CN108570328A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display assembly - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display assembly Download PDF

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CN108570328A
CN108570328A CN201810173678.8A CN201810173678A CN108570328A CN 108570328 A CN108570328 A CN 108570328A CN 201810173678 A CN201810173678 A CN 201810173678A CN 108570328 A CN108570328 A CN 108570328A
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liquid crystal
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蔡宗沛
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Chi Mei Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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

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  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display component, wherein the liquid crystal alignment agent comprises a polymer (A), polysiloxane (B) containing a photoreactive group and a solvent (C), wherein the polymer (A) is selected from a polyamic acid polymer, a polyimide block copolymer or any combination of the polymers. The liquid crystal alignment agent has the advantages of low liquid crystal contact angle, high bulk impedance and the like. In addition, the invention also provides a liquid crystal alignment film formed by the liquid crystal alignment agent, a manufacturing method of the liquid crystal alignment film and a liquid crystal display component comprising the alignment film.

Description

Crystal aligning agent, liquid crystal orienting film and LCD assembly
Technical field
The present invention relates to a kind of crystal aligning agent and its manufacturing method, liquid crystal orienting film and its manufacturing method and liquid crystals Show component, low especially with regard to a kind of liquid crystal contact angle and high body impedance crystal aligning agent and its manufacturing method, by above-mentioned liquid Brilliant orientation dosage form at liquid crystal orienting film and its manufacturing method and LCD assembly with above-mentioned liquid crystal orienting film.
Background technology
In general, in LCD assembly, not according to the physical property of electrode structure or used liquid crystal molecule Together, various type of drive have been developed.The LCD assembly type of drive being currently known is for example：TN types or STN types, VA types, Transverse electric field effect display technology type (IPS types) etc..Above-mentioned LCD assembly, to make liquid crystal alignment be configured with liquid crystal Alignment film.The material of liquid crystal orienting film may be, for example, known to polyimide acid or polyimide, polyester, polysiloxane etc. Material.
In recent years, the orientation of the liquid crystal molecule of LCD assembly in order to control, and propose such as polymer-stabilized alignment (Polymer Sustained Alignment；PSA new technology), such as Japanese publication number JP 2003-149647, described in Polymer-stabilized alignment technology be will with irradiation polymerism ingredient be added liquid crystal born of the same parents liquid crystal layer in, in apply voltage shape Make liquid crystal molecules tilt under state, then with light irradiating liquid crystal born of the same parents, and then the ingredient of irradiation polymerism is made to polymerize, thereby controls liquid crystal The orientation of molecule.
However, using polymer-stabilized alignment technical controlling liquid crystal molecule orientation when, need to be irradiated using relatively high light Amount, thus the defect of the decomposition of generation liquid crystal molecule, liquid crystal orienting film property-deterioration etc., in turn result in the display of LCD assembly Inhomogeneities and the deterioration of panel durability.On the other hand, it if reducing above-mentioned light irradiation amount, causes to be formed by liquid crystal Show that the liquid crystal molecule in component is slack-off to the reaction speed of voltage change.In order to make the crystal aligning agent to form film, to the greatest extent may be used Scheduled pre-tilt angle characteristic can be can reach with a small amount of light irradiation amount, and be formed by liquid crystal molecule pair in LCD assembly The reaction speed of voltage is fast, proposes the technology of Japanese Laid-Open 2011-118358 Patent Cases at present, discloses using containing such as The liquid crystal of polysiloxane and the polyimide acid of (methyl) acryloyl group or the irradiation polymerizable component of polyimide is matched To agent, in forming liquid crystal orienting film on substrate.Then, aforesaid substrate is formed into liquid crystal born of the same parents, and between substrate when application voltage, it is right Liquid crystal born of the same parents carry out light irradiation, and LCD assembly is made.
However, the above method is still because the liquid crystal contact angle of crystal aligning agent is excessively high so that liquid crystal can not be in liquid crystal orienting film Upper uniform fold.In addition, the body impedance of above-mentioned crystal aligning agent is still relatively low, and it cannot be satisfied industrial requirement.Therefore, at present there is an urgent need for It proposes a kind of crystal aligning agent, the disadvantage that liquid crystal contact angle is excessively high and body impedance is relatively low can be improved.
Invention content
The ingredients such as polysiloxanes of the present invention using special polymer is provided and containing photoreactivity base, and obtain liquid crystal and match To agent, being formed by liquid crystal orienting film and LCD assembly by above-mentioned crystal aligning agent has liquid crystal contact angle low and body impedance High advantage.
Therefore, the present invention is about a kind of crystal aligning agent, it includes：
Polymer (A) is selected from polyamic acid polymer, polyimide polymer, polyimides system block copolymerization The arbitrary combination of object or above-mentioned polymer；
Polysiloxanes (B) containing photoreactivity base；And
Solvent (C)；
Wherein the polymer (A) includes unit shown in formula (Ia)：
In formula (Ia), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
Ht is nitrogenous heterocycle；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；And
* it is at bond；
The polysiloxanes (B) containing photoreactivity base includes the structure as shown in formula (IIa)：
In formula (IIa), R1For methylene, C2To C10Linear chain or branched chain alkylidene, stretch phenyl or stretch cyclohexyl, the R1Official A part of hydrogen atom of energy base is substituted or unsubstituted；
R2For methylene or C2To C10Linear chain or branched chain alkylidene, the R2A part of hydrogen atom of functional group it is substituted or It is unsubstituted；
R3For singly-bound, methylene or C2To C10Linear chain or branched chain alkylidene, the R3A part of hydrogen atom quilt of functional group Substitution is unsubstituted；
R4For hydrogen atom or methyl；
L is-OCO- ,-O- or-S-；
A is integer of 0 to 10；
The integer that b is 0 to 1；
When b is 0, a is not 0；
When a is plural number, a plurality of R2And L is respectively identical or different；And
* it is at bond.
The present invention separately provides a kind of liquid crystal orienting film, is formed by crystal aligning agent above-mentioned.
The present invention also provides a kind of LCD assembly, and it includes liquid crystal orienting films above-mentioned.
The present invention provides a kind of manufacturing method of crystal aligning agent again, it includes mixed polymer (A), contains photoreactivity base Polysiloxanes (B) and solvent (C).
The present invention provides a kind of manufacturing method of liquid crystal orienting film again, and it includes form the LCD alignment by crystal aligning agent Film, the wherein crystal aligning agent are formed by the manufacturing method of crystal aligning agent above-mentioned.
The present invention provides a kind of manufacturing method of LCD assembly again, which includes liquid crystal orienting film, The manufacturing method includes to form the liquid crystal orienting film by crystal aligning agent, and wherein the crystal aligning agent is by LCD alignment above-mentioned The manufacturing method of agent is formed.
Specific implementation mode
The present invention provides a kind of crystal aligning agent, it includes：
Polymer (A) is selected from polyamic acid polymer, polyimide polymer, polyimides system block copolymerization The arbitrary combination of object or above-mentioned polymer；
Polysiloxanes (B) containing photoreactivity base；And
Solvent (C)；
Wherein the polymer (A) includes unit shown in formula (Ia)：
In formula (Ia), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
Ht is nitrogenous heterocycle；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；And
* it is at bond；
The polysiloxanes (B) containing photoreactivity base includes the structure as shown in formula (IIa)：
In formula (IIa), R1For methylene, C2To C10Linear chain or branched chain alkylidene, stretch phenyl or stretch cyclohexyl, the R1Official A part of hydrogen atom of energy base is substituted or unsubstituted；
R2For methylene or C2To C10Linear chain or branched chain alkylidene, the R2A part of hydrogen atom of functional group it is substituted or It is unsubstituted；
R3For singly-bound, methylene or C2To C10Linear chain or branched chain alkylidene, the R3A part of hydrogen atom quilt of functional group Substitution is unsubstituted；
R4For hydrogen atom or methyl；
L is-OCO- ,-O- or-S-；
A is integer of 0 to 10；
The integer that b is 0 to 1；
When b is 0, a is not 0；
When a is plural number, a plurality of R2And L is respectively identical or different；And
* it is at bond.
Polymer (A) according to the present invention is to be reacted by the first mixture and obtained, which includes tetrabasic carboxylic acid Dianhydride component component (a-1) and diamine components component (a-2).
Specifically, which is selected from embedding by polyamic acid polymer, polyimide polymer, polyimides system Section co-polymer and the arbitrary of above-mentioned polymer combine formed group.Wherein, polyimides system block copolymer includes poly- Amic acid block copolymer, polyimide block co-polymer, polyamic acid-polyimide block co-polymer are above-mentioned poly- Close the combination of object.Polyamic acid polymer, polyimide polymer and polyamic acid-polyimides in the polymer (A) is embedding Obtained by section co-polymer can all be reacted by the mixture of tetracarboxylic dianhydride's component component (a-1) and diamine components component (a-2).
The polymer (A) includes unit shown in formula (Ia)：
In formula (Ia), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
Ht is nitrogenous heterocycle；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；And
* it is at bond.
Preferably, the polymer (A) includes unit shown in formula (Ia-1), formula (Ia-2) or formula (Ia-3)：
In formula (Ia-1) to formula (Ia-3), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；RdFor hydrogen original Son or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；And
* it is at bond.
Tetracarboxylic dianhydride's compound (a-1) includes aliphatic tetracarboxylic dianhydride compound, two anhydridization of Alicyclic tetracarboxylic acid It closes in object, aromatic tetracarboxylic acid's dianhydride compound, tetracarboxylic dianhydride's compound for being indicated to formula (I-6) by formula (I-1) at least The combination of one kind or above compound.
It is exemplified below aliphatic tetracarboxylic dianhydride compound, Alicyclic tetracarboxylic acid dianhydride compound, aromatic tetracarboxylic acid two The concrete example of acid anhydride compound, but the present invention is not limited to these concrete examples.
The concrete example of aliphatic tetracarboxylic dianhydride's compound may include but be not limited to ethane tetracarboxylic dianhydride (ethane Tetracarboxylic dianhydride), butane tetracarboxylic acid dianhydride (butane tetracarboxylic ) or the combination of above compound dianhydride.
The concrete example of Alicyclic tetracarboxylic acid dianhydride compound may include but be not limited to 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- Two chloro- 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3, It is 4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylics dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydrides, suitable Formula -3,7- dibutyl suberyl -1,5- diene -1,2,5,6- tetracarboxylic dianhydrides, 2,3,5- tricarboxylics cyclopentyl acetic acid dianhydride or The combination of above compound.
The concrete example of aromatic tetracarboxylic acid's dianhydride compound may include but be not limited to 3,4- dicarboxyl -1,2,3,4- tetrahydrochysenes Naphthalene -1- ambers acid dianhydride, the equal tetracarboxylic dianhydride of benzene, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyl sulfones Tetracarboxylic dianhydride, 1,4,5,8- naphthalene tetracarboxylic acids dianhydride, 2,3,6,7- naphthalene tetracarboxylic acids dianhydride, 3,3 ', 4,4 '-diphenylethane tetracarboxylic acids Acid dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydrides, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydrides, 1, 2,3,4- furans tetracarboxylic dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 4,4 '-bis- (3,4- dicarboxyls Phenoxy group) diphenyl sulfone dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl propane dianhydride (4,4 '-bis (3,4- Dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid Dianhydride, 3,3 ', 4,4 '-biphenyltetracaboxylic dianhydrides, p- stretch the bis- (triphenyls of phenyl-at bis- (phthalic acid) phosphniline oxide dianhydrides Phthalic acid) dianhydride, m- stretch bis- (triphenylbenzene diacid) dianhydrides of phenyl -, bis- (triphenylbenzene diacid) -4,4 '-diphenyl ethers two Acid anhydride, bis- (triphenylbenzene diacid) -4,4 '-diphenyl methane dianhydrides, ethylene glycol-bis- (dehydration trimellitates), propylene glycol-are bis- (dehydration trimellitate), 1,4- butanediols-bis- (dehydration trimellitate), 1,6-HD-bis- (dehydration trimellitates), 1,8- ethohexadiols-bis- (dehydration trimellitate), bis- (4- hydroxyphenyls) propane-of 2,2- bis- (dehydration trimellitates), 2,3,4, 5- tetrahydrofurans tetracarboxylic dianhydride, 1,3,3a, 4,5,9b- hexahydros -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone { (1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3- Furanyl) naphtho [1,2-c] furan-1,3-dione) }, 1,3,3a, 4,5,9b- hexahydro -5- methyl -5- (tetrahydrochysene -2, Bis- side oxygroup -3- furyls of 5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- ethyls -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydros -7- Methyl -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- Hexahydro -7- ethyls -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- ethyls -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2-c]-furans -1, 3- diketone, 1,3,3a, 4,5,9b- hexahydro -5,8- dimethyl -5- (two side oxygroup -3- furyls of tetrahydrochysene -2,5-)-naphtho- [1,2- C]-furans -1,3- diketone, 5- (bis- side oxygroup tetrahydrofuran bases of 2,5-) -3- methyl -3- cyclohexene -1,2- dicarboxylic acid dianhydrides etc. The combination of aromatic tetracarboxylic acid's dianhydride compound or above compound.
The tetracarboxylic dianhydride's compound indicated to formula (I-6) by formula (I-1) is as follows.
In formula (I-5), A1Indicate the bivalent group containing aromatic rings；R indicates 1 to 2 integer；A2And A3Can be it is identical or Difference, and respectively can independently indicate hydrogen atom or alkyl.The concrete example of tetracarboxylic dianhydride's compound indicated by formula (I-5) includes At least one of the compound indicated by formula (I-5-1) to formula (I-5-3).
In formula (I-6), A4Indicate the bivalent group containing aromatic rings；A5And A6Can be it is identical or different, and respectively independent table Show hydrogen atom or alkyl.The tetracarboxylic dianhydride's compound indicated by formula (I-6) is preferably the compound indicated by formula (I-6-1).
Tetracarboxylic dianhydride's compound (a-1) can be used alone or combine a variety of use.
The concrete example of tetracarboxylic dianhydride's compound (a-1) preferably include 1,2,3,4- cyclobutane tetracarboxylic dianhydride (1,2, 3,4-cyclobutane tetracarboxylic dianhydride), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,5- Tricarboxylic cyclopentyl acetic acid dianhydride (2,3,5-tricarboxycyclopentylacetic dianhydride), 1,2,4,5- Cyclopentanetetracarboxylic's dianhydride, 3,4- dicarboxyl -1,2,3,4- naphthane -1- ambers acid dianhydride, the equal tetracarboxylic dianhydride of benzene (pyromellitic dianhydride), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic acids The combination for the compound or above compound that acid dianhydride, formula (I-1) indicate.
Total mole number based on diamine components component (a-2) is 100 moles, and tetracarboxylic dianhydride's component component (a-1's) makes Amount ranges are preferably 80 moles to 120 moles, more preferably 85 moles to 115 moles.
Diamine components component (a-2) according to the present invention includes diamine compound (a-2- shown at least one formula (Ib) 1)：
In formula (Ib), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
Ht is nitrogenous heterocycle；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；And
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1.
Preferably, the diamine compound (a-2-1) includes chemical combination shown in formula (Ib-1), formula (Ib-2) or formula (Ib-3) Object：
In formula (Ib-1) to formula (Ib-3), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；And
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1.
The concrete example of the diamine compound (a-2-1) is：
In the concrete example of the present invention, total usage amount based on diamine components component (a-2) is 100 moles, two amination The usage amount for closing object (a-2-1) is 3 to 40 moles, preferably 5 to 35 moles, more preferably 5 to 30 moles.If the diamines is not used Compound (a-2-1), then the body impedance of obtained crystal aligning agent is low, and liquid crystal contact angle is high.
Preferably, the diamine components component (a-2) of the present invention can additionally comprise other diamine compounds (a-2-2).
Other diamine compounds (a-2-2) include aliphatic diamine compound, alicyclic diamine compound, aromatic series two Amine compounds, with formula (a-2-2-1) to formula (a-2-2-26) diamine compound, or combinations thereof.
The concrete example of aliphatic diamine compound includes but not limited to 1,2- diamino-ethanes, bis- amido propane of 1,3-, 1, 4- diaminobutanes, 1,5- diaminopentanes, 1,6- phenylenediamines, 1,7- diamines base heptane, bis- amido octanes of 1,8-, 1,9- Two amido nonanes, bis- amido decane of 1,10-, 4,4 '-diamines base heptanes, bis- amido -2,2- dimethylpropanes of 1,3-, 1,6- diamines Base -2,5- dimethylhexanes, bis- amido -2,5- dimethyl heptanes of 1,7-, bis- amido -4,4- dimethyl heptanes of 1,7-, 1,7- bis- Amido -3- methyl heptanes, bis- amido -5- methylnonanes of 1,9-, bis- amido dodecanes of 2,11-, bis- amido octadecanes of 1,12-, 1, The combination of bis- (the 3- amidos propoxyl group) ethane of 2- or above compound.
The concrete example of alicyclic diamine compound includes but not limited to 4,4 '-two amido dicyclohexyl methyl hydrides, 4,4 '-diamines Base -3,3 '-dimethyidicyclohexyl amine, 1,3- diamines butylcyclohexane, 1,4- diamines butylcyclohexane, isophorone diamine, tetrahydrochysene Bicyclopentadiene diamines, tricyclic [6.2.1.02,7]-endecatylene dimethyl-p-phenylenediamine, 4,4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine), or The combination of above compound.
The concrete example of aromatic diamine compound includes but not limited to 4,4 '-two aminodiphenylmethanes, 4,4 '-two amidos Diphenylethane, 4,4 '-two amido diphenyl sulfones, 4,4 '-two amido benzanilides, 4,4 '-two amido stibene, 4, 4 '-two amido diphenyl ethers, 3,4 '-two amido diphenyl ethers, 3,3 '-two amido chalcone, bis- amido naphthalenes of 1,5-, 5- amidos- 1- (4 '-aminocarbonyl phenyl) -1,3,3- trimethyl hydrogen indenes, 6- amidos -1- (4 '-aminocarbonyl phenyl) -1,3,3- trimethyl hydrogen indenes, six Hydrogen -4,7- first bridges stretch hydrogen indenyl dimethylene diamines, 3,3 '-two aminobenzophenones, 3,4 '-two aminobenzophenones, 4,4 ' - Bis- [4- (the 4- amidos phenoxy group) phenyl] propane of two aminobenzophenones, 2,2-, 2,2- bis- [4- (4- amidos phenoxy group) phenyl] Bis- [4- (the 4- amidos phenoxy group) phenyl] sulfones of bis- (4- aminocarbonyl phenyls) hexafluoropropane of hexafluoropropane, 2,2-, 2,2-, the bis- (4- of 1,4- Amido phenoxy group) benzene, bis- (the 4- amidos phenoxy group) benzene of 1,3-, bis- (the 3- amidos phenoxy group) benzene of 1,3-, bis- (the 4- amido benzene of 9,9- Base) -10- hydrogen anthracene, bis- (4- aminocarbonyl phenyls) anthracenes of 9,10- [9,10-bis (4-aminophenyl) anthracene], 2,7- diamines Bis- (4- aminocarbonyl phenyls) Fluorene of base Fluorene, 9,9-, 4,4 '-methylene-bis- (2- chloroanilines), 4,4 '-(p- to stretch phenyl isopropylidene) are double Aniline, 4,4 '-(m- to stretch phenyl isopropylidene) dianils, 2,2 '-bis- [4- (4- amido -2- 4-trifluoromethylphenopendants) phenyl] Hexafluoropropane, 4,4 '-bis- [(4- amido -2- trifluoromethyls) phenoxy group]-octafluorobiphenyls, 5- [4- (4- pentanes butylcyclohexyl) Cyclohexyl] two amido benzene { 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] of phenyi-methylene -1,3- Phenylmethylene-1,3-diamino benzene }, bis- [4- (4- amidos phenoxy group) phenyl] -4- (the 4- ethylo benzenes of 1,1- Base) hexamethylene { 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane }, or The combination of above compound.
The diamine compound indicated to formula (a-2-2-30) by formula (a-2-2-1) is as follows.
In formula (a-2-2-1), B1It indicates B2Indicate base, trifluoromethyl, fluorine atom, C with steroid (cholesterol (steroid)) skeleton2To C30Alkyl, Or the univalent perssad derived from the nitrogen atoms cyclic structure such as pyridine, pyrimidine, triazine, piperidines or piperazine.
The concrete example of the compound indicated by formula (a-2-2-1) includes but not limited to bis- aminocarbonyl phenyl Ethyl formates of 2,4- (2,4-diaminophenyl ethyl formate), bis- aminocarbonyl phenyl Ethyl formate (3,5-diaminophenyl of 3,5- Ethyl formate), bis- aminocarbonyl phenyl propyl formates of 2,4- (2,4-diaminophenyl propyl formate), 3,5- Two aminocarbonyl phenyl propyl formates (3,5-diaminophenyl propyl formate), two amidos of 1- dodecyloxies -2,4- Benzene (1-dodecoxy-2,4-diaminobenzene), two amido benzene (1-hexadecoxy-2,4- of 1- hexadecane epoxides -2,4- Diaminobenzene), two amido benzene (1-octadecoxy-2,4-diaminobenzene) of 1- octadecane epoxides -2,4-, by At least one of or above compound combination in the compound that formula (a-2-2-1-1) is indicated to formula (a-2-2-1-6).
In formula (a-2-2-2), B1With the B in formula (a-2-2-1)1It is identical, B3And B4It is respectively independent to indicate bivalent aliphatic Ring, O divalent aromatic ring or divalent heterocyclic group；B5Indicate C3To C18Alkyl, C3To C18Alkoxy, C1To C5Fluothane Base, C1To C5Fluoroalkyloxy, cyano or halogen atom.
The concrete example of the compound indicated by formula (a-2-2-2) includes by formula (a-2-2-2-1) to formula (a-2-2-2-13) It is at least one of in the compound of expression.Specifically, the change indicated to formula (a-2-2-2-13) by formula (a-2-2-2-1) It is as follows to close object.
In formula (a-2-2-2-10) to formula (a-2-2-2-13), s indicates 3 to 12 integer.
In formula (a-2-2-3), B6It is respectively independent to indicate hydrogen atom, C1To C5Acyl group, C1To C5Alkyl, C1To C5Alkane Oxygroup or halogen atom, and the B in each repetitive unit6Can be identical or different；U indicates integer of 1 to 3.
The concrete example of the compound indicated by formula (a-2-2-3) includes when u is 1：It is p- diamines benzene, m- diamines benzene, o- Diamines benzene or 2,5- toluenediamines etc.；When u is 2：4,4 '-benzidines,-two amido of 2,2 '-dimethyl -4,4 ' connection Benzene, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 2,2 '-two chloro- 4,4 ' - Benzidine, 3,3 '-two chloro- 4,4 '-benzidines, 2,2 ', 5,5 '-four chloro- 4,4 '-benzidines, 2,2 '-two Chloro- 4,4 '-two amido -5,5 '-dimethoxy-biphenyl or bis- (trifluoromethyl) biphenyl of 4,4 '-two amidos -2,2 '-etc.；Or when u is When 3：Bis- (4 '-aminocarbonyl phenyl) benzene of 1,4- etc..
By formula (a-2-2-3) indicate compound concrete example preferably include p- diamines benzene, 2,5- toluenediamines, 4,4 '-benzidines, 3,3 '-dimethoxy-4 's, bis- (4 '-aminocarbonyl phenyl) benzene of 4 '-benzidines, 1,4- or above-mentioned chemical combination The combination of object.
In formula (a-2-2-4), v indicates 2 to 12 integer.
In formula (a-2-2-5), w indicates 1 to 5 integer.The compound indicated by formula (a-2-2-5) is preferably 4,4 '-two Amido-diphenylsulfide.
In formula (a-2-2-6), B7And B9It is respectively independent to indicate bivalent organic group, and B7And B9Can be identical or different；B8 Indicate the bivalent group derived from cyclic structures of nitrogen atoms such as pyridine, pyrimidine, triazine, piperidines or piperazines.
In formula (a-2-2-7), B10、B11、B12And B13It is respectively independent to indicate C1To C12Alkyl, and B10、B11、B12And B13 Can be identical or different；X1 respectively independently indicates integer of 1 to 3；X2 indicates integer of 1 to 20.
In formula (a-2-2-8), B14It indicates oxygen atom or stretches cyclohexyl；B15Expression methylene (methylene ,- CH2-)；B16Expression stretches phenyl or stretches cyclohexyl；B17Indicate hydrogen atom or heptyl.
The concrete example of the compound indicated by formula (a-2-2-8) includes the compound indicated by formula (a-2-2-8-1), by formula (a-2-2-8-2) combination of the compound or above compound that indicate.
The compound indicated to formula (a-2-2-25) by formula (a-2-2-9) is as follows.
In formula (a-2-2-17) to formula (a-2-2-25), B18Preferably indicate C1To C10Alkyl or C1To C10Alcoxyl Base；B19Preferably indicate hydrogen atom, C1To C10Alkyl or C1To C10Alkoxy.
In formula (a2-2-26), B20、B22Independently indicate singly-bound ,-O- ,-COO- or-OCO-；B21It is 1 to 3 for carbon number Stretch alkyl；B23 is singly-bound or carbon number is 1 to 3 to stretch alkyl.D and g respectively independently indicates 0 or 1；E indicates 0 to 2 integer；f Indicate integer of 1 to 20；It is 0 when wherein d and e differences.
In formula (a2-2-26), with "-B20-(B21-B22) to be preferably carbon number be 1 to 3 to stretch alkane to the bivalent groups that indicate of g- " (wherein, * is indicated at the bond being bonded with two aminocarbonyl phenyls by base, *-O-, *-COO- or *-O-C2H4-O-.).With "-CfH2f+1" table The group shown is preferably straight-chain.Two amidos in two aminocarbonyl phenyls, the position relative to other groups be preferably 2,4 or 3,5.
The concrete example of the compound indicated by formula (a2-2-26) can be enumerated by following formula (a2-2-26-1) to formula (a2-2- 26-4) the compound indicated：
Other diamine compounds (a-2-2) may be used alone or in combination a variety of use.
The concrete example of other diamine compounds (a-2-2) preferably includes but not limited to 1,2- diamino-ethanes, 3,3'- Two amido chalcone, bis- amido stibene of 4,4'-, 4,4 '-two amido dicyclohexyl methyl hydrides, 4,4 '-two amido diphenyl Methane, 4,4 '-two amido diphenyl ethers, two amidos of 5- [4- (4- pentanes butylcyclohexyl) cyclohexyl] phenylmethylene -1,3- Bis- [4- (4- amidos phenoxy group) phenyl] -4- (4- ethylphenyls) hexamethylenes of benzene, 1,1-, bis- aminocarbonyl phenyl Ethyl formates of 2,4-, Two amido benzene of 1- octadecane epoxides -2,4-, the compound indicated by formula (a-2-2-1-1), the change indicated by formula (a-2-2-1-2) Close object, by formula (a-2-2-1-4) indicate compound, by formula (a-2-2-1-5) indicate compound, by formula (a-2-2-2-1) The compound of expression, by formula (a-2-2-2-11) indicate compound, p- diamines benzene, m- diamines benzene, o- diamines benzene, by formula (a-2-2-8-1) compound indicated, the compound or above compound that are indicated to formula (a-2-2-30) by formula (a-2-2-26) Combination.
In the concrete example of the present invention, total usage amount based on diamine components component (a-2) is 100 moles, this other two The usage amount of amine compounds (a-2-2) is 60 to 97 moles, preferably 65 to 95 moles, more preferably 70 to 95 moles.
[method for preparing polymer (A)]
The polymer (A) may include at least one of polyamic acid and polyimides.In addition, polymer (A) can be wrapped more Include polyimides system block copolymer.The preparation method of above-mentioned various polymer further explained below.
<The method for preparing polyamic acid>
The method for preparing the polyamic acid is that first the first mixture is dissolved in solvent, wherein the first mixture includes four Carboxylic acid dianhydride component component (a-1) and diamine components component (a-2), and progress polycondensation is anti-at a temperature of 0 DEG C to 100 DEG C It answers.After reaction 1 hour to 24 hours, reaction solution is evaporated under reduced pressure with evaporator, you can obtain polyamic acid.Alternatively, Reaction solution is poured into a large amount of lean solvent, to obtain precipitate.Then, precipitate is dried in a manner of being dried under reduced pressure, i.e., Polyamic acid can be obtained.
Can be identical or different with the solvent in following crystal aligning agents for the solvent in polycondensation reaction, and it is used for bunching The solvent closed in reaction is not particularly limited, as long as can dissolve reactant and product.Preferred solvents be include but It is not limited to (1) non-proton system's polar solvent, such as：N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidinone； NMP), DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 4-methyl urea or pregnancy Non-proton system's polar solvent of base phosphoric acid triamine etc.；Or (2) phenol system solvent, such as：M-cresol, dimethlbenzene, phenol or halogenation phenol The phenol system solvent of class etc..Total usage amount based on the first mixture is 100 parts by weight, for making for the solvent in polycondensation reaction Dosage is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight are to 1800 parts by weight.
It is worth noting that, in polycondensation reaction, solvent can and with suitable lean solvent, wherein lean solvent will not cause Polyamic acid is precipitated.Lean solvent can be used using independent a kind of or combination is a variety of, and it includes but not limited to (1) alcohol Class, such as：The alcohols of methanol, ethyl alcohol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4- butanediols or triethylene glycol etc.； (2) ketone, such as：The ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；(3) esters, such as：Tumer The esters of ester, ethyl acetate, butyl acetate, diethy-aceto oxalate, diethyl malonate or glycol ethyl ether acetate etc.；(4) Ethers, such as：Anaesthetie Ether, Ethylene glycol methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, second The ethers of glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether etc.；(5) halogenated hydrocarbons, such as：Dichloromethane The halogenated hydrocarbons of alkane, 1,2- dichloroethanes, 1,4- dichloroetane, trichloroethanes, chlorobenzene or o-dichlorobenzene etc.；Or (6) hydro carbons, Such as：The arbitrary combination of the hydro carbons of tetrahydrofuran, hexane, heptane, octane, benzene, toluene or dimethylbenzene etc. or above-mentioned solvent.It is based on The usage amount of the diamine components component (a-2) is 100 parts by weight, and the dosage of lean solvent is preferably 0 parts by weight to 60 parts by weight, and More preferably 0 parts by weight are to 50 parts by weight.
<The method for preparing polyimides>
The method for preparing polyimides be by the made polyamic acid of the above-mentioned method for preparing polyamic acid in dehydrating agent and It is heated and is obtained in the presence of catalyst.During heating, the amide acid functional group in polyamic acid can be dead via dehydration Circular response is transformed into acid imide functional group (i.e. imidizate).
Solvent for being dehydrated in endless loop reaction can be identical as solvent (C) in crystal aligning agent, therefore does not go to live in the household of one's in-laws on getting married separately herein It states.Usage amount based on polyamic acid is 100 parts by weight, and the usage amount of the solvent for being dehydrated in endless loop reaction is preferably 200 parts by weight are to 2000 parts by weight, and more preferably 300 parts by weight are to 1800 parts by weight.
To obtain the degree of imidisation of preferable polyamic acid, the operation temperature of dehydration endless loop reaction is preferably 40 DEG C To 200 DEG C, more preferably 40 DEG C to 150 DEG C.If the operation temperature for being dehydrated endless loop reaction is less than 40 DEG C, the reaction of imidizate Not exclusively, the degree of imidisation of polyamic acid is reduced.However, if the operation temperature of dehydration endless loop reaction is higher than 200 DEG C When, the weight average molecular weight of the polyimides of gained is relatively low.
Dehydrating agent for being dehydrated in endless loop reaction can be selected from anhydride compound, specifically for example：Acetic anhydride, third The anhydride compound of acid anhydrides or trifluoro-acetic anhydride etc..It it is 1 mole based on polyamic acid, the usage amount of dehydrating agent is 0.01 mole To 20 moles.Catalyst for being dehydrated in endless loop reaction can be selected from (1) pyridine compounds and their, such as：Pyridine, trimethyl The pyridine compounds and their of pyridine or lutidines etc.；(2) three-level aminated compounds, such as：The three-level amine of triethylamine etc. Compound.Usage amount based on dehydrating agent is 1 mole, and the usage amount of catalyst can be 0.5 mole to 10 moles.
The acid imide rate of polymer (A) can be 30% to 80%, preferably 35% to 85%, and more preferably 35% to 75%.If the acid imide rate of the polymer (A) in above range, the liquid crystal contact angle of obtained crystal aligning agent compared with It is low.
<The method for preparing polyimides system block copolymer>
Polyimides system block copolymer is selected from polyamic acid block copolymer, polyimide block combined polymerization The arbitrary combination of object, polyamic acid-polyimide block co-polymer or above-mentioned polymer.
Starting material is preferably first dissolved in solvent by the method for preparing polyimides system block copolymer, and is gathered Condensation reaction, wherein starting material include at least one polyamic acid and/or at least one polyimides, and can further comprise carboxylic Anhydride component component and diamine components component.
Carboxylic acid anhydrides component component in starting material and diamine components component can with prepare used in the method for polyamic acid Tetracarboxylic dianhydride's component component (a-1) it is identical as diamine components component (a-2), and can be with for the solvent in polycondensation reaction Solvent (C) in following crystal aligning agents is identical, does not repeat separately herein.
Usage amount based on starting material is 100 parts by weight, and the usage amount for the solvent in polycondensation reaction is preferably 200 Parts by weight are to 2000 parts by weight, and more preferably 300 parts by weight are to 1800 parts by weight.The operation temperature of polycondensation reaction is preferably 0 DEG C to 200 DEG C, and more preferably 0 DEG C to 100 DEG C.
Starting material preferably includes but not limited to (1) two kind of polyamic acid that terminal groups are different and structure is different；(2) two kinds The polyimides that terminal groups are different and structure is different；(3) polyamic acid and polyimides that terminal groups are different and structure is different； (4) polyamic acid, carboxylic acid anhydrides component component and diamine components component, wherein carboxylic acid anhydrides component component divides it with diamine components group At least one of with formed polyamic acid used in carboxylic acid anhydrides component component it is different with the structure of diamine components component；(5) Polyimides, carboxylic acid anhydrides component component and diamine components component, wherein in carboxylic acid anhydrides component component and diamine components component extremely It is few a kind of different with the structure of diamine components component with carboxylic acid anhydrides component component used in formation polyimides；(6) polyamide Acid, polyimides, carboxylic acid anhydrides component component and diamine components component, wherein in carboxylic acid anhydrides component component and diamine components component It is at least one with the structure for forming carboxylic acid anhydrides component component and diamine components component used in polyamic acid or polyimides It is different；(7) two kinds of different polyamic acids of structure, carboxylic acid anhydrides component component and diamine components component；(8) two kinds of structures are different Polyimides, carboxylic acid anhydrides component component and diamine components component；(9) two kinds of terminal groups are anhydride group and the different polyamide of structure Acid and diamine components component；(10) two kinds of terminal groups are amido and the different polyamic acid and the grouping of carboxylic acid anhydrides group of structure Point；(11) two kinds of terminal groups are anhydride group and the different polyimides and diamine components component of structure；Or (12) two kinds of ends End group is amido and the different polyimides and carboxylic acid anhydrides component component of structure.
In the range of not influencing effect of the present invention, polyamic acid, polyimides and the block copolymerization of polyimides system It closes object and preferably first carries out the end modified type polymer after molecular-weight adjusting.It, can by using the polymer of end modified type Improve the coating performance of crystal aligning agent.The mode for preparing end modified type polymer can be by carrying out polycondensation in polyamic acid While reaction, monofunctional compounds are added to be made.
The concrete example of monofunctional compounds includes but not limited to (1) unitary acid anhydrides, such as：Maleic anhydride, O-phthalic Acid anhydrides, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride or hexadecane The unitary acid anhydrides such as base succinic anhydride；(2) monoamine compound, such as：Aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptan Amine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane The monoamine compounds such as amine, hexadecane amine, n-heptadecane amine, n-octadecane amine or n-eicosane amine；Or (3) monoisocyanates Object is closed, such as：The monoisocyanate compounds such as phenyl isocyanate or isocyanic acid naphthalene ester.
The weight average molecular weight of the polymer (A) of the present invention is 10000 to 100000；Preferably 20000 to 80000； More preferably 30000 to 70000.
Polysiloxanes (B) containing photoreactivity base is to be reacted by the second mixture and obtained, wherein the second mixture may include Polysiloxanes (b-1) containing epoxy group and ethylene unsaturated compound (b-2).Polysiloxanes (B) packet containing photoreactivity base Containing the structure as shown in formula (IIa)：
In formula (IIa), R1For methylene, C2To C10Linear chain or branched chain alkylidene, stretch phenyl or stretch cyclohexyl, the R1Official A part of hydrogen atom of energy base is substituted or unsubstituted；
R2For methylene or C2To C10Linear chain or branched chain alkylidene, the R2A part of hydrogen atom of functional group it is substituted or It is unsubstituted；
R3For singly-bound, methylene or C2To C10Linear chain or branched chain alkylidene, the R3A part of hydrogen atom quilt of functional group Substitution is unsubstituted；
R4For hydrogen atom or methyl；
L is-OCO- ,-O- or-S-；
A is integer of 0 to 10；
The integer that b is 0 to 1；
When b is 0, a is not 0；
When a is plural number, a plurality of R2And L is respectively identical or different；And
* it is at bond.
In one embodiment of the invention, above-mentioned second mixture further includes side chain compound (b-3).In above-described embodiment In, prepared by being reacted by the second mixture the polysiloxanes (B) containing photoreactivity base may include tying as shown in formula (IVa) Structure：
E1- L0- L1- * (IVa)
In formula (IVa), E1For C1To C30Alkyl, by C1To C20Alkyl or alkoxy substitution or unsubstituted C3Extremely C10Naphthenic base, or the C containing steroid skeleton17To C51Alkyl, the E1Alkyl and alkoxy a part of hydrogen atom quilt Substitution is unsubstituted；
L0For singly-bound, *-O-*, *-COO-* or *-OCO-*；
L1For singly-bound, C1To C20Stretch alkyl, stretch phenyl, stretch xenyl, stretch cyclohexyl, two stretch cyclohexyl or such as following formula (IV-1) or group shown in formula (IV-2)：
Work as L1For singly-bound when, L0For singly-bound；And
* it is at bond.
When second mixture includes polysiloxanes (b-1), ethylene unsaturated compound (b-2) and side containing epoxy group When chain compound (b-3), this contains the polysiloxanes (b-1) of epoxy group and the ethylene unsaturated compound (b-2) can be advanced Row reaction, then adds the side chain compound (b-3) and is reacted；Alternatively, this contains the polysiloxanes (b-1) of epoxy group, second Alkene unsaturated compound (b-2) and side chain compound (b-3) can be reacted jointly.
It below will be to polysiloxanes (b-1), ethylene unsaturated compound (b-2) and side chain compound containing epoxy group (b-3) concrete example and synthetic method illustrates.
Epoxy group contained by polysiloxanes (b-1) containing epoxy group is, for example, glycidyl (glycidyl Group), glycidyl ether (glycidyloxy group), epoxycyclohexyl (epoxycyclohexyl group) or ring Ethylene Oxide base (oxetanyl group).
The group containing epoxy group contained by polysiloxanes (b-1) containing epoxy group include the base indicated by formula (III-1), The base indicated by formula (III-2) and at least one of the base indicated by formula (III-3).
Specifically, as follows by the base that formula (III-1) indicates.
In formula (III-1), B indicates oxygen atom or singly-bound；C indicates integer of 1 to 3；D indicates 0 to 6 integer, wherein working as d When indicating 0, B is singly-bound.
In addition, as follows by the base that formula (III-2) indicates.
In formula (III-2), e indicates 0 to 6 integer.
The base indicated by formula (III-3) is as follows.
In formula (III-3), D indicates C2To C6Stretch alkyl；E indicates hydrogen atom or C1To C6Alkyl.
The base that it includes the base indicated by formula (III-1-1) that group containing epoxy group, which is preferably, is indicated by formula (III-2-1) with And at least one of the base indicated by formula (III-3-1).
The present invention the polysiloxanes (b-1) containing epoxy group include by third mixture through hydrolyzable and partial condensates and The copolymer obtained, the third mixture include the silane monomer (b-1-1) indicated by formula (III-4)；
Si(Rf)p(ORg)4-pFormula (III-4)
In formula (III-4), RfFor hydrogen atom, C1To C10Alkyl, C2To C10Alkenyl, C6To C15Aryl, contain ring The alkyl of oxygroup or alkoxy containing epoxy group, and at least one RfFor the alkyl containing epoxy group or contain the alkane of epoxy group Oxygroup；
When p is plural number, RfIt is respectively identical or different；
RgFor hydrogen atom, C1To C6Alkyl, C1To C6Acyl group or C6To C15Aryl；
When 4-p is plural number, RgIt is respectively identical or different；And
P is integer of 1 to 3.
More specifically, as the R in formula (III-4)fIndicate C1To C10Alkyl when, specifically, RfE.g. methyl, Ethyl, n-propyl, isopropyl, normal-butyl, tertiary butyl, n-hexyl or positive decyl.RfCan also be that there is other substitutions on alkyl The alkyl of base, specifically, RfE.g. trifluoromethyl, 3,3,3- trifluoro propyls, 3- amine propyl, 3- mercaptos propyl or 3- isocyanic acids Propyl.
R in formula (III-4)fIndicate C2To C10Alkenyl when, specifically, RfE.g. vinyl.RfCan also be Alkenyl with other substituent groups on alkenyl, specifically, RfE.g. 3- acryloxypropyls or 3- methacryloxypropyls Base propyl.
R in formula (III-4)fIndicate C6To C15Aryl when, specifically, RfE.g. phenyl, tolyl (tolyl) or naphthalene (naphthyl).RfCan also be the aryl with other substituent groups on aryl, specifically, RfE.g. P- hydroxy phenyl (o-hydroxyphenyl), 1- (p- hydroxy phenyl) ethyl (1- (o-hydroxyphenyl) ethyl), 2- (p- hydroxy phenyl) ethyl (2- (o-hydroxyphenyl) ethyl) or 4- hydroxyls -5- (p- hydroxy phenyl carbonyloxy group) amyl (4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl)。
Furthermore the R in formula (III-4)fWhen indicating the alkyl containing epoxy group or the alkoxy containing epoxy group, Rf's Concrete example is the epoxy group contained by the aforementioned polysiloxanes (b-1) containing epoxy group, is repeated no more in this.
In addition, as the R of formula (III-4)gIndicate C1To C6Alkyl when, specifically, RgE.g. methyl, ethyl, positive third Base, isopropyl or normal-butyl.R in formula (III-4)gIndicate C1To C6Acyl group when, specifically, RgE.g. acetyl group. R in formula (III-4)gIndicate C6To C15Aryl when, specifically, RgE.g. phenyl.
The concrete example of silane monomer (b-1-1) include 3- (N, N- diglycidyl) aminocarbonyl propyl trimethoxy silane, 3- (N- allyl-N- glycidyls) aminocarbonyl propyl trimethoxy silane, 3- glycidoxypropyltrimethoxysilanes alkane, 3- glycidyl ethers propyl-triethoxysilicane, 3- glycidyl ether hydroxypropyl methyls dimethoxysilane, 3- glycidols Ether hydroxypropyl methyl diethoxy silane, 3- glycidyl ether dimethylamines methoxylsilane, 3- glycidyl ethers third Base dimethylethoxysilane, 2- glycidyl ethers ethyl trimethoxy silane, 2- glycidyl ether ethyl triethoxies Silane, 2- glycidyl ether ethyl-methyls dimethoxysilane, 2- glycidyl ether ethyl-methyls diethoxy silane, 2- Glycidyl ether ethyl dimethyl methoxy silane, 2- glycidyl ether ethyls dimethylethoxysilane, 4- shrink sweet Oily ether butyl trimethoxy silane, 4- glycidyl ether butyl triethoxysilane, 4- glycidyl ether butyl methyls Dimethoxysilane, 4- glycidyl ether butyl methyls diethoxy silane, 4- glycidyl ether Butyldimethyl methoxies Base silane, 4- glycidyl ether Butyldimethyls Ethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl triethoxysilane, 3- (3,4- epoxycyclohexyls) propyl trimethoxy silicane, 3- (3,4- Epoxycyclohexyl) propyl-triethoxysilicane, ((3- ethyl -3- propylene oxide base) methoxyl group) propyl trimethoxy silicane, ((3- ethyl -3- propylene oxide base) methoxyl group) propyl-triethoxysilicane, ((3- ethyl -3- propylene oxide base) methoxyl group) third Ylmethyl dimethoxysilane or ((3- ethyl -3- propylene oxide base) methoxyl group) propane dimethyl methoxy silane, commercially available quotient The combination of product such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (JNC systems) or above compound.
It includes 3- glycidyl ethers propyl three that the concrete example for the silane monomer (b-1-1) that formula (III-4) indicates, which is preferably, Methoxy silane, 2- glycidyl ethers ethyl trimethoxy silane, 4- glycidyl ethers butyl trimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl triethoxysilane, ((3- ethyls- 3- propylene oxide base) methoxyl group) propyl trimethoxy silicane, three ethoxy of ((3- ethyl -3- propylene oxide base) methoxyl group) propyl The combination of base silane, DMS-E01, DMS-E12 or above compound.
Total amount based on the monomer in the third mixture is 1 mole, and the usage amount of the silane monomer (b-1-1) is 0.6 mole to 1 mole, preferably 0.65 to 1 mole, more preferably 0.7 to 1 mole.
To react generate the polysiloxanes (b-1) containing epoxy group third mixture preferably further include by Other silane monomers (b-1-2) that formula (III-5) indicates：
Si(Rh)q(ORi)4-qFormula (III-5)
In formula (III-5), RhFor hydrogen atom, C1To C10Alkyl, C2To C10Alkenyl, C6To C15Aryl or containing acid The alkyl of anhydride group；
When q is plural number, RhIt is respectively identical or different；
RiFor hydrogen atom, C1To C6Alkyl, C1To C6Acyl group or C6To C15Aryl；
When 4-q is plural number, RiIt is respectively identical or different；And
P is integer of 1 to 3.
R in formula (III-5)hIndicate C1To C10Alkyl, C2To C10Alkenyl, C6To C15Aryl when, it is specific Example and preferable for example aforementioned RfIt is shown, it is repeated no more in this.
R in formula (III-5)hWhen indicating the alkyl containing anhydride group, alkyl is preferably C1To C10Alkyl.It is specific and Speech, the alkyl containing anhydride group is, for example, shown in ethyl succinic acid acid anhydride, formula (III-5-2) shown in formula (III-5-1) Propyl glutaric anhydride shown in propyl succinimide acid anhydrides or formula (III-5-3).It is noted that anhydride group is by dicarboxylic acids (dicarboxylic acid) is formed by group through intramolecular dehydration (intramolecular dehydration), wherein Dicarboxylic acids is, for example, succinic acid or glutaric acid.
R in formula (III-5)iIndicate C1To C6Alkyl, C1To C6Acyl group or C6To C15Aryl when, concrete example With preferably for example aforementioned RgIt is shown, it is repeated no more in this.
Other silane monomers (b-1-2) indicated by formula (III-5) can be used alone or as a mixture, and by formula (III-5) table Other silane monomers (b-1-2) shown include the compound with 1 silicon atom.Compound with 1 silicon atom includes tool There are the silane compounds of 4 hydrolization groups, the silane compound with 3 hydrolization groups, with 2 hydrolization groups Silane compound, the silane compound with 1 hydrolization group, or combinations thereof.
The concrete example of silane compound with 4 hydrolization groups includes tetrachloro silicane, tetramethoxy-silicane, four ethoxies Base silane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silanes, four sec-butoxy silanes or above-mentioned chemical combination The combination of object.
The concrete example of silane compound with 3 hydrolization groups includes methyltrimethoxysilane (methyltrimethoxysilane abbreviation MTMS), methyltriethoxysilane (methyltriethoxysilane), methyl Three isopropoxy silane (methyltriisopropoxysilane), three n-butoxy silane (methyltri-n- of methyl Butoxysilane), ethyl trimethoxy silane (ethyltrimethoxysilane), ethyl triethoxysilane (ethyltriethoxysilane), three isopropoxy silane (ethyltriisopropoxysilane) of ethyl, ethyl three be just Butoxy silane (ethyltri-n-butoxysilane), n-propyl trimethoxy silane (n- Propyltrimethoxysilane), n-propyl triethoxysilane (n-propyltriethoxysilane), normal-butyl three Methoxy silane (n-butyltrimethoxysilane), ne-butyltriethoxysilaneand (n- Butyltriethoxysilane), n-hexyl trimethoxy silane (n-hexyltrimethoxysilane), three second of n-hexyl Oxysilane (n-hexyltriethoxysilane), ruthenium trimethoxysilane (decyltrimethoxysilane), ethylene Base trimethoxy silane (vinyltrimethoxysilane), vinyltriethoxysilane (vinyltriethoxysilane), 3- acryloyloxypropyltrimethoxysilanes (3- Acryoyloxypropyltrimethoxysilane), 3- methacryloxypropyl trimethoxy silanes (3- Methylacryloyloxypropyltrimethoxysilane, MPTMS), 3- methacryloxypropyl triethoxysilicanes Alkane (3-methylacryloyloxypropyltriethoxysilane), phenyltrimethoxysila,e (phenyltrimethoxysilane, PTMS), phenyl triethoxysilane (phenyltriethoxysilane, PTES), P- hydroxy phenyl trimethoxy silane (p-hydroxyphenyltrimethoxysilane), 1- (p- hydroxy phenyl) ethyl Trimethoxy silane (1- (p-hydroxyphenyl) ethyltrimethoxysilane), 2- (p- hydroxy phenyl) ethyl three Methoxy silane (2- (p-hydroxyphenyl) ethyltrimethoxysilane), 4- hydroxyls -5- (p- hydroxy phenyl carbonyls Oxygroup) amyltrimethoxysilane (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) Pentyltrimethoxysilane), trifluoromethyl trimethoxy silane (trifluoromethyltrimethoxysilane), trifluoromethyl triethoxysilane (trifluoromethyltriethoxysilane), 3,3,3- trifluoro propyls trimethoxy silane (3,3,3- Trifluoropropyltrimethoxysilane), 3- amine propyl trimethoxy silicane (3- Aminopropyltrimethoxysilane), 3- amine propyl-triethoxysilicane (3- Aminopropyltriethoxysilane), 3- mercaptopropyl trimethoxysilanes (3- Mercaptopropyltrimethoxysilane), 3- (triple phenoxyl silicon substrate) propyl succinimide acid anhydrides (3- Triphenoxysilyl propyl succinic anhydride), by the commercially available product manufactured by SHIN-ETSU HANTOTAI's chemistry：3- (trimethoxies Base silicon substrate) propyl succinimide acid anhydrides (3-trimethoxysilyl propyl succinic anhydride) (trade name X-12- 967), by the commercially available product manufactured by WACKER companies：3- (triethoxy silicon substrate) propyl succinimide acid anhydrides (3- (triethoxysilyl) propyl succinic anhydride) (trade name GF-20), 3- (trimethoxy silicon substrate) propyl Glutaric anhydride (3- (trimethoxysilyl) propyl glutaric anhydride, TMSG), 3- (triethoxy silicon substrate) Propyl glutaric anhydride (3- (triethoxysilyl) propyl glutaric anhydride), 3- (triple phenoxyl silicon substrate) third The combination of base glutaric anhydride (3- (triphenoxysilyl) propyl glutaric anhydride) or above compound.
The concrete example of silane compound with 2 hydrolization groups includes methyl dimethoxysilane, methyl diethoxy Base silane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, methyl [2- (n-perfluoro-octyl) ethyl] dimethoxy Silane, 3- mercapto hydroxypropyl methyls dimethoxysilane, dimethoxydiphenylsilane, dimethyl 2 acetoxyl group silane, two positive fourths The combination of base dimethoxysilane or above compound.
The concrete example of silane compound with 1 hydrolization group includes methoxyl group dimethylsilane, methoxyl group front three The combination of base silane, methoxy diphenyl silane, three normal-butyl Ethoxysilanes or above compound.
Other silane monomers (b-1-2) of structure shown in the formula (III-5) are preferably tetramethoxy-silicane, tetraethoxy-silicane Alkane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3- mercaptos third Base trimethoxy silane, 3- mercaptopropyltriethoxysilanes, thiopurine methyltransferase trimethoxy silane, thiopurine methyltransferase triethoxysilane, two The combination of methyl dimethoxysilane, dimethyl diethoxysilane or above compound.
Total amount based on the monomer in the third mixture is 1 mole, and the usage amount of the silane monomer (b-1-2) is 0 mole to 0.7 mole, preferably 0 to 0.6 mole, more preferably 0 to 0.5 mole.
Third mixture can further include the silane monomer of commercial goods, concrete example can enumerate KC-89, KC-89S, X-21-3153、X-21-5841、X-21-5842、X-21-5843、X-21-5844、X-21-5845、X-21-5846、X-21- 5847、X-21-5848、X-22-160AS、X-22-170B、X-22-170BX、X-22-170D、X-22-170DX、X-22- 176B、X-22-176D、X-22-176DX、X-22-176F、X-40-2308、X-40-2651、X-40-2655A、X-40-2671、 X-40-2672、X-40-9220、X-40-9225、X-40-9227、X-40-9246、X-40-9247、X-40-9250、X-40- 9323、X-41-1053、X-41-1056、X-41-1805、X-41-1810、KF6001、KF6002、KF6003、KR212、KR- 213、KR-217、KR220L、KR242A、KR271、KR282、KR300、KR311、KR401N、KR500、KR510、KR5206、 KR5230, KR5235, KR9218, KR9706 (SHIN-ETSU HANTOTAI's chemistry system)；Glass resin (GLASS RESIN, Showa electrician system)； SH804、SH805、SH806A、SH840、SR2400、SR2402、SR2405、SR2406、SR2410、SR2411、SR2416、 SR2420 (the beautiful DOW CORNING system in east)；FZ3711, FZ3722 (NUC systems)；DMS-S12、DMS-S15、DMS-S21、DMS-S27、 DMS-S31、DMS-S32、DMS-S33、DMS-S35、DMS-S38、DMS-S42、DMS-S45、DMS-S51、DMS-227、PSD- 0332, PDS-1615, PDS-9931, XMS-5025 (JNC systems)；MS51, MS56 (Mitsubishi Chemical's system)；And GR100, GR650, The partial condensate of GR908, GR950 (Showa electrician system) etc..
[preparation method of the polysiloxanes (b-1) containing epoxy group]
General method can be used to be formed for the polycondensation reaction of polysiloxane compound containing epoxy group, for example, above-mentioned Organic solvent, water are added in or mixtures thereof silane compound or selectively further adds catalyst, followed by oil bath Deng the heating for carrying out 50 DEG C to 150 DEG C, preferable heating time is 0.5 hour to 120 hours.In heating, mixed liquor can be carried out Stirring, can also be placed under counterflow condition.
Above-mentioned organic solvent is not particularly limited, and can be identical with solvent (C) contained in crystal aligning agent of the present invention Or it is different.
The concrete example of the organic solvent includes the hydrocarbon compound of toluene, dimethylbenzene etc.；Methyl ethyl ketone, methyl-isobutyl The ketones solvent of ketone, methyl-n-amyl ketone, metacetone, cyclohexanone, 2- butanone, methyl-n-butyl ketone etc.；The positive fourth of ethyl acetate, acetic acid The esters solvent of ester, isoamyl acetate, propylene glycol monomethyl ether acetate, acetic acid -3- methoxybutyls, lactic acid ethyl etc.；Second The ether solvent of glycol dimethylether, ethylene glycol Anaesthetie Ether, tetrahydrofuran, dioxanes (dioxane) etc.；1- hexanols, 4- first Base 2- amylalcohols, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, the third two The alcohols solvent of alcohol monomethyl ether, propylene glycol monoethyl, propylene glycol list n-propyl ether etc.；N-methyl-2-pyrrolidone, N, N- The amide of dimethylacetylamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3- dimethyl -2- imidazolidine ketone etc. The combination of class solvent or above-mentioned organic solvent.
Above-mentioned organic solvent may be used alone or in combination a variety of use.
It is 100 parts by weight based on all silane compounds, the usage amount of organic solvent is preferably 10 parts by weight to 1200 weights Measure part, more preferably 30 parts by weight to 1000 parts by weight.
Hydrolization group based on all silane compounds is 1 mole, and the usage amount of water is preferably 0.5 mole to 2 moles.
The catalyst is not particularly limited, preferably, the catalyst be selected from acid, alkali metal compound, organic base, Titanium compound, zirconium compounds, or combinations thereof.
The concrete example of acid includes hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoracetic acid, formic acid, polynary carboxylic Acid, multi-anhydride, or combinations thereof.
The concrete example of alkali metal compound includes sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, ethyl alcohol Potassium, or combinations thereof.
The concrete example of organic base includes ethamine, diethylamine, piperazine (piperazine), piperidines (piperidine), pyrroles The level-one of pyridine (pyrrolidine), pyrroles (pyrrole) etc. or the organic amine of two level；Triethylamine, Tri-n-Propylamine, tri-n-butylamine, The three-level of pyridine (pyridine), 4- dimethylamino pyridines, diazabicylo hendecene (diazabicycloundecene) etc. Organic amine；The combination of level Four organic amine of tetramethylammonium hydroxide etc. etc. or above compound.
The usage amount of catalyst is different according to reaction conditions such as type, temperature etc., and can suitably set, such as based on institute It is 1 mole to have silane compound, and the additive amount of the catalyst is 0.01 mole to 5 moles, preferably 0.03 mole to 3 moles, More preferably 0.05 mole to 1 mole.
Based on stability viewpoint, after waiting for polycondensation reaction, the organic solvent layer that will be preferably fractionated from reaction solution It is cleaned with water.When carrying out the cleaning, preferably use the ammonium nitrate of the water for including a small amount of salt, such as 0.2 weight % or so water-soluble Liquid etc. is cleaned.Until the water layer that cleaning may proceed to after cleaning becomes neutral, then by organic solvent layer optionally with nothing After the drier such as H 2 O calcium sulphate, molecular sieve (molecular sieves) are dried, organic solvent is removed, you can obtain and contain ring The polysiloxanes (b-1) of oxygroup.
When polysiloxanes (b-1) containing epoxy group or used poly- is not used in the polysiloxanes (B) containing photoreactivity base When siloxanes (b-1) is free of epoxy group, then the body impedance of obtained crystal aligning agent is low, and liquid crystal contact angle is excessively high.
The ethylene unsaturated compound (b-2) of the present invention may include the structure such as following formula (IIb).
In formula (IIb), R1For methylene, C2To C10Linear chain or branched chain alkylidene, stretch phenyl or stretch cyclohexyl, the R1Official A part of hydrogen atom of energy base is substituted or unsubstituted；
R2For methylene or C2To C10Linear chain or branched chain alkylidene, the R2A part of hydrogen atom of functional group it is substituted or It is unsubstituted；
R3For singly-bound, methylene or C2To C10Linear chain or branched chain alkylidene；
The R3A part of hydrogen atom of functional group is substituted or unsubstituted；
R4For hydrogen atom or methyl；
L is-OCO- ,-O- or-S-；
A is integer of 0 to 10；
The integer that b is 0 to 1；
When b is 0, a is not 0；
When a is plural number, a plurality of R2And L is respectively identical or different.
Specifically, the example of the compound of above formula (IIb) may include acrylic acid, methacrylic acid, 2- acrylic oxygen second Base -2- hydroxyethyls phthalic acid, 4- (2- methyl-propens acyl) benzoic acid, 2- acrylyl oxy-ethyl hexyl hydrogen neighbours benzene two Formic acid, 2- acrylyl oxy-ethyls succinic acid, methylacryoyloxyethyl succinic acid, 2- methylacryoyloxyethyl hexyl hydrogen neighbour's benzene Dioctyl phthalate, phthalic acid monohydroxy ethyl propylene acid esters.More than one can be selected to use from above-mentioned example.Above-mentioned change The commercially available product citing for closing object can be acrylic acid and methacrylic acid (Tokyo chemical conversion industry limited liability company system), Lightester HO-MS, Lightester HO-HH, HOA-MPL, HOA-MS, HOA-HH (chemistry limited liability company of common prosperity society system), M-5400 (East Asia synthesizes limited liability company's system).
The example of the compound of above formula (IIb) also may include the compound such as following formula (IIb-1) to formula (IIb-16).
In formula (IIb-10) to formula (IIb-16), R4Indicate hydrogen atom or methyl, t1 is integer of 1 to 10, t2+t3 is Integer of 1 to 10.
If the ethylene unsaturated compound (b-2) is not used, the body impedance of obtained crystal aligning agent is low, and liquid Brilliant contact angle is high.
Total amount based on the monomer in third mixture is 1 mole, and the usage amount of ethylene unsaturated compound (b-2) is 0.1 mole to 0.5 mole, preferably 0.15 mole to 0.5 mole, so with 0.15 mole to 0.45 mole for more preferably.If the second For the usage amount of alkene unsaturated compound (b-2) in above range, the liquid crystal contact angle of obtained crystal aligning agent is relatively low.
The side chain compound (b-3) of the present invention includes the structure as shown in formula (IVb)：
E1- L0- L1- Z formulas (IVb)
In formula (IVb), E1For C1To C30Alkyl, by C1To C20Alkyl or alkoxy substitution or unsubstituted C3Extremely C10Naphthenic base, or the C containing steroid skeleton17To C51Alkyl, the E1Alkyl and alkoxy a part of hydrogen atom quilt Substitution is unsubstituted；
L0For singly-bound, *-O-*, *-COO-* or *-OCO-*；
L1For singly-bound, C1To C20Stretch alkyl, stretch phenyl, stretch xenyl, stretch cyclohexyl, two stretch cyclohexyl or such as following formula (IV-1) or group shown in formula (IV-2)：
Work as L1For singly-bound when, L0For singly-bound；
* it is at bond；And
Z is the monovalent organic group formed with epoxy reaction in conjunction with base.
E in above formula (IVb)1The C of the straight-chain or branched1To C30Alkyl, for example, can be methyl, Ethyl, n- propyl, isopropyl, n- butyl, sec-butyl, tertiary butyl, n- amyls, 3- methyl butyls, 2- methyl butyls, 1- methyl fourths Base, 2,2- dimethyl propyls, n- hexyls, 4- methyl amyls, 3- methyl amyls, 2- methyl amyls, 1- methyl amyls, 3,3- diformazans Base butyl, 2,3- dimethylbutyls, 1,3- dimethylbutyls, 2,2- dimethylbutyls, 1,2- dimethylbutyls, 1,1- diformazans Base butyl, n- heptyl, 5- methylhexyls, 4- methylhexyls, 3- methylhexyls, 2- methylhexyls, 1- methylhexyls, 4,4- diformazans Base amyl, 3,4- dimethyl amyl groups, 2,4- dimethyl amyl groups, 1,4- dimethyl amyl groups, 3,3- dimethyl amyl groups, 2,3- dimethyl Amyl, 1,3- dimethyl amyl groups, 2,2- dimethyl amyl groups, 1,2- dimethyl amyl groups, 1,1- dimethyl amyl groups, 2,3,3- trimethyls Butyl, 1,3,3- trimethyl butyls, 1,2,3- trimethyl butyls, n- octyls, 6- methylheptyls, 5- methylheptyls, 4- methyl heptan Base, 3- methylheptyls, 2- methylheptyls, 1- methylheptyls, 2- ethylhexyls, n- nonyls, n- decyls, n- hendecyls, n- 12 Base, n- tritriacontyls, n- tetradecyls, n- pentadecyls, n- palmityls, n- heptadecyls, n- octadecyls, n- nonadecyls etc..
E in above formula (IVb)1The C3To C10Naphthenic base, for example, can be cyclopenta, cyclohexyl, cycloheptyl Base, cyclooctyl, cyclononyl, cyclodecyl etc..These above-mentioned naphthenic base can be through or without C1To C20Alkoxy substitution.The C1 To C20The concrete example of alkoxy can refer to above-mentioned C1To C30Alkyl illustrate lifted specific example.The C1To C20's The concrete example of alkoxy can refer to above-mentioned C1To C30Alkyl explanation in the alkyl of specific example lifted, with oxygen atom knot Group after conjunction.E1The alkyl and alkoxy, hydrogen atom that can be at least part of is substituted, and to replace hydrogen former The group of son, citing can be itrile group, fluorine atom, trifluoromethyl etc..
E in above formula (IVb)1The C containing steroid skeleton17To C51Alkyl, can be for example following formula (S- 1) L of above-mentioned group and formula (IVb) is represented to group shown in formula (S-3), wherein * 50Bond at.
Preferably, E1It can be selected from C1To C20Alkyl, C1To C20Fluoroalkyl, above formula (S-1) group and above formula (S-3) group that group is formed.Z is preferably carboxyl.L in above formula (IVb)1The C1To C20Stretch alkyl, citing For, can be by aforementioned C1To C30Each group for being lifted of alkyl get rid of group obtained by 1 hydrogen atom.
Above formula (IVb) compound represented preferably can be following formula (IVb-1) to (IVb-8) compound represented.
In formula (IVb-1) to (IVb-8), integer that integer that u is 1 to 5, v are 1 to 18, w are integer of 1 to 20, k 1 The integer that the integer and j that integer, the integer that p is 0 or 1, q is 1 to 18, r to 5 are 0 to 18 are 1 to 18.S and t are respectively only Found the integer for 0 to 2.However, being 0 when s with t differences.
Preferably, the integer that the v of above formula (IVb-1) is 1 to 18, is so more preferably with 1 to 12 integer.Above formula (IVb-2) W preferably can be 5 to 20 integer, so with 10 to 18 for more preferably.The w of above formula (IVb-3) preferably can be 1 to 17 integer, so It is more preferably with 3 to 12 integer.The w of above formula (IVb-4) preferably can be 1 to 15 integer, be so more preferably with 1 to 8 integer.On The w of formula (IVb-8) preferably can be 1 to 15 integer, be so more preferably with 1 to 8 integer.Above formula (IVb-5) and formula (IVb-6) R is preferably 0 to 15 integer, is so more preferably with 0 to 8 integer.The q of above formula (IVb-6) preferably can be 1 to 12 integer, so It is more preferably with 1 to 5 integer.The j of above formula (IVb-8) preferably can be 1 to 15 integer, be so more preferably with 1 to 8 integer.
In above compound, preferably above formula (IVb-2) to formula (IVb-5), formula (IVb-7) and formula (IVb-8) be extremely Few one.Specifically, following formula (IVb-1 ') to formula (IVb-8 ') is preferable.
Total amount based on the monomer in third mixture is 1 mole, and the usage amount of the side chain compound (b-3) is rubbed for 0.05 You are to 0.3 mole, preferably 0.08 mole to 0.3 mole, so with 0.08 mole to 0.27 mole for more preferably.If the side chain chemical combination The usage amount of object (b-3) is in above range, then the liquid crystal contact angle of obtained crystal aligning agent is relatively low.
Usage amount based on the polymer (A) is 100 parts by weight, the usage amount of the polysiloxanes (B) containing photoreactivity base For 3 parts by weight to 60 parts by weight, preferably 5 parts by weight are so more preferably with 5 parts by weight to 55 parts by weight to 60 parts by weight.
[preparation method of the polysiloxanes (B) containing photoreactivity base]
The polysiloxanes (B) containing photoreactivity base that the present invention uses can be by making the above-mentioned polysiloxanes containing epoxy group (b-1) it with acetyl unsaturated compound (b-2) and side chain compound (b-3), is synthesized in the presence of a catalyst to react.
As catalyst, it can use organic salt or use that the hardening of epoxide and anhydride reaction can be promoted to promote Compound well known to agent etc..
Above-mentioned organic salt can enumerate the level-ones organic amine such as ethylamine, diethylamide, piperazine, piperidines, pyrrolidines, pyrroles Or two level organic amine；Triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine, diazabicyclo Level Four organic amine such as the three-levels such as endecatylene organic amine and tetramethyl ammonium hydroxide etc..In these organic amines, preferably three Three-levels organic amine or the tetramethylphosphonihydroxide hydroxides such as ethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine The level Four organic amine such as base ammonium.
The concrete example of above-mentioned hardening accelerator includes benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) benzene The tertiary amines such as phenol, cyclohexyldimethyl amine, triethanolamine；2-methylimidazole, 2- n-heptyls imidazoles, 2- alkyls imidazoles, 2- benzene Base imidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2- cyano ethyls) -2-methylimidazole, 1- (2- cyano ethyls) -2-5- n-undecane base miaows Azoles, 1- (2- cyano ethyls) -2- phenylimidazoles, 1- (2- cyano ethyls) -2-ethyl-4-methylimidazole, 2- phenyl -4- methyl - 5- hydroxy methylimidazoles, 2- phenyl -4,5- two (methylol) imidazoles, two [(2 '-cyano of 1- (2- cyano ethyls) -2- phenyl -4,5- Ethyoxyl) methyl] imidazoles, l- (2- cyano ethyl -2- n-undecane base imidazoles benzene trimellitic acids salt, 1- (2- cyano ethyls) - 2- phenylimidazole trimellitic acids salt, 1- (2- cyano ethyls) -2-ethyl-4-methylimidazole trimellitic acid salt, 2,4- diamines Base -6- [2 '-methylimidazolyls-(1 ')] ethyl-S- triazines, bis- amido -6- of 2,4- (2 '-n-undecane base imidazoles) ethyl-S- Triazine, bis- amido -6- of 2,4- [2 '-ethyls -4 '-methylimidazolyl-(1 ')] ethyl-S- triazines, the trimerization of 2-methylimidazole are different Cyanic acid addition product, the cyamelide addition product of 2- phenylimidazoles, 2,4- bis- amido -6- [2 '-methylimidazolyls-(1 ')] second The imidazolium compounds such as the cyamelide addition product of base-S- triazines；Diphenylphosphine, triphenylphosphine, triphenyl etc. have Machine phosphorus compound；Benzyltriphenyl phosphonium phosphonium chloride (benzyl triphenyl phosphonium chloride), tetra-n-butyl bromine Change Phosphonium, three phenyl-bromide Phosphonium of first base, three phenyl-bromide Phosphonium of second base, three phenyl-bromide Phosphonium of normal-butyl, 4-phenyl phosphonium bromide, ethyl three Phenyl phosphonium iodide, Yi base triphenyl phosphoniums acetate, Si Zheng Ding Ji Phosphonium-O, O- diethyl idol phosphorus dithionates (tetra-n- Butyl phosphonium-O, O-diethyl phosphorodithionate), Si Zheng Ding Ji Phosphonium benzotriazole salt (tetra-n-butylphosphonium benzotriazolate), Si Zheng Ding Ji Phosphonium tetrafluoroborate, Si Zheng Ding Ji Phosphonium four The Si Ji phosphonium salts of phenylboronate, tetraphenylphosphoniphenolate tetraphenyl borate salts etc.；1,8- diazabicyclos [5.4.0] hendecene -7 or its The Diazabicycloalkene of acylate etc.；Zinc octoate, tin octoate, acetylacetone,2,4-pentanedione aluminium complex (aluminium Acetylacetone complex) etc. organo-metallic compound；Tetraethylammonium bromide, four-normal-butyl ammonium bromides, tetraethyl The quarternary ammonium salt of ammonium chloride, four-n-butylmagnesium chloride ammoniums etc.；Boron trifluoride (boron trifluoride), triphenyl borate etc. Boron compound；The metal halogen compound of zinc chloride, butter of tin etc.；Dicyandiamide (dicyandiamide) or amine and asphalt mixtures modified by epoxy resin The high-melting-point dispersing type potentiality hardening accelerator of the amine add-on type accelerating agent such as addition product of fat etc.；By above-mentioned imidazolium compounds, The surface of the hardening accelerators such as organic phosphorus compound or Si Ji phosphonium salts is with microcapsules (microcapsule) type of polymer overmold Potentiality hardening accelerator；Amine salt type potentiality hardening accelerator；Lewis's hydrochlorate, cloth bear this special hydrochlorate (Bronsted acid The potentialities hardening accelerator such as hot cationic polymerization type potentiality hardening accelerator of high temperature dissociative type etc. such as salt).
It includes tetraethylammonium bromide, four-normal-butyl ammonium bromides, etamon chloride that the concrete example of hardening accelerator, which is preferably, And four-n-butylmagnesium chloride ammonium etc. quarternary ammonium salt.
It includes tetraethylammonium bromide, four-normal-butyl ammonium bromides, etamon chloride that the concrete example of hardening accelerator, which is preferably, And four-n-butylmagnesium chloride ammonium etc. quarternary ammonium salt.
Reaction temperature is preferably 0 DEG C to 200 DEG C, and better is 50 DEG C to 150 DEG C.Reaction time is preferably 0.1 hour To 50 hours, more preferably 0.5 hour to 20 hours.
The synthetic reaction of polysiloxanes (B) containing photoreactivity base is as needed, under the conditions of can be existing for organic solvent It carries out.The organic solvent is not particularly limited, and can be had used in the preparation with the polysiloxanes (b-1) containing epoxy group Solvent and be identical or differ with solvent (C) contained in crystal aligning agent of the present invention.Above-mentioned organic solvent it is specific Example is preferably 2- butanone, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK), n-butyl acetate, or combinations thereof.
The weight average molecular weight of the polysiloxanes (B) containing photoreactivity base of the present invention is 2000 to 20000；Preferably 3000 to 18000；More preferably 5000 to 15000.
Solvent used in the crystal aligning agent of the present invention is not particularly limited, as long as soluble polymeric object (A), Polysiloxanes (B) containing photoreactivity base and any other ingredient and not generated with it reacts, preferably with aforementioned conjunction At the solvent used in polyamic acid, meanwhile, also can and with used lean solvent when synthesizing the polyamic acid.
The concrete example of solvent (C) includes but not limited to n-methyl-2-pyrrolidone, gamma-butyrolacton, butyrolactam, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol single methyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethoxy-propionic acid Ethyl ester, Ethylene glycol methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol n-butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol two Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether second Acid esters, diethylene glycol monoethyl ether acetic acid esters or N,N-dimethylformamide or DMAC N,N' dimethyl acetamide (N, N-dimethyl Acetamide) etc..Solvent (C) can be used alone or combine a variety of use.
Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of solvent (C) is 800 to 3000 parts by weight, compared with Good is 1000 to 3000 parts by weight, and more preferably 1000 to 2500 parts by weight.
In the range of not influencing effect of the present invention, crystal aligning agent also optionally adds additive (D), wherein Additive (D) includes the compound at least two epoxy groups, the silane compound with functional groups, or combinations thereof.
Compound at least two epoxy groups includes but not limited to ethylene glycol bisglycidyl ethers, two ring of polyethylene glycol Oxygen propyl group ether, propylene glycol bisglycidyl ethers, tripropylene glycol bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, new penta 2 Alcohol bisglycidyl ethers, 1,6-HD bisglycidyl ethers, glycerine bisglycidyl ethers, two ring of 2,2- dibromoneopentyl glycols Oxygen propyl group ether, tetra- glycidyl -2,4- hexylene glycols of 1,3,5,6-, N, N, N ',-four glycidyl of N '-m-xylenedimaine, 1, Bis- (N, the N- diepoxy propyl aminomethyl) hexamethylenes of 3-, N, N, N ',-two amido diphenylmethyl of-four glycidyl -4,4 ' of N ' The combination of alkane, 3- (N, N- diepoxy propyl) aminocarbonyl propyl trimethoxy silanes or above compound.
Compound at least two epoxy groups may be used alone or in combination a variety of use.
Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of the compound at least two epoxy groups can For 0 to 40 parts by weight, and preferably 0.1 parts by weight are to 30 parts by weight.
The concrete example of silane compound with functional groups include but not limited to 3- aminocarbonyl propyl trimethoxy silanes, 3- aminocarbonyl propyl triethoxysilanes, 2- aminocarbonyl propyl trimethoxy silanes, 2- aminocarbonyl propyl triethoxysilanes, N- (2- amine Base ethyl) -3- aminocarbonyl propyl trimethoxy silanes, N- (2- amidos ethyl) -3- aminocarbonyl propyls dimethoxysilane, 3- urea groups third Base trimethoxy silane (3-ureidopropyltrimethoxy silane), 3- ureidopropyltriethoxysilanes, N- ethoxies Base carbonyl -3- aminocarbonyl propyl trimethoxy silanes, N- ethoxy carbonyl -3- aminocarbonyl propyl triethoxysilanes, N- triethoxies Ethoxysilylpropyl three stretches second triamine, N- trimethoxysilylpropyls three stretch second triamine, 10- trimethoxy silane bases -1,4,7- Three a word used for translation decane, three a word used for translation decane of 10- triethoxysilicane alkyl -1,4,7-, two a word used for translation nonyl acetic acid of 9- trimethoxy silane bases -3,6- Ester, two a word used for translation nonyl acetates of 9- triethoxysilicane alkyl -3,6-, N- Benzyl base -3- aminocarbonyl propyl trimethoxy silanes, N- Benzyl bases - 3- aminocarbonyl propyl triethoxysilanes, N- phenyl -3- aminocarbonyl propyl trimethoxy silanes, three ethoxy of N- phenyl -3- aminocarbonyl propyls Bis- three ethoxies of (ethylene oxide) -3- aminocarbonyl propyls of bis- (the ethylene oxide) -3- aminocarbonyl propyl trimethoxy silanes of base silane, N-, N- The combination of base silane or above compound.
Silane compound with functional groups can be used alone or combine a variety of use.
Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of the silane compound with functional groups can For 0 to 10 parts by weight, and preferably 0.5 parts by weight are to 10 parts by weight.
Total usage amount based on polymer (A) is 100 parts by weight, and the usage amount of additive (D) is preferably 0.5 parts by weight extremely 50 parts by weight, and more preferably 1 parts by weight are to 45 parts by weight.
[manufacturing method of crystal aligning agent]
The present invention provides a kind of manufacturing method of crystal aligning agent again, it includes mixed polymer (A), contains photoreactivity base Polysiloxanes (B) and solvent (C).
The preparation method of the crystal aligning agent of the present invention is not particularly limited, and general mixed method can be used to make It is standby.For example, first that the polymer being prepared in the above described manner (A) and polysiloxanes (B) containing photoreactivity base is mixed Conjunction is formed uniformly mixture.Then, addition solvent (C) under conditions of being 0 DEG C to 200 DEG C in temperature, and be selectively added and add Add agent (D), dissolving is finally continued stirring until with agitating device.In addition, it is preferred that add at a temperature of 20 DEG C to 60 DEG C Solubilizer (C).
At 25 DEG C, the viscosity of crystal aligning agent of the invention be usually 15cps to 35cps, preferably 17cps extremely 33cps, and more preferably 20cps to 30cps.
[manufacturing method of liquid crystal orienting film and LCD assembly]
The present invention separately provides a kind of liquid crystal orienting film, is formed by crystal aligning agent above-mentioned.
The present invention provides a kind of manufacturing method of liquid crystal orienting film again, and it includes form the LCD alignment by crystal aligning agent Film, the wherein crystal aligning agent are formed by the manufacturing method of crystal aligning agent above-mentioned.
The present invention also provides a kind of LCD assembly, and it includes liquid crystal orienting films above-mentioned.
The present invention provides a kind of manufacturing method of LCD assembly again, which includes liquid crystal orienting film, The manufacturing method includes to form the liquid crystal orienting film by crystal aligning agent, and wherein the crystal aligning agent is by LCD alignment above-mentioned The manufacturing method of agent is formed.
The liquid crystal orienting film of the present invention is formed using the crystal aligning agent of above-mentioned modulation.Furthermore liquid crystal of the invention Display module has is formed by liquid crystal orienting film by above-mentioned crystal aligning agent.The operation mode of LCD assembly has no especially Limitation, preferably can be vertical orientation type.
The liquid crystal orienting film of the present invention and the manufacturing method of LCD assembly, may include：The liquid crystal of the present invention is matched It to agent, is coated on the conductive film of a pair of substrate with conductive film, then heats aforesaid substrate to form the of film One step；Above-mentioned a pair of of the substrate for being formed with film is oppositely arranged, with the second step of construction liquid crystal born of the same parents；And will have This of conductive film is to substrate, in the case where applying voltage, with the third step of light irradiating liquid crystal born of the same parents.
[first step：The formation of film]
In this step, the substrate for being equipped with patterned transparent conductive film using two pieces is being formed with transparent lead as a pair On the surface of the substrate of electrolemma, it is respectively coated the crystal aligning agent of the present invention, lithography, rotary coating preferably can be used Print process, rolling method or ink-jet method carry out the coating of crystal aligning agent.Substrate referred to herein can be for example using float glass, sodium The glass such as glass；Polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, makrolon, poly- (ester ring type alkene Hydrocarbon) etc. plastic, transparents substrate.Set on the transparent conductive film of substrate surface, can be used by tin oxide (SnO2) it is formed by NESA films (the login trade mark of PPG companies of the U.S.), by indium oxide and tin oxide (In2O3-SnO2) it is formed by ito film.It is patterned transparent The formation of conductive film, after being for example initially formed non-patterned transparent conductive film, with the pattern of photoetch (Photo-etching) Forming method, and reached using the modes such as mask of predetermined pattern when there is transparent conductive film formation.When coating of liquid crystalline orientation agent, In order to make that there is good adherence between substrate surface and transparent conductive film and film, can also the substrate of film be being formed Surface is coated the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.
After coating of liquid crystalline orientation agent, to prevent be coated with crystal aligning agent from dripping, can preferably it carry out pre-baked (Prebake).Pre-baked temperature can be 30 DEG C to 200 DEG C, be preferable with 40 DEG C to 150 DEG C, so with 40 DEG C to 100 DEG C for more It is good.The pre-baked time can be 0.25 point to 10 points, preferably 0.5 point to 5 points.Later, solvent is completely removed, it must in order to be formed The hot-imide for wanting the structure of existing polymer and amic acid, the step of aforesaid substrate is sintered and (is baked afterwards).Afterwards Roasting temperature can be 80 DEG C to 300 DEG C, preferably 120 DEG C to 250 DEG C.The roasting time can be 5 points to 200 points afterwards, preferably 10 Divide to 100 points.Therefore, the thickness for being formed by film can be 0.001 μm to 1 μm, preferably 0.005 μm to 0.5 μm.
Heating stepses after coating of liquid crystalline orientation agent can remove organic solvent, thus form the film of liquid crystal orienting film.This When, polymer contained in crystal aligning agent of the invention includes polyamic acid or has imide structure and an amic acid structure Imide polymer.Later, it will be further formed by film heating, it is anti-that above-mentioned polymer can then carry out dehydration endless loop It answers, to form the film of imidizate.The film that method described above is formed, can use, but also may be used directly as liquid crystal orienting film Carry out scheduled friction treatment.
[second step：The construction of liquid crystal born of the same parents]
In this step, two pieces of substrates for being formed with above-mentioned liquid crystal orienting film are provided, and in two pieces of substrates of relative configuration Between be arranged the liquid crystal layer containing liquid crystal compounds and photopolymerizable compound, to form liquid crystal born of the same parents.The method for manufacturing liquid crystal born of the same parents It can be exemplified below and state two kinds of methods.
First method is existing method (vacuum impregnation).First, two pieces of substrates are oppositely arranged, make to be oppositely arranged Liquid crystal orienting film between formed gap (cell gap；Cell Gap).It will be bonded with adhesive agent around two pieces of substrates, Yu Li With substrate surface and adhesive agent mark off come cell gap in, inject liquid crystal compounds and photopolymerizable compound simultaneously After filling up, injection hole is sealed, liquid crystal born of the same parents are made.
Second method is known as liquid crystal and instills technique (One Drop Filling；ODF).It is being formed with liquid crystal orienting film Book office on the substrate of one of which in two pieces of substrates is coated with the adhesive agent of such as ultraviolet light photopolymerization.Then, above-mentioned The book office of liquid crystal orienting film drip liquid crystal compounds and photopolymerizable compound mixture after, by above-mentioned liquid crystal orienting film It is oppositely arranged with the liquid crystal orienting film of another substrate, two pieces of substrates is bonded, so that liquid crystal is spread in the whole surface of substrate, connects It with the entire substrate of ultraviolet light, adhesive agent is made to harden, to manufacture liquid crystal born of the same parents.No matter which above-mentioned method is used, in formation After stating liquid crystal born of the same parents, aforesaid substrate is heated to used liquid crystal compounds and is changed into iso temperature, then Slow cooling To room temperature, to remove flowing orientation when liquid crystal filling.
As above-mentioned adhesive agent, it can be used as curing agent and the epoxy resin of spacer, contain alumina balls. The nematic liquid crystal with negative dielectric anisotropic preferably can be selected in the liquid crystal compounds, and dicyanobenzenes base fluid can be used for example Crystalline substance, pyridazinyl liquid crystal, schiff bases base fluid crystalline substance, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexyl liquid crystal, terphenyl liquid crystal Deng.In addition, the response speed of liquid crystal display in order to make PSA patterns is faster, alkenyl liquid crystal is preferably used in combination, for one Mono-functional's liquid-crystal compounds of a alkenyl or fluorine alkenyl.Existing alkenyl liquid crystal, such as following formula can be used in the alkenyl liquid crystal (L1-1) to formula (L1-9) compound represented etc..
The photopolymerizable compound can be used, and there is acryloyl group, methylpropenyl, vinyl etc. can carry out radical polymerization Close the compound of the functional group of reaction.From the viewpoint of reactivity, wherein preferably using with acryloyl group and metering system The compound of at least two functional groups in base.In addition, from the viewpoint of maintaining the regiospecific of liquid crystal molecule to stablize, the light is poly- Conjunction property compound is liquid crystal skeleton, preferably using the compound at least two rings in cyclohexane ring and phenyl ring.Furthermore it should Photopolymerizable compound can use existing photopolymerizable compound.The usage amount of the photopolymerizable compound preferably accounts for liquid crystal The 0.1% to 0.5% of property compound entirety weight.The thickness of liquid crystal layer is preferably 1 μm to 5 μm.
[third step：Step of exposure]
After construction liquid crystal born of the same parents, apply voltage between the conductive film to substrate, and irradiated simultaneously with light.This place applies Voltage may be, for example, 5V to 50V direct current or alternating current.Furthermore the light irradiated may be, for example, comprising wavelength be 150nm extremely The ultraviolet light and visible light of the light of 800nm are so preferable with the ultraviolet light comprising the light that wavelength is 300nm to 400nm.Irradiation light Light source can be for example using Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halid lamp, argon gas resonance lamp, xenon lamp, quasi-molecule It is radium-shine etc..In addition, the collocation such as light source and optical filter, diffraction grating can be used, and obtain the purple of above-mentioned preferable wave-length coverage Outer light.
The exposure of light can be 1000J/m2Less than 100,000J/m2, preferably 1000J/m2To 50,000J/ m2.Such as it is existing when manufacturing the LCD assembly of PSA patterns, need 100,000J/m2Light irradiation amount, however it is of the invention LCD assembly using be less than 100,000J/m2, even less than 50,000J/m2Irradiate light quantity, be made have it is predetermined Pre-tilt angle characteristic LCD assembly, and reduce the manufacturing cost of LCD assembly.Furthermore it also can inhibit because of intense light irradiation Penetrate and caused by the deteriorations of electrical properties, the reactive deterioration of liquid crystal molecule.
Then, polarizer is fitted in the outer surface of liquid crystal born of the same parents, then the LCD assembly of the present invention can be made.It is above-mentioned Polarizer, which can be exemplified as extending with polyvinyl alcohol, orientation and absorbs iodine solution, is referred to as the light polarizing film of " H films ", and by above-mentioned polarisation Film is located in the protective film of intermediate cellulose acetate, is formed by polarizer.
The LCD assembly of the present invention, is applicable in various devices, such as：Wrist-watch, portable game machine, word processing Device, laptop, navigation system, video camera, PDA, digital camera, mobile phone, smartphone, various screens, LCD TV, The various display equipment such as electronic bill-board.
It hereby is described in detail the present invention with following Examples, but is not intended to that present invention is limited only by disclosed in these examples Content.
[preparation of polymer (A)]
<Synthesis example A-1-1>
Setting nitrogen inlet, blender, condenser pipe and thermometer on four cervical vertebra bottles of 500 milliliters of volume, and import nitrogen Gas.Then, in four cervical vertebra bottles, a-2-1-1,0.04 mole of p- diamines benzene shown in 0.005 mole of table 1 is added (referred to as For a-2-2-1), a-2-2-5 and 80 gram of n-methyl-2-pyrrolidone (N-methyl-2- shown in 0.005 mole of table 1 Pyrrolidone, referred to as NMP), and stirring is extremely dissolved at room temperature.Then, 0.05 mole of 1,2,3,4- cyclobutane are added Tetracarboxylic dianhydride (referred to as a-1-2) and 20 grams of NMP, and react 2 hours at room temperature.It waits for after reaction, to react Solution pours into 1500 milliliters of water, so that polymer is precipitated.Then, filter gained polymer, and repeat with methanol cleaning and Filtering three times, is placed in vacuum drying oven, after being dried with temperature 60 C, you can obtains polymer (A-1-1).
<Synthesis example A-1-2 and compare synthesis example A-3-1 to A-3-2>
Synthesis example A-1-2 and to compare synthesis example A-3-1 to A-3-2 prepared with the step identical as synthesis example A-1-1 The polymer, different places are：Change tetracarboxylic dianhydride's compound or the type and its usage amount of diamine compound, such as table 1 and table 2 shown in.
<Synthesis example A-2-1>
Setting nitrogen inlet, blender, condenser pipe and thermometer on four cervical vertebra bottles of 500 milliliters of volume, and import nitrogen Gas.Then, in four cervical vertebra bottles, a-2-1-1,0.0435 mole of p- diamines benzene shown in 0.0015 mole of table 1 is added A-2-2-4 and 80 gram of NMP shown in (referred to as a-2-2-1), 0.005 mole of table 1, and stirring is extremely dissolved at room temperature. Then, 2,3, the 5- tricarboxylic cyclopentyl acetic acid dianhydrides (referred to as a-1-1) and 20 grams of NMP of 0.05 mole of addition.In room After the lower reaction of temperature 6 hours, 97 grams of NMP, 2.55 grams of acetic anhydride and 19.75 grams of pyridine is added, is warming up to 60 DEG C, and continue Stirring 2 hours, to carry out imidization reaction.It waits for that after reaction, reaction solution being poured into 1500 milliliters of water, so that polymerization Object is precipitated.Then, the polymer of gained is filtered, and repeats to clean and filter with methanol three times, is placed in vacuum drying oven, with temperature After 60 DEG C are dried, you can obtain polymer (A-2-1).
<Synthesis example A-2-2 to A-2-12 and compare synthesis example A-3-2 to A-3-4>
Synthesis example A-2-2 to A-2-12 and to compare synthesis example A-3-2 to A-3-4 be with step identical with synthesis example A-2-1 Rapid to prepare the polymer, different places is：Change the type of tetracarboxylic dianhydride's compound or diamine compound and its makes Dosage, as shown in table 1 and table 2；And change dehydrating agent and the type and its usage amount that are dehydrated the catalyst that endless loop is reacted.
Table 2：
In table 1 and table 2：
[preparing the polysiloxanes (B) containing photoreactivity base]
<Synthesis example B-1>
Setting blender, condenser pipe and thermometer on the three-neck flask of 500 milliliters of volume.Then, in three-neck flask, Be added 1.00 moles 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane (hereinafter referred to as ECETS) and 600 grams Propylene glycol monomethyl ether (hereinafter referred to as PGME), and in while stirring add triethylamine in 30 minutes at room temperature (Triethylamine, hereinafter referred to as TEA) aqueous solution (20 grams of TEA/200 grams of H2O).Then, three-neck flask is impregnated in 30 DEG C oil bath in and stir 30 minutes, then in oil bath is warming up to 90 DEG C in 30 minutes, when the interior temperature of solution reaches 75 DEG C, Continuous heating stirring carries out polycondensation 6 hours.It waits for after reaction, taking out organic layer and using the ammonium nitrate of 0.2wt% water-soluble After liquid is cleaned, you can obtain the solution of the polysiloxane compound containing epoxy group.
Then, by 0.50 mole of ethylene unsaturated compound b-2-1 and 0.2 gram of hardening accelerator UCAT 18X (three Ya Puluo (SAN-APRO) corporation) solution of the polysiloxane compound containing epoxy group is added.Then, three-neck flask is impregnated It in 30 DEG C of oil bath and stirs 10 minutes, then in oil bath is warming up to 115 DEG C in 30 minutes, waits for that the interior temperature of solution reaches At 100 DEG C, continuous heating stirs 24 hours.It waits for after reaction, after taking out organic layer and being washed, carrying out using magnesium sulfate It is dry, after removing solvent, you can obtain the polysiloxanes (B-1) containing photoreactivity base.
<Synthesis example B-2 to synthesis example B-10 and compare synthesis example B ' -1 to comparing synthesis example B ' -3>
Synthesis example B-2 to synthesis example B-10 and compare synthesis example B ' -1 to compare synthesis example B ' -3 be with synthesis example B-1 Identical step prepares the polysiloxanes containing photoreactivity base, and its difference be in：Change containing photoreactivity base The type and its usage amount of the reactant of polysiloxanes (B), the type of catalyst and solvent and its usage amount, reaction temperature and poly- It is condensed the time (as shown in table 3-1, table 3-2).
In table 3-1, table 3-2：
[preparation of crystal aligning agent, liquid crystal orienting film and LCD assembly]
<Embodiment 1>
Weigh the polymer (A-2-1) of 100 parts by weight, the polysiloxanes (B-1) containing photoreactivity base of 3 parts by weight, The n-methyl-2-pyrrolidone (abbreviation C-1) of 1200 parts by weight and ethylene glycol n-butyl ether (the referred to as C- of 300 parts by weight 2) dissolving, and at room temperature, is continued stirring until with agitating device, you can form the crystal aligning agent of embodiment 1.
The crystal aligning agent is subjected to each detection project evaluation, acquired results are as shown in table 4.
<Embodiment 2 to 16 and comparative example 1 to 8>
Embodiment 2 to 16 and comparative example 1 to 8 are to prepare the crystal aligning agent with step same as Example 1, different Place be：The type and its usage amount for changing polymer composition, solvent and additive, as shown in table 4 and 5.By these Crystal aligning agent carries out each detection project evaluation, and acquired results are as shown in table 4 and 5.
Table 4：
Table 5：
In table 4 and table 5：
[evaluation method]
<Body impedance>
The crystal aligning agent modulated is instilled in the aluminum dish of diameter 32mm, and after being toasted with heating plate, is obtained about The film of 0.01mm film thickness.It connects thin with resistance measuring instrument (AGILENT 4339b High resistance meter) measurement The positive and negative electrode of instrument is sandwiched in the both ends of the aluminum dish containing film by the resistance value of film, under 50 volts of voltage, records the resistance measured Value, evaluation criterion are as follows：
○：Zhi≤1.0 × 10 electricity Zu12
╳：Resistance value ＜ 1.0 × 1012
<Liquid crystal contact angle>
By above-mentioned crystal aligning agent, ITO is coated on using liquid crystal orienting film printing machine (description printing firm of Japan system) Surface is equipped on the transparent electrode surface of the glass substrate of electrode structure, and heats 1 minute (pre-baked) on hot plate with 80 DEG C, To remove solvent.Later, 10 minutes (rear roasting) is heated with 200 DEG C on hot plate, is to form average film thicknessPainting Film.By the MLC-2038 liquid crystal (Merck ＆ Co., Inc.'s system) of 7 μ l drop on aforesaid substrate and placing 30 seconds, later using consonance interface The contact angle determination device (DropMaster 700) of corporation is learned, and contact angle, the following institute of bioassay standard are measured with the methods of θ/2 Show：
◎：Jiao≤13 ° liquid crystal Jie Chu
○：13 ° of Jiao≤15 ° ＞ liquid crystal Jie Chu
╳：15 ° of liquid crystal contact angle ＞.
Above-described embodiment is only to illustrate the principle of the present invention and its effect, is not intended to limit the present invention.Those skilled in the art The modification and variation made to above-described embodiment are still without prejudice to the spirit of the present invention.The scope of the present invention answers application model as be described hereinafter It encloses listed.

Claims (19)

1. a kind of crystal aligning agent, it includes：
Polymer (A), be selected from polyamic acid polymer, polyimide polymer, polyimides system block copolymer or The arbitrary combination of above-mentioned polymer；
Polysiloxanes (B) containing photoreactivity base；And
Solvent (C)；
Wherein the polymer (A) includes unit shown in formula (Ia)：
In formula (Ia), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
Ht is nitrogenous heterocycle；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；And
* it is at bond；
The polysiloxanes (B) containing photoreactivity base includes the structure as shown in formula (IIa)：
In formula (IIa), R1For methylene, C2To C10Linear chain or branched chain alkylidene, stretch phenyl or stretch cyclohexyl, R1Functional group's A part of hydrogen atom is substituted or unsubstituted；
R2For methylene or C2To C10Linear chain or branched chain alkylidene, the R2A part of hydrogen atom of functional group it is substituted or not by Substitution；
R3For singly-bound, methylene or C2To C10Linear chain or branched chain alkylidene, the R3A part of hydrogen atom of functional group is substituted Or it is unsubstituted；
R4For hydrogen atom or methyl；
L is-OCO- ,-O- or-S-；
A is integer of 0 to 10；
The integer that b is 0 to 1；
When b is 0, a is not 0；
When a is plural number, a plurality of R2And L is respectively identical or different；And
* it is at bond.
2. crystal aligning agent according to claim 1, wherein the polymer (A) includes formula (Ia-1), formula (Ia-2) or formula (Ia-3) unit shown in：
In formula (Ia-1) to formula (Ia-3), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；And
* it is at bond.
3. crystal aligning agent according to claim 1, which includes such as formula (IVa) Shown in structure：
E1- L0- L1- * (IVa)
In formula (IVa), E1For C1To C30Alkyl, by C1To C20Alkyl or alkoxy substitution or unsubstituted C3To C10's Naphthenic base, or the C containing steroid skeleton17To C51Alkyl, the E1Alkyl and alkoxy a part of hydrogen atom it is substituted Or it is unsubstituted；
L0For singly-bound, *-O-*, *-COO-* or *-OCO-*；
L1For singly-bound, C1To C20Stretch alkyl, stretch phenyl, stretch xenyl, stretch cyclohexyl, two stretch cyclohexyl or such as following formula (IV-1) Or group shown in formula (IV-2)：
Work as L1For singly-bound when, L0For singly-bound；And
* it is at bond.
4. crystal aligning agent according to claim 1, wherein the acid imide rate of the polymer (A) is 30% to 80%.
5. a kind of liquid crystal orienting film is formed using crystal aligning agent according to any one of claims 1 to 4.
6. a kind of LCD assembly, it includes liquid crystal orienting films as claimed in claim 5.
7. a kind of manufacturing method of crystal aligning agent, it includes the following steps：
(i) by including that polymer (A) is made in the first mixture reaction of tetracarboxylic dianhydride's component (a-1) and diamine components (a-2), Wherein the polymer (A) be selected from polyamic acid polymer, polyimide polymer, polyimides system block copolymer or on State the combination of polymer；
Wherein, which includes diamine compound (a-2-1) shown at least one formula (Ib)：
In formula (Ib), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
Ht is nitrogenous heterocycle；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；And
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1；
(ii) polysiloxanes (B) of photoreactivity base is reacted and must contained by the second mixture, which includes to contain epoxy The polysiloxanes (b-1) and ethylene unsaturated compound (b-2) of base, and the ethylene unsaturated compound (b-2) includes such as The structure of formula (IIb)：
In formula (IIb), R1For methylene, C2To C10Linear chain or branched chain alkylidene, stretch phenyl or stretch cyclohexyl, the R1Functional group A part of hydrogen atom substituted or unsubstituted；
R2For methylene or C2To C10Linear chain or branched chain alkylidene, the R2A part of hydrogen atom of functional group it is substituted or not by Substitution；
R3For singly-bound, methylene or C2To C10Linear chain or branched chain alkylidene, the R3A part of hydrogen atom of functional group is substituted Or it is unsubstituted；
R4For hydrogen atom or methyl；
L is-OCO- ,-O- or-S-；
A is integer of 0 to 10；
The integer that b is 0 to 1；
When b is 0, a is not 0；
When a is plural number, a plurality of R2And L is respectively identical or different；And
(iii) mix the polymer (A), this contain the polysiloxanes (B) and solvent (C) of photoreactivity base.
8. the manufacturing method of the crystal aligning agent according to claim 7, wherein the diamine compound (a-2-1) includes formula (Ib-1), formula (Ib-2) or formula (Ib-3) compound represented：
In formula (Ib-1) to formula (Ib-3), Y is singly-bound ,-COO- ,-CONRdOr-Re- NRd；
RdFor hydrogen atom or C1To C10Linear or branched alkyl group；
ReFor singly-bound or C1To C10Linear or branched alkyl group；
RaFor singly-bound or C1To C10Linear or branched alkyl group；
RbFor C1To C10Linear chain or branched chain oxyalkyl, itrile group or carbonyl；
RcFor C1To C10Linear or branched alkyl group；Or
RbWith RcEach other in combination with formation monocycle；
The integer that a1 is 0 to 1；
The integer that a2 is 0 to 2；
When Y is singly-bound, a1 0；And
When Y is-COO- ,-CONRdOr-Re- NRdWhen, a1 1.
9. the manufacturing method of crystal aligning agent according to claim 7, which further includes side chain compound (b- 3), which includes the structure such as formula (IVb)：
E1- L0- L1- Z formulas (IVb)
In formula (IVb), E1For C1To C30Alkyl, by C1To C20Alkyl or alkoxy substitution or unsubstituted C3To C10's Naphthenic base, or the C containing steroid skeleton17To C51Alkyl, the E1Alkyl and alkoxy a part of hydrogen atom it is substituted Or it is unsubstituted；
L0For singly-bound, *-O-*, *-COO-* or *-OCO-*；
L1For singly-bound, C1To C20Stretch alkyl, stretch phenyl, stretch xenyl, stretch cyclohexyl, two stretch cyclohexyl or such as following formula (IV-1) Or group shown in formula (IV-2)：
Work as L1For singly-bound when, L0For singly-bound；
* it is at bond；And
Z is the monovalent organic group formed with epoxy reaction in conjunction with base.
10. the manufacturing method of crystal aligning agent according to claim 7, the wherein polysiloxanes (b-1) for containing epoxy group Include at least one in the base indicated by formula (III-1), the base indicated by formula (III-2) and the base indicated by formula (III-3) Person：
In formula (III-1), B is oxygen atom or singly-bound；
C is integer of 1 to 3；And
The integer that d is 0 to 6；
When d is 0, B is singly-bound；
In formula (III-2), e be 0 to 6 integer；
In formula (III-3), D C2To C6Stretch alkyl；And
E is hydrogen atom or C1To C6Alkyl.
11. the manufacturing method of crystal aligning agent according to claim 10 is further included by third mixture through hydrolyzable And partial condensates and the polysiloxanes (b-1) containing epoxy group, the third mixture include the silane as shown in formula (III-4) Monomer (b-1-1)：
Si(Rf)p(ORg)4-pFormula (III-4)
In formula (III-4), RfFor hydrogen atom, C1To C10Alkyl, C2To C10Alkenyl, C6To C15Aryl, contain epoxy group Alkyl or alkoxy containing epoxy group, and at least one RfFor the alkyl containing epoxy group or contain the alkoxy of epoxy group；
When p is plural number, RfIt is respectively identical or different；
RgFor hydrogen atom, C1To C6Alkyl, C1To C6Acyl group or C6To C15Aryl；
When 4-p is plural number, RgIt is respectively identical or different；And
P is integer of 1 to 3.
12. the manufacturing method of crystal aligning agent according to claim 7, wherein always being made based on diamine components (a-2) Dosage is 100 moles, and the usage amount of diamine compound (a-2-1) shown in the formula (Ib) is 3 to 40 moles.
13. the manufacturing method of crystal aligning agent according to claim 11, wherein based on the monomer in the third mixture Total amount be 1 mole, the usage amount of the silane monomer (b-1-1) is 0.6 mole to 1 mole.
14. the manufacturing method of crystal aligning agent according to claim 7, wherein based on the monomer in the third mixture Total amount is 1 mole, and the usage amount of the ethylene unsaturated compound (b-2) is 0.1 mole to 0.5 mole.
15. the manufacturing method of crystal aligning agent according to claim 9, wherein based on the monomer in the third mixture Total amount is 1 mole, and the usage amount of the side chain compound (b-3) is 0.05 mole to 0.3 mole.
16. the manufacturing method of crystal aligning agent according to claim 7, wherein step (iii) are based on the polymer (A) Usage amount be 100 parts by weight, this contain the polysiloxanes (B) of photoreactivity base usage amount be 3 parts by weight to 60 parts by weight, and should The usage amount of solvent (C) is 800 parts by weight to 3000 parts by weight.
17. the manufacturing method of crystal aligning agent according to claim 7, wherein the acid imide rate of the polymer (A) is 30% to 80%.
18. a kind of manufacturing method of liquid crystal orienting film, it includes the liquid crystal orienting film is formed by crystal aligning agent, the wherein liquid crystal Orientation agent is formed by the manufacturing method of the crystal aligning agent according to any one of claim 7 to 17.
19. a kind of manufacturing method of LCD assembly, which includes liquid crystal orienting film, which includes The liquid crystal orienting film is formed by crystal aligning agent, wherein the crystal aligning agent is by according to described in any one of claim 7 to 17 The manufacturing method of crystal aligning agent formed.
CN201810173678.8A 2017-03-10 2018-03-02 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display assembly Pending CN108570328A (en)

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TW106107898 2017-03-10

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