CN102591071A

CN102591071A - Process for producing liquid crystal display device, the liquid crystal display device, and liquid crystal aligning agent

Info

Publication number: CN102591071A
Application number: CN2012100198530A
Authority: CN
Inventors: 宫本佳和; 德久博昭; 吉泽纯司; 清水成夫; 谏山纯; 西川通则; 樫下幸志
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2011-01-11
Filing date: 2012-01-11
Publication date: 2012-07-18
Anticipated expiration: 2032-01-11
Also published as: TW201229139A; TWI531619B; JP2012159826A; KR101809988B1; CN102591071B; KR20120081552A; JP5927859B2

Abstract

The invention relates to process for producing liquid crystal display device, liquid crystal display device and a liquid crystal aligning agent. In the invention, the viewing angle of the liquid crystal display device is wide, the responsive speed of the liquid molecular is high, the display characteristic and the long-term stability are excellent. The manufacturing method provided in the utility model possesses the steps as following: (1) a coating film is formed on the conductive films of a pair of base plates with the liquid crystal aligning agent, wherein the liquid crystal aligning agent includes polymer [A] including the following fomular (A1) as the group of the polymer; (2) the pair of the base plates are arranged with the pair of coating films oppositely arranged and clamping the liquid crystal layer to form the liquid crystal unit; and (3) the liquid crystal unit is illuminated under the condition that a voltage is applied between the conductive filmes of the pair of base plates.

Description

The manufacturing approach of liquid crystal display cells, liquid crystal display cells and aligning agent for liquid crystal

Technical field

The present invention relates to a kind of manufacturing approach, liquid crystal display cells and aligning agent for liquid crystal of liquid crystal display cells.In more detail, relate to a kind of new method that is used to make the liquid crystal display cells that the visual angle is wide, response speed is fast, according to the liquid crystal display cells of this method manufacturing be suitable for the aligning agent for liquid crystal of this method.

Background technology

In the liquid crystal display cells, as vertical alignment mode and known MVA (multiple domain vertical alignment) profile plate through in liquid crystal panel, forming thrust, limit the reverses direction of liquid crystal molecule thus, seek the expansion at visual angle.But, through this mode, the transmitance of unavoidably bringing by thrust and the deficiency of contrast, and then have the slow problem of liquid crystal molecule response speed.

In recent years, in order to solve the problem of above-mentioned MVA profile plate, PSA (macromolecule continues alignment) pattern has been proposed.The PSA pattern is such technology: in the gap of a pair of substrate that the gap of a pair of substrate that substrate that has the pattern-like conducting film and the substrate that has the conducting film that does not have pattern constitute or substrate that two have the pattern-like conducting film constitute, clamp the liquid-crystal compsn that contains polymerizable compound; Irradiation ultraviolet radiation makes the polymerizable compound polymerization under the state that applies voltage between conducting film; Find the tilt angle characteristic thus, the direction of orientation of control liquid crystal.According to this technology, can obtain the high speed of expansion and the liquid crystal molecule response at visual angle through conducting film with specific formation, can also solve the inevitably problem of transmitance and contrast deficiency of MVA profile plate institute.But in order to make above-mentioned polymerizable compound polymerization, necessity for example will shine 100,000J/m ²A large amount of like this ultraviolet rays; Decompose so bad situation except producing liquid crystal molecule thus; Also can remain in the liquid crystal layer by the unreacted compound of not polymerization after the ultraviolet ray irradiation; It is uneven to produce demonstration together, and the voltage retention performance is had a negative impact, and perhaps produces the problem of the long-term reliability of panel.

With respect to this, the method for the liquid crystal orientation film that a kind of use forms by the polyimide aligning agent for liquid crystal that contains reactive internal compensation (メソゲ Application) is disclosed in the non-patent literature 1.According to non-patent literature 1, the response speed of its liquid crystal molecule of liquid crystal display cells with the liquid crystal orientation film that is formed by this method is fast.But for how to use reactive internal compensation and should use not record fully,, still worry display characteristic, particularly voltage retention performance unavoidably in the non-patent literature 1 if perhaps still need bigger ultraviolet irradiation amount with which kind of amount.

[prior art document]

[non-patent literature]

[non-patent literature 1] Y.-J.Lee etc., SID 09 DIGEST, the 666th page (2009)

Summary of the invention

The present invention proposes in view of the above problems, and its purpose is to provide that a kind of visual angle is wide, the response speed of liquid crystal molecule is fast, the manufacturing approach of display characteristic and long-term reliability liquid crystal display device with excellent.

The invention that is used to address the above problem is:

A kind of manufacturing approach of liquid crystal display cells, it has following operation:

(1) use aligning agent for liquid crystal (below; Be called " aligning agent for liquid crystal (A) ") on this conducting film of a pair of substrate with conducting film, form the operation film; This aligning agent for liquid crystal contain component of polymer (below; Be called " [A] component of polymer "), this component of polymer has the group of the group that contains the polymerism carbon-carbon double bond and following formula (A1) expression in identical or different polymkeric substance.

(2) will form above-mentioned a pair of substrate of filming with said a pair of film relatively and mode that folder is established liquid crystal layer disposes, form the operation of liquid crystal cells, and

(3) under the state that applies voltage between the conducting film to above-mentioned a pair of substrate, above-mentioned liquid crystal cells is carried out light-struck operation.

In the formula (A1), R ¹Alkylidene, phenylene or cyclohexylidene for methylene, carbon number 2～30.Partly or entirely can being substituted of the hydrogen atom that these groups have.R ²It is the arbitrary linking group that comprises in two keys, triple bond, ehter bond, ester bond and the oxygen atom.R ³For having the group of at least two single ring architectures.A is 0 or 1.

Manufacturing approach according to liquid crystal display cells of the present invention; Promptly in (1) operation, using the aligning agent for liquid crystal that comprises [A] component of polymer with above-mentioned ad hoc structure to form films; Simultaneously in (3) operation; Under the state that applies voltage between the conducting film of a pair of substrate,, can make that the visual angle is wide, the response speed of liquid crystal molecule is fast, display characteristic and long-term reliability liquid crystal display device with excellent to the liquid crystal cells irradiates light.

[A] component of polymer preferably contains the polymkeric substance (below, be called " [A-1] polymkeric substance ") of [A-1] group that contains the polymerism carbon-carbon double bond and group with above-mentioned formula (A1) expression.

According to the manufacturing approach of this liquid crystal display cells, [A] component of polymer contains [A-1] polymkeric substance, can improve the visual angle of the liquid crystal display cells that obtains, response speed, display characteristic and the long-term reliability of liquid crystal molecule.

[A] component of polymer preferably contains the polymkeric substance that the polymkeric substance that [A-2] have the group that contains the polymerism carbon-carbon double bond (below, be called " [A-2] polymkeric substance ") and [A-3] have above-mentioned formula (A1) expression group (below, be called " [A-3] polymkeric substance ").

According to the manufacturing approach of this liquid crystal display cells, [A] component of polymer contains [A-2] polymkeric substance and [A-3] polymkeric substance, can make liquid crystal display cells more easily.

R in the above-mentioned formula (A1) ³The group of preferred following formula (A2) expression,

In the formula (A2), R ⁴Heterocyclic radical for phenylene, biphenylene, naphthylene, cyclohexylidene, inferior dicyclohexyl, cyclohexylidene phenylene or divalence.Partly or entirely can being substituted of the hydrogen atom that these groups have.R ⁵For comprising any at least linking group in the alkylidene that substituent methylene and carbon number 2～10 can be arranged, two key, triple bond, ehter bond, ester bond and the heterocyclic radical.R ⁶For remove (c+1) valency group of (c+1) individual hydrogen atom from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexyl benzene or heterogeneous ring compound.Partly or entirely can being substituted of the hydrogen atom that this group has.R ⁷Be hydrogen atom, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl or alkoxy.B is 0 or 1.C is 1～9 integer.D is 1 or 2.R ⁴, R ⁵, R ⁷Respectively do for oneself a plurality of R when a plurality of with b ⁴, R ⁵, R ⁷With b each other can be identical or different.

According to the manufacturing approach of this liquid crystal display cells, R in [A] component of polymer of aligning agent for liquid crystal (A) ³Have above-mentioned ad hoc structure, can further improve the visual angle of the liquid crystal display cells of gained, response speed, display characteristic and the long-term reliability of liquid crystal molecule.

[A] component of polymer preferably has the poly organo alkyl structure.According to the manufacturing approach of liquid crystal display cells, aligning agent for liquid crystal (A) has the poly organo alkyl structure, can improve the photostability of the liquid crystal display cells that obtains.

[A] component of polymer preferably also contains at least a polymkeric substance of selecting in the group that is made up of polyamic acid and polyimide.

According to the manufacturing approach of this liquid crystal display cells, also contain above-mentioned specific polymkeric substance as [A] component of polymer, can improve the solution properties of the aligning agent for liquid crystal (A) of gained, can also improve the electrical characteristics of the liquid crystal display cells of gained in addition.

The present invention also comprises the liquid crystal display cells of making through the manufacturing approach of this liquid crystal display cells.

Aligning agent for liquid crystal of the present invention contains [A] component of polymer, and it has the group of the group that contains the polymerism carbon-carbon double bond and following formula (A1) expression in identical or different polymkeric substance,

In the formula (A1), R ¹Alkylidene, phenylene or cyclohexylidene for methylene, carbon number 2～30.Partly or entirely can being substituted of the hydrogen atom that these groups have.R ²For containing arbitrary linking group in two keys, triple bond, ehter bond, ester bond and the oxygen atom.R ³For having the group of at least two single ring architectures.A is 0 or 1.

This aligning agent for liquid crystal can compatibly be used for the manufacturing approach of above-mentioned liquid crystal display cells because contain the component of polymer with above-mentioned ad hoc structure.

Liquid crystal display cells through manufacturing approach manufacturing of the present invention has that the visual angle is wide, the response speed of liquid crystal molecule is fast, show sufficient transmitance and contrast, and under the good especially situation of display effect, long time continuous working can not damage display characteristic yet.

In addition, manufacturing method according to the invention, because it is few to shine required light quantity, the manufacturing cost that helps to cut down liquid crystal display cells.

Therefore, the liquid crystal display cells of method manufacturing constructed in accordance all is superior to present liquid crystal display cells aspect two of performance and costs, can be used for compatibly comprising that two dimension shows and the various uses of the LCD TV of 3-D display.

Description of drawings

Fig. 1 is the key diagram of the electrically conducting transparent film figure in the liquid crystal cells of the nesa coating with patterning made in expression embodiment and the comparative example.

Fig. 2 is the key diagram of the electrically conducting transparent film figure in the liquid crystal cells of the nesa coating with patterning made in expression embodiment and the comparative example.

Embodiment

< manufacturing approach of liquid crystal display cells >

The manufacturing approach of liquid crystal display cells of the present invention has following operation:

(1) use aligning agent for liquid crystal on this conducting film of a pair of substrate with conducting film, to form the operation of filming; This aligning agent for liquid crystal contains [A] component of polymer, and this component of polymer has the group of the group that contains the polymerism carbon-carbon double bond and following formula (A1) expression in identical or different polymkeric substance;

Then, dispose Polarizer on the two sides through the liquid crystal cells after the irradiates light of above-mentioned acquisition, can make liquid crystal display cells.Below, each operation is described.

[(1) operation]

Be to use the aligning agent for liquid crystal (A) that contains [A] component of polymer in this operation, on this conducting film of a pair of substrate with conducting film, form and film.This aligning agent for liquid crystal (A) as after state.

When making TN type, STN type or VA type liquid crystal display cells; With the substrate of two nesa coatings that are provided with patterning as a pair of; On their each nesa coating formation face; Preferably, then, film through heating each coated face formation through glue print process, spin-coating method or ink jet printing method difference coating of liquid crystalline alignment agent (A).Here, as substrate, for example can use glass such as float glass, soda-lime glass; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, gather the transparency carrier that plastics such as (ester ring type alkene) constitute.Nesa coating as the one side at substrate is provided with can use tin oxide (SnO ₂) the NESA film (registered trademark of U.S. PPG company), the indium oxide-tin oxide (In that constitute ₂O ₃-SnO ₂) the ITO film that constitutes etc., photoetch formed method of patterning, uses the method for the mask with desired pattern etc. when forming nesa coating after the nesa coating that obtains patterning for example can use the nesa coating that forms patterning not.During coating of liquid crystalline alignment agent (A), for make substrate surface and nesa coating, to be coated with intermembranous cementability better, also can will form the pre-treatment that the face of filming implements to be coated with in advance functional silanes compound, functionality titanium compound etc. at substrate surface.

Behind the coating of liquid crystalline alignment agent (A), for the purposes such as dropping liquid of the aligning agent for liquid crystal (A) that prevents to be coated with, preferred enforcement preheats.Pre-warmed temperature is preferably 30 ℃～200 ℃, more preferably 40 ℃～150 ℃, is preferably 40 ℃～100 ℃ especially.The pre-warmed time is preferably 0.25 minute～and 10 minutes, more preferably 0.5 minute～5 minutes.Then, desolvate in order to remove fully, so after remove residual dicarboxylic acid when adopting manufacturing approach 1 in the manufacturing of the polyorganosiloxane compounds (A) stated, preferably implement to burn till (afterwards curing) operation.This temperature of burning till (afterwards curing) is preferably 80 ℃～300 ℃, more preferably 120 ℃～250 ℃.After time of curing be preferably 5 minutes～200 minutes, more preferably 10 minutes～100 minutes.The thickness of the film that forms like this is preferably 0.001 μ m～1 μ m, more preferably 0.005 μ m～0.5 μ m.

On the other hand; When making IPS type liquid crystal display cells; Form on the one side of face and the opposing substrates that conducting film is not set coating of liquid crystalline alignment agent (A) respectively at the conducting film of the substrate that is provided with the nesa coating that forms broach shape pattern, follow through heating each coated face and form and film.The coating process of the patterning method of the substrate that at this moment uses and the material of nesa coating, nesa coating, the pre-treatment of substrate, aligning agent for liquid crystal (A) be coated with after the preferred thickness of filming of heating means and formation identical during with manufacturing above-mentioned TN type, STN type or VA type liquid crystal display cells.

Filming after the formation can former state be supplied in (2) operation, also can implement friction treatment arbitrarily.

Friction treatment can be through to above-mentioned such coated surface that forms, and the roller of the cloth that for example makes with the fibers such as nylon, rayon, cotton of having reeled rubs with certain orientation.Thus, form the liquid crystal orientation film of having given the liquid crystal molecular orientation ability to filming.

And then; For liquid crystal orientation film like above-mentioned formation; For example shown in japanese kokai publication hei 6-222366 communique and japanese kokai publication hei 6-281937 communique; Through the processing that a part of irradiation ultraviolet radiation of liquid crystal orientation film is changed the tilt angle of liquid crystal orientation film subregion, that kind shown in japanese kokai publication hei 5-107544 communique, on the part on liquid crystal orientation film surface, form carry out with it behind the etchant resist before the different friction treatment of friction treatment direction, and then the processing of removing etchant resist; Thereby liquid crystal orientation film is had with the different and different liquid crystal aligning ability in zone, improve the visual field characteristic of the liquid crystal display cells that obtains etc.

[(2) operation]

In this operation,, form liquid crystal cells with having formed above-mentioned a pair of substrate of filming with said a pair of film relatively and mode that folder is established liquid crystal layer disposes.

Prepare two substrates that as above-mentioned, form liquid crystal orientation film,, make liquid crystal cells through between two substrates of configuration relatively, disposing liquid crystal.Here, when carrying out friction treatment to filming, two substrate configurations relatively by this way, the frictional direction of respectively filming is in certain angle, for example vertical or antiparallel.

As the method for making liquid crystal cells, following two kinds of methods for example can have been enumerated.

First method is present known method.At first each liquid crystal orientation film is placed two substrates relatively across gap (cell gap), with the periphery of two substrates of sealant applying, behind injection liquid crystal in the unit gap of substrate surface and sealant division, the sealing filling orifice is made liquid crystal cells.

Second method is the method that is called ODF (under the liquid crystal drop) mode.Be coated with the for example encapsulant of ultraviolet light curable on the certain position of a substrate in having formed two substrates of liquid crystal orientation film; And then behind the liquid crystal that drips on the liquid crystal aligning face; With liquid crystal orientation film another piece substrate of fitting vis-a-vis; Then to the whole surface irradiation ultraviolet light of substrate, curing sealant is made liquid crystal cells.

As above-mentioned sealant, for example can use the epoxy resin of the alumina balls that contain hardening agent and conduct interval etc.

As above-mentioned liquid crystal, preferably have the nematic crystal of negative dielectric anisotropy, for example can use dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Xi Fushi bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal etc.The thickness of liquid crystal layer is preferably 1 μ m～5 μ m.

According to the liquid crystal cells of any method such as above-mentioned manufacturing further be heated to make used liquid crystal become the temperature of isotropic phase after, cool to room temperature slowly, the flow orientation in the time of can expecting to remove the liquid crystal filling.

[(3) operation]

Applying between conducting film under the state of voltage in this operation, to above-mentioned liquid crystal cells irradiates light above-mentioned a pair of substrate.

As the light of irradiation, for example can use the ultraviolet ray and the luminous ray of the light of the wavelength that comprises 150nm～800nm, preferably comprise the ultraviolet ray of the light of 300nm～400nm wavelength.As the light source of irradiates light, for example can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon gas resonance lamp, xenon lamp, PRK etc.The ultraviolet ray in above-mentioned preferred wavelength zone can obtain above-mentioned light source and for example combination such as light filter, grating.As the exposure of light, be preferably 1,000J/m ²More than, less than 100,000J/m ², more preferably 1,000J/m ²～50,000J/m ²In the manufacturing of the liquid crystal display cells of present known PSA pattern, must shine 100,000J/m ²The light of level, but in the method for the invention, though the rayed amount 50,000J/m ²Below, and then 10,000J/m ²When following, the liquid crystal display cells that also can obtain expecting, except helping to cut down the manufacturing cost of liquid crystal display cells, the electrical characteristics that can also avoid strong illumination to cause reduce, the reduction of long-term reliability.

Then, through implementing the outer surface applying Polarizer of the liquid crystal cells after the above-mentioned processing, can obtain liquid crystal display cells.As this Polarizer, can enumerate and be called Polarizer that polarization film that limit stretch orientation polyvinyl alcohol, limit absorb " the H film " of iodine clamps with the cellulose acetate diaphragm or the Polarizer that itself constitutes by the H film.

< aligning agent for liquid crystal >

The aligning agent for liquid crystal that uses in the inventive method (A) contains [A] component of polymer, and this component of polymer has the group of the group that contains the polymerism carbon-carbon double bond and above-mentioned formula (A1) expression in identical or different polymkeric substance.In addition, this aligning agent for liquid crystal (A) is as [A] component of polymer, can comprise " other polymkeric substance " stated behind at least a polymkeric substance selected in the group that is made up of polyamic acid and polyimide (below, be called " polymkeric substance (B) ") etc.And then, in the scope of harmless effect of the present invention, also can contain other compositions.Below, each composition is elaborated.

< [A] component of polymer >

[A] component of polymer has the group of the group that contains the polymerism carbon-carbon double bond and above-mentioned formula (A1) expression in identical or different polymkeric substance.

[group that contains the polymerism carbon-carbon double bond]

As the group that contains the polymerism carbon-carbon double bond, for example can enumerate the group of following formula (A) expression etc.,

In the above-mentioned formula (A), R ^ABe hydrogen atom or methyl.

X ^IAnd X ^IIBe 1 independently of one another, 4-phenylene, methylene, 1,2-ethylidene, 1,2-propylidene or 1,3-propylidene.

A, B, C and D are 0 or 1 independently of one another.

Wherein, C be 0 and D be 1 o'clock, X ^IIBe 1, the 4-phenylene.

In addition, B is 0 o'clock, and D is 0.

As the object lesson of the group of above-mentioned formula (A) expression, vinyl, allyl for example can have been enumerated, to styryl, (methyl) acryloyl-oxy ylmethyl, 2-((methyl) acryloxy) ethyl, 3-((methyl) acryloxy) propyl group, 4-((methyl) acryloxy) butyl, 5-((methyl) acryloxy) amyl group, 6-((methyl) acryloxy) hexyl, 7-((methyl) acryloxy) heptyl, 8-((methyl) acryloxy) octyl group, 9-((methyl) acryloxy) nonyl, 10-((methyl) acryloxy) decyl, 4-(2-((methyl) acryloxy) ethyl) phenyl, 2-((4-(methyl) acryloxy) phenyl) ethyl, 4-((methyl) acryloyl-oxy ylmethyl) phenyl, 4-(methyl) acryloxy phenyl methyl, 4-(3-((methyl) acryloxy) propyl group) phenyl, 3-(4-(methyl) acryloxy phenyl) propyl group, 4-((methyl) acryloyl-oxy ylmethoxy) phenyl, 4-(2-((methyl) acryloxy) ethoxy) phenyl, 4-(3-((methyl) acryloxy) propoxyl group) phenyl, (methyl) acryloxy methoxy, 2-((methyl) acryloyl-oxy ylmethoxy) ethyl, 2-(2-((methyl) acryloxy) ethoxy) ethyl, 2-(2-(2-((methyl) acryloxy) ethoxy) ethoxy) ethyl, 3-(3-((methyl) acryloxy) propoxyl group) propyl group, acryloyl-oxy ylmethyl etc.Preferred vinyl in them, allyl, to styryl, (methyl) acryloyl-oxy ylmethyl, 2-((methyl) acryloxy) ethyl and 3-((methyl) acryloxy) propyl group.

As the above-mentioned group that contains the polymerism carbon-carbon double bond, be preferably the group of above-mentioned formula (A) expression, more preferably be selected from more than one groups in the above-mentioned concrete group of enumerating.

[group of above-mentioned formula (A1) expression]

The R of above-mentioned formula (A1) ¹Alkylidene, phenylene or cyclohexylidene for methylene, carbon number 2～30.Partly or entirely can being substituted of the hydrogen atom that these groups have.

As above-mentioned R ¹The alkylidene of the carbon number 2～30 of expression can have been enumerated ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior nonyl, inferior decyl, inferior undecyl, inferior dodecyl, inferior myristyl, inferior cetyl, inferior octadecyl, inferior nonadecyl, inferior eicosyl, inferior heneicosyl, inferior docosyl, inferior tricosyl, inferior tetracosyl, inferior pentacosyl, inferior cerul, inferior heptacosane base, inferior octacosyl, inferior nonacosyl, inferior melissyl etc.In them; In order stably to find liquid crystal aligning, carbon numbers such as preferred pentylidene, hexylidene, Ya Xinji, inferior nonyl, inferior decyl, inferior undecyl, inferior dodecyl, inferior myristyl, inferior cetyl, inferior octadecyl, inferior nonadecyl, inferior eicosyl are the alkylidene more than 5, below 20.

R ²For comprising the arbitrary linking group in two keys, triple bond, ehter bond, ester bond and the oxygen atom.As R ², for example can enumerate ethene two bases, acetylene two bases, ester group, methane two basic oxygen bases, fluomethane two basic oxygen bases, difluoromethane two basic oxygen bases etc.In addition, R ²Also can contain any of above-mentioned key, also can make up and contain each key.In addition, R ¹During for phenylene or cyclohexylidene, the orientation of the alignment films that consider to form and to the dissolubility of solvent, preferred R ²The alkylidene that contains methylene or carbon number 2～30.In addition, a is 0 or 1.

R ³For having the group of at least two single ring architectures, be preferably the group of the dielectric anisotropy that shows plus or minus.Single ring architecture is meant that a ring structure is independent of other ring structures and exists, and does not have a ring structure and other ring structure public keys, is the structure of so-called condensed ring structure.In addition, as single ring architecture, can be any of ester ring type structure, fragrant ring type structure, hetero ring type structure, also can have their combination.

R ³So long as have the group of plural at least single ring architecture, not special restriction, but R ³Be preferably the group of following formula (A2) expression.

In the above-mentioned formula (A2), R ⁴Heterocyclic radical for phenylene, biphenylene, naphthylene, cyclohexylidene, inferior dicyclohexyl, cyclohexylidene phenylene or divalence.Partly or entirely can being substituted of the hydrogen atom that these groups have.R ⁵For comprising in the alkylidene that substituent methylene and carbon number 2～10 can be arranged, two key, triple bond, ehter bond, ester bond and the heterocyclic radical any one linking group at least.R ⁶For remove (c+1) valency group of (c+1) individual hydrogen atom from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexyl benzene or heterogeneous ring compound.Partly or entirely can being substituted of the hydrogen atom that this group has.R ⁷Be hydrogen atom, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxy, trifluoromethoxy or alkyl-carbonyl oxygen base.B is 0 or 1.C is 1～9 integer.D is 1 or 2.R ⁴, R ⁵, R ⁷Respectively do for oneself a plurality of R when a plurality of with b ⁴, R ⁵, R ⁷With b each other can be identical or different.

Through introducing the structure of above-mentioned formula (A2) expression, can make the further high speed of electrooptics response of the liquid crystal display cells of acquisition.In the formula (A2), R ⁴Heterocyclic radical for phenylene, biphenylene, naphthyl, cyclohexylidene, inferior dicyclohexyl, cyclohexylidene phenylene or divalence.As the heterocyclic radical of divalence, inferior pyridine radicals, inferior pyridazinyl, inferior pyrimidine radicals etc. for example can have been enumerated.

In the above-mentioned formula (A2), R ⁵Be to comprise the R that is connected that any one can be arranged in substituent methylene and the alkylidene of carbon number 2～10, two key, triple bond, ehter bond, ester bond and the heterocyclic radical at least ⁴And R ⁶Linking group, can be in [A] component of polymer as required orientation and dielectric anisotropy and suitable the selection.As R ⁵, can enumerate methane two bases, ethane two bases, propane two bases, ethene two bases, acetylene two bases, ether, ester group, methane two basic oxygen bases, ethane two basic oxygen bases, fluomethane two basic oxygen bases, difluoromethane two basic oxygen bases etc.In them, preferred ethane two bases, acetylene two bases, ester group, methane two basic oxygen bases, difluoromethane two basic oxygen bases.In addition, b is 0 or 1, in the design of side-chain structure, can contain R ⁵Can not contain yet.

In the above-mentioned formula (A2), R ⁶For from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexyl benzene or heterogeneous ring compound, removing (c+1) valency group of (c+1) individual hydrogen atom.C is 1～9 integer.As R ⁶, for example c is 1 o'clock, can enumerate and above-mentioned R ⁴The group that the divalent group of enumerating is identical etc.

In the above-mentioned formula (A2), R ⁷Be hydrogen atom, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxy, trifluoromethoxy or alkyl-carbonyl oxygen base.As alkoxy carbonyl; For example methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl etc. can have been enumerated; As alkyl; For example can enumerate carbon numbers such as methyl, ethyl, propyl group, normal-butyl, isobutyl and be alkyl of 1～20 straight or branched etc.,, for example can enumerate methoxyl, ethoxy, propoxyl group etc. as alkoxy.

In the above-mentioned formula (A2), R ⁶Have a plurality of substituting group (R ⁷) time, can make up different substituting groups and use.As R ⁶Combination when having a plurality of substituting group is in order stably to find the dielectric anisotropy of expectation, the combination of combination, cyanic acid and the alkyl of combination, fluorine atom and the alkyl of preferred fluorine atom and cyanic acid.In addition, c is 1～9 integer.

< polymkeric substance [A-1], [A-2], [A-3] >

As [A] component of polymer, preferably contain the polymkeric substance that [A-1] has the group of the group that contains the polymerism carbon-carbon double bond and above-mentioned formula (A1) expression.

In addition, as [A] component of polymer, also preferably contain [A-2] and have the polymkeric substance of the group that contains the polymerism carbon-carbon double bond and the polymkeric substance that [A-3] has the group of above-mentioned formula (A1) expression.

These polymkeric substance are as having above-mentioned special groups; Can suit to select known main polymer chain; With polysiloxane, polyimide, polyamic acid, polyacrylate, polymethacrylate, gather (styrene-phenyl maleimide) derivant, cellulose derivative, polyester, polyamide, polystyrene derivative, poly amic acid ester and make backbone structure and consider it is preferred from the electrical characteristics aspect; Consider preferred polysiloxane (below, can be described as " polyorganosiloxane compounds (A) ") from photostability.

Polyorganosiloxane compounds (A) is preferably 500～1,000,000, more preferably 1,000～100,000, and then preferred 1,000～50,000 through gel permeation chromatography (GPC) weight-average molecular weight that measure, polystyrene conversion.

Such polyorganosiloxane compounds (A) can through which kind of method preparation in having the scope of above-mentioned characteristic.

Polyorganosiloxane compounds (A) for example can have the silane compound that contains polymerism carbon-carbon double bond group and alkoxy through making (below; Can be described as " silane compound (a1) ") or the potpourri of silane compound (a1) and other alkoxysilane compound containing trialkylsilyl group in molecular structure (below, can be described as " silane compound (a2) ") method (manufacturing approach 1) of in the presence of dicarboxylic acid and alkanol, reacting or the method (manufacturing approach 2) of hydrolytic condensation make.

In the above-mentioned

manufacturing approach

1 or 2; Through using silane compound (a2) in addition at silane compound (a1); And as the part of silane compound (a2) use group with above-mentioned formula (A1) expression and alkoxy silane compound (below; Can be described as " silane compound (a2-1) "), can obtain beyond the group that contains the polymerism carbon-carbon double bond, also to have the polyorganosiloxane compounds (A) that above-mentioned formula (A1) is represented the group of structure.

And then; Polyorganosiloxane compounds (A) can also as the manufacturing of getting off: in above-mentioned manufacturing approach 1 or 2; Outside silane compound (a1), use silane compound (a2); And as at least a portion of silane compound (a2) use silane compound with epoxy radicals and alkoxy (below; Can be described as " silane compound (a2-2) "), at first synthetic polysiloxane with the group that contains the polymerism carbon-carbon double bond and epoxy radicals (below, can be described as " the polysiloxane precursor (A ') "); Then with its method (manufacturing approach 3) with the carboxylic acid reaction of the compound that comprises group with above-mentioned formula (A1) expression and carboxyl (below, can be described as " specific carboxylic acid 2 "); Or in manufacturing approach 1 or 2; Use the silane compound (a2) that contains silane compound (a2-1) as the raw silicon hydride compounds; At first synthetic polysiloxane with epoxy radicals (below; Can be described as " polysiloxane (A) precursor "), then with itself and specific carboxylic acid 2 and/or comprise the method (manufacturing approach 4) of carboxylic acid reaction of the compound (below, can be described as " specific carboxylic acid 1 ") of the group that contains the polymerism carbon-carbon double bond and carboxyl.

For above-mentioned any situation, also can in addition silane compound (a2) of silane compound (a2-1) and silane compound (a2-2) (below, can be described as " silane compound (a2-3) ") be used in combination as silane compound (a2).

As above-mentioned silane compound (a1), for example can enumerate the compound of following formula (a-1) expression etc.

In the above-mentioned formula (a-1), R ^A, X ^I, X ^II, A, B, C be identical with above-mentioned formula (A) definition with D.R ^BBe the alkyl of carbon number 1～12 or the aryl of carbon number 6～12.E is 1～3 integer.

In the above-mentioned formula (a-1), as R ^EThe alkyl of the carbon number 1～12 of expression, the alkyl of preferred carbon number 1～4, its object lesson for example can have been enumerated methyl, ethyl, n-pro-pyl, normal-butyl, sec-butyl, the tert-butyl group etc., is preferably methyl, ethyl or n-pro-pyl, is preferably ethyl especially.As R ¹The aryl of the carbon number 6～12 of expression for example can have been enumerated phenyl, p-methylphenyl etc.

E in the above-mentioned formula (a1) is preferably 1 or 2, is preferably 1 especially.

Object lesson as silane compound (a1); For example can enumerate vinyltrimethoxy silane, VTES, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyl three n-butoxy silane, vinyl three isobutoxy silane, vinyl three tert-butoxy silane, allyltrimethoxysilanis, allyltriethoxysilane, allyl tripropoxy silane, allyl three isopropoxy silane, allyl three n-butoxy silane, allyl three isobutoxy silane, allyl three tert-butoxy silane, to the styryl trimethoxy silane, to the styryl triethoxysilane, to styryl tripropoxy silane, to styryl three isopropoxy silane, to styryl three n-butoxy silane, to styryl three isobutoxy silane, to styryl three tert-butoxy silane, (methyl) acryloxy MTMS, (methyl) acryloxy MTES, (methyl) acryloyl-oxy ylmethyl three positive propoxy silane, (methyl) acryloyl-oxy ylmethyl three isopropoxy silane, (methyl) acryloyl-oxy ylmethyl three n-butoxy silane, (methyl) acryloxy methyl-propyl three sec-butoxy silane, 2-(methyl) acryloxy ethyl trimethoxy silane, 2-(methyl) acryloxy ethyl triethoxysilane, 2-(methyl) acryloxy ethyl three positive propoxy silane, 2-(methyl) acryloxy ethyl three isopropoxy silane, 2-(methyl) acryloxy ethyl three n-butoxy silane, 2-(methyl) acryloxy ethyl propyl three sec-butoxy silane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group three positive propoxy silane, 3-(methyl) acryloxy propyl group three isopropoxy silane, 3-(methyl) acryloxy propyl group three n-butoxy silane, 3-(methyl) acryloxy propyl group three sec-butoxy silane, 4-(methyl) acryloxy butyl trimethoxy silane, 4-(methyl) acryloxy butyl triethoxysilane, 4-(methyl) acryloxy butyl three positive propoxy silane, 4-(methyl) acryloxy butyl three isopropoxy silane, 4-(methyl) acryloxy butyl three n-butoxy silane, 4-(methyl) acryloxy butyl propyl group three sec-butoxy silane, 5-(methyl) acryloxy amyltrimethoxysilane, 5-(methyl) acryloxy amyl triethoxysilane, 5-(methyl) acryloxy amyl group three positive propoxy silane, 5-(methyl) acryloxy amyl group three isopropoxy silane, 5-(methyl) acryloxy amyl group three n-butoxy silane, 5-(methyl) acryloxy amyl group propyl group three sec-butoxy silane, 6-(methyl) acryloxy hexyl trimethoxy silane, 6-(methyl) acryloxy hexyl triethoxysilane, 6-(methyl) acryloxy hexyl three positive propoxy silane, 6-(methyl) acryloxy hexyl three isopropoxy silane, 6-(methyl) acryloxy hexyl three n-butoxy silane, 6-(methyl) acryloxy hexyl propyl group three sec-butoxy silane, acryloxy MTMS etc., can select more than one to use in them.More preferably by select in vinyltrimethoxy silane, VTES, allyltrimethoxysilanis, allyltriethoxysilane, the group that constitutes to the styryl trimethoxy silane, to styryl triethoxysilane, (methyl) acryloxy MTMS, 2-(methyl) acryloxy ethyl trimethoxy silane and 3-(methyl) acryloxy propyl trimethoxy silicane more than one.

Above-mentioned silane compound (a2-1) is to have the group of above-mentioned formula (A1) expression and the silane compound of alkoxy, and then also can combine the silane compound of following formula (a2-1a) expression to use.

(R ^C) _f(R ^D) _gSi(OR ^E) _4-f-g (a2-1a)

In the above-mentioned formula (a2-1a), R ^CFor the fluoro-alkyl of the alkyl of carbon number 4～30, carbon number 1～30 or have the carbon number 17～51 of steroid skeleton alkyl, have carbon number 2～24 alkoxy alkoxyl phenyl or have the alkyl of the carbon number 12～30 of bicyclohexane skeleton.

R ^DAlkyl for carbon number 1～3.

R ^EBe the alkyl of carbon number 1～12 or the aryl of carbon number 6～12.

F is 1～3 integer.G is 0～2 integer.F+g≤3 wherein.

For the R in the above-mentioned formula (a2-1a) ^C, the group described in the group of above-mentioned formula (A1) expression that can have arbitrarily with polyorganosiloxane compounds (A) is the same.As R ^DBe preferably methyl.For R ^EAnd the R in the above-mentioned formula (a-1) ^BThe same.F is preferably 1, and g is preferably 0 or 1.

As the silane compound of above-mentioned formula (a2-1a) expression, can enumerate as follows:

As the silane compound of alkyl, normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, normal-butyl three positive propoxy silane, normal-butyl three isopropoxy silane, normal-butyl three n-butoxy silane, normal-butyl three n-butoxy silane, normal-butyl three n-pentyloxy silane, normal-butyl three sec-butoxy silane, normal-butyl triple phenoxyl silane, n-pentyl trimethoxy silane, n-pentyl triethoxysilane, n-pentyl triple phenoxyl silane, hexyl trimethoxy silane, hexyl triethoxysilane, heptyl trimethoxy silane, heptyl triethoxysilane, n-octyl trimethoxy silane, positive decyl trimethoxy silane, dodecyl trimethoxy silane, n-octadecane base trimethoxy silane etc. for example can have been enumerated with carbon number 4～30.

In addition; Silane compound as fluoro-alkyl with carbon number 1～30; For example can enumerate 3,3,3-trifluoro propyl trimethoxy silane, 3; 3,3-trifluoro propyl triethoxysilane, 2-(trifluoromethyl) ethyl trimethoxy silane, 2-(perfluor n-pro-pyl) ethyl trimethoxy silane, 2-(perfluor n-hexyl) ethyl trimethoxy silane, 2-(perfluor n-octyl) ethyl trimethoxy silane etc.

As the silane compound of the alkyl of the carbon number with steroid skeleton 17～51,3-cholestane base trimethoxy silane, 3-cholestane ethyl triethoxy silicane alkane, 3-cholestane base three positive propoxy silane, 3-cholestane base three isopropoxy silane, 3-cholestane base three n-butoxy silane, 3-cholestane base three sec-butoxy silane, 3-cholesteryl trimethoxy silane etc. for example can have been enumerated.

As the silane compound of the alkoxyl phenyl of alkoxy, 4-amoxy phenyl trimethoxy silane, 4-amoxy phenyl triethoxysilane, the own oxygen base of 4-phenyltrimethoxysila,e, 4-octyloxyphenyl trimethoxy silane, 4-dodecyloxy phenyltrimethoxysila,e etc. for example can have been enumerated with carbon number 2～24.

Above-mentioned silane compound (a2-2) is the silane compound with epoxy radicals and alkoxy, is preferably the compound of following formula (a2-2) expression.

(R ^F) _h(R ^G) _iSi(OR ^H) _4-h-I (a2-2)

In the above-mentioned formula (a2-2), R ^FFor having 1 valency group of epoxy radicals.

R ^GAlkyl for carbon number 1～3.

R ^HBe the alkyl of carbon number 1～12 or the aryl of carbon number 6～12.H is 1～3 integer.I is 0～2 integer.Wherein, h+i≤3.

As the R in the formula (a2-2) ^F, for example can enumerate 3-glycidoxy propyl group, 2-(3,4-epoxy radicals cyclohexyl) ethyl etc.As R ^G, be preferably methyl.For R ^HAnd the R in the above-mentioned formula (a-1) ^BThe same.H is preferably 1, and i is preferably 0 or 1.

Concrete example as silane compound (a2-2); 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-dimethyl methoxy silane, 3-glycidoxy propyl-dimethyl Ethoxysilane, 2-(3 for example can have been enumerated; 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 2-(3; 4-epoxy radicals cyclohexyl) ethyl triethoxysilane etc. can select more than one to use in them.

Above-mentioned silane compound (a2-3) is silane compound (a2-1) and (a2-2) in addition silane compound (a2), for example can enumerate the silane compound of following formula (a2-3) expression etc.

(R ^P) _jSi(OR ^Q) _4-j (a2-3)

In the above-mentioned formula (a2-3), R ^PAlkyl or phenyl for carbon number 1～3.

R ^QBe the alkyl of carbon number 1～12 or the aryl of carbon number 6～12.J is 0～3 integer.

R in the above-mentioned formula (a2-3) ^QWith the R in the above-mentioned formula (a-1) ^BThe same.

Object lesson as silane compound (a2-3); As j is 0 compound, for example can enumerate tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four sec-butoxy silane, four n-butoxy silane, four sec-butoxy silane etc.

As j is 1 compound, for example can enumerate MTMS, MTES, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three n-pentyloxy silane, methyl three sec-butoxy silane, methyl triple phenoxyl silane, three pairs of methylenedioxy phenoxy base silanes of methyl, ethyl trimethoxy silane, n-pro-pyl trimethoxy silane, phenyltrimethoxysila,e etc.

As j is 2 compound, for example can enumerate dimethyldimethoxysil,ne, diethyl dimethoxy silane, di dimethoxy silane, diisopropyl dimethoxy silane, dimethyldiethoxysilane, diethyl diethoxy silane etc.

As j is 3 compound, for example can enumerate trimethyl methoxy silane, triethyl methoxy silane, three n-pro-pyl methoxy silane, triisopropyl methoxy silane, trimethylethoxysilane, triethyl-ethoxy-silicane alkane etc.In them; J is 0 or 1 compound in the more preferably above-mentioned formula (a2-3); And then be preferably ethyl trimethoxy silane, ethyl triethoxysilane, MTMS, MTES, tetramethoxy-silicane and tetraethoxysilane; Be preferably j in the above-mentioned formula (a2-3) especially and be 0 compound, most preferably tetramethoxy-silicane and tetraethoxysilane.

When making polyorganosiloxane compounds (A) through

manufacturing approach

1 or 2; Silane compound as the raw material use; All preferably contain 1 mole more than the % with respect to silane compound; More preferably contain 1 mole of %～60 mole %, and then preferably contain 2 moles of %～50 mole %, especially preferably contain the above-mentioned silane compound (a1) of 2 moles of %～30 mole %.

Through

manufacturing approach

1 or 2, when making the polyorganosiloxane compounds (A) of the group that except the group that contains the polymerism carbon-carbon double bond, also has above-mentioned formula (A1) expression, use silane compound (a1) and silane compound (a2-1) simultaneously.The usage ratio of silane compound this moment (a2-1) is all with respect to silane compound, is preferably 60 moles below the %, and more preferably 5 moles of %～50 mole % are preferably 10 moles of %～40 mole % especially.

In the

manufacturing approach

1 or 2, preferably except above-mentioned silane compound, be used in combination silane compound (a2-3).Its usage ratio is all with respect to silane compound, is preferably 60 moles below the %, and more preferably 0 mole of %～40 mole % is preferably 0 mole of %～20 mole % especially.

When carrying out the manufacturing of polyorganosiloxane compounds (A) with manufacturing approach 3; The silane compound that uses as raw material does; All preferably contain 1 mole more than the % with respect to silane compound; More preferably contain 1 mole of %～60 mole %, and then be preferably and contain 2 moles of %～50 mole %, be preferably the above-mentioned silane compound (a1) that contains 2 moles of %～30 mole % especially.

When carrying out the manufacturing of polyorganosiloxane compounds (A), except above-mentioned silane compound (a1), also use silane compound (a2-2) with manufacturing approach 3.The usage ratio of this silane compound (a2-2) is all with respect to silane compound, is preferably 10 moles more than the %, and more preferably 20 moles of %～90 mole % are preferably 30 moles of %～70 mole % especially.

When carrying out the manufacturing of polyorganosiloxane compounds (A) with manufacturing approach 4, the silane compound that uses as raw material does, all with respect to silane compound preferably contained 20 moles more than the %, more preferably contains the above-mentioned silane compound (a2-2) of 40 moles of %.

In the manufacturing approach 3 and 4, preferably do not use silane compound (a2-3).

Polyorganosiloxane compounds (A), polysiloxane precursor (A ') or polysiloxane precursor (A ") can be made through make the method (manufacturing approach 1) that above-mentioned silane compound reacts or the method (manufacturing approach 2) of hydrolytic condensation in the presence of dicarboxylic acid and alkanol respectively.

Below, manufacturing approach 1 and manufacturing approach 2 are described successively.

[manufacturing approach 1]

Manufacturing approach 1 is the method that above-mentioned silane compound is reacted in the presence of dicarboxylic acid and alkanol.

As dicarboxylic acid used herein, can enumerate the compound that combines two carboxyls to obtain on the alkylidene of oxalic acid, malonic acid, carbon number 2～4, benzene dicarboxylic acid etc.Concrete for example can enumerate oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, phthalic acid, m-phthalic acid, terephthalic acid (TPA) etc., preferably uses in them more than one.Be preferably oxalic acid especially.

As the usage ratio of dicarboxylic acid, for the alkoxy that has with respect to the silane compound that uses as raw material added up to 1 mole, the amount of carboxyl was preferably 0.2 mole～2.0 moles amount, more preferably 0.5 mole～1.5 moles amount.

As above-mentioned alkanol, can be fit to use 1 grade of alkanol.Its object lesson; Methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamylol, 2-methyl butanol, tert-pentyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol-3, n-octyl alcohol, 2-Ethylhexyl Alcohol, n-nonyl alcohol, 2 for example can have been enumerated; 6-dimethyl enanthol-4, Decanol, phenol, cyclohexanol, methyl cyclohexanol, 3; 3; 5-cyclonol, benzylalcohol, two acetone alkanols etc. preferably select more than one to use from them.As alkanol used herein; Be preferably 1 grade of alkanol of aliphatics of carbon number 1～4; More than one that select in the group that more preferably is made up of methyl alcohol, ethanol, isopropyl alcohol, n-propanol, isobutyl alcohol, sec-butyl alcohol and the tert-butyl alcohol use, more than one that select in the group that especially preferably uses methyl alcohol and ethanol to constitute.

As the usage ratio of the alkanol in the manufacturing approach 1, with respect to the total amount of reaction solution, the ratio of silane compound and dicarboxylic acid is preferably and accounts for 3 quality %～80 quality %, more preferably accounts for 25 quality %～70 quality %.

Temperature of reaction is preferably 1 ℃～100 ℃, more preferably 15 ℃～80 ℃.Reaction time is preferably 0.5 hour～and 24 hours, more preferably 1 hour～8 hours.

In the manufacturing approach 1, preferably beyond above-mentioned alkanol, do not use other solvents.

In the manufacturing approach 1, the intermedium that is generated by silane compound and dicarboxylic acid reaction passes through the alkanol effect, infers to have generated the condensation body of silane compound (a1) or the cocondensation zoarium-polysiloxane of silane compound (a1) and silane compound (a2).

[manufacturing approach 2]

Manufacturing approach 2 is the methods with above-mentioned silane compound hydrolytic condensation.

This hydrolysis-condensation reaction is under the existence of preferred catalyst, and silane compound and water react in appropriate organic solvent.

The ratio of water used herein, the alkoxy that has with respect to the silane compound that uses as raw material adds up to 1 mole amount, is preferably 0.5 mole～2.5 moles.

As above-mentioned catalyzer, acid, alkali, metallic compound etc. can have been enumerated.As the object lesson of such catalyzer, for example hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid etc. can have been enumerated as acid.

As alkali, can use any one of inorganic base and organic base, inorganic base for example can have been enumerated ammonia, NaOH, potassium hydroxide, sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide etc.; Organic base for example can have been enumerated uncle's organic amines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; TMAH etc.

As metallic compound, for example titanium compound, zirconium compounds etc. can have been enumerated.

The usage ratio of catalyzer adds up to 100 mass parts with respect to the silane compound that uses as raw material, is preferably below 10 mass parts, and 0.001 mass parts～10 mass parts more preferably, and then be preferably 0.001 mass parts～1 mass parts.

As above-mentioned organic solvent, alkanol, ketone, acid amides, ester and other aprotic compounds for example can have been enumerated.As above-mentioned alkanol, can use alkanol, have the alkanol of a plurality of hydroxyls and have part ester any of the alkanol of a plurality of hydroxyls with 1 hydroxyl.As above-mentioned ketone, preferably use single ketones and beta-diketon.

Object lesson as such organic solvent; As alkanol with 1 hydroxyl; Methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamylol, 2-methyl butanol, tert-pentyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol-3, n-octyl alcohol, 2-Ethylhexyl Alcohol, positive nonanone, 2 for example can have been enumerated; 6-dimethyl enanthol-4, Decanol, phenol, cyclohexanol, methyl cyclohexanol, 3; 3,5-cyclonol, benzylalcohol, two acetone alkanols etc.

As alkanol, for example can enumerate monoethylene glycol, 1,2-propylene glycol, 1 with a plurality of hydroxyls; 3-butylene glycol, pentanediol-2,4,2 hexylene glycol-2,4, hexanediol-2; 5, heptandiol-2; 4,2-ethohexadiol-1,3, diethylene glycol, DPG, triethylene glycol, tripropylene glycol etc.

As the part ester of the alkanol of a plurality of hydroxyls, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol ether, ethyleneglycol monophenylether, glycol monomethyl-2-b-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPG list ether, DPG list propyl ether etc. for example can have been enumerated.

In addition; As single ketones; Acetone, MEK, methyl-positive acetone, methyl-positive butanone, diethyl ketone, methyl-isobutyl ketone, methyl-positive pentanone, ethyl-positive butanone, methyl-positive hexanone, two-isobutyl ketone, trimethyl nonanone, cyclohexanone, methyl-n-butyl ketone, methyl cyclohexanone, 2 for example can have been enumerated; 4-pentanedione, acetonyl acetone, acetophenone, fenchone etc.

As above-mentioned beta-diketon, for example can enumerate diacetone, 2,4-acetyl butyryl, 2,4-heptadione, 3,5-heptadione, 2,4-acetyl caproyl, 3; 5-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 3,5-diketone in the ninth of the ten Heavenly Stems, 5-methyl-2,4-acetyl butyryl, 2,2; 6,6-tetramethyl-3,5-heptadione, 1,1,1; 5,5,5-hexafluoro-2,4-heptadione etc.

As acid amides; Formamide, N-NMF, N for example can have been enumerated; Dinethylformamide, N-ethyl-formamide, N; N-DEF, acetamide, N-methylacetamide, DMAC N,N, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetyl group morpholine, N-acetyl group piperidines, N-acetyl-pyrrolidine etc.

As ester, diethyl carbonate, ethylene carbonate, carbonic allyl ester, diethyl carbonate, methyl carbonate, ethyl acetate, gamma-butyrolacton, gamma-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, benzyl acetate, cyclohexyl acetate, acetic acid methyl cyclohexane ester, acetic acid ester in the positive ninth of the ten Heavenly Stems, acetyl methyl carbonate, ethyl acetoacetate, acetic acid glycol monoethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid dihydroxypropane single-ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol monobutyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid DPG list ether, ethylene diacetate, acetic acid methoxyl three second diester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethy-aceto oxalate, oxalic acid di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid n-pentyl ester, diethyl malonate, repefral, diethyl phthalate etc. for example can have been enumerated.

As other non-protonic solvents; For example acetonitrile, dimethyl sulfoxide (DMSO), N can have been enumerated; N; N ', N '-tetraethyl sulfonamide, HPT, N-methylmorpholine (モ Le ホロ Application), N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrrolin, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-methylimidazole, N-methyl-4-piperidones, N-methyl-2-piperidones, N-N-methyl-2-2-pyrrolidone N-, 1; 3-dimethyl-2-imidazolone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.

As the usage ratio of organic solvent, the ratio that the total quality of the composition in the reaction solution beyond the organic solvent accounts for the reaction solution total amount is preferably 1 quality %～90 quality %, more preferably 10 quality %～70 quality %.

In the manufacturing approach 2, the water that when the manufacturing of polysiloxane, adds can be discontinuously or add to continuously in the solution that has dissolved silane compound in the raw silicon hydride compounds or in organic solvent.

Catalyzer can add in the solution that has dissolved silane compound in the raw silicon hydride compounds or in organic solvent in advance, or the dissolving or be dispersed in the water of interpolation.

Adopt manufacturing approach 1 or at 2 o'clock as the manufacturing approach of polyorganosiloxane compounds (A), as stated, can obtain polyorganosiloxane compounds (A).

When adopting manufacturing approach 3 as the manufacturing approach of polyorganosiloxane compounds (A), the polysiloxane precursor that will as above-mentioned, obtain (A ') again with the carboxylic acid reaction that contains specific carboxylic acid 2, can obtain polyorganosiloxane compounds (A).

When adopting manufacturing approach 4 as the manufacturing approach of polyorganosiloxane compounds (A); The polysiloxane precursor that will as above-mentioned, obtain (A ") again with the carboxylic acid reaction that contains specific carboxylic acid 1 and/or specific carboxylic acid 2, can obtain polyorganosiloxane compounds (A).

The reaction of carboxylic acid [the polysiloxane precursor (A ') with]

The specific carboxylic acid 2 that in manufacturing approach 3, uses is to have the group of above-mentioned formula (A1) expression and the compound of carboxyl.

As the specific carboxylic acid 2 that uses in the manufacturing approach 3, can enumerate the compound of carboxyl with following formula (A1-C) expression.

In the above-mentioned formula (A1-C), R ¹Alkylidene, phenylene or cyclohexylidene for methylene, carbon number 2～30.Partly or entirely can being substituted of the hydrogen atom that these groups have.R ²For comprising the arbitrary linking group in two keys, triple bond, ehter bond, ester bond and the oxygen atom.R ³For having the group of at least two single ring architectures.A is 0 or 1.

Utilize the reactivity between epoxy radicals and the carboxyl, can easily on as the polysiloxane of main chain, introduce structure with dielectric anisotropy as above-mentioned formula (A1-C) expression of side chain.

As specific carboxylic acid 2, for example can enumerate the compound of following formula (D-1)～(D-25) expression etc.

In the above-mentioned formula (D-1)～(D-25), R ³Identical with above-mentioned formula (A1-C) definition.M is 1～30 integer.

As the group of above-mentioned formula (A2) expression, for example can enumerate the group of following formula (E-1)～(E-123) expression.

In the above-mentioned formula (E-1)～(E-123), R is the alkyl of carbon number 1～20 or the alkoxy of carbon number 1～20.X is hydrogen atom or fluorine atom independently of one another.

The alkyl of the carbon number of representing as above-mentioned R 1～20; For example methyl, ethyl, propyl group, normal-butyl, isobutyl, n-pentyl, n-hexyl etc. can have been enumerated; As the alkoxy of carbon number 1～20, for example methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy etc. can have been enumerated.

[synthetic method of specific carboxylic acid]

The not special restriction of the synthetic order of specific carboxylic acid can be made up present known method and carried out.Synthetic order as representative; For example enumerate: (1) will have the compound of phenol skeleton and react under alkali condition with the compound that halogen has replaced the alkyl chain part of high-grade aliphatic ester; The substituted carbon of the hydroxyl of phenol skeleton and halogen forms key; Ester reduction then makes the method for specific carboxylic acid; The compound and the ethylene carbonate that (2) will have the phenol skeleton react; Generate terminal alkanol compound, the reaction of this hydroxyl and halogeno-benzene sulfonic acid chloride and activate, this activate part and contain the benzoic acid methyl esters reaction of hydroxyl then; When breaking away from the sulfonyl part; The hydroxyl of terminal alkanol compound generates key with the hydroxyl of the benzoic acid methyl esters that contains hydroxyl as substituting group, and then ester reduction makes the method for specific carboxylic acid etc.But the synthetic method of specific carboxylic acid is not limited thereto.

In the manufacturing approach 3, can only use specific carboxylic acid 2, or in the scope of not damaging effect of the present invention, use a part that replaces specific carboxylic acid by the compound of following formula (4) expression as carboxylic acid.At this moment, the potpourri of the compound represented of the synthetic polysiloxane through having epoxy radicals of polyorganosiloxane compounds (A) and specific carboxylic acid 2 and following formula (4) reacts and carries out.

A ¹-L ⁰-L ¹-Z (4)

In the above-mentioned formula (4), A ¹For the alkyl of the straight chain shape of carbon number 1～30 or branched, can or have the alkyl of the carbon number 17～51 of steroid skeleton with the naphthenic base of the alkyl of carbon number 1～20 or the substituted carbon number 3～10 of alkoxy.Wherein, the substituting groups such as cyanic acid, fluorine atom, trifluoromethyl of partly or entirely can using of the hydrogen atom of abovementioned alkyl and alkoxy replace.

L ⁰For singly-bound ,-O-,-COO-or-OCO-.

L ¹Alkylidene, phenylene, biphenylene, cyclohexylidene, inferior dicyclohexyl or following formula (L for singly-bound, methylene, carbon number 2～20 ¹-1) or (L ¹-2) group of expression.

Z is the organic group that can form 1 valency that combines base with the epoxy reaction in the polyorganosiloxane compounds (A).

Wherein, L ¹During for singly-bound, L ⁰Be singly-bound.

Above-mentioned formula (L ¹-1) and (L ¹The associative key of the band-2) " * " combines with Z respectively.

Z is preferably carboxyl.

In the above-mentioned formula (4), as A ¹The straight chain shape of the carbon number 1～30 of expression or the alkyl of branched for example can have been enumerated methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, 3-methyl butyl, 2-methyl butyl, 1-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3; 3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2; 2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1; 1-dimethylbutyl, n-heptyl, 5-methyl hexyl, 4-methyl hexyl, 3-methyl hexyl, 2-methyl hexyl, 1-methyl hexyl, 4,4-dimethyl amyl group, 3,4-dimethyl amyl group, 2; 4-dimethyl amyl group, 1,4-dimethyl amyl group, 3,3-dimethyl amyl group, 2; 3-dimethyl amyl group, 1,3-dimethyl amyl group, 2,2-dimethyl amyl group, 1; 2-dimethyl amyl group, 1; 1-dimethyl amyl group, 2,3,3-trimethyl butyl, 1; 3; 3-trimethyl butyl, 1,2,3-trimethyl butyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base etc.

As the naphthenic base of the alkyl that can use carbon number 1～20 or the substituted carbon number 3～10 of alkoxy, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, cyclo-dodecyl etc. for example can have been enumerated.

As the alkyl of the carbon number with steroid skeleton 17～51, for example can enumerate the group of following formula (H-1)～(H-3) expression.

As the A in the above-mentioned formula (4) ¹, alkyl, carbon number 1～20 fluoro-alkyl of preferred carbon number 1～20 and be selected from above-mentioned formula (H-1) or group (H-3).

As the compound of above-mentioned formula (4) expression, the compound of preferred following formula (4-1)～(4～6) expression.

C _uF _2u+1-C _vH _2v-COOH (4-1)

C _wH _2w+1-COOH (4-2)

In the above-mentioned formula (4-1)～(4-6), u is 1～5 integer.V is 1～18 integer.W is 1～20 integer.K is 1～5 integer.P is 0 or 1.Q is 0～18 integer.R is 0～18 integer.S and t are 0～2 integer independently of one another.

In these compounds, the compound of more preferably following formula (5-1)～(5-7) expression.

C ₁₇H ₃₅-COOH (5-1)

The compound of above-mentioned formula (4) expression is simultaneously and specific carboxylic acid and the polysiloxane reaction with epoxy radicals, becomes the liquid crystal orientation film of the giving gained compound with the position of manifesting property of tilt angle.Compound with above-mentioned formula (4) expression in this instructions is called following " other manifesting property of tilt angle compounds ".

Among the present invention; When using specific carboxylic acid simultaneously with other manifesting property of tilt angle compounds; The total usage ratio of specific carboxylic acid and other manifesting property of tilt angle compounds is for the epoxy radicals that 1 mole of polysiloxane has; Be preferably 0.001 mole～1.5 moles, more preferably 0.01 mole～1 mole, and then be preferably 0.05 mole～0.9 mole.At this moment, other manifesting property of tilt angle compounds are preferably 75 moles below the % with the total with respect to specific carboxylic acid, and more preferably 50 moles of following scopes of % are used.The usage ratio of other manifesting property of tilt angle compounds surpasses 75 moles of %, has the situation that the high-speed response property to liquid crystal has a negative impact.

The reaction of polysiloxane precursor (A ') and carboxylic acid is preferably carried out in the presence of suitable catalyzer and suitable organic solvent.

The catalyzer that uses in the reaction as polysiloxane precursor (A ') and carboxylic acid for example can compatibly use organic base, is used in addition promote that the so-called curing accelerator of epoxy compound and anhydride reaction also can be used as this catalyst for reaction.As above-mentioned organic base, organic primary, secondary amine, trimethylamine, organic quaternary amine etc. for example can have been enumerated.

As above-mentioned curing accelerator, for example can enumerate tertiary amine (except uncle's organic amine), imdazole derivatives, organic phosphorus compound 、 quaternary alkylphosphonium salt, diazabicylo alkene, organometallics, halo quaternary ammonium, metal halide, potentiality curing accelerator etc. as organic base.As above-mentioned potentiality curing accelerator etc., for example can enumerate hot cationic polymerization type potentiality curing accelerator of high-melting-point decentralized potentiality curing accelerator (for example amine add-on type promoter etc.), microcapsule-type potentiality curing accelerator, amine salt type potentiality hardening agent promoter, high temperature dissociative type etc.

As the object lesson of this catalyzer,, for example ethamine, diethylamine, piperazine, piperidines, pyrrolidine, pyrroles etc. can have been enumerated as above-mentioned organic primary, secondary amine.

As above-mentioned trimethylamine, triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicylo undecylene etc. for example can have been enumerated.

As above-mentioned organic quaternary amine, for example can enumerate TMAH etc.

As above-mentioned tertiary amine (except uncle's organic amine), for example can enumerate benzyl dimethylamine, 2,4,6-three (dimethylaminomethyl) phenol, cyclohexyl dimethylamine, triethanolamine etc. as organic base.

As above-mentioned imdazole derivatives; Glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1 for example can have been enumerated; 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 2-phenyl-4; 5-two (methylol) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4; 5-two ((2 '-cyanic acid ethoxy) methyl) imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyano ethyl)-2-phenylimidazole trimellitate, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole trimellitate, 2; 4-diamido-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine, 2; 4-diamido-6-(2 '-n-undecane base imidazole radicals) ethyl-s-triazine, 2; 4-diamido-6-(2 '-ethyl-4 '-methylimidazolyl-(1 ')) ethyl-s-triazine, the cyamelide addition product of glyoxal ethyline, the cyamelide addition product, 2 of 2-phenylimidazole, the cyamelide addition product of 4-diamido-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine etc.

In addition, as above-mentioned organic phosphorus compound, diphenylphosphine, triphenylphosphine, tricresyl phosphite phenyl etc. for example can have been enumerated.

As above-mentioned quaternary alkylphosphonium salt; Bian base triphenyl phosphonium chloride, tetra-n-butyl phosphonium bromide, Jia base triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, normal-butyl triphenyl phosphonium bromide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, Yi base triphenyl phosphonium acetic acid esters, Si Zheng Ding Ji Phosphonium o for example can have been enumerated, o-diethyl idol phosphorus dithionic acid ester, Si Zheng Ding Ji Phosphonium benzotriazole ester, Si Zheng Ding Ji Phosphonium tetrafluoro boric acid ester, Si Zheng Ding Ji Phosphonium tetraphenyl borate, tetraphenylphosphoniphenolate tetraphenyl borate etc.;

As above-mentioned diazabicylo alkene, for example can enumerate 1,8-diazabicylo [5.4.0] undecylene-7, its acylate etc.

As above-mentioned organometallics, zinc octoate, acrylic acid tin (ア Network チ Le acid tin), aluminium acetylacetonate complex etc. for example can have been enumerated.

As above-mentioned halo quaternary ammonium, for example tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride etc. can have been enumerated.

As above-mentioned metal halide, for example can enumerate the boron compound of boron trifluoride, boric acid triphenyl and so on; Zinc chloride, tin chloride etc.

As above-mentioned high-melting-point decentralized potentiality curing accelerator, for example can enumerate the addition product of dicyandiamide or amine and epoxy resin etc.

As above-mentioned microcapsule-type potentiality curing accelerator, the potentiality curing accelerator that the surface that for example can enumerate curing accelerators such as above-mentioned imdazole derivatives, organic phosphorus compound 、 quaternary alkylphosphonium salt covers with polymkeric substance etc.

As the hot cationic polymerization type potentiality curing accelerator of above-mentioned high temperature dissociative type, lewis acid, Bronsted hydrochlorate etc. for example can have been enumerated.

In them, preferably use organic quaternary amine or halo quaternary ammonium.

The usage ratio of catalyzer is preferably 0.01 mass parts～100 mass parts, more preferably 0.1 mass parts～20 mass parts with respect to 100 mass parts polysiloxane precursors (A ').

The organic solvent that uses in the reaction as polysiloxane precursor (A ') and carboxylic acid for example can have been enumerated ketone, ether, ester, acid amides, alkanol etc.As the object lesson of this organic solvent, as above-mentioned ketone, for example can enumerate MEK, methylisobutylketone, MAK, diethyl ketone, cyclohexanone etc.,

As above-mentioned ether, for example can enumerate glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran 、 diox etc.,

As above-mentioned ester, for example can enumerate ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol methyl ether acetate, 3-methoxyl butylacetic acid ester, ethyl lactate etc.,

As above-mentioned acid amides; Formamide, N-NMF, N for example can have been enumerated; Dinethylformamide, N-ethyl-formamide, N, N-DEF, acetamide, N-methylacetamide, DMAC N,N, N-ethyl acetamide, N; N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetyl group morpholine, N-acetyl group piperidines, N-acetyl-pyrrolidine etc.

As above-mentioned alkanol, 1-hexanol, 4-methyl-2-amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol monomethyl n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether etc. for example can have been enumerated.

The usage ratio of organic solvent accounts for the ratio of the total amount of reaction solution as the one-tenth subtotaling quality beyond the organic solvent in the reaction solution, is preferably 0.1 quality %～50 quality %, more preferably 5 quality %～50 quality %.

The reaction of polysiloxane precursor (A ') and carboxylic acid preferably 0 ℃～200 ℃, more preferably under 50 ℃～150 ℃ temperature, preferably carry out 0.1 hour～50 hours, more preferably carried out 0.5 hour～20 hours.

The reaction of carboxylic acid [the polysiloxane precursor (A ") with]

The specific carboxylic acid 1 that uses in the manufacturing approach (4) is for having the group that contains the polymerism carbon-carbon double bond and the compound of carboxyl.The group that contains the polymerism carbon-carbon double bond that has for specific carboxylic acid 1 is the same with the situation of above-mentioned explanation in the group that contains the polymerism carbon-carbon double bond that polyorganosiloxane compounds (A) is had.

As the specific carboxylic acid 1 that uses in the manufacturing approach 4; For example can enumerate (methyl) acrylic acid, crotonic acid, α-Yi Jibingxisuan, α-n-pro-pyl acrylic acid, α-normal-butyl acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc., can select more than one to use in them.

In the manufacturing approach 4, can only use specific carboxylic acid 1, or only use above-mentioned specific carboxylic acid 2 together, or they are used in combination with specific carboxylic acid 1 as carboxylic acid.

Among the present invention, in the scope of not damaging effect of the present invention, can the compound that the part of specific carboxylic acid is represented with above-mentioned formula (4) be replaced and use.At this moment, polyorganosiloxane compounds (A) synthetic is to react through the potpourri that makes polysiloxane with epoxy radicals and the compound of specific carboxylic acid and above-mentioned formula (4) expression to carry out.The compound of above-mentioned formula (4) expression the same with shown in the manufacturing approach 3.

Among the present invention; When using specific carboxylic acid simultaneously with other manifesting property of tilt angle compounds; The total usage ratio of specific carboxylic acid and other manifesting property of tilt angle compounds is for the epoxy radicals that 1 mole of polysiloxane has; Be preferably 0.001 mole～1.5 moles, more preferably 0.01 mole～1 mole, and then be preferably 0.05 mole～0.9 mole.At this moment, other manifesting property of tilt angle compounds are with respect to the total of specific carboxylic acid, preferably with 75 moles below the %, more preferably use with 50 moles of scopes below the %.The usage ratio of other manifesting property of tilt angle compounds surpasses 75 moles of %, has the situation that the high-speed response property to liquid crystal has a negative impact.

The suitable usage ratio of each carboxylic acid is represented as follows respectively in the manufacturing approach 4.

As the total usage ratio of carboxylic acid, the epoxy radicals with respect to 1 mole of polysiloxane precursor (A ") has is preferably 0.1 mole～0.9 mole, and more preferably 0.2 mole～0.7 mole, and then be preferably 0.3 mole～0.5 mole.

As the usage ratio of specific carboxylic acid 1, with respect to whole carboxylic acids, be preferably 50 moles more than the %, more preferably 70 moles more than the %, and then be preferably 90 moles more than the %.

As the usage ratio of specific carboxylic acid 2, with respect to whole carboxylic acids, be preferably 50 moles below the %, 1 mole of %～30 mole % more preferably, and then be preferably 5 moles of %～10 mole %.

The reaction of polysiloxane precursor in the manufacturing approach 4 (A ") and carboxylic acid is except using polysiloxane precursor (A ") and the above-mentioned carboxylic acid, can with manufacturing approach 3 in as the same enforcement the described in the reaction of polysiloxane precursor (A ') and carboxylic acid.

As stated, can obtain polyorganosiloxane compounds of the present invention (A).

In the aligning agent for liquid crystal (A),, except above-mentioned polyorganosiloxane compounds (A) etc., also can contain in addition polymkeric substance of polyorganosiloxane compounds (A) (below, be called " other polymkeric substance ") as [A] component of polymer.

[other polymkeric substance]

Other polymkeric substance can be for the electrical characteristics of the liquid crystal display cells of the solution properties that further improves aligning agent for liquid crystal (A) and gained and are used.As other polymkeric substance, for example can enumerate at least a polymkeric substance of selecting in the group that constitutes by polyamic acid and polyimide (polymkeric substance (B)); At least a (below, be also referred to as " other polysiloxane ") who selects in the group that constitutes by the condensation product of polysiloxane, its hydrolysate and its hydrolysate of following formula (a1) expression; Poly amic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, gather (styrene-phenyl maleimide) derivant, gather (methyl) acrylic ester etc.

In the above-mentioned formula (a1), X ^ABe the alkyl of hydroxyl, halogen atom, carbon number 1～20, the alkoxy of carbon number 1～6 or the aryl of carbon number 6～20.Y ^AAlkoxy for hydroxyl or carbon number 1～10.

[polymkeric substance (B)]

Polymkeric substance (B) is at least a polymkeric substance of selecting in the group that is made up of polyamic acid and polyimide.Below, specify polyamic acid, polyimide.

[polyamic acid]

Polyamic acid reacts through tetracarboxylic dianhydride and diamine compound and obtains.

As the tetracarboxylic dianhydride, aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. for example can have been enumerated.These tetracarboxylic dianhydrides can use separately or two or more combination.

As the aliphatics tetracarboxylic dianhydride, four butyric acid dianhydrides etc. for example can have been enumerated.

As the ester ring type tetracarboxylic dianhydride, for example can enumerate 1,2,3,4-cyclo-butane tetracarboxylic acid dianhydride, 2,3; 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2; 5-dioxy-3-furyl)-and naphtho-[1,2-c] furans-1,3-diketone, 1,3,3a, 4; 5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxy-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 '; 5 '-diketone), 5-(2,5-dioxy tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-ethyloic norbornane-2:3,5:6-dianhydride, 2; 4,6,8-tetracarboxylic two ring [3.3.0] suffering-2:4,6:8-dianhydride, 4,9-dioxa three ring [5.3.1.0 ^2,6] 11-3,5,8,10-tetraketone etc.

As aromatic tetracarboxylic acid's dianhydride, for example can enumerate PMDA etc., also have the special tetracarboxylic dianhydride who is willing to record in 2010-97188 number of Japan in addition.

Among these tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride or 1,2,3,4-cyclo-butane tetracarboxylic acid dianhydride, preferred especially 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride.

As 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride or 1,2; 3, the use amount of 4-cyclo-butane tetracarboxylic acid dianhydride is preferably 10 moles more than the % with respect to whole tetracarboxylic dianhydrides, more preferably 20 moles more than the %; Preferred especially only by 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride or 1; 2,3,4-cyclo-butane tetracarboxylic acid dianhydride constitutes.

As diamine compound, aliphatic diamine, ester ring type diamines, diamido organosiloxane, aromatic diamine etc. for example can have been enumerated.These diamine compounds can use separately or two or more combination is used.

As aliphatic diamine, for example can enumerate m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine etc.

As the ester ring type diamines, for example can enumerate 1,4-DACH, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexylamine), 1, two (amino methyl) cyclohexanes of 3-etc.

As the diamido organosiloxane, for example can enumerate 1, two (3-the aminopropyl)-tetramethyl disiloxanes of 3-etc. also have the special diamines of being willing to record in 2009-97188 number of Japan in addition.

As aromatic diamine, for example can enumerate p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1; 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido-2; 2 '-two (trifluoromethyl) biphenyl, 2,7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2, two [4-(4-amino-benzene oxygen) phenyl] propane, 9 of 2-; Two (4-aminophenyl) fluorenes, 2 of 9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 2 of 2-, two (4-aminophenyl) HFC-236fas, 4 of 2-, 4 '-(to the phenylene diisopropylidene) two (aniline), 4; 4 '-(metaphenylene diisopropylidene) two (aniline), 1, two (4-amino-benzene oxygen) benzene, 4 of 4-, 4 '-two (4-amino-benzene oxygen) biphenyl, 2,6-diamino-pyridine, 3; 4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamido carbazole, N-methyl-3; 6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl)-biphenylamine, N; N '-two (4-aminophenyl)-N, N '-dimethylbenzidine, 1,4-pair-(4-aminophenyl)-piperazine, 3,5-diamido benzoic acid, lauroyl oxygen base-2; 4-diaminobenzene, myristoyl oxygen base-2,4-diaminobenzene, pentadecanoyl oxygen base-2,4-diaminobenzene, palmityl oxygen base-2; 4-diaminobenzene, 18 acyloxy-2,4-diaminobenzene, lauroyl oxygen base-2,5-diaminobenzene, myristoyl oxygen base-2; 5-diaminobenzene, pentadecanoyl oxygen base-2,5-diaminobenzene, palmityl oxygen base-2,5-diaminobenzene, 18 acyloxy-2; 5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2; 4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diamido benzoic acid cholestane base, 3; 5-diamido benzoic acid cholesteryl, 3,5-diamido benzoic acid lanostane base, 3, two (the 4-aminobenzoic acyl-oxygen base) cholestane, 3 of 6-; Two (4-amino-benzene oxygen) cholestane of 6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1; Two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexanes, 1 of 1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptyl cyclohexanes, 1 of 1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptyl cyclohexanes, 1 of 1-; Two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) cyclohexanes, 2 of 1-, 4-diamino-N, the diamine compound of N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine and following formula (A-1) expression etc.

In the above-mentioned formula (A-1), X ^BBe methylene,

carbon number

2 or 3 alkylidene ,-O-,-COO-or-OCO-.R is 0 or 1.S is 0～2 integer.T is 1～20 integer.

The usage ratio that supplies to tetracarboxylic dianhydride and diamine compound in the synthetic reaction of polyamic acid is with respect to the contained amino of 1 equivalent diamine compound, and preferred tetracarboxylic dianhydride's anhydride group is 0.2 equivalent～2 equivalents, more preferably 0.3 equivalent～1.2 equivalents.

Synthetic reaction is preferably carried out in organic solvent.Temperature of reaction is preferably-20 ℃～150 ℃, more preferably 0 ℃～100 ℃.Reaction time is preferably 0.5 hour～and 24 hours, more preferably 2 hours～12 hours.

As organic solvent; So long as can dissolve the solvent of synthetic polyamic acid; Not special restriction for example can have been enumerated N-N-methyl-2-2-pyrrolidone N-(NMP), DMAC N,N, N; Dinethylformamide, N, non-proton type of polar solvent such as N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, hexamethyl phosphinylidyne triamide; Phenol solvents such as metacresol, xylenol, phenol, halogenated phenol.

As the use amount (a) of organic solvent, for the total (a+b) of the use amount (a) of the total amount (b) of tetracarboxylic dianhydride and diamine compound and organic solvent, be preferably 0.1 quality %～50 quality %, more preferably 5 quality %～30 quality %.

The polyamic acid solution that obtains after the reaction; Can former state be supplied in the preparation of aligning agent for liquid crystal (A); Be supplied in the preparation of aligning agent for liquid crystal (A) behind the contained polyamic acid in also can first separating reaction solution, be supplied in the preparation of aligning agent for liquid crystal (A) after can also be with the polyamic acid that separates refining.As the separation method of polyamic acid, for example reaction solution is injected in a large amount of poor solvents, the method for the precipitate drying under reduced pressure that obtains, distillate the method for reaction solution etc. with evaporator decompression.As the process for purification of polyamic acid, can enumerate that the polyamic acid after separating is dissolved in the organic solvent again, the method for separating out with poor solvent, distillate organic solvent etc. with the evaporator decompression and carry out once or repeat method for several times.

[polyimide]

Polyimide can be made through amic acid structure dehydration closed-loop, imidizate that above-mentioned polyamic acid is had.Polyimide can be the complete imidizate thing of the amic acid structure fully dehydrating closed loop that has of its precursor polyamic acid, also can be a part of dehydration closed-loop, amic acid structure and the imide ring structure of amic acid structure and the part imidizate thing of depositing.

Synthetic method as polyimide; For example can enumerate (i) heating polyamic acid method (below; Be called " method (i) "), (ii) polyamic acid is dissolved in the organic solvent; In this solution, add dewatering agent and dehydration closed-loop catalyzer, as required the dehydration closed-loop of polyamic acid such as the method for heating (below, be called " the method (ii) ") method of reacting.

As the temperature of reaction in the method (i), be preferably 50 ℃～200 ℃, more preferably 60 ℃～170 ℃.Temperature of reaction is less than 50 ℃, and the dehydration closed-loop reaction can not fully be carried out, and temperature of reaction surpasses 200 ℃, and the molecular weight of the polyimide that obtains can reduce.As the reaction time, be preferably 0.5 hour～48 hours, more preferably 2 hours～20 hours.

Can former state be supplied in the preparation of aligning agent for liquid crystal (A) as the polyimide that obtains in the method (i); Also can separate polyimide earlier resupplies in the preparation of aligning agent for liquid crystal (A); Or resupply in the preparation of aligning agent for liquid crystal (A) on the basis of the polyimide after refining the separation or on the basis of the refining polyimide that obtains.

As the dewatering agent of method in (ii), for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoro-acetic anhydride can have been enumerated.

As the use amount of dewatering agent, can suit according to the imidizate rate of expectation to select, still, be preferably 0.01 mole～20 moles with respect to the amic acid structure of 1 mole of polyamic acid.

As the dehydration closed-loop catalyzer of method in (ii), for example pyridine, collidine, lutidines, triethylamine etc. can have been enumerated.

As the use amount of dehydration closed-loop catalyzer,, be preferably 0.01 mole～10 moles with respect to 1 mole of dewatering agent that contains.In addition, the amount of above-mentioned dewatering agent and dehydration closed-loop agent is many more, can make the imidizate rate high more.

As the organic solvent that method is used in (ii), for example can enumerate the same organic solvent of the organic solvent that in polyamic acid synthetic, also uses etc.

As the temperature of reaction of method in (ii), be preferably 0 ℃～180 ℃, more preferably 10 ℃～150 ℃.As the reaction time, be preferably 0.5 hour～20 hours, more preferably 1 hour～8 hours.Reaction conditions is controlled in the above-mentioned scope, and the dehydration closed-loop reaction can be carried out fully, and in addition, the molecular weight of the polyimide of gained can suitableization.

Method obtains containing the reaction solution of polyimide in (ii).This reaction solution can former state be supplied in the preparation of aligning agent for liquid crystal (A); Also can, reaction solution resupply in the preparation of aligning agent for liquid crystal (A) after removing dewatering agent and dehydration closed-loop catalyzer; Resupply in the preparation of aligning agent for liquid crystal (A) after perhaps separating polyimide, or resupply in the preparation of aligning agent for liquid crystal (A) behind the polyimide after refining the separation.As the method for removing dewatering agent and dehydration closed-loop catalyzer from reaction solution, for example can enumerate the method for solvent exchange etc.As the separation method and the process for purification of polyimide, for example have with the separation method of polyamic acid and process for purification in the same method enumerated etc.

[other polysiloxane]

Aligning agent for liquid crystal (A) also can contain other polysiloxane except polyorganosiloxane compounds (A).That selects in the group that other polysiloxane preferably are made up of the condensation product of polysiloxane, its hydrolysate and its hydrolysate of above-mentioned formula (5) expression is at least a.In addition; When aligning agent for liquid crystal (A) contains other polysiloxane; The major part of other polysiloxane can be that relative polyorganosiloxane compounds (A) has an independent existence, also can its part to exist with the condensation product of polyorganosiloxane compounds (A).

X in the above-mentioned formula (5) ¹And Y ¹Can enumerate:

As the alkyl of carbon number 1～20, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive lauryl, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc. for example can have been enumerated;

As the alkoxy of carbon number 1～16, for example methoxyl, ethoxy etc. can have been enumerated;

As the aryl of carbon number 6～20, for example can enumerate phenyl etc.

Other polysiloxane; For example can be through preferably in appropriate organic solvent; At least a silane compound of selecting in the group that hydrolysis or hydrolytic condensation are made up of alkoxysilane compound containing trialkylsilyl group in molecular structure and halogenated silanes compound in the presence of water and catalyzer (below, be called " raw silicon hydride compounds ") comes synthetic.

As the raw silicon hydride compounds that can use, tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane for example can have been enumerated here; Tetrachloro silicane; Methyl trialkoxysilane such as MTMS, MTES; Methyl triaryl TMOSs such as methyl triple phenoxyl silane; Methyl trichlorosilane; Ethyl trialkoxy silanes such as ethyl trimethoxy silane; Phenyl such as phenyltrimethoxysila,e, phenyl triethoxysilane trialkoxy silane; Phenyl trichlorosilane; Dimethyl such as dimethyldimethoxysil,ne, dimethyldiethoxysilane dialkoxy silicane; Dimethyldichlorosilane; Trimethyl alkoxy silanes such as trimethyl methoxy silane, trimethylethoxysilane; Trimethyl chlorosilane etc.In them, preferred tetramethoxy-silicane, tetraethoxysilane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethyl methoxy silane, trimethylethoxysilane.

When synthesizing other polysiloxane, the arbitrarily used organic solvent of ability for example can have been enumerated alkanol compound, ketonic compound, amide compound or ester compounds or other aprotic compounds.These compounds can use separately with each solvated compounds or two or more combination is used.

As the alkanol compound, for example can enumerate:

Single alkanol compounds such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol;

Monoethylene glycol, 1,2-propylene glycol, 1,3 butylene glycol, pentanediol-2; 4,2 hexylene glycol-2,4, hexanediol-2,5, heptandiol-2; 4, multivalence alkanol compounds such as 2-ethohexadiol-1,3, diethylene glycol, DPG, triethylene glycol, tripropylene glycol;

Glycol monoethyl ether; Ethylene glycol monoethyl ether; Ethylene glycol ether; Ethylene glycol monobutyl ether; Ethylene glycol ether; Ethyleneglycol monophenylether; Glycol monomethyl-2-b-butyl ether; Diethylene glycol monomethyl ether; Diethylene glycol monoethyl ether; Diethylene glycol monopropyl ether; Diethylene glycol monobutyl ether; The diethylene glycol monohexyl ether; Propylene glycol monomethyl ether; Dihydroxypropane single-ether; Propylene glycol monopropyl ether; Propylene glycol monobutyl ether; Dipropylene glycol monomethyl ether; DPG list ether; The part ether of multivalence alkanol compounds such as DPG list propyl ether etc.

As ketonic compound, acetone, MEK, methyl-positive acetone, methyl-single ketones compounds such as positive butanone for example can have been enumerated; Diacetone, 2,4-acetyl butyryl, 2,4-heptadione, 3,5-heptadione, 2, beta-diketone compounds such as 4-acetyl caproyl etc.

As above-mentioned amide compound; Formamide, N-NMF, N for example can have been enumerated; Dinethylformamide, acetamide, N-methylacetamide, N; N-dimethyl acetamide, N-ethyl acetamide, N, N-diethyl acetamide, N-carbonyl pyrrolidine, N-acetyl group morpholine, N-acetyl group piperidines, N-acetyl-pyrrolidine etc.

As ester compounds, diethyl carbonate, ethylene carbonate, carbonic allyl ester, diethyl carbonate, methyl carbonate, ethyl acetate, gamma-butyrolacton, gamma-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, benzyl acetate, cyclohexyl acetate, acetic acid methyl cyclohexane ester, acetic acid ester in the positive ninth of the ten Heavenly Stems, acetyl methyl carbonate, ethyl acetoacetate, acetic acid glycol monoethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid dihydroxypropane single-ether, acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol monobutyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid DPG list ether, ethylene diacetate, acetic acid methoxyl three second diester esters, ethyl propionate, n-butyl propionate, isoamyl propionate, diethy-aceto oxalate, oxalic acid di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid n-pentyl ester, diethyl malonate, repefral, diethyl phthalate etc. for example can have been enumerated.

As other aprotic compounds; For example acetonitrile, dimethyl sulfoxide (DMSO), N can have been enumerated; N; N ', N '-tetraethyl sulfonamide, HPT, N-methylmorpholine, N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrrolin, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-methylimidazole, N-methyl-4-piperidones, N-methyl-2-piperidones, N-N-methyl-2-2-pyrrolidone N-, 1; 3-dimethyl-2-imidazolone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.In these solvents, the part ether or the ester compounds of preferred especially multivalence alkanol compound, multivalence alkanol compound.

The employed water yield during as synthetic other polysiloxane; 1 mole of the alkoxy that has with respect to the raw silicon hydride compounds and the total amount of halogen atom; Be preferably 0.01 mole～100 moles, more preferably 0.1 mole～30 moles, and then be preferably 1 mole～1.5 moles.

As the catalyzer that can when synthesizing other polysiloxane, use, for example metallo-chelate, organic acid, mineral acid, organic base, ammonia, alkali metal compound etc. can have been enumerated.

As above-mentioned metallo-chelate, tri-alkoxy list (acetopyruvic acid) titaniums such as triethoxy list (acetopyruvic acid) titanium for example can have been enumerated; Two (acetopyruvic acid) titaniums of dialkoxy such as two (acetopyruvic acid) titaniums of diethoxy; Monoalkoxy three (acetopyruvic acid) titaniums such as monosubstituted ethoxy three (acetopyruvic acid) titanium; Four (acetopyruvic acid) titanium; Tri-alkoxy list (oacetic acid) titaniums such as triethoxy list (oacetic acid) titanium; Two (oacetic acid) titaniums of dialkoxy such as two (oacetic acid) titaniums of diethoxy; Monoalkoxy three (oacetic acid) titaniums such as monosubstituted ethoxy three (oacetic acid) titanium; Four (oacetic acid) titanium; The two or more titanium chelates such as titanium compound that contain cheland such as single (acetopyruvic acid) three (oacetic acid) titanium, two (acetopyruvic acids) two (oacetic acid) titanium, single (oacetic acid) titanium of three (acetopyruvic acids);

Tri-alkoxy list (acetopyruvic acid) zirconiums such as triethoxy list (acetopyruvic acid) zirconium; Two (acetopyruvic acid) zirconiums of dialkoxy such as two (acetopyruvic acid) zirconiums of diethoxy; Monoalkoxy three (acetopyruvic acid) zirconiums such as monosubstituted ethoxy three (acetopyruvic acid) zirconium; Four (acetopyruvic acid) zirconium; Tri-alkoxy list (oacetic acid) zirconiums such as triethoxy list (oacetic acid) zirconium; Two (oacetic acid) zirconiums of dialkoxy such as two (oacetic acid) zirconiums of diethoxy; Monoalkoxy three (oacetic acid) zirconiums such as monosubstituted ethoxy three (oacetic acid) zirconium; Four (oacetic acid) zirconium; The two or more zirconium chelates such as zirconium compounds that contain cheland such as single (acetopyruvic acid) three (oacetic acid) zirconium, two (acetopyruvic acids) two (oacetic acid) zirconium, single (oacetic acid) zirconium of three (acetopyruvic acids);

Aluminium chelate compounds such as three (acetopyruvic acid) aluminium, three (oacetic acid) aluminium etc.

As above-mentioned organic acid, for example aliphatics saturated carboxylic acids such as formic acid, acetic acid, propionic acid can have been enumerated; Aliphatics such as malonic acid, fumaric acid unsaturated carboxylic acid; Aromatic carboxylic acids such as salicylic acid, benzoic acid, phthalic acid; Aromatic sulphonic acid such as p-toluenesulfonic acid, benzene sulfonic acid; Halogen-containing carboxylic acids such as monochloro acetic acid, trichloroacetic acid, trifluoracetic acid; Citric acid, tartrate etc.

As above-mentioned mineral acid, for example hydrochloric acid, nitric acid, sulfuric acid, hydrofluorite, phosphoric acid etc. can have been enumerated.

As above-mentioned organic base, pyridine, pyrroles, piperazine, pyrrolidine, piperidines, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicylo undecylene, tetramethyl-ammonium oxyhydroxide etc. for example can have been enumerated.

As above-mentioned alkali metal compound, for example NaOH, potassium hydroxide, baryta hydrate, calcium hydroxide etc. can have been enumerated.These catalyzer can use separately or two or more combination is used.

In these catalyzer, be preferably metallo-chelate, organic acid, mineral acid.As metallo-chelate, titanium chelate more preferably.

The use amount of catalyzer is preferably 0.001 mass parts～10 mass parts with respect to 100 mass parts raw silicon hydride compounds, more preferably 0.001 mass parts～1 mass parts.

Catalyzer can add in the solution that has dissolved silane compound in the raw silicon hydride compounds or in organic solvent in advance, or the dissolving or be distributed in the water of interpolation.

The water that when synthesizing other polysiloxane, adds can be discontinuously or is added to continuously in the solution that has dissolved silane compound in the raw silicon hydride compounds or in organic solvent.

Temperature of reaction during as synthetic other polysiloxane is preferably 0 ℃～100 ℃, more preferably 15 ℃～80 ℃.Reaction time is preferably 0.5 hour～and 24 hours, more preferably 1 hour～8 hours.

When aligning agent for liquid crystal (A) contains polyorganosiloxane compounds (A) and other polymkeric substance,,, be preferably below 10,000 mass parts with respect to 100 mass parts polyorganosiloxane compounds (A) as the amount of other polymkeric substance.The preferred amount of other polymkeric substance is according to the kind of other polymkeric substance and difference.

When aligning agent for liquid crystal (A) contains polyorganosiloxane compounds (A) and polymkeric substance (B); As both preferred usage ratios; With respect to 100 mass parts polyorganosiloxane compounds (A), the total amount of polymkeric substance (B) is preferably 100 mass parts～5,000 mass parts; 200 mass parts～3,000 mass parts more preferably.

On the other hand; When aligning agent for liquid crystal (A) contains polyorganosiloxane compounds (A) and other polysiloxane; Both preferred usage ratios are generally 5 mass parts～2,000 mass parts as the amount of other polysiloxane for 100 mass parts polyorganosiloxane compounds (A); Be preferably 100 mass parts～2,000 mass parts.

When aligning agent for liquid crystal (A) contains polyorganosiloxane compounds (A) and other polymkeric substance, as other polymkeric substance, preferred polymers (B) or other polysiloxane.

< other compositions >

Aligning agent for liquid crystal (A) is in the scope of not damaging effect of the present invention; Other compositions such as compound (below, be called " epoxy compound "), functional silanes compound, surfactant that also can contain hardening agent, curing catalysts, curing accelerator, in molecule, have at least one epoxy radicals.

[hardening agent, curing catalysts and curing accelerator]

Hardening agent and curing catalysts can be included in the aligning agent for liquid crystal (A) for the more firm purpose of cross-linking reaction that makes polyorganosiloxane compounds (A).Curing accelerator can be included in the aligning agent for liquid crystal (A) for the purpose that promotes the curing reaction that hardening agent is taken charge of.

As hardening agent, can use normally used hardening agent in the curing of curable compound with epoxy radicals or the solidification compound of the compound that includes epoxy radicals.As such hardening agent, for example polyamine, polybasic acid anhydride, polybasic carboxylic acid can have been enumerated.

As polyvalent carboxylic acid's acid anhydride, cyclohexane tricarboxylic acid anhydride and other polybasic acid anhydrides for example can have been enumerated.

As the cyclohexane tricarboxylic acid anhydride, for example can enumerate cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride, cyclohexane-1,3,5-tricarboxylic acids-3,5-acid anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydrides etc.As other polybasic acid anhydrides; For example normally used tetracarboxylic dianhydride in the compound of 4-methyl tetrahydrophthalic anhydride, methyl norbornene dioic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, following formula (6) expression, polyamic acid synthetic also has α-terpinene, alloocimene etc. to have ester ring type compound and the maleic anhydride Diels-Alder reaction product and their hydrogenation products etc. of conjugated double bond in addition.

In the above-mentioned formula (6), x is 1～20 integer.

As curing catalysts, antimony hexafluoride compound, phosphorus hexafluoride compound, praseodynium acid aluminium etc. for example can have been enumerated.These catalyzer can be the catalyzer of the cationic polymerization of the epoxy radicals of carrying out through heating.

As above-mentioned curing accelerator, for example can enumerate imidazolium compounds; Quaternary phosphonium compound; Quaternary ammonium compound; 1, diazabicylo alkenes such as 8-diazabicylo [5.4.0] undecylene-7 or its acylate; Organometallicss such as zinc octoate, tin octoate, aluminium acetylacetonate complex; Boron compounds such as boron trifluoride, boric acid triphenyl; Metal halide such as zinc chloride, tin chloride; High-melting-point decentralized potentiality curing accelerators such as amine add-on type promoter such as the addition product of dicyandiamide, amine and epoxy resin; The microcapsule-type potentiality curing accelerator that surface such as quaternary alkylphosphonium salt covers with polymkeric substance; Amine salt type potentiality curing accelerator; The hot cationic polymerization type potentiality curing accelerator of high temperature dissociative types such as lewis acid, Bronsted hydrochlorate etc.

[epoxy compound]

From improving the liquid crystal orientation film that forms the cementability of substrate surface is considered, can in aligning agent for liquid crystal (A), be contained above-mentioned epoxy compound.

As epoxy compound, preferred ethylene glycol bisthioglycolate glycidyl ether, polyglycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1; 3,5,6-four glycidyl group-2,4-hexanediol, N; N, N ', N '-four glycidyl group-m-xylene diamine, 1; Two (N, the N-diglycidyl amino methyl) cyclohexanes of 3-, N, N; N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N; N ,-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl cyclohexane.

Aligning agent for liquid crystal (A) is when containing epoxy compound; Its content ratio is for total 100 mass parts of above-mentioned [A] polyorganosiloxane compounds and arbitrarily used other polymkeric substance; Be preferably 0.01 mass parts～40 mass parts, more preferably 0.1 mass parts～30 mass parts.

In addition, aligning agent for liquid crystal (A) in order to make this cross-linking reaction more efficient, can be used in combination base catalysts such as 1 benzyl 2 methyl imidazole when containing epoxy compound.

[functional silanes compound]

The functional silanes compound can be for the cementability of the liquid crystal orientation film that improves acquisition and substrate and is used.As the functional silanes compound; 3-TSL 8330,3-aminopropyltriethoxywerene werene, 2-TSL 8330,2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1 for example can have been enumerated; 4; 7-three azepine decane, 10-triethoxysilyl-1; 4; 7-three azepine decane, 9-trimethoxysilyl-3; 6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3; 6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, two (the oxyethylene group)-3-TSL 8330s of N-, two (the oxyethylene group)-3-aminopropyl triethoxies of N-, 3-glycidoxypropyltrime,hoxysilane, 2-(3; 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc., and the tetracarboxylic dianhydride who puts down in writing in the japanese kokai publication sho 63-291922 communique and reactant etc. with amino silane compound.

When aligning agent for liquid crystal (A) contained the functional silanes compound, its content ratio was preferably below 50 mass parts, more preferably below 20 mass parts for above-mentioned [A] polyorganosiloxane compounds and arbitrarily used other polymkeric substance add up to 100 mass parts.

[surfactant]

As surfactant, non-ionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, polysiloxane surfactant, polyoxyalkylene surfactant, fluorochemical surfactant etc. for example can have been enumerated.

Aligning agent for liquid crystal (A) is when containing surfactant, and its content ratio is all with respect to 100 mass parts aligning agent for liquid crystal (A), is preferably below 10 mass parts, more preferably below 1 mass parts.

< preparation method of aligning agent for liquid crystal (A) >

Aligning agent for liquid crystal (A) contains [A] component of polymer as necessary composition as stated, can contain other optional members as required, but preferably each composition is dissolved in the solution shape composition of processing in the organic solvent.

As the organic solvent that can be used to prepare aligning agent for liquid crystal (A), preferably can dissolve [A] component of polymer and arbitrarily used other compositions but not with the solvent of its reaction.Can be preferred for organic solvent in the aligning agent for liquid crystal (A) according to the kind of other polymkeric substance that add arbitrarily and difference.

When aligning agent for liquid crystal (A) contains [A] component of polymer and polymkeric substance (B), as preferred organic, can enumerate as use in the synthesizing polyamides acid like the above-mentioned organic solvent of enumerating.At this moment, also can be used in combination the poor solvent of enumerating as using in the synthetic polyamic acid of the present invention.These organic solvents can use in independent or two or more combinations.

On the other hand; When [A] component of polymer of aligning agent for liquid crystal (A) only contains polyorganosiloxane compounds (A); Or preferred organic when containing polyorganosiloxane compounds (A) and other polysiloxane, for example can enumerate 1-ethoxy-2-propyl alcohol, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, DPG ether, DPG propyl ether, DPG dimethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (butyl cellosolve), glycol monomethyl amyl ether, ethylene glycol ether, diethylene glycol, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic acid esters, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl group carbitol, BC, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, benzyl acetate, the just own ester of acetic acid, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate etc.In them, preferred n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid.

The preferred solvent that uses uses other polymkeric substance and its kind according to having or not in the preparation of aligning agent for liquid crystal (A), and more than one that can make up above-mentioned organic solvent obtain.Such solvent is that under following preferred solid component concentration, can not make each that contain in the aligning agent for liquid crystal (A) become to analyze and to make the surface tension of aligning agent for liquid crystal (A) be the solvent of 25～40mN/m scope.

The solid component concentration of aligning agent for liquid crystal (A), be beyond desolventizing in the aligning agent for liquid crystal (A) all the quality of the compositions ratio that accounts for aligning agent for liquid crystal (A) gross mass consider viscosity, volatility etc. and select, be preferably the scope of 1 quality %～10 quality %.Aligning agent for liquid crystal (A) is coated on the substrate surface, forms filming that liquid crystal orientation film constitutes, but solid component concentration when 1 quality % is above, it is too little that this thickness of filming can not become, and can obtain good liquid crystal orientation film.On the other hand, solid component concentration is 10 quality % when following, and the good liquid crystal orientation film that the thickness that can obtain to suppress to film becomes excessive in addition, can also prevent that the viscosity of aligning agent for liquid crystal (A) from increasing, and obtains good coating characteristics.The method that the scope of preferred especially solid component concentration adopts during according to coating of liquid crystalline alignment agent (A) on substrate and difference.Be preferably the scope of 1.5 quality %～4.5 quality % during for example with spin-coating method especially.When using print process, solid component concentration is controlled at the scope of 3 quality %～9 quality %, and solution viscosity is preferred especially in the scope of 12mPas～50mPas thus.When using ink-jet method, solid component concentration is controlled at the scope of 1 quality %～5 quality %, and solution viscosity is preferred especially in the scope of 3mPas～15mPas thus.Temperature during preparation aligning agent for liquid crystal (A) is preferably 0 ℃～200 ℃, more preferably 0 ℃～40 ℃.

[embodiment]

Below, embodiments of the invention more specifically are described, but are the invention is not restricted to these embodiment.

The polysiloxane with epoxy radicals that obtains among the following embodiment is the value of measuring through the GPC method of following method by polystyrene conversion with the weight-average molecular weight (Mw) of [A] polyorganosiloxane compounds.

Post: eastern ソ one manufactured, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf/cm ²

In addition, starting compound that uses among the following embodiment and polymer loading will guarantee to repeat as required the synthetic of starting compound and polymkeric substance under the synthetic scale shown in the following synthetic example.

< synthesizing of specific carboxylic acid >

[synthesizing of specific carboxylic acid 1]

According to the synthetic specific carboxylic acid 1 of reactions route.

[synthetic example 1]

In having the 500mL three-neck flask of condenser pipe, add 4-cyanic acid-4 '-xenol 6.3g, 11-bromine methyl undecylate 10g, sal tartari 14.2g, N, dinethylformamide 200mL was 160 ℃ of following heated and stirred 5 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is put in the 500mL water, mixed and stir.The white solid that filtration is separated out, water cleans again.The solid that obtains obtains 11g compound 1 80 ℃ of following vacuum drying.

[synthetic example 2]

Then, in having the 200mL three-neck flask of condenser pipe, add 10g compound 1, lithium hydroxide monohydrate 1.6g, methyl alcohol 30mL, water 15mL, 80 ℃ of following heated and stirred 4 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is under the stirring, in reaction solution, slowly drips watery hydrochloric acid.The solid that filtration is separated out, water, ethanol clean successively.The solid that obtains obtains the specific carboxylic acid 1 of 8g 80 ℃ of following vacuum drying.

[synthesizing of specific carboxylic acid 2]

According to the reactions route, synthetic specific carboxylic acid 2.

[synthetic example 3]

In having the 500mL three-neck flask of condenser pipe, add 4-cyanic acid-4 '-xenol 15g, ethylene carbonate 13.5g, bromination tetrabutylammonium (TBAB) 2.5g, N, dinethylformamide 300mL was 150 ℃ of following heated and stirred 9 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is with mixed solution separating liquid and the cleaning of ethyl acetate 300mL, 1N-sodium hydrate aqueous solution 100mL.After extracting organic layer, use 1N-sodium hydrate aqueous solution 100mL, water 100mL separating liquid and cleaning more successively.Organic layer with dried over mgso after, distillate organic solvent.Behind the solid that vacuum drying obtains,, obtain 13.1g compound 2 with ethanol 100mL/ hexane 250mL crystallization again.

[synthetic example 4]

In having the 200mL three-neck flask of condenser pipe, tap funnel, add 12g compound 2,12.7g4-chlorobenzene sulfonyl chloride, the 60mL methylene chloride that dewater, mixing.Under the state with the ice bath cooled reaction solution, dripped dehydration methylene chloride (10mL) solution of 6.6g triethylamine through 10 minutes.Keep the ice bath state to stir 30 minutes, be returned to room temperature and stirred again 6 hours.Add chloroform 150mL at reaction solution, water 100mL carries out 4 separating liquids and cleaning.The organic layer that extracts is used dried over mgso, distillates organic solvent.The solid that obtains cleans with ethanol, obtains 16.1g compound 3.

[synthetic example 5]

In having the 300mL three-neck flask of condenser pipe, add 15g compound 3,4-Para Hydroxy Benzoic Acid methyl esters 11g, sal tartari 12.5g, N, dinethylformamide 180mL was 80 ℃ of following heated and stirred 9 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is put in the 500mL water, mixed and stir.The white solid that filtration is separated out cleans with ethanol again.The solid that obtains obtains 10g compound 4 80 ℃ of following vacuum drying.

[synthetic example 6]

In having the 100mL three-neck flask of condenser pipe, add 9.5g compound 4, lithium hydroxide monohydrate 1.6g, methyl alcohol 30mL, tetrahydrofuran 15mL, water 15mL, 80 ℃ of following heated and stirred 4 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is under the stirring, in reaction solution, slowly drips watery hydrochloric acid.The solid that filtration is separated out, water, ethanol clean successively.The solid that obtains obtains the specific carboxylic acid 2 of 9g 80 ℃ of following vacuum drying.

[synthesizing of specific carboxylic acid 3]

According to the reactions route, synthetic specific carboxylic acid 3.

[synthetic example 7]

In synthetic example 1, replace 4-cyanic acid-4 '-xenol, use 10.7g2,3,5,6-tetrafluoro-4-(pentafluorophenyl group) phenol, obtain 13.7g compound 5.

[synthetic example 8]

In synthetic example 2, replace compound 1, use 13.5g compound 5, obtain the specific carboxylic acid 3 of 11.2g.

[synthesizing of specific carboxylic acid 4]

According to the reactions formula, synthetic specific carboxylic acid 4.

[synthetic example 9]

In synthetic example 3, replace 4-cyanic acid-4 '-xenol, use 25.5g2,3,5,6-tetrafluoro-4-(pentafluorophenyl group) phenol, obtain 23.1g compound 6.

[synthetic example 10]

In synthetic example 4, replace compound 2, use 18.9g compound 6, obtain 24.1g compound 7.

[synthetic example 11]

In synthetic example 5, replace compound 3, use 20g compound 7, obtain 15.4g compound 8.

[synthetic example 12]

In synthetic example 6, replace compound 4, use 13g compound 8, obtain the specific carboxylic acid 4 of 11.4g.

[synthesizing of specific carboxylic acid 5]

According to the reactions route, synthetic specific carboxylic acid 5.

[synthetic example 13]

Synthetic the same with specific carboxylic acid 1, synthetic 15g becomes 5 specific carboxylic acid 5 with the methylene radix from 10.

[synthesizing of specific carboxylic acid 6]

According to the reactions route, synthetic specific carboxylic acid 6.

[synthetic example 14]

In having the 500mL three-neck flask of condenser pipe, add 2,2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol 10.1g, 11-bromine methyl undecylate 10g, sal tartari 14.2g, N, dinethylformamide 200mL was 160 ℃ of following heated and stirred 5 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is put in the 500mL water, mixed and stir.The white solid that filtration is separated out, water cleans again.The solid that obtains obtains 10.8g compound 9 80 ℃ of following vacuum drying.

[synthetic example 15]

Then, in having the 200mL three-neck flask of condenser pipe, add 10g compound 9, lithium hydroxide monohydrate 1.6g, methyl alcohol 30mL, water 15mL, 80 ℃ of following heated and stirred 4 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is under the stirring, in reaction solution, slowly drips watery hydrochloric acid.The solid that filtration is separated out, water, ethanol clean successively.The solid that obtains obtains the specific carboxylic acid 6 of 6g 80 ℃ of following vacuum drying.

[synthesizing of specific carboxylic acid 7]

According to the reactions route, synthetic specific carboxylic acid 7.

[synthetic example 16]

Except with 10.1g initial compounds (2,2 ', 3; 3 '-tetrafluoro-4 '-propyl group-4-xenol) changes into the 9.1g compound of putting down in writing in the above-mentioned reaction scheme (2; 3-two fluoro-4-(4-propyl group-cyclohexyl) phenol) in addition, synthetic the same with above-mentioned specific carboxylic acid 6 obtains the specific carboxylic acid 7 of 5.9g.

[synthesizing of specific carboxylic acid 8]

According to the reactions route, synthetic specific carboxylic acid 8.

[synthetic example 17]

Except with 10.1g initial compounds (2,2 ', 3; 3 '-tetrafluoro-4 '-propyl group-4-xenol) changes to the 12.9g compound of putting down in writing in the above-mentioned reaction scheme (2; 2 ', 3,3 '-tetrafluoro-4-propyl group-4 "-the hydroxyl terphenyl) in addition; synthetic the same with above-mentioned specific carboxylic acid 6 obtains the specific carboxylic acid 8 of 7.1g.

[synthesizing of specific carboxylic acid 9]

According to the reactions route, synthetic specific carboxylic acid 9.

[synthetic example 18]

Except with 10.1g initial compounds (2; 2 '; 3; 3 '-tetrafluoro-4 '-propyl group-4-xenol) changes to the 10.2g compound (2,3-two fluoro-4-(4-propyl group cyclohexyl methoxyl) phenol) put down in writing in the above-mentioned reaction scheme in addition, with the synthetic the same specific carboxylic acid 9 of 6.5g that obtains of above-mentioned specific carboxylic acid 6.

[synthesizing of specific carboxylic acid 10]

According to the reactions route, synthetic specific carboxylic acid 10.

[synthetic example 19]

Except with 10.1g initial compounds (2; 2 '; 3; 3 '-tetrafluoro-4 '-propyl group-4-xenol) changes to the 12.6g compound (2,3-two fluoro-4 '-(4-propyl group phenylethyl) biphenyl) put down in writing in the above-mentioned reaction scheme in addition, with the synthetic the same specific carboxylic acid 10 of 7.2g that obtains of above-mentioned specific carboxylic acid 6.

[synthesizing of specific carboxylic acid 11]

According to the reactions route, synthetic specific carboxylic acid 11.

[synthetic example 20]

Except 10.1g initial compounds (2,2 ', 3,3 '-tetrafluoro-4 '-propyl group-4-xenol) is changed to beyond the 14.2g compound of putting down in writing in the above-mentioned reaction scheme, with the synthetic the same specific carboxylic acid 11 of 7.6g that obtains of above-mentioned specific carboxylic acid 6.

[synthesizing of specific carboxylic acid 12]

According to the reactions route, synthetic specific carboxylic acid 12.

[synthetic example 21]

In having the 500mL three-neck flask of condenser pipe; Add 4-[difluoro (4-amyl group cyclohexyl) methoxyl]-2; 3-difluorophenol 12.5g, 11-bromine methyl undecylate 10g, sal tartari 14.2g, N, dinethylformamide 200mL was 160 ℃ of following heated and stirred 5 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is put in the 500mL water, mixed and stir.The white solid that filtration is separated out, water cleans again.The solid that obtains obtains 14.8g compound 10 80 ℃ of following vacuum drying.

[synthetic example 22]

Then, in having the 200mL three-neck flask of condenser pipe, add 10g compound 10, lithium hydroxide monohydrate 1.6g, methyl alcohol 30mL, water 15mL, 80 ℃ of following heated and stirred 4 hours.Behind TLC affirmation reaction terminating, with the reaction solution cool to room temperature.Reaction solution is under the stirring, in reaction solution, slowly drips watery hydrochloric acid.The solid that filtration is separated out, water, ethanol clean successively.The solid that obtains obtains the specific carboxylic acid 12 of 6g 80 ℃ of following vacuum drying.

< polysiloxane (polysiloxane precursor) synthetic>with epoxy radicals

[hydrolysis-condensation reaction]

[synthetic routine S-1]

In the reaction vessel that has stirrer, thermometer, tap funnel and reflux condensing tube, add 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane (ECETS) 100.0g, methylisobutylketone 500g and triethylamine 10.0g, at room temperature mix.Then, after dripping deionized water 100g in 30 minutes, the limit is mixed the limit and was reacted 6 hours down at 80 ℃ under refluxing with tap funnel.After reaction finishes, extract organic layer, after cleaning water after cleaning and be neutrality with 0.2 quality % aqueous ammonium nitrate solution, under reduced pressure distillate solvent and water, acquisition is as the polysiloxane S-1 with epoxy radicals of the transparency liquid of thickness.

Have the polysiloxane of epoxy radicals for this, carry out ¹H-NMR analyzes, and near chemical shift (δ)=3.2ppm, obtains the epoxy base peak of theoretical strength, confirms not cause in the reaction subsidiary reaction of epoxy radicals.The weight-average molecular weight (Mw) of the polysiloxane S-1 with epoxy radicals that wherein obtains is Mw=2,200, and epoxide equivalent is the 186g/ mole.

[synthetic routine S-2]

In the reaction vessel that has stirrer, thermometer, tap funnel and reflux condensing tube, add 2-(3 as water-disintegrable silane compound; 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane (ECETS) 73.9g and γ-methacryloxypropyl trimethoxy silane (GMPTS) 24.8g (ECETS: GMPTS=75: 25 (mol ratios)) and as the methylisobutylketone 500g of solvent with as the triethylamine 10.0g of catalyzer, at room temperature mix.Then, after dripping deionized water 100g in 30 minutes, the limit is stirred the limit and was reacted 6 hours down at 80 ℃ under refluxing with tap funnel.After the reaction end, extract organic layer, clean after the water after the cleaning is neutrality with 0.2 quality % aqueous ammonium nitrate solution, distillate solvent and water under the decompression, acquisition has the transparency liquid S-2 of the hydrolytic condensate thickness of epoxy radicals.

This hydrolytic condensate is carried out ¹H-NMR analyzes, and near chemical shift (δ)=3.2ppm, obtains the epoxy base peak of theoretical strength, confirms not cause in the reaction subsidiary reaction of epoxy radicals.The weight-average molecular weight (Mw) of the polysiloxane S-2 with epoxy radicals that wherein obtains is Mw=2,900.

[synthetic routine S-3]

In the reaction vessel that has stirrer, thermometer, tap funnel and reflux condensing tube, add 2-(3 as water-disintegrable silane compound; 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane (ECETS) 123.2g and γ-methacryloxypropyl trimethoxy silane (GMPTS) 124.2g (ECETS: GMPTS=50: 50 (mol ratios)) and as the methylisobutylketone 1250g of solvent with as the triethylamine 25.0g of catalyzer, at room temperature mix.Then, after dripping deionized water 250g in 45 minutes, the limit is stirred the limit and was reacted 6 hours down at 80 ℃ under refluxing with tap funnel.After reacting end, extract organic layer, clean after the water after the cleaning is neutrality with 0.2 quality % aqueous ammonium nitrate solution, through under reduced pressure distillating solvent and water, acquisition has the transparency liquid S-3 of the hydrolytic condensate thickness of epoxy radicals.

This hydrolytic condensate is carried out ¹H-NMR analyzes, and near chemical shift (δ)=3.2ppm, obtains the epoxy base peak of theoretical strength, confirms in reaction, not cause the subsidiary reaction of epoxy radicals.The weight-average molecular weight (Mw) of the polysiloxane S-3 with epoxy radicals that wherein obtains is Mw=3,200.

[synthetic routine S-4]

In the reaction vessel that has stirrer, thermometer, tap funnel and reflux condensing tube, add 2-(3 as water-disintegrable silane compound; 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane (ECETS) 88.7g and γ-methacryloxypropyl trimethoxy silane (GMPTS) 9.93g (ECETS: GMPTS=90: 10 (mol ratios)) and as the methylisobutylketone 500g of solvent with as the triethylamine 10.0g of catalyzer, at room temperature mix.Then, after dripping deionized water 100g in 30 minutes, the limit is stirred the limit and was reacted 6 hours down at 80 ℃ under refluxing with tap funnel.After reacting end, extract organic layer, clean after the water after the cleaning is neutrality with 0.2 quality % aqueous ammonium nitrate solution, under reduced pressure distillate solvent and water, acquisition has the thickness transparency liquid S-4 of the hydrolytic condensate of epoxy radicals.

This hydrolytic condensate is carried out ¹H-NMR analyzes, and near chemical shift (δ)=3.2ppm, obtains the epoxy base peak of theoretical strength, confirms in reaction, not cause the subsidiary reaction of epoxy radicals.The weight-average molecular weight (Mw) of the polysiloxane S-4 with epoxy radicals that wherein obtains is Mw=2,700.

< synthesizing of polyorganosiloxane compounds (A) >

[synthetic routine A-1]

Add at the 100mL three-neck flask that 9.8g that above-mentioned synthetic routine S-1 obtains has the specific carboxylic acid of the polysiloxane S-1 of epoxy radicals, 5.0g that methylisobutylketone 28g, above-mentioned synthetic routine 2 obtains 1,4-octyloxy benzoic acid (tilt angle composition 1) 3.3g and UCAT 18X (quaternary amine of the サ Application アプロ Co., Ltd.) 0.20g of formula (5-5) expression enumerated as one of compound of above-mentioned formula (5) expression, 80 ℃ of stirrings 12 hours down.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, obtains solution, after this solution washing 3 times, through distillating solvent, obtains the white powder of 14.5g polyorganosiloxane compounds A-1.The Mw of polyorganosiloxane compounds A-1 is 6,500.

[synthetic routine A-2]

Except replacing 4-octyloxy benzoic acid; 4-(the 4-amyl group cyclohexyl) benzoic acid (tilt angle composition 2) of formula (5-7) expression that one of compound that use 3.6g representes as above-mentioned formula (5) is enumerated in addition; With synthetic routine A-1 is the same operates, obtain the white powder of 13.4g polyorganosiloxane compounds A-2.The Mw of A-2 is 7,900.

[synthetic routine A-3]

In the 100mL three-neck flask; Add the 9.8g that obtains among the above-mentioned synthetic routine S-1 and have 4-(4-amyl group cyclohexyl) benzoic acid (the tilt angle composition 2) 1.4g and UCAT 18X (quaternary amine that the サ Application アプロ Co., Ltd. makes) 0.20g of the specific carboxylic acid of the 8.0g that obtains among the polysiloxane S-1, methylisobutylketone 28g, above-mentioned synthetic routine 2 of epoxy radicals 1, above-mentioned formula (5-7) expression, 80 ℃ of stirrings 12 hours down.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, and this solution distillates solvent after washing 3 times, obtains the white powder of 13.9g polyorganosiloxane compounds A-3.The Mw of A-3 is 8,900.

[synthetic routine A-4]

In the 100mL three-neck flask, add the 9.8g that obtains among the above-mentioned synthetic routine S-1 and have 4-(4-amyl group cyclohexyl) benzoic acid (the tilt angle composition 2) 5.8g and UCAT 18X (quaternary amine that the サ Application アプロ Co., Ltd. makes) 0.20g of the specific carboxylic acid of the 2.0g that obtains among the polysiloxane S-1, methylisobutylketone 28g, above-mentioned synthetic routine 2 of epoxy radicals 1, above-mentioned formula (5-7) expression, 80 ℃ of stirrings 12 hours down.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, obtains solution, and this solution distillates solvent after washing 3 times, obtains the white powder of 13.4g polyorganosiloxane compounds A-4.The Mw of A-4 is 7,600.

[synthetic routine A-5]

Except replacing specific carboxylic acid 1, use beyond the specific carboxylic acid 3 of 6.8g that obtains in the synthetic example 8, with synthetic routine A-1 is the same operates, obtain the white powder of 14.7g polyorganosiloxane compounds A-5.The Mw of A-5 is 8,100.

Silsesquioxane with acryloyl group is as follows,

(silsesquioxane) with acryloyl group

AC-SQ: " AC-SQ TA-100 ", East Asia Synesis Company makes.

[synthetic routine A-6]

[reaction] with silsesquioxane and nucleophilicity compound (mercaptan) of acryloyl group

In having the 500mL three-neck flask of stirrer and thermometer, add silsesquioxane AC-SQ TA-100 (East Asia is synthetic makes) 165.0g with acryloyl group, as dodecyl-1-mercaptan (DT) 40.5g (acryloyl group of AC-SQ) of nucleophilicity compound, as the acetonitrile 160mL of solvent with as the triethylamine 22.3g of catalyzer; Be warmed up to 50 ℃; Stirred 90 minutes, and implemented reaction.After reaction finishes, extract organic layer, clean after the water after the cleaning is neutrality, under reduced pressure distillate solvent and catalyzer, obtain the thickness transparency liquid of 205.0g polysiloxane A-6 with 0.2 quality % aqueous ammonium nitrate solution.It is 5,900 that this polysiloxane A-6 is used the weight-average molecular weight Mw of the polystyrene conversion of GPC mensuration.

[synthetic routine A-7]

[having the hydrolytic condensate of epoxy radicals and the reaction of carboxylic acid]

The hydrolytic condensate S-2 that the 80g that in the 200mL three-neck flask, obtains among the synthetic routine S-2 of adding has epoxy radicals; Adding is as the methylisobutylketone 25.0g of solvent, as 4-octyloxy benzoic acid (the tilt angle composition 1) 33.8g of carboxylic acid with as UCAT 18X (curing accelerator of the epoxy compound that the サ Application アプロ Co., Ltd. makes) 1.0g of catalyzer, stirs down at 100 ℃ and reacts in 48 hours.Reaction adds ethyl acetate after finishing in reaction mixture, the organic layer washing of acquisition 3 times after dried over mgso, distillates solvent, obtains 100.2g polysiloxane A-7.To this polysiloxane A-7, the weight-average molecular weight Mw of the polystyrene conversion of measuring with gel permeation chromatography (GPC) is 7,100.

[synthetic routine A-8]

In the 100mL three-neck flask, add the 9.8g that obtains among the above-mentioned synthetic routine S-1 and have succinic acid 5 ξ-cholestane-3-base (the tilt angle composition 3) 2.6g and UCAT 18X (quaternary amine that the サ Application アプロ Co., Ltd. makes) 0.20g of the specific carboxylic acid of the 8.0g that obtains among the polysiloxane S-1, methylisobutylketone 28g, above-mentioned synthetic routine 2 of epoxy radicals 1, above-mentioned formula (5-6) expression, 80 ℃ of stirrings 12 hours down.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, after this solution washing 3 times, distillates solvent, obtains the white powder of 15.5g polyorganosiloxane compounds A-8.The Mw of A-10 is 9,200.

[synthetic routine A-9]

In the 200mL three-neck flask, add the 80g that obtains among the synthetic routine S-2 have the hydrolytic condensate S-2 of epoxy radicals, as the specific carboxylic acid 1 of methylisobutylketone 25.0g, the 42.7g of solvent with as UCAT 18X (curing accelerator of the epoxy compound that the サ Application アプロ Co., Ltd. makes) 0.8g of catalyzer, stir down at 100 ℃ and to react in 48 hours.After reaction finishes, add ethyl acetate at reaction mixture, the organic layer washing of acquisition 3 times after dried over mgso, distillates solvent, obtains 98.2g polysiloxane A-9.To this polysiloxane A-9, the weight-average molecular weight Mw of the polystyrene conversion of measuring with gel permeation chromatography (GPC) is 8,100.

[synthetic routine A-10]

In the 200mL three-neck flask; Add the 80g that obtains among the synthetic routine S-2 have the hydrolytic condensate S-2 of epoxy radicals, as the 4-octyloxy benzoic acid (tilt angle composition 1) of the specific carboxylic acid 1 of the methylisobutylketone 25.0g of solvent, 42.7g, 28.2g with as UCAT 18X (curing accelerator of the epoxy compound that the サ Application アプロ Co., Ltd. makes) 1.7g of catalyzer, stir down at 100 ℃ and to react in 48 hours.Reaction adds ethyl acetate after finishing in reaction mixture, the organic layer washing of acquisition 3 times after dried over mgso, distillates solvent, obtains 125.7g polysiloxane A-10.To this polysiloxane A-10, the weight-average molecular weight Mw of the polystyrene conversion of measuring with gel permeation chromatography (GPC) is 10,200.

[synthetic routine A-11]

Except replacing 4-octyloxy benzoic acid (tilt angle composition 1) 28.2g, 4-(the 4-amyl group cyclohexyl) benzoic acid (tilt angle composition 2) that uses above-mentioned formula (5-7) expression is beyond the 30.9g, the same 128.5g polysiloxane A-11 that obtains with synthetic routine A-10.The weight-average molecular weight Mw of the polystyrene conversion that this polysiloxane A-11 is measured with gel permeation chromatography (GPC) is 11,500.

[synthetic routine A-12]

In the 200mL three-neck flask; Add the 60g that obtains among the synthetic routine S-3 have the hydrolytic condensate S-3 of epoxy radicals, as the specific carboxylic acid 2 of methylisobutylketone 20.0g, the 20.1g of solvent with as UCAT 18X (curing accelerator of the epoxy compound that the サ Application アプロ Co., Ltd. makes) 0.5g of catalyzer, stir down at 100 ℃ and to react in 48 hours.Reaction adds ethyl acetate after finishing in reaction mixture, the organic layer washing of acquisition 3 times after the use dried over mgso, distillates solvent, obtains 56.8g polysiloxane A-12.To this polysiloxane A-12, the weight-average molecular weight Mw of the polystyrene conversion of measuring with gel permeation chromatography (GPC) is 8,600.

[synthetic routine A-13]

In the 200mL three-neck flask, add the 60g that obtains among the synthetic routine S-3 have the hydrolytic condensate S-3 of epoxy radicals, as 4-(4-amyl group cyclohexyl) benzoic acid (the tilt angle composition 2) 12.3g of the specific carboxylic acid of methylisobutylketone 20.0g, the 11.1g of solvent 4, above-mentioned formula (5-7) expression with as UCAT 18X (curing accelerator of the epoxy compound that the サ Application アプロ Co., Ltd. makes) 0.6g of catalyzer, stir down at 100 ℃ and to react in 48 hours.Reaction adds ethyl acetate after finishing in reaction mixture, the organic layer washing of acquisition 3 times after dried over mgso, distillates solvent, obtains 55.9g polysiloxane A-13.To this polysiloxane A-13, the weight-average molecular weight Mw of the polystyrene conversion of measuring with gel permeation chromatography (GPC) is 8,300.

[synthetic routine A-14]

In the 100mL three-neck flask; Add the 10g that obtains among the above-mentioned synthetic routine S-4 and have specific carboxylic acid 5 of 4.35g and UCAT 18X (quaternary amine that the サ Application アプロ Co., Ltd. makes) 0.10g that obtains among the polysiloxane S-4, methylisobutylketone 20g, above-mentioned synthetic routine 13 of epoxy radicals, stirred 12 hours down at 80 ℃.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, obtains solution, after this solution washing 3 times, distillates solvent, obtains the white powder of 10.9g polyorganosiloxane compounds A-14.The Mw of polyorganosiloxane compounds A-14 is 6,400.

[synthetic routine A-15]

In the 100mL three-neck flask, add the 10g that obtains among the above-mentioned synthetic routine S-4 and have 4-(4-amyl group cyclohexyl) benzoic acid (the tilt angle composition 2) 1.54g and UCAT 18X (quaternary amine that the サ Application アプロ Co., Ltd. makes) 0.20g of the specific carboxylic acid of the 6.95g that obtains among the polysiloxane S-4, methylisobutylketone 20g, above-mentioned synthetic routine 13 of epoxy radicals 5, above-mentioned formula (5-7) expression, 80 ℃ of stirrings 12 hours down.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, obtains solution, after this solution washing 3 times, distillates solvent, obtains the white powder of 13.7g polyorganosiloxane compounds A-15.The Mw of polyorganosiloxane compounds A-15 is 7,700.

[synthetic routine A-16]

Except replacing 4-(4-amyl group cyclohexyl) the benzoic acid 1.54g of above-mentioned formula (5-7) expression; The succinic acid 5 ξ-cholestane-3-base (tilt angle composition 3) that uses above-mentioned formula (5-6) expression is beyond the 2.75g, with the same white powder that obtains 15.1g polyorganosiloxane compounds A-16 of synthetic routine A-15.The Mw of polyorganosiloxane compounds A-16 is 8,200.

[synthetic routine A-17]

In the 100mL three-neck flask, add the 10g that obtains among the above-mentioned synthetic routine S-4 and have the specific carboxylic acid of the 7.26g that obtains among the polysiloxane S-4, methylisobutylketone 20g, above-mentioned synthetic routine 8 of epoxy radicals 3,4-octyloxy benzoic acid (tilt angle composition 1) 3.52g and UCAT 18X (quaternary amine that サ Application アプロ Co., Ltd. makes) 0.20g, 80 ℃ of stirrings 12 hours down.Reaction precipitates with methyl alcohol after finishing again, and sediment is dissolved in the ethyl acetate, obtains solution, after this solution washing 3 times, distillates solvent, obtains the white powder of 15.8g polyorganosiloxane compounds A-17.The Mw of polyorganosiloxane compounds A-17 is 9,100.

[synthetic routine A-18]

Except replacing 4-octyloxy benzoic acid (tilt angle composition 1) 3.52g; 4-(the 4-amyl group cyclohexyl) benzoic acid (tilt angle composition 2) that uses above-mentioned formula (5-7) expression is beyond the 3.86g; The same with synthetic routine A-17, the white powder of acquisition 15.4g polyorganosiloxane compounds A-18.The Mw of polyorganosiloxane compounds A-18 is 8,900.

[synthetic routine A-19]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 6 of 6.17g that obtains in above-mentioned synthetic routine 15, with the same white powder that obtains 15.5g polyorganosiloxane compounds A-19 of synthetic routine A-17.The Mw of polyorganosiloxane compounds A-19 is 9,100.

[synthetic routine A-20]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 7 of 5.78g that obtains in above-mentioned synthetic routine 16, the same with synthetic routine A-17, the white powder of acquisition 15.3g polyorganosiloxane compounds A-20.The Mw of polyorganosiloxane compounds A-20 is 9,000.

[synthetic routine A-21]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 8 of 7.18g that obtains in above-mentioned synthetic routine 17, the same with synthetic routine A-17, the white powder of acquisition 15.6g polyorganosiloxane compounds A-21.The Mw of polyorganosiloxane compounds A-21 is 9,300.

[synthetic routine A-22]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 9 of 6.18g that obtains in above-mentioned synthetic routine 18, the same with synthetic routine A-17, the white powder of acquisition 15.2g polyorganosiloxane compounds A-22.The Mw of polyorganosiloxane compounds A-22 is 8,900.

[synthetic routine A-23]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 10 of 7.07g that obtains in above-mentioned synthetic routine 19, the same with synthetic routine A-17, the white powder of acquisition 15.8g polyorganosiloxane compounds A-23.The Mw of polyorganosiloxane compounds A-23 is 9,500.

[synthetic routine A-24]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 11 of 8.39g that obtains in above-mentioned synthetic routine 20, the same with synthetic routine A-17, the white powder of acquisition 15.6g polyorganosiloxane compounds A-24.The Mw of polyorganosiloxane compounds A-24 is 9,200.

[synthetic routine A-25]

Except replacing the specific carboxylic acid 3 of 7.26g, use beyond the specific carboxylic acid 12 of 7.02g that obtains in above-mentioned synthetic routine 22, the same with synthetic routine A-17, the white powder of acquisition 15.5g polyorganosiloxane compounds A-25.The Mw of polyorganosiloxane compounds A-19 is 9,100.

The synthetic result of above polyorganosiloxane compounds (A) gather with below table 1 in, this compound is not used in "-" in the table 1 expression.

[table 1]

Other manifesting property of tilt angle compounds in the above-mentioned table 1 are shown in following compound.In addition, use amount (mole %) is to use the mole % with respect to the Si atom in the polysiloxane precursor to represent.

Tilt angle composition 1:4-octyloxy benzoic acid

Tilt angle composition 2:4-(4-amyl group cyclohexyl) benzoic acid

Tilt angle composition 3: succinic acid 5 ξ-cholestane-3-base

< synthesizing of polymkeric substance (B) >

[synthetic routine P-1]

In the N-of 367.6g N-methyl-2-2-pyrrolidone N-, dissolve 1,2,3,4-cyclo-butane tetracarboxylic acid dianhydride 19.61g (0.1 mole) and 4,4 '-diamido-2,2 '-dimethyl diphenyl 21.23g (0.1 mole) at room temperature reacted 6 hours.Then, reaction mixture is injected excessive a lot of methyl alcohol, precipitation reaction product.Sediment is used washed with methanol, and under reduced pressure 40 ℃ were descended dry 15 hours, obtained 35g polyamic acid PA-1.

[synthetic routine P-2]

Dissolving 18.85g is as tetracarboxylic dianhydride's 2 in the 140gN-N-methyl-2-2-pyrrolidone N-; 3; 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 8.84g, reacted 4 hours down at 60 ℃ inferior aniline (p-Off エニレ Application アミ Application) as the diamines of following formula (G-4) expression of diamine compound and 7.31g.Measuring the viscosity of this polymer fluid, is 2,150mPas.Reaction solution is injected in excessive a lot of methyl alcohol the precipitation reaction product.Then, use washed with methanol, under reduced pressure 40 ℃ were descended dry 24 hours, obtained polyamic acid.The polyamic acid that obtains all is dissolved in the 465g N-N-methyl-2-2-pyrrolidone N-again; Add pyridine 6.65g and acetic anhydride 8.59g; Under 110 ℃, carried out dehydration closed-loop 4 hours; With above-mentioned the same, precipitate, cleaning, drying under reduced pressure, obtain the polyimide PI-1 of 23.1g imidizate rate 50%.

[synthetic routine P-3]

Dissolving is as tetracarboxylic dianhydride's 2 in the 200gN-N-methyl-2-2-pyrrolidone N-; 3; 5-tricarboxylic basic ring amyl group acetic acid dianhydride 24.94g, as the diamines 11.24g and 3 of the following formula (G-5) of diamine compound expression, 5-diamido benzoic acid 13.82g is 60 ℃ of reactions 4 hours down.Measuring the viscosity of this polymer fluid, is 1,400mPas.Reaction solution is injected excessive a lot of methyl alcohol, precipitation reaction product.Then, use washed with methanol,, obtain polyamic acid under reduced pressure in 40 ℃ of dryings 24 hours.All be dissolved in the polyamic acid that obtains in the 450gN-N-methyl-2-2-pyrrolidone N-again; Add pyridine 13.20g and acetic anhydride 17.04g; 110 ℃ of following dehydration closed-loops 4 hours, with above-mentionedly equally precipitate, cleaning, drying under reduced pressure, obtain the polyimide PI-2 of 27.8g imidizate rate 69%.

[synthetic routine P-4]

Dissolving is as tetracarboxylic dianhydride's 2 in the 200gN-N-methyl-2-2-pyrrolidone N-; 3; 5-tricarboxylic basic ring amyl group acetic acid dianhydride 23.06g, as 3 of diamine compound; The diamines 5.12g of the diamines 10.81g of 5-diamido benzoic acid 11.01g, above-mentioned formula (G-4) expression and above-mentioned formula (G-5) expression reacted 4 hours down at 60 ℃.Measuring the viscosity of this polymer fluid, is 1,300mPas.Reaction solution is injected excessive a lot of methyl alcohol, precipitation reaction product.Then, use washed with methanol,, obtain polyamic acid under reduced pressure in 40 ℃ of dryings 24 hours.All be dissolved in the polyamic acid that obtains in the 450gN-N-methyl-2-2-pyrrolidone N-again; Add pyridine 8.14g and acetic anhydride 10.50g; Under 110 ℃, carried out dehydration closed-loop 4 hours; With above-mentionedly equally precipitate, cleaning, drying under reduced pressure, obtain the polyimide PI-3 of 30.5g imidizate rate 55%.

< preparation of aligning agent for liquid crystal >

[embodiment 1]

As other polymkeric substance; Is a great deal of of 100 mass parts for the solution that contains polyamic acid PA-1 that obtains among the above-mentioned synthetic routine P-1 with the polyamic acid PA-1 that is converted into it and contains; Add the above-mentioned polyorganosiloxane compounds A-1 of 5 mass parts, the above-mentioned polyorganosiloxane compounds A-6 of 5 mass parts therein respectively; And then add N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve, processing solvent composition is the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=50: 50 (mass ratio), solid component concentration are the solution of 3.5 quality %.This solution filters with the filtrator of aperture 0.2 μ m, preparation aligning agent for liquid crystal E-1.

< manufacturing of liquid crystal cells and evaluation >

Use the aligning agent for liquid crystal of above-mentioned preparation, being described below changes the pattern (two kinds) and the ultraviolet irradiation amount (3 levels) of transparency electrode, makes totally 6 also evaluations of liquid crystal display cells.

[having the not manufacturing of the liquid crystal cells of the transparency electrode of patterning]

On the transparency electrode face of the glass substrate that has the transparency electrode that the ITO film constitutes, use spin-coating method to be coated with the aligning agent for liquid crystal E-1 of above-mentioned preparation; After carrying out 1 minute preheat on 80 ℃ the hot plate; In the constant temperature oven of nitrogen replacement; Heated 1 hour down at 200 ℃, form film (liquid crystal orientation film) of thickness 0.08 μ m.Repeat this operation, make a pair of (two) substrate with liquid crystal orientation film.

Film with respect to this, through with the strigil of roller, be pressed into length 0.1mm and carry out friction treatment with roller rotating speed 400rpm, platform translational speed 3cm/ second, fine hair with the rayon cloth of having reeled.Then, the ultrasonic that in ultrapure water, carried out 1 minute cleans, and then in 100 ℃ of cleaning constant temperature ovens, in dry 10 minutes, obtains to have the substrate of liquid crystal orientation film.Repeat this operation, obtain to have a pair of (two) substrate of liquid crystal orientation film.

Then, after being coated with the epoxy adhesive of the alumina balls that added diameter 5.5 μ m on the outer rim of the liquid crystal orientation film that one of above-mentioned a pair of substrate has, make the relative pressed and overlapped of liquid crystal aligning face cure adhesive.Then, by liquid crystal injecting port between a pair of substrate, fill nematic crystal (メ Le Network is made, MLC-6608) after, with acrylic compounds Photocurable adhesive sealing liquid crystal injecting port, manufacturing liquid crystal cells.

Repeat aforesaid operations, make 3 and have the not liquid crystal cells of the transparency electrode of patterning.The evaluation of 1 tilt angle of stating after carrying out same as before in them.To two remaining liquid crystal cells, respectively through following method behind irradiates light under the state that applies voltage between the ITO electrode, supply in the evaluation of tilt angle and voltage retention.

Two alternating voltage 10V that between the ITO electrode, apply frequency 60Hz respectively in the liquid crystal cells of above-mentioned acquisition to drive the state of liquid crystal, use the ultraviolet lamp of light source as metal halide lamp, and are ultraviolet with 10,000J/m ²Or 100,000J/m ²Exposure irradiation.In addition, this exposure is for using the value of measuring as the metraster of reference measurement with wavelength 365nm.

[evaluation of tilt angle]

Each liquid crystal cells to above-mentioned manufacturing; Respectively based on non-patent literature 2 (T.J.Scheffer et.al.; J.Appl.Phys.vo.48, p.1783 (1977)) and non-patent literature 3 (F.Nakano et.al., JPN.J.Appl.Phys.vo.19; P.2013 (1980)) in the method for record, the angle that the liquid crystal molecule of measuring through the crystallization rotary process of using He-Ne laser is tilted by real estate is as tilt angle.

The not liquid crystal cells of irradiates light, exposure 10,000J/m ²Liquid crystal cells and exposure 100,000J/m ²Liquid crystal cells tilt angle separately be shown in Table 2.

[evaluation of voltage retention]

To each liquid crystal cells of above-mentioned manufacturing, after applying the 5V voltage of 60 microseconds with 167 milliseconds span under 23 ℃, measure from removing the voltage retention after 167 milliseconds of the pressurizations.That determinator use Dongyang Mechanology Inc. makes, VHR-1.

Exposure 10,000J/m ²Liquid crystal cells and exposure 10,000J/m ²Liquid crystal cells voltage retention separately be shown in Table 2.

[the manufacturing (1) of liquid crystal cells] with transparency electrode of patterning

On each electrode surface of the glass substrate A of the ITO electrode that is a plurality of area dividing that has slit-shaped pattern shown in Figure 1 respectively and B, be coated with the aligning agent for liquid crystal E-1 of above-mentioned preparation through spin-coating method; Heating 1 minute (preheating) on 80 ℃ the hot plate except that after desolvating; In the constant temperature oven of nitrogen replacement, 200 ℃ of down heating 1 hour, form thickness 0.08 μ m film (liquid crystal orientation film).Repeat this operation, obtain to have a pair of (two) substrate of liquid crystal orientation film.

Then, after coating adds the epoxy adhesive of diameter 5.5 μ m alumina balls on the outer rim of the liquid crystal orientation film that one of above-mentioned a pair of substrate has, the relative pressed and overlapped of liquid crystal aligning face cure adhesive.Then, by liquid crystal injecting port between a pair of substrate, fill nematic crystal (メ Le Network is made, MLC-6608) after, with acrylic compounds Photocurable adhesive sealing liquid crystal injecting port, manufacturing liquid crystal cells.

Repeat aforesaid operations, make 3 liquid crystal cells with transparency electrode of patterning.The response speed evaluation of stating after 1 former state in them is supplied in.Remaining two liquid crystal cells and the same method during above-mentioned liquid crystal cells with patterned transparent electrode is made, under the state that applies voltage between conducting film with 10,000J/m ²Or 100,000J/m ²The exposure irradiates light after, supply in the evaluation of response speed.

In addition, electrode pattern used herein is the pattern with the electrode pattern identical type of PSA pattern.

[evaluation of response speed]

To each liquid crystal cells of above-mentioned manufacturing, do not apply earlier voltage, the irradiation visible lamp, with the luminance brightness of light multitester measuring through liquid crystal cells, this value conduct is transmitance 0% relatively.Then, between the electrode of liquid crystal cells, apply the alternating voltage 60V in 5 seconds, the transmitance and above-mentioned the same mensuration of this moment, this value is as relative transmitance 100%.

At this moment, when each liquid crystal cells is applied alternating voltage 60V, measure relative transmitance and change into for 90% time from 10%, this timing definition is a response speed, estimates.

The not liquid crystal cells of irradiates light, exposure 10,000J/m ²Liquid crystal cells and exposure 100,000J/m ²The response speed of liquid crystal cells be shown in Table 2 respectively.

[the manufacturing (2) of liquid crystal cells] with transparency electrode of patterning

Use the aligning agent for liquid crystal of above-mentioned preparation; Use has respectively with the glass substrate A of the ITO electrode of fishbone shape pattern shown in Figure 2 with beyond the B; The same with the manufacturing (1) of the liquid crystal cells of above-mentioned transparency electrode with patterning, make not liquid crystal cells, the exposure 10 of irradiates light, 000J/m ²Liquid crystal cells and exposure 100,000J/m ²Liquid crystal cells, respectively with the above-mentioned the same evaluation that is supplied in response speed in.Evaluation result is shown in Table 2.

[embodiment 2～34 and comparative example 1 and 2]

In the foregoing description 1; The kind of polymkeric substance (B) and polyorganosiloxane compounds (A) (composition 1 and the composition 2 that adds as required) and combined amount respectively as putting down in writing in the table 2 beyond; With the embodiment 1 the same aligning agent for liquid crystal for preparing, use this aligning agent for liquid crystal to make various liquid crystal cells and evaluation.Evaluation result is shown in Table 2.

[table 2]

Result by table 2 can know, in the method for the present invention, ultraviolet irradiation amount is with 100,000J/m ²(the value that adopts before the PSA type order.) degree of the tilt angle that obtains of irradiation be excessive, with 10,000J/m ²Or the tilt angle that following exposure obtains is more suitable.In addition, even exposure also can obtain fully fast response speed after a little while, and then voltage retention is also good.

Therefore, according to the method for the invention, can realize the advantage of PSA pattern with few rayed amount, and can make and compare the present fireballing liquid crystal display cells of PSA mode liquid crystal display element liquid crystal response.

Industrial applicibility

According to the present invention, can provide that a kind of visual angle is wide, the response speed of liquid crystal molecule is fast, the manufacturing approach of display characteristic and long-term reliability liquid crystal display device with excellent.

Symbol description

The 1:ITO electrode

2: slit portion

3: photomask.

Claims

1. the manufacturing approach of a liquid crystal display cells is characterized in that having following operation:

(1) use aligning agent for liquid crystal on this conducting film of a pair of substrate with conducting film, to form the operation of filming; This aligning agent for liquid crystal contains [A] component of polymer; This component of polymer has the group of the group that contains the polymerism carbon-carbon double bond and following formula (A1) expression in identical or different polymkeric substance

(2) will form above-mentioned a pair of substrate of filming and dispose, form the operation of liquid crystal cells with the said a pair of mode relative and the insertion liquid crystal layer of filming, and

(3) under the state that applies voltage between the conducting film to above-mentioned a pair of substrate, above-mentioned liquid crystal cells is carried out light-struck operation,

In the formula (A1), R ¹Be alkylidene, phenylene or the cyclohexylidene of methylene, carbon number 2～30, the hydrogen atom that these groups have partly or entirely can be substituted R ²Be the arbitrary linking group that comprises in two keys, triple bond, ehter bond, ester bond and the oxygen atom, R ³Be the group with at least two single ring architectures, a is 0 or 1.

2. like the manufacturing approach of liquid crystal display cells of record in the claim 1, wherein [A] component of polymer comprises the polymkeric substance that [A-1] has the group of the group that contains the polymerism carbon-carbon double bond and above-mentioned formula (A1) expression.

3. like the manufacturing approach of liquid crystal display cells of record in the claim 1, wherein [A] component of polymer comprises following two kinds of polymkeric substance: [A-2] has the polymkeric substance that the polymkeric substance that contains polymerism carbon-carbon double bond group and [A-3] have the group of above-mentioned formula (A1) expression.

4. like the manufacturing approach of liquid crystal display cells of record in claim 1, claim 2 or the claim 3, the R in the wherein above-mentioned formula (A1) ³By following formula (A2) expression,

In the formula (A2), R ⁴Be the heterocyclic radical of phenylene, biphenylene, naphthylene, cyclohexylidene, inferior dicyclohexyl, cyclohexylidene phenylene or divalence, the hydrogen atom that these groups have partly or entirely can be substituted R ⁵Be to comprise any one at least linking group in the alkylidene that substituent methylene and carbon number 2～10 can be arranged, two key, triple bond, ehter bond, ester bond and the heterocyclic radical, R ⁶For removing the group of (c+1) valency of (c+1) individual hydrogen atom from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexyl benzene or heterogeneous ring compound, the hydrogen atom that this group has partly or entirely can be substituted R ⁷Be hydrogen atom, cyanic acid, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl or alkoxy, b is 0 or 1, and c is 1～9 integer, and d is 1 or 2, R ⁴, R ⁵, R ⁷Respectively do for oneself a plurality of R when a plurality of with b ⁴, R ⁵, R ⁷With b each other can be identical or different.

5. like the manufacturing approach of the liquid crystal display cells of record in claim 1, claim 2 or the claim 3, wherein [A] component of polymer has the poly organo alkyl structure.

6. like the manufacturing approach of the liquid crystal display cells of record in claim 1, claim 2 or the claim 3, wherein [A] component of polymer further contains at least a polymkeric substance of selecting in the group that is made up of polyamic acid and polyimide.

7. liquid crystal display cells of making through the manufacturing approach of the liquid crystal display cells put down in writing in any one of claim 1～6.

8. aligning agent for liquid crystal, it contains [A] component of polymer, and this component of polymer has the group that contains the polymerism carbon-carbon double bond and the group of following formula (A1) expression in identical or different polymkeric substance,

In the formula (A1), R ¹Be alkylidene, phenylene or the cyclohexylidene of methylene, carbon number 2～30, the hydrogen atom that these groups have partly or entirely can be substituted R ²For comprising the arbitrary linking group in two keys, triple bond, ehter bond, ester bond and the oxygen atom, R ³For having the group of at least two single ring architectures, a is 0 or 1.