquid crystal orientation film of voltage retention reduction under hot and humid condition.
Hereinafter illustrate in greater detail embodiments of the present invention.
<the specific polysiloxane of specific alkoxysilane (a) (A)>
Specific polysiloxane (A) in (A) composition of the present invention is the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the specific alkoxysilane (a) shown in following formula [1a] and obtain. Now, this organoalkoxysilane composition is not containing aforementioned specific alkoxysilane (b).
(A1)m1Si(A2)n1(OA3)p1[1a]
In formula [1a], A1Represent the particular side chain structure shown in following formula [1-1] or formula [1-2].
In formula [1-1], Y1Represent singly-bound ,-(CH2)a-(a is the integer of 1��15) ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-. Wherein, from the view point of raw material availability, synthesis easily degree, it is preferable to singly-bound ,-(CH2)a-(a is the integer of 1��15) ,-O-,-CH2O-or-COO-.It is more preferably singly-bound ,-(CH2)a-(a is the integer of 1��10) ,-O-,-CH2O-or-COO-.
In formula [1-1], Y2Represent singly-bound or-(CH2)b-(b is the integer of 1��15). Wherein, it is preferable to singly-bound or-(CH2)b-(b is the integer of 1��10).
In formula [1-1], Y3Represent singly-bound ,-(CH2)c-(c is the integer of 1��15) ,-O-,-CH2O-,-COO-or-OCO-. Wherein, from the view point of synthesis is easily spent, it is preferable to singly-bound ,-(CH2)c-(c is the integer of 1��15) ,-O-,-CH2O-or-COO-. It is more preferably singly-bound ,-(CH2)c-(c is the integer of 1��10) ,-O-,-CH2O-or-COO-.
In formula [1-1], Y4For the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom. And then, Y42 valency organic groups in the organic group of the carbon number 17��25 that can have steroid skeleton for being selected from. Wherein, from the view point of synthesis easily degree, it is preferable to phenyl ring, cyclohexane ring or there is the organic group of the carbon number 17��51 of steroid skeleton.
In formula [1-1], Y5Representing the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom. Wherein, it is preferable to phenyl ring or cyclohexane ring.
In formula [1-1], n represents the integer of 0��4. Wherein, from the view point of raw material availability, synthesis easily degree, it is preferable to 0��3. It is more preferably 0��2.
In formula [1-1], Y6Represent the fluoroalkoxy of the alkyl of carbon number 1��18, the fluorine-containing alkyl of carbon number 1��18, the alkoxyl group of carbon number 1��18 or carbon number 1��18. Wherein, it is preferable to the alkyl of carbon number 1��18, the fluorine-containing alkyl of carbon number 1��10, the alkoxyl group of carbon number 1��18 or the fluoroalkoxy of carbon number 1��10. It is more preferably the alkyl of carbon number 1��12 or the alkoxyl group of carbon number 1��12. It is particularly preferably the alkyl of carbon number 1��9 or the alkoxyl group of carbon number 1��9.
As the Y in formula [1-1]1��Y2��Y3��Y4��Y5��Y6With the preferably combination of n, the combination that (2-1)��(2-629) is identical that the table 6��table 47 of 13 with International Publication publication the 2011/132751st (2011.10.27 is open)��34 is recorded can be listed. It should be noted that, in each table of International Publication publication, the Y in the present invention1��Y6It is shown as Y1��Y6, but Y1��Y6 can be regarded as Y1��Y6. In addition, in (2-605)��(2-629) of each token load of International Publication publication, the organic group of the carbon number 17��51 with steroid skeleton in the present invention is illustrated as the organic group of the carbon number 12��25 with steroid skeleton, but the organic group with the carbon number 12��25 of steroid skeleton can be regarded as the organic group of the carbon number 17��51 with steroid skeleton.
-Y7--Y8[1-2]
In formula [1-2], Y7Represent singly-bound ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-. Wherein, it is preferable to singly-bound ,-O-,-CH2O-��-CONH-��-CON(CH3)-or-COO-. It is more preferably singly-bound ,-O-,-CONH-or-COO-.
In formula [1-2], Y8Represent the alkyl of carbon number 8��22 or the fluorine-containing alkyl of carbon number 6��18. Wherein, it is preferable to the alkyl of carbon number 8��18.
As the particular side chain structure of the present invention, from the view point of high and stable liquid crystal vertical-tropism can be obtained, it is preferred to use the structure shown in formula [1-1].
In formula [1a], A2It is the alkyl of hydrogen atom or carbon number 1��5 independently of one another. Wherein, it is preferable to the alkyl of hydrogen atom or carbon number 1��3.
In formula [1a], A3It is the alkyl of carbon number 1��5 independently of one another. Wherein, from the view point of polycondensation, it is preferable to the alkyl of carbon number 1��3.
In formula [1a], m1 is the integer of 1 or 2. Wherein, from the view point of synthesize, it is preferable to 1.
In formula [1a], n1 is the integer of 0��2.
In formula [1a], p1 is the integer of 0��3. Wherein, from the view point of polycondensation, it is preferable to the integer of 1��3. It is more preferably 2 or 3.
In formula [1a], m1+n1+p1 is 4.
As the concrete example of the specific alkoxysilane (a) shown in formula [1a], the organoalkoxysilane shown in following formula [1a-1]��formula [1a-10] and formula [1a-13]��formula [1a-32] can be listed.
(in formula [1a-1]��formula [1a-10] and formula [1a-13]��formula [1a-18], R1Represent the alkyl of carbon number 1��3 independently of one another, R2Independently of one another represent carbon number 1��3 alkyl, m represent 2 or 3, n represent 0 or 1, wherein, m+n is 3).
(in formula [1a-19]��formula [1a-22], R1Represent the alkyl of carbon number 1��3 independently of one another, R2Independently of one another represent carbon number 1��3 alkyl, m represent 2 or 3, n represent 0 or 1, wherein, m+n is 3, R3Represent-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH independently of one another3)-��-N(CH3)CO-��-OCH2-��-CH2O-��-COOCH2-or-CH2OCO-, R4The alkyl of expression carbon number 1��12, alkoxyl group, fluorine-containing alkyl or fluoroalkoxy independently of one another).
(in formula [1a-23] and formula [1a-24], R1Represent the alkyl of carbon number 1��3 independently of one another, R2Independently of one another represent carbon number 1��3 alkyl, m represent 2 or 3, n represent 0 or 1, wherein, m+n is 3, R3Represent-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH independently of one another3)-��-N(CH3)CO-��-OCH2-��-CH2O-��-COOCH2-or-CH2OCO-, R4Represent fluorine-based independently of one another, cyano group, fluoroform alkyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl).
(in formula [1a-25]��formula [1a-31], R1Represent the alkyl of carbon number 1��3 independently of one another, R2Independently of one another represent carbon number 1��3 alkyl, m represent 2 or 3, n represent 0 or 1, wherein, m+n is 3, R3Represent-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CON (CH independently of one another3)-��-N(CH3)CO-��-OCH2-��-CH2O-��-COOCH2-or-CH2OCO-, R4The alkyl of expression carbon number 1��12, alkoxyl group, fluorine-containing alkyl or fluoroalkoxy independently of one another).
(in formula [1a-32], R1Represent the alkyl of carbon number 1��3 independently of one another, R2Independently of one another represent carbon number 1��3 alkyl, m represent 2 or 3, n represent 0 or 1, wherein, m+n is 3, B4Represent the alkyl of the carbon number 3��20 being optionally replaced by fluorine atoms, B3Represent 1,4-cyclohexylene or 1,4-phenylene, B2Wherein, represent Sauerstoffatom or COO-* (subsidiary " * " key and B3It is bonded. ), B1Wherein, for Sauerstoffatom or COO-* (subsidiary " * " key and (CH2)a2It is bonded. ). In addition, a1Represent the integer of 0 or 1, a2Represent the integer of 2��10, a3Represent the integer of 0 or 1).
In organoalkoxysilane shown in above-mentioned formula [1a-1]��formula [1a-10] and formula [1a-13]��formula [1a-32], from the view point of liquid crystal vertical-tropism, it is particularly preferred to the organoalkoxysilane of structure is the organoalkoxysilane shown in formula [1a-9], formula [1a-10], formula [1a-13]��formula [1a-21], formula [1a-25]��formula [1a-28] or formula [1a-32].
Specific alkoxysilane (a) in the specific polysiloxane (A) of the present invention can according to specific polysiloxane (A) solvability in a solvent, make vertical liquid crystal tropism film time the characteristic such as liquid crystal vertical-tropism and use a kind or be mixed with two or more. In addition, it is possible to other organoalkoxysilane of mixing (such as specific alkoxysilane (c) described later) in one kind or two or more specific alkoxysilane (a) also uses.
<the specific polysiloxane of specific alkoxysilane (b) (B)>
Specific polysiloxane (B) in (B) composition of the present invention is the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the specific alkoxysilane (b) shown in following formula [1b] and obtain. Now, this organoalkoxysilane composition is not containing aforementioned specific alkoxysilane (a).
(B1)m2si(B2)n2(oB3)p2[1b]
In formula [1b], B1Independently of one another for having the organic group of the carbon number 2��12 of vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl. Wherein, from the view point of obtain easily degree, it is preferable to have the organic group of the carbon number 2��12 of vinyl, epoxy group(ing), amino, methacryloyl, acryl or urea groups. It is more preferably the organic group of the carbon number 2��12 with methacryloyl, acryl or urea groups.
In formula [1b], B2It is the alkyl of hydrogen atom or carbon number 1��5 independently of one another. Wherein, it is preferable to the alkyl of hydrogen atom or carbon number 1��3.
In formula [1b], B3It is the alkyl of carbon number 1��5 or the alkoxyalkyl of carbon number 1��5 independently of one another. Wherein, from the view point of polycondensation, it is preferable to the alkyl of carbon number 1��3.
In formula [1b], m2 is the integer of 1 or 2. Wherein, from the view point of synthesize, it is preferable to 1.
In formula [1b], n2 is the integer of 0��2.
In formula [1b], p2 is the integer of 0��3. Wherein, from the view point of polycondensation, it is preferable to the integer of 1��3. It is more preferably 2 or 3.
In formula [1b], m2+n2+p2 is 4.
As the concrete example of the specific alkoxysilane (b) shown in formula [1b], allyl group triethoxyl silane can be listed, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, between styryl ethyl triethoxysilane, to styryl ethyl triethoxysilane, isophthalic vinyl methyl triethoxyl silane, to styryl Union carbide A-162, 3-(N-styryl methyl-2-amino ethylamino) propyl trimethoxy silicane, diethoxy (3-glycidoxy propyl group) methyl-monosilane, 3-glycidoxy propyl group (dimethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane, 2-(the own base of 3,4-oxirane ring) ethyl trimethoxy silane, 3-(2-amino ethylamino) propyl group dimethoxy-methyl silane, 3-(2-amino ethylamino) propyl-triethoxysilicane, 3-(2-amino ethylamino) propyl trimethoxy silicane, 3-aminopropyl diethoxymethyl silane, APTES, 3-TSL 8330, trimethoxy [3-(phenyl amino) propyl group] silane, 3-mercaptopropyi (dimethoxy) methyl-monosilane, (3-mercaptopropyi) triethoxyl silane, (3-mercaptopropyi) Trimethoxy silane, 3-(triethoxysilyl) propyl group isocyanic ester, methacrylic acid 3-(triethoxysilyl) propyl ester, methacrylic acid 3-(trimethoxysilyl) propyl ester, vinylformic acid 3-(triethoxysilyl) propyl ester, vinylformic acid 3-(trimethoxysilyl) propyl ester, methacrylic acid 2-(triethoxysilyl) second ester, methacrylic acid 2-(trimethoxysilyl) second ester, vinylformic acid 2-(triethoxysilyl) second ester, vinylformic acid 2-(trimethoxysilyl) second ester, methacrylic acid (triethoxysilyl) methyl esters, methacrylic acid (trimethoxysilyl) methyl esters, vinylformic acid (triethoxysilyl) methyl esters, vinylformic acid (trimethoxysilyl) methyl esters, ��-urea propyl-triethoxysilicane, ��-urea propyl trimethoxy silicane, ��-urea propyl group three propoxy-silane, (R)-N-1-phenylethyl-N '-triethoxysilylpropyltetrasulfide urea, (R)-N-1-phenylethyl-N '-trimethoxy-silylpropyl urea, 1-[3-(trimethoxysilyl) propyl group] urea etc.
Wherein, preferably, the allyl group triethoxyl silane of free radical reaction, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl ester, vinylformic acid 3-(trimethoxysilyl) propyl ester or methacrylic acid 3-(trimethoxysilyl) propyl ester is there is because of light.
Further preferably, 3-glycidoxy propyl group (dimethoxy) methyl-monosilane of crosslinking reaction, 3-glycidoxy propyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane or 2-(the own base of 3,4-oxirane ring) ethyl trimethoxy silane is there is because of heat.
Specific alkoxysilane (b) in the specific polysiloxane (B) of the present invention can according to specific polysiloxane (B) solvability in a solvent, make vertical liquid crystal tropism film time the characteristic such as liquid crystal vertical-tropism and use a kind or be mixed with two or more. In addition, it is possible to other organoalkoxysilane of mixing (such as specific alkoxysilane (c) described later) in one kind or two or more specific alkoxysilane (b) also uses.
<the specific polysiloxane of specific alkoxysilane (c) (C)>
The aligning agent for liquid crystal of the present invention preferably uses the polysiloxane (also referred to as specific polysiloxane (c)) that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane (also referred to as specific alkoxysilane (c)) shown in following formula [1c] and obtain. Now, this organoalkoxysilane composition is not containing aforementioned specific alkoxysilane (a) and aforementioned specific alkoxysilane (b).
(D1)n3si(oD2)4-n3[1c]
In formula [1c], D1Being the alkyl of hydrogen atom or carbon number 1��5 independently of one another, they are optionally replaced by halogen atom, nitrogen-atoms, Sauerstoffatom, sulphur atom. Wherein, it is preferable to the alkyl of hydrogen atom or carbon number 1��3.
In formula [1c], D2It is the alkyl of carbon number 1��5 independently of one another. Wherein, from the view point of polycondensation, it is preferable to the alkyl of carbon number 1��3.
In formula [1c], n3 is the integer of 0��3.
As the concrete example of the organoalkoxysilane shown in formula [1c], tetramethoxy-silicane can be listed, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl three propoxy-silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethoxy diethylsilane, dibutoxy dimethylsilane, (chloromethyl) triethoxyl silane, 3-chloropropyl dimethoxy-methyl silane, 3-chloropropyl triethoxy silane, 2-cyano ethyl triethoxyl silane, trimethoxy (3, 3, 3-trifluoro propyl) silane, own base Trimethoxy silane or 3-trimethoxy-silylpropyl muriate etc.
It is the organoalkoxysilane of 0 as the n in formula [1c], tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes can be listed.
Specific alkoxysilane (c) in the specific polysiloxane (C) of the present invention can according to specific polysiloxane (C) solvability in a solvent, make vertical liquid crystal tropism film time the characteristic such as liquid crystal vertical-tropism and use a kind or be mixed with two or more.
<making method of specific polysiloxane>
The making method of the specific polysiloxane (A) of the present invention, specific polysiloxane (B) and specific polysiloxane (C) (being also referred to as specific polysiloxane) is not particularly limited.Include, for example out following method: the specific polysiloxane (A) in the present invention by the organoalkoxysilane composition comprising aforementioned specific alkoxysilane (a) in a solvent polycondensation obtain. Utilize identical method, the specific polysiloxane (B) of the present invention can use aforementioned specific alkoxysilane (b) and obtain, and specific polysiloxane (C) can use aforementioned specific alkoxysilane (c) and obtain.
The polycondensation method of each specific polysiloxane of the present invention is not particularly limited. Include, for example the method that organoalkoxysilane of sening as an envoy to occurs hydrolysis/condensation to react in alcohol series solvent, glycol series solvent. Now, hydrolysis/condensation reaction can be partial hydrolysis, it is also possible to complete hydrolysis. During complete hydrolysis, the water of 0.5 times of molar weight of all alkoxyl groups in organoalkoxysilane can be added in theory, it is preferable that add and be in a ratio of excessive water with 0.5 times of molar weight. In order to obtain the specific polysiloxane of the present invention, the water yield used in said hydrolyzed/polycondensation suitably can be selected according to object, it is preferable to 0.5 times of all alkoxyl groups in organoalkoxysilane��2.5 times of molar weights.
In addition, in order to facilitation of hydrolysis/polycondensation, it is possible to use acidic cpds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, toxilic acid or fumaric acid; The basic cpds such as ammonia, first amine, ethamine, thanomin or triethylamine; Or the catalyzer such as the metal-salt of hydrochloric acid, nitric acid or oxalic acid etc. In addition, by the solution heating of organoalkoxysilane will be dissolved with, it is also possible to facilitation of hydrolysis/polycondensation. Heating temperature and heat-up time now suitably can be selected according to object. Include, for example out: with 50 DEG C of heated and stirred 24 hours, under reflux conditions stir thereafter the condition waited for 1 hour.
And then, as other polycondensation method, can list: the method that the heating of the mixture of organoalkoxysilane, solvent and oxalic acid is carried out polycondensation. Specifically, it is after adding oxalic acid in solvent in advance and making oxalic acid solution, the method for mixed oxyalkyl silane when heated this solution. Now, relative to all alkoxyl groups in organoalkoxysilane 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 carry out under the solution temperature of 50��180 DEG C, in order to not make solvent evaporation, be vaporized, it is preferable that carry out several tens minutes��tens of hours under reflux.
Make in the polycondensation of each specific polysiloxane of the present invention, when using the multiple specific alkoxysilane corresponding with it, the mixture by multiple specific alkoxysilane has been pre-mixed can be used to react, it is also possible to add multiple specific alkoxysilane successively while reacting.
As the solvent used in the polycondensation of organoalkoxysilane, as long as dissolve the solvent of organoalkoxysilane, just it is not particularly limited. In addition, even not dissolving the solvent of organoalkoxysilane, as long as dissolving along with the propelling of polycondensation of organoalkoxysilane. As the solvent used in polycondensation, in general, produce alcohol due to the polycondensation of organoalkoxysilane, therefore, it is possible to use alcohol series solvent, glycol series solvent, glycol ethers series solvent or the solvent good with the consistency of alcohol. As the concrete example of the solvent used in this kind of polycondensation, the alcohol series solvents such as methyl alcohol, ethanol, propyl alcohol, butanols or Pyranton can be listed; Ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propylene glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-PD, 2, the glycol series solvents such as 3-pentanediol or 1,6-HD;Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, Diethylene Glycol single-butyl ether, Diethylene Glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dipropyl ether, Diethylene Glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, propylene glycol single-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, the glycol ethers series solvents such as propylene glycol dipropyl ether or propylene glycol dibutyl ether, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N, the solvents good with the intermiscibility of alcohol such as dinethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), tetramethyl-urea, hexamethyl phosphorus triamide or meta-cresol.
In addition, in the present invention, when polycondensation, these solvents can use a kind or be mixed with two or more.
About the solution of the specific polysiloxane obtained by aforementioned method, the Siliciumatom having in all organoalkoxysilanes dropped into as raw material is converted into SiO2Concentration (also referred to as SiO2Conversion concentration) it is preferably below 20 quality %. Wherein, it is preferable to 5��15 quality %. By selecting any concentration in this concentration range, it is possible to suppress solution produces gel, it is possible to obtain the solution of uniform specific polysiloxane.
In the present invention, the solution of the specific polysiloxane obtained by aforementioned method can be directly used in the aligning agent for liquid crystal of the present invention, as required, it is also possible to concentrated for the solution of the specific polysiloxane utilizing aforementioned method to obtain or interpolation solvent are carried out diluting or be replaced as other solvent and uses.
The solvent (also referred to as adding solvent) used when aforementioned interpolation solvent dilutes can be solvent, other solvent of use in polycondensation. Just it is not particularly limited as long as this interpolation solvent evenly dissolves specific polysiloxane, it is possible to select arbitrarily and use one kind or two or more. Add solvent as this kind, except the solvent used in aforementioned polycondensation, also can list the ketone series solvents such as acetone, methylethylketone or methyl iso-butyl ketone (MIBK); The ester series solvents etc. such as ritalin, vinyl acetic monomer or ethyl lactate.
And then, in the present invention, when aligning agent for liquid crystal uses the polymkeric substance beyond specific polysiloxane, it is preferred that, before polymkeric substance beyond the specific polysiloxane of mixing, under normal or reduced pressure the alcohol produced during the polycondensation of specific polysiloxane is carried out distillation and remove.
<aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention is the coating solution for the formation of liquid crystal orientation film, is containing the present invention's (A) composition and specific polysiloxane (A), (B) composition of the present invention and the coating solution of specific polysiloxane (B) and solvent.
About the ratio of the specific polysiloxane (A) in the aligning agent for liquid crystal of the present invention Yu the functional quality of specific polysiloxane (B), when the ratio of specific polysiloxane (A) is set to 1 mass parts, the ratio of specific polysiloxane (B) is 0.05��20 mass parts, wherein, it is preferable to 0.1��9 mass parts. Wherein, it is preferable to 0.25��4 mass parts, be particularly preferably 0.4��2.5 mass parts.
When the aligning agent for liquid crystal of the present invention uses specific polysiloxane (C), about the ratio of the functional quality of specific polysiloxane (A), specific polysiloxane (B) and specific polysiloxane (C), when the ratio of specific polysiloxane (A) is set to 1 mass parts, the ratio of specific polysiloxane (B) is 0.05��20 mass parts, and the ratio of specific polysiloxane (C) is 0.05��20 mass parts.Wherein, the ratio of specific polysiloxane (B) is preferably ratio preferably 0.1��9 mass parts of 0.1��9 mass parts, specific polysiloxane. The ratio of specific polysiloxane (B) is more preferably 0.25��4 mass parts, the ratio of specific polysiloxane (C) is more preferably 0.25��4 mass parts, and the ratio of specific polysiloxane (B) is particularly preferably 0.4��2.5 mass parts, the ratio of specific polysiloxane (C) is particularly preferably 0.4��2.5 mass parts.
All component of polymer in the aligning agent for liquid crystal of the present invention can be all the specific polysiloxane of the present invention, it is also possible to is mixed with other polymkeric substance in addition. As polymkeric substance in addition, at least a kind of polymkeric substance being selected from acrylic polymers, methacrylic polymer, novolac resin, polycarboxylated styrene, polymeric amide, polyester, polyamic acid or polyimide can be listed. Now, the content of other polymkeric substance in addition is 0.5 mass parts��15 mass parts relative to specific polysiloxane 100 mass parts of the present invention, is preferably 1 mass parts��10 mass parts.
From the view point of the coating process of aligning agent for liquid crystal, obtain target film thickness, the solvent in the aligning agent for liquid crystal of the present invention can suitably be selected. Wherein, from the view point of form uniform liquid crystal orientation film by being coated with, the solvent in aligning agent for liquid crystal is preferably 50��99.9 quality %. Wherein, it is preferable to 60��99 quality %, be particularly preferably 65��99 quality %.
As long as the solvent that the solvent used in the aligning agent for liquid crystal of the present invention dissolves specific polysiloxane based polymer is just not particularly limited. Hereinafter enumerate its concrete example, it is not limited to these examples.
Include, for example out N, dinethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 1,3-dimethyl-imidazolinone, methylethylketone, pimelinketone, cyclopentanone, 4-hydroxy-4-methyl-2 pentanone, ethanol, Virahol, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, tertiary amyl alcohol, 3-methyl-2-butanols, neopentyl alcohol, the own alcohol of 1-, 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, the own alcohol of 2-ethyl-1-, hexalin, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,5-pentanediol, 2-methyl-2,4-PD, 2-ethyl-1,3-hexylene glycol, dipropyl ether, dibutyl ether, hexyl ether, two alkane, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, 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, dipropyl ketone, 3-ethoxybutyl acetic ester, 1-methyl amyl acetic ester, 2-ethyl-butyl acetic ester, 2-ethylhexyl acetate, glycol-monoacetin, ethylene diacetate, Texacar PC, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol list isopentyl ether, ethylene glycol mono hexyl ether, 2-(hexyloxy) ethanol, furfuryl alcohol, Diethylene Glycol, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, Diethylene Glycol sec.-propyl ether, Diethylene Glycol single-butyl ether, propylene glycol, propylene glycol single-butyl ether, 1-(butoxy oxyethyl group) propyl alcohol, propylene glycol monomethyl ether acetate, dipropylene glycol, DPGME, dihydroxypropane single-ethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol butyl ether acetate, glycol-monoacetin, ethylene diacetate, TC acetic ester, Diethylene Glycol single-butyl ether acetic ester, 2-(2-ethoxy ethoxy) ethyl acetate, Diethylene Glycol acetic ester, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, ritalin, vinyl acetic monomer, n-butyl acetate, acetic acid propylene glycol list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxypropionic acid methyl esters, 3-ethoxy-c acid methyl second ester, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc.And then, the solvent shown in the solvent shown in following formula [X1], following formula [X2] and the solvent shown in following formula [X3] can be listed.
(in formula [X1], X1Represent the alkyl of carbon number 1��3, in formula [X2], X2Represent the alkyl of carbon number 1��3, in formula [X3], X3Represent the alkyl of carbon number 1��4).
Wherein, it is preferably methylethylketone, pimelinketone, cyclopentanone, 4-hydroxy-4-methyl-2 pentanone, 2-methyl-1-butene alcohol, the own alcohol of 1-, hexalin, 1, ammediol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 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 ester, ethylene glycol monopropyl ether, ethylene glycol isobutyl-ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, propylene glycol single-butyl ether, DPGME, dipropylene glycol list propyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol, solvent shown in previously described formula [X1], solvent shown in previously described formula [X2] and the solvent shown in previously described formula [X3].
It is particularly preferably methylethylketone, pimelinketone, cyclopentanone, 4-hydroxy-4-methyl-2 pentanone, the own alcohol of 1-, hexalin, 1, ammediol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol single-butyl ether, DPGME, dipropylene glycol dimethyl ether or furfuryl alcohol, solvent shown in previously described formula [X1], solvent shown in previously described formula [X2] and the solvent shown in previously described formula [X3].
In addition, in order to improve the viscosity of aligning agent for liquid crystal, it is also preferred that use N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolactone or 1,3-dimethyl-imidazolinone. Wherein, it is preferable to METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolactone or 1,3-dimethyl-imidazolinone.
Above-mentioned solvent can according to the film of liquid crystal orientation film when the solvability of specific polysiloxane, coating of liquid crystalline aligning agent, the characteristic of surface smoothness and use a kind or be mixed with two or more.
In the aligning agent for liquid crystal of the present invention, in the scope not damaging effect of the present invention, it is also possible to import the compound with epoxy group(ing), isocyanate group, oxetanyl or cyclocarbonate radical; There is the compound (being also referred to as cross-linked compound) of at least a kind of substituting group in the group selecting free hydroxyl, hydroxyalkyl and low-grade alkoxy alkyl composition. Now, these substituting groups need there are more than 2 in cross-linked compound.
As the cross-linked compound with epoxy group(ing) or isocyanate group, include, for example out bisphenol acetone glycidyl ether, phenol phenolic resin varnish, cresols phenolic resin varnish, triglycidyl group isocyanuric acid ester, four glycidyl group phenylaniline, four glycidyl group m-xylene diamine, two (amino-ethyl) hexanaphthene of four glycidyl group-1,3-, tetraphenyl glycidyl ether ethane, trisphenyl glycidyl ether ethane, bis-phenol six acetyl fluoride base diglycidylether, two (1-(2,3-the glycidoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl) benzene of 1,3-, 4,4-two (2,3-glycidoxy) eight fluorine biphenyl, triglycidyl group p-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-glycidoxy) phenyl)-2-(4-(two (4-(2,3-glycidoxy) phenyl) ethyl of 1,1-) phenyl) propane, or 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��59 cross-linked compounds shown in formula [4a]��formula [4k] recorded of International Publication publication the 2011/132751st (2011.10.27 is open) can be listed.
As the cross-linked compound with cyclocarbonate radical, it it is the cross-linked compound with the cyclocarbonate radical shown at least 2 following formula [5].
Specifically, 76��82 cross-linked compounds shown in formula [5-1]��formula [5-42] recorded of International Publication publication the 2012/014898th (2012.2.2 is open) can be listed.
As the cross-linked compound of at least a kind of substituting group having in the group selecting free hydroxyl and alkoxyl group composition, include, for example out the aminoresin with hydroxyl or alkoxyl group, such as melmac, urea resin, guanamine resin, sweet urea-formaldehyde resins, succinic diamide-formaldehyde resin or ethylene urea-formaldehyde resins etc. Specifically, it is possible to use the hydrogen atom of amino is by methylol or alkoxy methyl or melamine derivative, benzoguanamine derivative or sweet urea that both replaces and becomes. This melamine derivative or benzoguanamine derivative can also exist with the form of dipolymer or trimer. They preferably every 1 triazine ring there is methylol or the alkoxy methyl of average more than 3 and less than 6.
As the example of this kind of melamine derivative or benzoguanamine derivative, every 1 triazine ring that can list commercially available product replaces the MX-750 having average 3.7 methoxymethyies, every 1 triazine ring replaces the MW-30 (being Sanwa Chemical Co., Ltd above) having average 5.8 methoxymethyies, the close amine of methoxymethylization such as CYMEL300,301,303,350,370,771,325,327,703,712; The close amine of methoxymethyl butoxymethylization such as CYMEL235,236,238,212,253,254; CYMEL506, the close amine of butoxymethylization such as 508; The carboxylic close amine of methoxymethyl isobutoxymethylization of CYMEL1141 and so on; The methoxymethyl ethoxyl methyl benzoguanamine of CYMEL1123 and so on; The methoxymethyl butoxymethyl benzoguanamine of CYMEL1123-10 and so on; The butoxymethyl benzoguanamine of CYMEL1128 and so on; The carboxylic methoxymethyl ethoxyl methyl benzoguanamine of CYMEL1125-80 and so on (be above Mitsui �� �� �� Na �� De Inc.). In addition, as the example of sweet urea, the sweet urea of butoxymethylization of CYMEL1170 and so on can be listed; The sweet urea of methylolation etc. of CYMEL1172 and so on; The methoxyl group sweet urea of methylolation etc. of Powderlink1174 and so on.
As benzene or the benzene phenoloid with hydroxyl or alkoxyl group, include, for example out 1,3,5-tri-(methoxymethyl) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, 1,4-two (sec-butoxymethyl) benzene or 2,6-dihydroxyl methyl p-tert-butylphenol etc.
More specifically, 62 pages��66 pages cross-linked compounds shown in formula [6-1]��formula [6-48] recorded of International Publication publication the 2011/132751st (2011.10.27 is open) can be listed.
As the cross-linked compound with polymerizability unsaturated link(age), include, for example out the cross-linked compound in poly-(methyl) the acrylate equimolecular of trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxy base oxethyl TriMethylolPropane(TMP) or glycerine polyglycidyl ether with 3 polymerizability unsaturated groups;And then, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, four ethylene glycol bisthioglycolates (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxyethane bisphenol A-type two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) acrylate, glycerine two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, Diethylene Glycol diglycidylether two (methyl) acrylate, there is in o-phthalic acid diglycidyl ester two (methyl) acrylate or hydroxypivalic acid neopentyl glycol two (methyl) acrylate equimolecular the cross-linked compound of 2 polymerizability unsaturated groups, and then, there is in (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 2-phenoxy group-2-hydroxy propyl ester, 2-(methyl) acryloxy-2-hydroxypropyl phthalate, the chloro-2-hydroxy propyl ester of (methyl) vinylformic acid 3-, glycerine list (methyl) acrylate, 2-(methyl) acryloxy ethyl phosphoric acid ester or N-methylol (methyl) acrylamide equimolecular the cross-linked compound of 1 polymerizability unsaturated group.
In addition, it is possible to use the compound shown in following formula [7].
(in formula [7], E1Represent the group in the group being selected from and being made up of cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene ring, fluorenes ring, anthracene nucleus or luxuriant and rich with fragrance ring, E2Representing the group being selected from following formula [7a] or formula [7b], n represents the integer of 1��4).
Above-claimed cpd is an example of cross-linked compound, but is not limited to them. In addition, the cross-linked compound used in the aligning agent for liquid crystal of the present invention can be a kind, it is also possible to combines two or more.
The content of the cross-linked compound in the aligning agent for liquid crystal of the present invention is preferably 0.1��150 mass parts relative to all component of polymer 100 mass parts in aligning agent for liquid crystal. Target effect is shown, relative to all component of polymer 100 mass parts, it is more preferable to be 0.1��100 mass parts, most especially preferably be 1��50 mass parts in order to advance crosslinking reaction.
In the aligning agent for liquid crystal of the present invention, as promoting the compound that the electric charge in liquid crystal orientation film moves, it is preferable that add 69 pages��73 pages nitrogen heterocyclic ring amine compound shown in formula [M1]��formula [M156] recorded of International Publication publication the 2011/132751st (2011.10.27 is open). This amine compound can be added directly in aligning agent for liquid crystal, it is preferable that making concentration with suitable solvent is add after 0.1 quality %��10 quality %, the solution preferably making 1 quality %��7 quality % again. As this solvent, as long as the solvent dissolving specific polysiloxane is just not particularly limited.
In the scope not damaging effect of the present invention, the compound that the film uniformity of the liquid crystal orientation film when aligning agent for liquid crystal of the present invention can use coating of liquid crystalline aligning agent, surface smoothness improve. And then, it is possible to use make the compound etc. that the adaptation of liquid crystal orientation film and substrate improves.
As making the film uniformity of liquid crystal orientation film, the compound of surface smoothness raising, fluorine system tensio-active agent, silicone based surfactants, nonionic system tensio-active agent etc. can be listed.
More specifically, include, for example out EftopEF301, EF303, EF352 (being TohkemproductsCorporation system above);MegafacF171, F173, R-30 (being big 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 use ratio of these tensio-active agents is preferably 0.01��2 mass parts relative to all component of polymer 100 mass parts 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 liquid crystal orientation film and substrate improve, can list following illustrate the compound containing functional silanes, containing the compound of epoxy group(ing).
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-aminopropyl 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-1,4,7-three nitrogen is mixed decane, 10-triethoxysilyl-1,4,7-three nitrogen is mixed decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (oxygen base the ethene)-3-TSL 8330 of N-, two (oxygen base the ethene)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-or 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 in aligning agent for liquid crystal, it is preferable to 0.1��30 mass parts, be more preferably 1��20 mass parts. During less than 0.1 mass parts, cannot expect to improve the effect of adaptation, during more than 30 mass parts, the preservation bad stability of aligning agent for liquid crystal sometimes.
In the aligning agent for liquid crystal of the present invention, outside compound in addition to the foregoing, as long as in the scope not damaging effect of the present invention, then can also add dielectric substance, the conducting material of the electrical characteristic such as the specific inductivity for changing liquid crystal orientation film, electroconductibility.
<liquid crystal orientation film liquid crystal represents element>
The aligning agent for liquid crystal of the present invention is coated on substrate and after burning till, processed by brushing, illumination is penetrated etc. carries out orientation process, it is possible to as liquid crystal orientation film. In addition, represent element for the liquid crystal making liquid crystal vertical-tropism carry out representing, even if not carrying out orientation process also can be used as liquid crystal orientation film. As the substrate now used, as long as the high substrate of the transparency is just not particularly limited, except glass substrate, it is also possible to use the plastic bases etc. such as acrylic acid or the like substrate, polycarbonate plate or PET (polyethylene terephthalate) substrate.From the view point of Simplified flowsheet, it is preferred to use it is formed with the substrate of the ITO electrode etc. for driving liquid crystal. In addition, for the liquid crystal of reflection-type represents element, if being only single sided substrate, then the opaque substrates such as silicon wafer can also be used, as electrode now, it is possible to use aluminium etc. can the material of reflected light.
The coating process of aligning agent for liquid crystal is not particularly limited, and industrial is generally the method utilizing silk screen printing, offset printing, flexible printing or ink jet method etc. to carry out. As other coating process, there are dip coating, rolling method, slot coated method, spin-coating method or spraying method etc., it is possible to use them according to object.
Aligning agent for liquid crystal is coated on substrate, then the heater meanses such as hot plate, thermal cycling type baking oven or IR (infrared rays) type baking oven are utilized, according to the solvent used in aligning agent for liquid crystal, with 30��300 DEG C, preferably with the temperature of 30��250 DEG C, solvent is evaporated such that it is able to make liquid crystal orientation film. When the thickness of the liquid crystal orientation film after burning till is crossed thick, representing it is disadvantageous in the current consumption of element at liquid crystal, when thickness is crossed thin, liquid crystal represents that the reliability of element reduces sometimes, it is preferred to be 5��300nm, be more preferably 10��100nm. When making liquid crystal horizontal alignment, tilted alignment, by brushing or polarized UV rays irradiation etc., the liquid crystal orientation film after burning till is processed.
Liquid crystal about the present invention represents element, obtained the substrate of band liquid crystal orientation film by the aligning agent for liquid crystal of the present invention by aforesaid method after, utilizes known method to make liquid crystal cells, thus makes liquid crystal and represent element.
As the making method of liquid crystal cells, following method can be exemplified: prepare to be formed liquid crystal orientation film one to substrate, the liquid crystal orientation film of a substrate scatters spacer, in the way of inner side, is pasted on another substrate by liquid crystal orientation film, the method reducing pressure and injecting liquid crystal and seal; Or, after being scattered with the liquid crystal orientation film face dropping liquid crystalline substance of spacer, the method etc. that adhesive substrate carrying out seals.
And then, the aligning agent for liquid crystal of the present invention also can be preferably used for possess electrode one to substrate between there is liquid crystal layer and the liquid crystal that manufactures via following operation represents element, described operation is: configure liquid-crystal composition between one pair of substrate, described liquid-crystal composition comprises the polymerizable compound being polymerized because of active energy beam and at least one hankered, while to applying voltage between electrode, while by the irradiation of active energy beam with add at least one hankered and make polymerizable compound be polymerized. Herein, as active energy beam, ultraviolet is applicable. As ultraviolet, wavelength is 300��400nm, is preferably 310��360nm. When utilizing heating to be polymerized, Heating temperature is 40��120 DEG C, is preferably 60��80 DEG C. In addition, it is possible to carry out ultraviolet and heating simultaneously.
Above-mentioned liquid crystal represents that element utilizes PSA (PolymerSustainedAlignment) mode to control the pre-dumping of liquid crystal molecule. In PSA mode, in liquid crystal material, it is mixed into a small amount of optical polymerism compound in advance, such as it is mixed into photopolymerization monomer, after assembling liquid crystal cells, when liquid crystal layer is applied assigned voltage, to optical polymerism compound irradiation ultraviolet radiation etc., utilize the pre-dumping of the polymer controls liquid crystal molecule generated. Even if the state of orientation of liquid crystal molecule when generating polymkeric substance is remembered after removing voltage, therefore by the electric field etc. of formation in control liquid crystal layer, it is possible to the pre-dumping of adjustment liquid crystal molecule.In addition, in PSA mode, it is not necessary to brushing processes, and therefore is suitable for being difficult to being processed the formation of the liquid crystal layer of the vertical orientating type controlling pre-dumping by brushing.
Namely, liquid crystal in the present invention represents in element, after utilizing aforesaid method to obtain the substrate of band liquid crystal orientation film by the aligning agent for liquid crystal of the present invention, make liquid crystal cells, utilize ultraviolet irradiation and add at least one hankered and polymerizable compound is polymerized such that it is able to the orientation of control liquid crystal molecule.
If listing an example of the liquid crystal cells making PSA mode, then can list following method: prepare to be formed liquid crystal orientation film one to substrate, the liquid crystal orientation film of a substrate scatters spacer, in the way of inner side, another substrate is pasted, the method reducing pressure and injecting liquid crystal and seal by liquid crystal orientation film; Or, after being scattered with the liquid crystal orientation film face dropping liquid crystalline substance of spacer, the method etc. that adhesive substrate carrying out seals.
The polymerizable compound being polymerized because of hot, uviolizing is mixed in liquid crystal. As polymerizable compound, the compound with more than 1 the polymerizability unsaturated group such as acrylate-based, methacrylate based can be listed in molecule. Now, polymerizable compound is preferably 0.01��10 mass parts relative to liquid crystal composition 100 mass parts, is more preferably 0.1��5 mass parts. When polymerizable compound is less than 0.01 mass parts, polymerizable compound can not be polymerized and the orientation of uncontrollable liquid crystal, and when polymerizable compound is more than 10 mass parts, the after image characteristic that unreacted polymerizable compound becomes many, liquid crystal represents element reduces.
Make after liquid crystal cells, liquid crystal cells applied the voltage of exchange or direct current, while heat, irradiation ultraviolet radiation and polymerizable compound is polymerized. Consequently, it is possible to the orientation of control liquid crystal molecule.
In addition, the aligning agent for liquid crystal of the present invention it is also preferred that for possess electrode one to substrate between there is liquid crystal layer and the liquid crystal that manufactures via following operation represents element, i.e. SC-PVA pattern, described operation is: aforementioned one to substrate between configure liquid crystal orientation film, described liquid crystal orientation film comprises the polymerizable group being polymerized because of active energy beam and at least one hankered, applies voltage between electrode. Herein, as active energy beam, ultraviolet is applicable. As ultraviolet, wavelength is 300��400nm, is preferably 310��360nm. When utilizing heating to be polymerized, Heating temperature is 40��120 DEG C, is preferably 60��80 DEG C. In addition, it is possible to carry out ultraviolet and heating simultaneously.
The liquid crystal orientation film comprising the polymerizable group being polymerized because of active energy beam and at least one hankered to obtain, can list: the method that is added in aligning agent for liquid crystal by the compound comprising this polymerizable group, the method using the component of polymer comprising polymerizable group. From the view point of control objectives tilt angle, liquid crystal represent the electrical characteristic of element, it is possible to suitably select these methods.
If listing an example of the liquid crystal cells making SC-PVA pattern, following method can be listed: prepare to be formed the present invention liquid crystal orientation film one to substrate, the liquid crystal orientation film of a substrate scatters spacer, in the way of inner side, another substrate is pasted, the method reducing pressure and injecting liquid crystal and seal by liquid crystal orientation film; Or, after being scattered with the liquid crystal orientation film face dropping liquid crystalline substance of spacer, the method etc. that adhesive substrate carrying out seals.
After making liquid crystal cells, liquid crystal cells is applied the voltage of exchange or direct current, while heating, irradiation ultraviolet radiation such that it is able to the orientation of control liquid crystal molecule.
Operate as above, it may also be useful to the liquid crystal that the aligning agent for liquid crystal of the present invention makes represents the of excellent in reliability of element, is applicable to the LCD TV etc. of big picture and high-resolution.
Embodiment
Hereinafter list embodiment to further describe the present invention, but it is not limited to them.
" abbreviation used in the synthesis example of the present invention, embodiment and comparative example "
The abbreviation used in synthesis example, embodiment and comparative example is as follows.
<for making the alkoxy silane monomer of the specific polysiloxane of the present invention>
A1: the alkoxy silane monomer (specific alkoxysilane (a) with the particular side chain structure shown in formula [1-1] of the present invention) shown in following formula [A1]
A2: octadecyltriethoxy silane (specific alkoxysilane (a) with the particular side chain structure shown in formula [1-2] of the present invention)
A3:3-methacryloxypropyl trimethoxy silane (specific alkoxysilane (b) of the present invention)
A4:3-urea propyl-triethoxysilicane (specific alkoxysilane (b) of the present invention)
A5: tetraethoxysilane (specific alkoxysilane (c) of the present invention)
<solvent used in the present invention>
EC: TC
PGME: propylene glycol monomethyl ether
ECS: ethylene glycol monomethyl ether
BCS: ethylene glycol monobutyl ether
PB: propylene glycol single-butyl ether
NMP:N-N-methyl-2-2-pyrrolidone N-
NEP:N-ethyl-2-pyrrolidone
��-BL: gamma-butyrolactone
" synthesis of the specific polysiloxane of the present invention "
<synthesis example 1>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (29.8g), A1 (4.10g) and A5 (39.6g), thus prepares the solution of alkoxy silane monomer. Expend 30 points of these solution of clockwise drip at 25 DEG C and add solution EC (14.9g), water (10.8g) and the oxalic acid (0.90g) as catalyzer mixed in advance, and then at room temperature stir 30 minutes with 25 DEG C. Thereafter, it may also be useful to oil bath carries out naturally cooling, thus obtains SiO after heating and refluxing 60 minutes2Conversion concentration is the polysiloxane solution (1) of 12 quality %.
<synthesis example 2>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (29.7g), A2 (4.20g) and A5 (39.6g), thus prepares the solution of alkoxy silane monomer. Expend 30 points of these solution of clockwise drip at 25 DEG C and add solution EC (14.9g), water (10.8g) and the oxalic acid (0.90g) as catalyzer mixed in advance, and then at room temperature stir 30 minutes with 25 DEG C. Thereafter, it may also be useful to oil bath carries out naturally cooling, thus obtains SiO after heating and refluxing 60 minutes2Conversion concentration is the polysiloxane solution (2) of 12 quality %.
<synthesis example 3>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (29.5g), A3 (14.9g) and A5 (29.2g), thus prepares the solution of alkoxy silane monomer. At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (14.7g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C. Thereafter, it may also be useful to oil bath carries out naturally cooling, thus obtains SiO after heating and refluxing 60 minutes2Conversion concentration is the polysiloxane solution (3) of 12 quality %.
<synthesis example 4>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (30.3g) and A5 (40.8g), thus prepares the solution of alkoxy silane monomer.At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (15.2g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C. Thereafter, it may also be useful to oil bath carries out heating and after refluxing 30 minutes, the content adding previously prepared A4 is the methanol solution (1.15g) of 92 quality % and the mixing solutions of EC (0.90g). Backflow is after 30 minutes further, carries out naturally cooling, thus obtains SiO2Conversion concentration is the polysiloxane solution (4) of 12 quality %.
<synthesis example 5>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (28.7g), A3 (14.9g) and A5 (28.3g), thus prepares the solution of alkoxy silane monomer. At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (14.4g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C. Thereafter, it may also be useful to oil bath carries out heating and after refluxing 30 minutes, the content adding previously prepared A4 is the methanol solution (1.15g) of 92 quality % and the mixing solutions of EC (0.90g). Backflow is after 30 minutes further, carries out naturally cooling, thus obtains SiO2Conversion concentration is the polysiloxane solution (5) of 12 quality %.
<synthesis example 6>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (31.1g) and A5 (41.7g), thus prepares the solution of alkoxy silane monomer. At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (15.5g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C. Thereafter, it may also be useful to oil bath carries out naturally cooling, thus obtains SiO after heating and refluxing 60 minutes2Conversion concentration is the polysiloxane solution (6) of 12 quality %.
<synthesis example 7>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (28.2g), A1 (4.10g), A3 (14.9g) and A5 (27.1g), thus prepares the solution of alkoxy silane monomer. At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (14.1g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C. Thereafter, it may also be useful to oil bath carries out naturally cooling, thus obtains SiO after heating and refluxing 60 minutes2Conversion concentration is the polysiloxane solution (7) of 12 quality %.
<synthesis example 8>
The 200ml tetra-neck reaction flask possessing thermometer and return line mixes EC (28.1g), A2 (4.20g), A3 (14.9g) and A5 (27.1g), thus prepares the solution of alkoxy silane monomer. At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (14.1g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C. Thereafter, it may also be useful to oil bath carries out naturally cooling, thus obtains SiO after heating and refluxing 60 minutes2Conversion concentration is the polysiloxane solution (8) of 12 quality %.
<synthesis example 9>
The four neck reaction flasks of 200ml possessing thermometer and return line mix EC (27.4g), A1 (4.10g), A3 (14.9g) and A5 (26.3g), thus prepares the solution of alkoxy silane monomer. At 25 DEG C, expend the solution dripping in 30 points of these solution of clockwise and adding and EC (13.7g), water (10.8g) and the oxalic acid (0.90g) as catalyzer are mixed and prepare in advance, and then stir 30 minutes at 25 DEG C.Thereafter, it may also be useful to oil bath carries out heating and after refluxing 30 minutes, the content adding previously prepared A4 is the methanol solution (1.15g) of 92 quality % and the mixing solutions of EC (0.90g). Backflow is after 30 minutes further, carries out naturally cooling, thus obtains SiO2Conversion concentration is the polysiloxane solution (9) of 12 quality %.
The polysiloxane (polysiloxane solution) of the present invention is shown in table 1.
[table 1]
" composition of the present invention and the manufacture of aligning agent for liquid crystal "
Following embodiment 1��embodiment 16 and comparative example 1��comparative example 7 are recorded the Production Example of aligning agent for liquid crystal. In addition, these aligning agent for liquid crystal are also evaluated for it.
The aligning agent for liquid crystal of the present invention is shown in table 2��table 4.
Use the aligning agent for liquid crystal obtained in embodiments of the invention and comparative example, carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping ", " evaluation (normal cells) of the voltage retention after hot and humid keeping ", " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning ", and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning ".
" making of liquid crystal cells and the evaluation (normal cells) of tilt angle "
Aligning agent for liquid crystal (the 1)��aligning agent for liquid crystal (3) that will obtain in embodiments of the invention 1��embodiment 3, the aligning agent for liquid crystal (5) obtained in embodiment 5��embodiment 9��aligning agent for liquid crystal (9), the aligning agent for liquid crystal (11) obtained in embodiment 11��embodiment 14��aligning agent for liquid crystal (14), the aligning agent for liquid crystal (16) obtained in embodiment 16, and the membrane filter that the aligning agent for liquid crystal (17) obtained in comparative example 1��comparative example 7��aligning agent for liquid crystal (23) is 1 ��m with aperture carries out pressure filtration, thus carry out the making (normal cells) of liquid crystal cells. this solution is spin-coated on the ito surface of the substrate (vertical 40mm �� horizontal 30mm, thickness are 0.7mm) of the 30 �� 40mm band ITO electrode through cleaning with pure water and IPA, with 100 DEG C of heat treated 5 minutes on hot plate, and with the cleaning baking oven of thermal cycling type with 230 DEG C of heat treated 30 minutes, thus obtain the ito substrate that band thickness is the liquid crystal orientation film of 100nm. utilize the brushing device that roller footpath is 120mm, it may also be useful to artificial silk cloth, at roller rotating speed: 300rpm, roller rate of advance: 20mm/ second, intrusion: when 0.4mm, the coated surface of this ito substrate is carried out brushing process.
Prepare the ito substrate of 2 resulting tape liquid crystal orientation films, with liquid crystal orientation film facing to inner side and the spacer clamping 6 ��m combine, the sealing agent of printing ultraviolet hardening. Then, in the way of liquid crystal orientation film face is face-to-face and after another substrate sticking, to carry out making ultraviolet hardening sealing agent that the process of solidification occur, thus to obtain dummy cell. Specifically, it may also be useful to illumination is the metal halide lamp of 60mW, cut out the wavelength of below 310nm, irradiate and be scaled 5J/cm with 365nm2Ultraviolet, thereafter, with 120 DEG C of heat treated 60 minutes in the cleaning baking oven of thermal cycling type, thus obtain dummy cell. In this dummy cell, inject nematic liquid crystal (MLC-6608) (MERCKCORPORATION system) by decompression injection method, seal inlet and obtain liquid crystal cells (normal cells).
Carry out the mensuration of the tilt angle of the liquid crystal cells (normal cells) utilizing aforesaid method and obtain. Specifically, the tilt angle (also referred to as initial stage tilt angle) of the liquid crystal cells utilizing aforesaid method and obtain, the liquid crystal cells obtained utilizing the aforesaid method tilt angle (tilt angle also referred to as pyroprocessing after) of keeping after 72 hours and the liquid crystal cells that obtains utilizing aforesaid method in the high temperature groove of temperature 80 DEG C irradiate and are scaled 10J/cm with 365nm2Ultraviolet after tilt angle (tilt angle also referred to as after UV treatment). It should be noted that, tilt angle uses PAS-301 (ELSICON Inc.) at room temperature to measure. And then, ultraviolet irradiation uses desktop UV solidification equipment (HCT3B28HEX-1) (�� Application �� �� �� Inc.) to carry out.
About evaluation, initial stage tilt angle is more high, namely vertical orientated property is more high, and then, tilt angle and the difference change more little, that namely cause by pyroprocessing and UV treatment of initial stage tilt angle after pyroprocessing and after UV treatment are more little, then regard as this evaluation more excellent.
Table 5��table 7 illustrates the result obtained in embodiment and comparative example.
" evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping "
Aligning agent for liquid crystal (the 1)��aligning agent for liquid crystal (3) that will obtain in embodiments of the invention 1��embodiment 3, the aligning agent for liquid crystal (5) obtained in embodiment 5��embodiment 9��aligning agent for liquid crystal (9), the aligning agent for liquid crystal (11) obtained in embodiment 11��embodiment 14��aligning agent for liquid crystal (14), the aligning agent for liquid crystal (16) obtained in embodiment 16, and the membrane filter that the aligning agent for liquid crystal (17) obtained in comparative example 1��comparative example 7��aligning agent for liquid crystal (23) is 1 ��m with aperture carries out pressure filtration, thus carry out the making (normal cells) of liquid crystal cells. this solution is spun on the ito surface of the substrate (vertical 100mm �� horizontal 100mm, thickness are 0.7mm) of the 100 �� 100mm band ITO electrode through cleaning with pure water and IPA, with 100 DEG C of heat treated 5 minutes on hot plate, and with the cleaning baking oven of thermal cycling type with 230 DEG C of heat treated 30 minutes, thus obtain the ito substrate that band thickness is the liquid crystal orientation film of 100nm. utilize the brushing device that roller footpath is 120mm, it may also be useful to artificial silk cloth, at roller rotating speed: 300rpm, roller rate of advance: 20mm/ second, intrusion: when 0.4mm, the coated surface of this ito substrate is carried out brushing process.
Thereafter, prepare 2 ito substrates with the liquid crystal orientation film having carried out brushing process, the liquid crystal orientation film face of the substrate of a band liquid crystal orientation film is scattered the spacer of 6 ��m wherein. Thereafter, draw ultraviolet hardening sealing agent to the surrounding of this substrate, utilize ODF (OneDropFilling) method to inject nematic liquid crystal (MLC-6608) (MERCKCORPORATION system), thus obtain liquid crystal cells. Thereafter, in order to make the sealing agent of ultraviolet hardening solidify, it may also be useful to illumination is the metal halide lamp of 60mW, cuts out the wavelength of below 310nm, this liquid crystal cells is irradiated and is scaled 5J/cm with 365nm2Ultraviolet. Thereafter, with 120 DEG C of heat treated 60 minutes in the cleaning baking oven of thermal cycling type, thus obtain liquid crystal cells (normal cells).
Using polaroid and backlight, by visual observation, when carrying out the evaluation of the liquid crystal aligning near sealing agent for gained liquid crystal cells (normal cells), any liquid crystal cells obtained in embodiment and comparative example all shows the liquid crystal aligning of equal.
Thereafter, by liquid crystal cells keeping 72 hours in the hot and humid groove of temperature 80 DEG C, humidity 90%, when same as described above, carry out the evaluation of the liquid crystal aligning near sealing agent.Specifically, near sealing agent, do not observe the disorder of liquid crystal aligning, then regard as this evaluation excellent.
Table 5��table 7 illustrates the result obtained in embodiment and comparative example. It should be noted that, in table, when not observing liquid crystal aligning disorderly, it is denoted as zero, be denoted as when observing liquid crystal aligning disorderly ��.
" evaluation (normal cells) of the voltage retention after hot and humid keeping "
Aligning agent for liquid crystal (the 1)��aligning agent for liquid crystal (3) that will obtain in embodiments of the invention 1��embodiment 3, the aligning agent for liquid crystal (5) obtained in embodiment 5��embodiment 9��aligning agent for liquid crystal (9), the aligning agent for liquid crystal (11) obtained in embodiment 11��embodiment 14��aligning agent for liquid crystal (14), the aligning agent for liquid crystal (16) obtained in embodiment 16, and the membrane filter that the aligning agent for liquid crystal (17) obtained in comparative example 1��comparative example 7��aligning agent for liquid crystal (23) is 1 ��m with aperture carries out pressure filtration, thus carry out the making (normal cells) of liquid crystal cells. this solution is spun on the ito surface of the substrate (vertical 40mm �� horizontal 30mm, thickness are 0.7mm) of the 30 �� 40mm band ITO electrode through cleaning with pure water and IPA, with 100 DEG C of heat treated 5 minutes on hot plate, and with the cleaning baking oven of thermal cycling type with 230 DEG C of heat treated 30 minutes, thus obtain the ito substrate that band thickness is the liquid crystal orientation film of 100nm. utilize the brushing device that roller footpath is 120mm, it may also be useful to artificial silk cloth, at roller rotating speed: 300rpm, roller rate of advance: 20mm/ second, intrusion: when 0.4mm, the coated surface of this ito substrate is carried out brushing process.
Prepare the ito substrate of 2 resulting tape liquid crystal orientation films, with liquid crystal orientation film facing to inner side and the spacer clamping 6 ��m combine, the sealing agent of printing ultraviolet hardening. Then, in the way of liquid crystal orientation film face is face-to-face and after another substrate sticking, to carry out making ultraviolet hardening sealing agent that the process of solidification occur, thus to obtain dummy cell. Specifically, it may also be useful to illumination is the metal halide lamp of 60mW, cut out the wavelength of below 310nm, irradiate and be scaled 5J/cm with 365nm2Ultraviolet, thereafter, with 120 DEG C of heat treated 60 minutes in the cleaning baking oven of thermal cycling type, thus obtain dummy cell. By decompression injection method, in this dummy cell, inject nematic liquid crystal (MLC-6608) (MERCKCORPORATION system), seal inlet and obtain liquid crystal cells (normal cells).
At the temperature of 80 DEG C, gained liquid crystal cells is applied the 1V voltage of 60 �� s, measures the voltage after 50ms, voltage can be remained which kind of degree and calculate as voltage retention (also referred to as VHR). It should be noted that, measure and use voltage retention determinator (VHR-1) (TOYOCorporation system), at voltage (Voltage): �� 1V, pulse width (PulseWidth): 60 �� s, frame period (FlamePeriod): carry out under the setting of 50ms.
And then, the liquid crystal cells after the mensuration of voltage retention being terminated is keeping 96 hours in the hot and humid groove of temperature 80 DEG C, humidity 90%, again utilize condition same as described above to carry out the mensuration of voltage retention.
About evaluation, in hot and humid groove, voltage retention value after keeping is little relative to the reduction degree of the voltage retention value after just making liquid crystal cells, then be considered as good (the voltage retention value at initial stage shown in table 8��table 10 and voltage retention value after keeping in hot and humid groove).
" evaluation of the ink-jet application of aligning agent for liquid crystal "
The aligning agent for liquid crystal (15) obtained in the aligning agent for liquid crystal (10) obtained in the aligning agent for liquid crystal obtained in embodiments of the invention 4 (4), embodiment 10 and embodiment 15 is carried out pressure filtration with the membrane filter that aperture is 1 ��m, carries out the evaluation of ink-jet application. Ink-jet application machine uses HIS-200 (HitachiPlantTechnologies, Ltd. system). About coating, steam on plated substrate at the ITO (tin indium oxide) through cleaning with pure water and IPA, to utilize surface covered to be 70 �� 70mm, nozzle pitch to be 0.423mm, scanning interval to be 0.5mm, surface covered be the 40mm/ second, from coating to pre-dry time be 60 seconds, pre-dry carry out taking the condition of 70 DEG C as 5 minutes on hot plate.
Confirm the film of the substrate of resulting tape liquid crystal orientation film. Specifically, undertaken by visual observation film under sodium vapor lamp, confirm there is free of pinholes. Its result, the liquid crystal orientation film obtained in any embodiment does not all observe pin hole on film, it is possible to obtain the liquid crystal orientation film of film excellence.
And then, use the substrate of resulting tape liquid crystal orientation film, in above-mentioned " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", when " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping ", carry out the evaluation (normal cells) of tilt angle, the evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping, and the evaluation (normal cells) of the voltage retention after hot and humid keeping.
Table 5 and table 6 illustrate the result of the evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after the evaluation (normal cells) of tilt angle and hot and humid keeping. In addition, table 8 and table 9 illustrate the result of the evaluation (normal cells) of the voltage retention after hot and humid keeping.
" making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning "
The aligning agent for liquid crystal (16) obtained in the aligning agent for liquid crystal (8) obtained in the aligning agent for liquid crystal (7) obtained in the aligning agent for liquid crystal obtained in embodiment 2 (2), embodiment 7, embodiment 8 and embodiment 16 is carried out pressure filtration with the membrane filter that aperture is 1 ��m, thus carries out the making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning. The center through cleaning with pure water and IPA that is spun on by this solution is spaced apart the substrate (vertical 40mm �� horizontal 30mm, thickness are 0.7mm) of the ITO electrode of 20 ��m and the center ito surface with the substrate (indulge 40mm �� horizontal 30mm, thickness be 0.7mm) of the ITO electrode of 10 �� 40mm with 10 �� 10mm and pattern, with 100 DEG C of heat treated 5 minutes on hot plate, and utilize the cleaning baking oven of thermal cycling type with 230 DEG C of heat treated 30 minutes, thus obtain the substrate that band thickness is the liquid crystal orientation film of 100nm.
Taking liquid crystal orientation film face as inner side, the spacer of the substrate clamping with this liquid crystal orientation film 6 ��m is combined, make dummy cell around with sealing agent is bonding. In this dummy cell, liquid crystal is injected by decompression injection method, described liquid crystal is the liquid crystal become so that the polymerizable compound (1) shown in following formula mixes 0.3 quality % polymerizable compound (1) relative to nematic liquid crystal (MLC-6608) 100 quality % in nematic liquid crystal (MLC-6608) (MERCKCORPORATION system), seals inlet and obtains liquid crystal cells.
While gained liquid crystal cells being applied the voltage of exchange 5V, using the metal halide lamp that illumination is 60mW, cutting out the wavelength of below 350nm, carry out 20J/cm according to 365nm conversion2Uviolizing, thus obtain the liquid crystal cells (PSA unit) that liquid crystal aligning direction is controlled. It it is 50 DEG C to the temperature in irradiating unit during liquid crystal cells irradiation ultraviolet radiation.
Liquid crystal response speed before measuring the uviolizing of this liquid crystal cells and after uviolizing. Response speed measures the T90 �� T10 till transmissivity 90% to transmissivity 10%.
About the PSA unit obtained in any embodiment, compared with the liquid crystal cells before irradiation ultraviolet radiation, the response speed of the liquid crystal cells after irradiation ultraviolet radiation becomes fast, therefore confirms that the differently-oriented directivity of liquid crystal is controlled. In addition, any liquid crystal cells all confirms the equal orientation of liquid crystal by the observation of polarization microscope (ECLIPSEE600WPOL) (Nikon Co., Ltd. system).
" making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning "
In the aligning agent for liquid crystal (16) obtained in the aligning agent for liquid crystal (8) obtained in the aligning agent for liquid crystal (7) that obtains in the aligning agent for liquid crystal (2) that obtains in example 2, embodiment 7, embodiment 8 and embodiment 16, interpolation, relative to the aforementioned shown polymerizable compound (1) that all component of polymer 100 quality % in aligning agent for liquid crystal is 2 quality %, is stirred 4 hours at 25 DEG C. Thereafter, the membrane filter that gained aligning agent for liquid crystal aperture is 1 ��m is carried out pressure filtration, carry out the making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning. The center through cleaning with pure water and IPA that is spun on by this solution is spaced apart the substrate (vertical 40mm �� horizontal 30mm, thickness are 0.7mm) of the ITO electrode of 20 ��m and the center ito surface with the substrate (indulge 40mm �� horizontal 30mm, thickness be 0.7mm) of the ITO electrode of 10 �� 40mm with 10 �� 10mm and pattern, with 100 DEG C of heat treated 5 minutes on hot plate, and utilize the cleaning baking oven of thermal cycling type with 200 DEG C of heat treated 30 minutes, thus obtain the substrate that band thickness is the liquid crystal orientation film of 100nm.
Taking liquid crystal orientation film face as inner side, the spacer of the substrate clamping with this liquid crystal orientation film 6 ��m is combined, make dummy cell around with sealing agent is bonding. In this dummy cell, inject nematic liquid crystal (MLC-6608) (MERCKCORPORATION system) by decompression injection method, seal inlet and obtain liquid crystal cells.
While gained liquid crystal cells being applied the voltage of exchange 5V, using the metal halide lamp that illumination is 60mW, cutting out the wavelength of below 350nm, carry out 20J/cm according to 365nm conversion2Uviolizing, thus obtain the liquid crystal cells (SC-PVA unit) that liquid crystal aligning direction is controlled. It it is 50 DEG C to the temperature in irradiating unit during liquid crystal cells irradiation ultraviolet radiation.
Liquid crystal response speed before measuring the uviolizing of this liquid crystal cells and after uviolizing. Response speed measures the T90 �� T10 till transmissivity 90% to transmissivity 10%.
About the SC-PVA unit obtained in any embodiment, compared with the liquid crystal cells before irradiation ultraviolet radiation, the response speed of the liquid crystal cells after irradiation ultraviolet radiation becomes fast, therefore confirms that the differently-oriented directivity of liquid crystal is controlled. In addition, any liquid crystal cells all confirms the equal orientation of liquid crystal by the observation of polarization microscope (ECLIPSEE600WPOL) (Nikon Co., Ltd. system).
<embodiment 1>
EC (1.00g) and PB (15.7g) is added in polysiloxane solution (1) (5.00g) that utilize the method for synthesis example 1 to obtain and polysiloxane solution (3) (11.7g) that utilize the method for synthesis example 3 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (1). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (1), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 2>
To polysiloxane solution (1) (10.0g) that utilize the method for synthesis example 1 to obtain, polysiloxane solution (3) (8.00g) that utilize the method for synthesis example 3 to obtain and polysiloxane solution (6) (2.00g) middle interpolation EC (1.20g) utilizing the method for synthesis example 6 to obtain, BCS (11.3g) and ��-BL (7.50g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (2). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (2), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping ", " evaluation (normal cells) of the voltage retention after hot and humid keeping ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning " according to above-mentioned condition.
<embodiment 3>
EC (1.10g), PB (13.2g) and NMP (3.30g) is added in polysiloxane solution (1) (10.5g) that utilize the method for synthesis example 1 to obtain and polysiloxane solution (4) (7.00g) that utilize the method for synthesis example 4 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (3). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (3), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 4>
To polysiloxane solution (1) (5.00g) that utilize the method for synthesis example 1 to obtain, polysiloxane solution (4) (6.90g) that utilize the method for synthesis example 4 to obtain and polysiloxane solution (6) (0.60g) middle interpolation EC (9.70g) utilizing the method for synthesis example 6 to obtain, PB (16.5g) and NEP (4.10g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (4). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (4), carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 5>
EC (1.20g) and PB (18.8g) is added in polysiloxane solution (1) (10.0g) that utilize the method for synthesis example 1 to obtain and polysiloxane solution (5) (10.0g) that utilize the method for synthesis example 5 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (5). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (5), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 6>
To polysiloxane solution (1) (7.50g) that utilize the method for synthesis example 1 to obtain, polysiloxane solution (5) (7.50g) that utilize the method for synthesis example 5 to obtain and polysiloxane solution (6) (3.80g) middle interpolation EC (1.10g) utilizing the method for synthesis example 6 to obtain, BCS (8.80g) and NEP (8.80g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (6). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (6), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 7>
To polysiloxane solution (1) (10.0g) that utilize the method for synthesis example 1 to obtain, polysiloxane solution (3) (6.00g) that utilize the method for synthesis example 3 to obtain and polysiloxane solution (4) (4.00g) middle interpolation EC (1.20g) utilizing the method for synthesis example 4 to obtain, PB (11.3g) and ECS (7.50g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (7). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (7), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping ", " evaluation (normal cells) of the voltage retention after hot and humid keeping ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning " according to above-mentioned condition.
<embodiment 8>
To polysiloxane solution (1) (7.50g) that utilize the method for synthesis example 1 to obtain, polysiloxane solution (3) (5.63g) that utilize the method for synthesis example 3 to obtain, polysiloxane solution (4) (3.75g) that utilize the method for synthesis example 4 to obtain and utilize the method for synthesis example 6 to obtain polysiloxane solution (6) (1.88g) in add EC (1.10g) and BCS (17.6g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (8). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (8), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping ", " evaluation (normal cells) of the voltage retention after hot and humid keeping ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning " according to above-mentioned condition.
<embodiment 9>
EC (1.10g) and PB (17.6g) is added in polysiloxane solution (2) (7.50g) that utilize the method for synthesis example 2 to obtain and polysiloxane solution (3) (11.3g) that utilize the method for synthesis example 3 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (9). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (9), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 10>
To polysiloxane solution (2) (6.50g) that utilize the method for synthesis example 2 to obtain, polysiloxane solution (3) (3.25g) that utilize the method for synthesis example 3 to obtain and polysiloxane solution (6) (1.08g) middle interpolation EC (8.40g) utilizing the method for synthesis example 6 to obtain, PB (10.8g) and BCS (7.20g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (10). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (10), carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 11>
EC (1.10g), BCS (10.5g) and ��-BL (7.00g) is added in polysiloxane solution (2) (6.50g) that utilize the method for synthesis example 2 to obtain and polysiloxane solution (4) (12.1g) that utilize the method for synthesis example 4 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (11). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (11), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 12>
To polysiloxane solution (2) (6.50g) that utilize the method for synthesis example 2 to obtain, polysiloxane solution (4) (2.32g) that utilize the method for synthesis example 4 to obtain and polysiloxane solution (6) (0.46g) middle interpolation EC (0.60g) utilizing the method for synthesis example 6 to obtain, PGME (3.50g) and ECS (5.20g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (12). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (12), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 13>
EC (1.10g) and PB (17.1g) is added in polysiloxane solution (2) (10.0g) that utilize the method for synthesis example 2 to obtain and polysiloxane solution (5) (8.18g) that utilize the method for synthesis example 5 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (13).This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (13), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 14>
To polysiloxane solution (2) (7.50g) that utilize the method for synthesis example 2 to obtain, polysiloxane solution (5) (6.56g) that utilize the method for synthesis example 5 to obtain and polysiloxane solution (6) (4.69g) middle interpolation EC (1.10g) utilizing the method for synthesis example 6 to obtain, PB (10.6g) and NEP (7.10g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (14). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (14), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 15>
To polysiloxane solution (2) (4.50g) that utilize the method for synthesis example 2 to obtain, polysiloxane solution (3) (3.38g) that utilize the method for synthesis example 3 to obtain and polysiloxane solution (4) (3.38g) middle interpolation EC (8.70g) utilizing the method for synthesis example 4 to obtain, PB (11.2g) and ��-BL (7.40g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (15). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (15), carry out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<embodiment 16>
To polysiloxane solution (2) (8.50g) that utilize the method for synthesis example 2 to obtain, polysiloxane solution (3) (4.72g) that utilize the method for synthesis example 3 to obtain, polysiloxane solution (4) (2.83g) that utilize the method for synthesis example 4 to obtain and utilize the method for synthesis example 6 to obtain polysiloxane solution (6) (2.83g) in add EC (1.10g) and PB (17.8g), stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (16). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (16), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping ", " evaluation (normal cells) of the voltage retention after hot and humid keeping ", " making of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning " and " making of liquid crystal cells and the evaluation (SC-PVA unit) of liquid crystal aligning " according to above-mentioned condition.
<comparative example 1>
EC (0.90g) and PB (14.1g) is added in polysiloxane solution (1) (15.0g) that utilize the method for synthesis example 1 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (17).This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (17), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<comparative example 2>
EC (0.90g) and PB (14.1g) is added in polysiloxane solution (2) (15.0g) that utilize the method for synthesis example 2 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (18). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (18), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<comparative example 3>
EC (0.90g) and PB (14.6g) is added in polysiloxane solution (3) (15.5g) that utilize the method for synthesis example 3 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (19). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (19), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<comparative example 4>
EC (0.90g) and PB (14.1g) is added in polysiloxane solution (5) (15.0g) that utilize the method for synthesis example 5 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (20). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (20), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<comparative example 5>
EC (0.90g) and PB (14.6g) is added in polysiloxane solution (7) (15.5g) that utilize the method for synthesis example 7 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (21). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (21), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<comparative example 6>
EC (0.90g) and PB (14.6g) is added in polysiloxane solution (8) (15.5g) that utilize the method for synthesis example 8 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (22).This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (22), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
<comparative example 7>
EC (0.90g) and PB (14.1g) is added in polysiloxane solution (9) (15.0g) that utilize the method for synthesis example 9 to obtain, stir 3 hours with 25 DEG C, thus obtain aligning agent for liquid crystal (23). This aligning agent for liquid crystal does not observe the exceptions such as the generation of muddiness, precipitate, confirms as uniform solution.
Use gained aligning agent for liquid crystal (23), carry out " making of liquid crystal cells and the evaluation (normal cells) of tilt angle ", " evaluation (normal cells) of the uneven characteristic of the expression near the frame of the liquid crystal cells after hot and humid keeping " and " evaluation (normal cells) of the voltage retention after hot and humid keeping " according to above-mentioned condition.
[table 2]
* 1: the ratio (mass parts) representing specific polysiloxane when institute's polysiloxane composition is set to 100 mass parts.
[table 3]
* 2: the ratio (mass parts) representing specific polysiloxane when institute's polysiloxane composition is set to 100 mass parts.
[table 4]
* 3: the ratio (mass parts) representing polysiloxane when institute's polysiloxane composition is set to 100 mass parts.
[table 5]
[table 6]
[table 7]
* 4: near sealing agent, the central part of (near the frame of liquid crystal cells) and liquid crystal cells can be observed the disorder of liquid crystal aligning.
* 5: liquid crystal is not vertical orientated, therefore cannot measure.
* 6: near sealing agent, (near the frame of liquid crystal cells) can be observed the disorder of liquid crystal aligning.
[table 8]
[table 9]
[table 10]
From the above results: compared with the aligning agent for liquid crystal of comparative example, even if after the aligning agent for liquid crystal of embodiments of the invention can obtain being exposed to for a long time high temperature and illumination penetrates, the liquid crystal orientation film that the vertical orientated property of liquid crystal also can not reduce. In addition, can obtain can improve sealing agent and liquid crystal orientation film on the basis of this characteristic cementability, suppress liquid crystal to represent near the frame of element to occur to represent uneven and then that voltage retention can be suppressed to reduce liquid crystal orientation film under hot and humid condition.
Specifically, employ the specific polysiloxane (A) of the present invention and the embodiment of specific polysiloxane (B) and only use contrast, the i.e. embodiment 1 of the comparative example of specific polysiloxane (A) with the contrast of comparative example 1 and the contrast of embodiment 9 and comparative example 2, the tilt angle of the aligning agent for liquid crystal of these comparative examples after just making liquid crystal cells shows identical numerical value with embodiment, but after the keeping of high temperature groove and after uviolizing, tilt angle considerable change. And then, after the keeping of hot and humid groove, near the frame of liquid crystal cells, observe the disorder of liquid crystal aligning. Further, due to the keeping of hot and humid groove, voltage retention is much slower also.
And then, only used in the comparative example of specific polysiloxane (B), i.e. comparative example 3 and comparative example 4, liquid crystal is not vertical orientated.
And, employ the specific polysiloxane (A) of the present invention and the embodiment of specific polysiloxane (B) and employ the specific alkoxysilane (a) comprising the present invention, the contrast of the comparative example of the polysiloxane of specific alkoxysilane (b) and specific alkoxysilane (c), the i.e. contrast of embodiment 1 and comparative example 5, the contrast of embodiment 9 and comparative example 6, and embodiment 5 is with the contrast of comparative example 7, the characteristic of the voltage retention of the aligning agent for liquid crystal of these comparative examples after just making liquid crystal cells and after the keeping of hot and humid groove is good, but tilt angle is low, namely the vertical orientated property of liquid crystal becomes low.And then, due to the keeping of hot and humid groove, near the frame of liquid crystal cells, observe the disorder of liquid crystal aligning.
Utilizability in industry
The aligning agent for liquid crystal containing the polysiloxane obtained by the organoalkoxysilane of ad hoc structure of the present invention can provide the cementability showing high and stable vertical orientated property and can improving sealing agent and liquid crystal orientation film, suppress liquid crystal to represent the liquid crystal orientation film producing near the frame of element to represent inequality and then suppress voltage retention to reduce under hot and humid condition. Therefore, the liquid crystal with the liquid crystal orientation film thus obtained represents that element becomes the liquid crystal with high reliability and represents element.
Therefore, the liquid crystal with the liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention represents the of excellent in reliability of element, can, applicablely for the LCD TV etc. of big picture and high-resolution, be especially useful for the vertical alignment-type liquid crystal of VA pattern, PSA pattern and SC-PVA pattern etc. represents element.

Claims (13)

1. an aligning agent for liquid crystal, it contains the polysiloxane of (A) composition and the polysiloxane of (B) composition,
(A) composition is the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane shown in following formula [1a] and obtain, and wherein, this organoalkoxysilane composition does not contain the organoalkoxysilane shown in following formula [1b],
(A1)m1Si(A2)n1(OA3)p1[1a]
In formula [1a], A1Represent at least a kind of structure being selected from structure shown in following formula [1-1] and formula [1-2],
A2Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another,
A3Represent the alkyl of carbon number 1��5 independently of one another,
M1 represents the integer of 1 or 2,
N1 represents the integer of 0��2,
P1 represents the integer of 0��3, and wherein, m1+n1+p1 is 4,
-Y7-Y8[1-2]
In formula [1-1] and formula [1-2],
Y1Represent singly-bound ,-(CH2)a-��-O-��-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-, wherein, a is the integer of 1��15,
Y2Represent singly-bound or-(CH2)b-, wherein, b is the integer of 1��15,
Y3Represent singly-bound ,-(CH2)c-��-O-��-CH2O-,-COO-or-OCO-, wherein, c is the integer of 1��15,
Y4Represent the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle or the 2 valency organic groups with the carbon number 17��51 of steroid skeleton, any hydrogen atom on described cyclic group is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom
Y5Represent the 2 valency cyclic groups being selected from phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom on these cyclic groups is optionally replaced by the alkoxyl group of the alkyl of carbon number 1��3, carbon number 1��3, the fluorine-containing alkyl of carbon number 1��3, the fluoroalkoxy of carbon number 1��3 or fluorine atom
N represents the integer of 0��4,
Y6Represent the fluoroalkoxy of the alkyl of carbon number 1��18, the fluorine-containing alkyl of carbon number 1��18, the alkoxyl group of carbon number 1��18 or carbon number 1��18,
Y7Represent singly-bound ,-O-,-CH2O-��-CONH-��-NHCO-��-CON(CH3)-��-N(CH3) CO-,-COO-or-OCO-, and
Y8Represent the alkyl of carbon number 8��22 or the fluorine-containing alkyl of carbon number 6��18,
(B) composition is the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane shown in following formula [1b] and obtain, and wherein, this organoalkoxysilane composition does not contain the organoalkoxysilane shown in described formula [1a],
(B1)m2Si(B2)n2(OB3)p2[1b]
In formula [1b], B1Represent the organic group of the carbon number 2��12 with vinyl, epoxy group(ing), amino, sulfydryl, isocyanate group, methacryloyl, acryl, urea groups or cinnamoyl independently of one another,
B2Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another,
B3Represent the alkyl of carbon number 1��5 or the alkoxyalkyl of carbon number 1��5 independently of one another,
M2 represents the integer of 1 or 2,
N2 represents the integer of 0��2,
P2 represents the integer of 0��3, and wherein, m2+n2+p2 is 4.
2. aligning agent for liquid crystal according to claim 1, wherein, organoalkoxysilane shown in formula [1b] is for being selected from by allyl group triethoxyl silane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, methacrylic acid 3-(triethoxysilyl) propyl ester, in the group of vinylformic acid 3-(trimethoxysilyl) propyl ester and methacrylic acid 3-(trimethoxysilyl) propyl ester composition at least a kind.
3. aligning agent for liquid crystal according to claim 1, wherein, in the group that organoalkoxysilane shown in formula [1b] is made up of 3-glycidoxy propyl group (dimethoxy) methyl-monosilane, 3-glycidoxy propyl group (diethoxy) methyl-monosilane, 3-glycidoxypropyltrime,hoxysilane and 2-(the own base of 3,4-oxirane ring) ethyl trimethoxy silane for being selected from least a kind.
4. aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, as (C) composition, containing the polysiloxane that will comprise the organoalkoxysilane composition polycondensation of the organoalkoxysilane shown in following formula [1c] and obtain, wherein, this organoalkoxysilane composition is not containing the organoalkoxysilane shown in described formula [1a] and described formula [1b]
(D1)n3Si(OD2)4-n3[1c]
In formula [1c], D1Represent the alkyl of hydrogen atom or carbon number 1��5 independently of one another,
D2Represent the alkyl of carbon number 1��5,
N3 represents the integer of 0��3.
5. aligning agent for liquid crystal according to any one of Claims 1 to 4, it contains and is selected from by methylethylketone, pimelinketone, cyclopentanone, 4-hydroxy-4-methyl-2 pentanone, the own alcohol of 1-, hexalin, 1, ammediol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol single-butyl ether, DPGME, dipropylene glycol dimethyl ether, furfuryl alcohol, and following formula [X1], at least one solvent in the group of the composition of solvent shown in formula [X2] and formula [X3],
In formula [X1], formula [X2] and formula [X3], X1Represent the alkyl of carbon number 1��3, X2Represent the alkyl of carbon number 1��3, X3Represent the alkyl of carbon number 1��4.
6. aligning agent for liquid crystal according to any one of Claims 1 to 5, it contains at least one solvent in the group being selected from and being made up of METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolactone and 1,3-dimethyl-imidazolinone.
7. a liquid crystal orientation film, it uses the aligning agent for liquid crystal according to any one of claim 1��6 to obtain.
8. a liquid crystal orientation film, it uses the aligning agent for liquid crystal according to any one of claim 1��6 to be obtained by ink jet method.
9. liquid crystal represents an element, and it has the liquid crystal orientation film described in claim 7 or 8.
10. liquid crystal orientation film according to claim 7 or 8, it is characterized in that, its be used to possess electrode one to substrate between there is liquid crystal layer and the liquid crystal that manufactures via following operation represents element, described operation is: described one to substrate between configure liquid-crystal composition, described liquid-crystal composition comprises the polymerizable compound being polymerized because of active energy beam and at least one hankered, while make described polymerizable compound be polymerized to applying voltage limit between described electrode.
11. 1 kinds of liquid crystal represent element, it is characterised in that, it has liquid crystal orientation film according to claim 10.
12. liquid crystal orientation films according to claim 7 or 8, it is characterized in that, its be used to possess electrode one to substrate between there is liquid crystal layer and the liquid crystal that manufactures via following operation represents element, described operation is: described one to substrate between configure liquid crystal orientation film, described liquid crystal orientation film comprises the polymerizable group being polymerized because of active energy beam and at least one hankered, while make described polymerizable group be polymerized to applying voltage limit between described electrode.
13. 1 kinds of liquid crystal represent element, it is characterised in that, it has liquid crystal orientation film according to claim 12.
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