CN103080153A

CN103080153A - Polymerizable compound, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and method for producing liquid crystal display device

Info

Publication number: CN103080153A
Application number: CN2011800416242A
Authority: CN
Inventors: 樱叶汀丹尼尔安东尼; 松本欣也; 元山贤一; 后藤耕平; 芦泽亮一; 山之内洋一
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2010-06-30
Filing date: 2011-06-30
Publication date: 2013-05-01
Anticipated expiration: 2031-06-30
Also published as: WO2012002513A1; KR101912955B1; TWI564339B; TW201215640A; KR20130135822A; JP2015148827A; CN103080153B; JP5776908B2; JPWO2012002513A1; JP5967391B2

Abstract

Disclosed is a polymerizable compound represented by formula (1). In formula (1), V represents a single bond or -R1O-, wherein R1 represents a linear or branched alkylene group having 1 to 10 carbon atoms, and W represents a single bond or -OR2-, wherein R2 represents a linear or branched alkylene group having 1 to 10 carbon atoms.

Description

The manufacture method of polymerizable compound, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device and liquid crystal display device

Technical field

The present invention relates to the manufacture method of a kind of polymerizable compound, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device and liquid crystal display device, this polymerizable compound can be used for the manufacturing by the liquid crystal display device of the vertical orientation mode of making in the method for liquid crystal molecule being executed irradiation ultraviolet radiation under the alive state.

Background technology

Liquid crystal display device generally includes electrode and liquid crystal, is formed be used to the liquid crystal orientation film that makes liquid crystal aligning on this electrode.As the material of the liquid crystal aligning agent that is used to form this liquid crystal orientation film, the liquid crystal aligning mould material of the organics such as known polyimide and make organoalkoxysilane carry out polycondensation etc. and polysiloxane-based liquid crystal aligning mould material (with reference to patent documentation 1 and patent documentation 2).Display mode as such liquid crystal display device, the mode (being also referred to as vertical orientation mode) that makes the liquid crystal molecule response vertical orientated with respect to substrate by electric field is arranged, in this liquid crystal display device, while in its manufacturing processed, comprise the operation that liquid crystal molecule is applied the voltage irradiation ultraviolet radiation.

Liquid crystal display device about such vertical orientation mode, known following technology: in liquid-crystal composition, add in advance the optical polymerism compound, use together with the vertical alignment layer of polyimide etc., the liquid crystal structure cell while applying the voltage irradiation ultraviolet radiation, is accelerated the response speed (for example with reference to patent documentation 3, patent documentation 4 and non-patent literature 1) (PSA (polymer stabilizing orientation) type liquid-crystal display) of liquid crystal by this.Usually, the vergence direction of the liquid crystal molecule of response electric field shows with the controls such as slit on the electrode by being arranged on the projection on the substrate or being arranged on, but, it is said by in liquid-crystal composition, add the optical polymerism compound and to the liquid crystal structure cell while applying the voltage irradiation ultraviolet radiation, form the polymer architecture thing of the vergence direction of having remembered liquid crystal molecule at liquid crystal orientation film, so compare with the method for only controlling the vergence direction of liquid crystal molecule by projection and slit, the response speed of liquid crystal display device accelerates.

Also report, the optical polymerism compound is not added in the liquid-crystal composition, but be added in the liquid crystal orientation film, also can make the response speed of liquid crystal display device accelerate (SC-PVA type liquid-crystal display) (for example with reference to non-patent literature 2).

The prior art document

Patent documentation

Patent documentation 1: Japanese patent laid-open 09-281502 communique

Patent documentation 2: Japanese Patent Laid-Open 2005-250244 communique

Patent documentation 3: Japanese Patent Laid-Open 2003-307720 communique

Patent documentation 4: Japanese Patent Laid-Open 2004-302061 communique

Non-patent literature

Non-patent literature 1:K.Hanaoka, SID 04 DIGEST, P.1200-1202

Non-patent literature 2:K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

Summary of the invention

Invent technical problem to be solved

But, wish the further response speed of quickening liquid crystal display device.Although think the response speed that to accelerate liquid crystal display device by the addition that increases the optical polymerism compound, if but this optical polymerism compound does not react and remains in the liquid crystal, then become impurity (pollutent), therefore the reliability decrease that causes liquid crystal display device wishes to develop the polymerizable compound that can accelerate with less addition response speed.

Problem of the present invention is the problem that solves above-mentioned prior art, and polymerizable compound, liquid crystal aligning agent, liquid crystal orientation film and the liquid crystal display device of the response speed of the liquid crystal display device that can improve vertical orientation mode and the manufacture method of liquid crystal display device are provided.

The technical scheme that the technical solution problem adopts

The polymerizable compound of the present invention that solves above-mentioned problem is characterised in that, represents with following formula (1);

[changing 1]

In the formula (1), V is singly-bound or with-R ¹O-represents, R ¹Be the alkylidene group of the carbon number 1～10 of straight chain or branch, W is singly-bound or with-OR ²-expression, R ²It is the alkylidene group of the carbon number 1～10 of straight chain or branch.

Liquid crystal aligning agent of the present invention is characterised in that, comprises: described polymerizable compound, the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism, solvent.

The described polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism can comprise be selected from the polyimide precursor with the side chain that makes liquid crystal vertical-tropism and make this polyimide precursor imidization and polyimide at least a.

The described polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism can comprise the polysiloxane with the side chain that makes liquid crystal vertical-tropism.

Described polysiloxane better is to have the photoreactivity side chain.

Described polysiloxane better is to make at least a polysiloxane that carries out polycondensation and get that is selected from organoalkoxysilane and the condenses thereof.

Described organoalkoxysilane can comprise the organoalkoxysilane shown in the following formula (7).

R ¹¹Si(OR ¹²) ₃ (7)

R ¹¹The alkyl of the hydrogen atom carbon number 8～30 that can be replaced by fluorine atom, R ¹²The alkyl of expression carbon number 1～5.

Described organoalkoxysilane can comprise following formula (8).

R ¹³Si(OR ¹⁴) ₃ (8)

R ¹³The alkyl that at least a group that the expression hydrogen atom is selected from acryl, methacryloyl, vinyl, epoxy group(ing), vinyloxy group and acryloxy has replaced, R ¹⁴The alkyl of expression carbon number 1～5.

Liquid crystal orientation film of the present invention is characterised in that, obtains by described liquid crystal aligning agent is coated substrate and burnt till.

Liquid crystal display device of the present invention is characterised in that to have the liquid crystal structure cell, while this liquid crystal structure cell is to make in the liquid crystal or contain described polymerizable compound in the liquid crystal orientation film, it is applied the voltage irradiation ultraviolet radiation and the liquid crystal structure cell made.

The manufacture method of liquid crystal indicator of the present invention is characterised in that, makes in the liquid crystal or contains described polymerizable compound in the liquid crystal orientation film, makes the liquid crystal structure cell while it is applied the voltage irradiation ultraviolet radiation.

The effect of invention

By the present invention, can provide the novel polymerizable compounds of the response speed of the liquid crystal display device that can improve vertical orientation mode.And, by using this polymerizable compound, can provide the liquid crystal display device of the vertical orientation mode of fast response time.And, even in the situation that the addition of the polymerizable compound in this liquid crystal aligning agent is few or the ultraviolet irradiation amount is few, also can improve fully response speed.

The mode that carries out an invention

Below, the present invention is described in detail.

Polymerizable compound of the present invention represents with following formula (1).In the following formula (1), V is singly-bound or with-R ¹O-represents, R ¹Being the alkylidene group of the carbon number 1～10 of straight chain or branch, better is with-R ¹O-represents, R ¹It is the alkylidene group of the carbon number 2～6 of straight chain or branch.W is singly-bound or with-OR ²-expression, R ²Being the alkylidene group of the carbon number 1～10 of straight chain or branch, better is with-OR ²-expression, R ²It is the alkylidene group of the carbon number 2～6 of straight chain or branch.The structure of V and W can be the same or different, and is if the same easily synthetic.

Polymerizable compound shown in this following formula (1) is the compound that two ends have the ad hoc structure of polymerizable group alpha-methylene-gamma-butyrolactone base, therefore polymkeric substance is firm structure, the orientation immobilization ability of liquid crystal is excellent, so shown in following embodiment, the manufacturing of the liquid crystal display device by being used for the vertical orientation modes such as PSA type liquid-crystal display or SC-PVA type liquid-crystal display can significantly improve response speed.Among the present invention, the polymerizable group that two ends have must be the alpha-methylene-gamma-butyrolactone base, if such as the compound with polymerizable groups such as acrylate-based, methacrylate based, vinyl, vinyloxy group, epoxy group(ing) of record in the patent documentation 1, then by a small amount of interpolation as the compound shown in the following formula of the present invention (1), it is the response speed that can't significantly improve the liquid crystal display device of vertical orientation mode.And, in general, in the forming process of liquid crystal orientation film, comprise the operation of at high temperature burning till in order to remove solvent fully, but the compound with polymerizable groups such as acrylate-based, methacrylate based, vinyl, vinyloxy group, epoxy group(ing) lacks thermostability, is difficult to burning till under the withstand high temperatures.On the other hand, the polymerizable compound shown in the following formula of the present invention (1) is the poor structure of thermopolymerization, therefore is enough to withstand high temperatures, for example is enough to tolerate the firing temperature more than 200 ℃.

Polymerizable compound of the present invention shown in such following formula (1) can be by Synthetic Organic Chemistry the combination of method synthesize, its synthesis method is not particularly limited.Such as can by represent with following reaction formula, by Talaga etc. at P.Talaga, M.Schaeffer, C.Benezra and J.L.Stampf, Synthesis, the methods that propose in 530 (1990) are used SnCl ₂Make 2-(brooethyl) vinylformic acid (2-(bromomethyl) propenoic acid) and aldehydes or ketones reaction come synthetic.Amberlyst15 is Rhom and Hass

The strong-acid ion exchange resin of system.

[changing 2]

(in the formula, the organic group of R ' expression monovalence.)

2-(brooethyl) vinylformic acid can by represent with following reaction formula, by Ramarajan etc. at K.Ramarajan, K.Kamalingam, D.J.O ' Donnell and K.D.Berlin, Organic Synthesis, the method that proposes among the vol.61,56-59 (1983) is synthesized.

[changing 3]

As concrete synthesis example, at synthetic V be-R ¹O-, W are-OR ²-, R ¹And R ²In the situation of the polymerizable compound shown in the identical following formula (1), can exemplify two kinds of methods that represent with following reaction formula.

[changing 4]

[changing 5]

At synthetic R ¹And R ²In the situation of the polymerizable compound shown in the different following formula (1), can exemplify the method that represents with following reaction formula.

[changing 6]

In the situation of synthesizing the polymerizable compound shown in the following formula (1) that V and W are singly-bound, can exemplify the method that represents with following reaction formula.

[changing 7]

Can make the polymerizable compound shown in the following formula (1) be contained in liquid crystal aligning agent.Particularly, liquid crystal aligning agent of the present invention comprises: the polymerizable compound shown in the following formula (1), the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism, solvent.For example have and in the liquid crystal aligning agent of known vertical orientated usefulness, add the liquid crystal aligning agent that the polymerizable compound shown in the following formula (1) forms.Liquid crystal aligning agent refers to for the solution of making liquid crystal orientation film, and liquid crystal orientation film is that to instigate liquid crystal be film towards the vertical direction orientation in the direction orientation of regulation, the present invention.

As long as be used to form the polymkeric substance of the liquid crystal orientation film that makes liquid crystal vertical-tropism the mesomorphic phase on the liquid crystal orientation film that forms on the substrate vertically is orientated for substrate; be not particularly limited; both can be polyimide precursor or make this polyimide precursor imidization and the liquid crystal aligning mould material of the organics such as polyimide; it also can be polyester; (methyl) acryl; polysiloxane-based liquid crystal aligning mould material; for example better be the polymkeric substance with the side chain that makes liquid crystal vertical-tropism, can exemplify and be selected from the polyimide precursor that for example has the side chain that makes liquid crystal vertical-tropism; the polyimide that makes this polyimide precursor imidization and get; and polysiloxane at least a with the side chain that makes liquid crystal vertical-tropism.The polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism can only have a kind of, also can be two or more.As polyimide precursor, can exemplify polyamic acid or poly amic acid ester.

Make the side chain of liquid crystal vertical-tropism so long as mesomorphic phase is got final product for the vertical orientated structure of substrate, do not limit, can exemplify the group that is substituted by fluorine atom such as chain alkyl, at alkyl such as the group that has ring structure or branched structure midway of chain alkyl, steroid radical, with part or all of the hydrogen atom of these groups etc.Obviously also can have the two or more side chains that makes liquid crystal vertical-tropism.Make the side chain of liquid crystal vertical-tropism can be bonded directly to the main chain of the polymkeric substance such as polyimide precursor, polyimide or polysiloxane, namely be bonded directly to polyamic acid skeleton, polyimide skeleton or polysiloxane skeleton etc., bonding perhaps also can be situated between with suitable concatenating group.As the side chain that makes liquid crystal vertical-tropism, can exemplify the carbon number that hydrogen atom for example can replace by fluorine and be 8～30, be preferably 8～22 alkyl, but concrete exemplified by alkyl groups, fluoro-alkyl, alkenyl, styroyl, styryl alkyl, naphthyl, fluorophenyl alkyl etc.As other the side chain that makes liquid crystal vertical-tropism, can exemplify for example side chain shown in the following formula (a).

[changing 8]

(in the formula (a), l, m and n represent respectively 0 or 1 integer, R independently ³The alkylidene group of expression carbon number 2～6 ,-O-,-COO-,-OCO-,-NHCO-,-alkylidene group-ether of CONH-or carbon number 1～3, R ⁴, R ⁵And R ⁶Represent independently respectively phenylene or cycloalkylidene, R ⁷The alkyl of expression hydrogen atom, carbon number 2～24 or contain the heterocycle of aliphatics ring, monovalence of aromatic nucleus, the monovalence of fluoroalkyl, monovalence or the large ring-type of the monovalence that is made of these groups replaces body.)

Consider the R in the following formula (a) from the viewpoint of synthetic complexity ³Better be-O-,-COO-,-alkylidene group-ether of CONH-, carbon number 1～3.

Consider the R in the formula (a) from the viewpoint of synthetic complexity and the ability that makes liquid crystal vertical-tropism ⁴, R ⁵And R ⁶Better be the l shown in the following table 1, m, n, R ⁴, R ⁵And R ⁶Combination.

[table 1]

l	m	n	R ⁴	R ⁵	R ⁶
						1	1	1	Phenylene	Phenylene	Cyclohexylidene
1	1	1	Phenylene	Cyclohexylidene	Cyclohexylidene
						1	1	1	Cyclohexylidene	Cyclohexylidene	Cyclohexylidene
1	1	0	Phenylene	Phenylene	－
						1	1	0	Phenylene	Cyclohexylidene	－
1	1	0	Cyclohexylidene	Cyclohexylidene	－

And at least one of l, m, n is 1 o'clock, the R in the formula (a) ⁷Better be the alkyl of hydrogen atom or carbon number 2～14 or contain fluoroalkyl, be more preferably the alkyl of hydrogen atom or carbon number 2～12 or contain fluoroalkyl.L, m, n are at 0 o'clock, R ⁷The large ring-type of the monovalence that better is the heterocycle of aliphatics ring, the monovalence of the alkyl of carbon number 12～22 or the aromatic nucleus that contains fluoroalkyl, monovalence, monovalence, is made of these groups replaces body, is more preferably the alkyl of carbon number 12～20 or contains fluoroalkyl.

The amount of the side chain of liquid crystal vertical-tropism is needed only in liquid crystal orientation film can make the scope of liquid crystal vertical-tropism, be not particularly limited.But in the scope of the display characteristic of the elements such as accumulating of the voltage retention of not damaging the liquid crystal display device with above-mentioned liquid crystal orientation film and residual DC voltage, the amount that makes the side chain of liquid crystal vertical-tropism better is few as much as possible.

The ability that polymkeric substance with the side chain that makes liquid crystal vertical-tropism makes liquid crystal vertical-tropism is according to the structure of the side chain that makes liquid crystal vertical-tropism and difference, in general, if the amount of the side chain of liquid crystal vertical-tropism is increased, the ability of liquid crystal vertical-tropism is improved, if the amount of the side chain of liquid crystal vertical-tropism is reduced, the ability of liquid crystal vertical-tropism is reduced.If have ring texture, then compare with the situation that does not have ring texture, the higher tendency of ability that makes liquid crystal vertical-tropism is arranged.

The polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism better is to have the photoreactivity side chain.If have the photoreactivity side chain, then can further improve response speed.The photoreactivity side chain refers to have the side chain that can react by the irradiation of ultraviolet ray light such as (UV) functional group that forms covalent linkage (below be also referred to as photoreactive group), as long as have this ability, then its structure does not limit.As the photoreactivity side chain; the side chain that has such as groups such as the vinyl of photoreactive group, acryl, methacryloyl, allyl group, styryl, cinnamoyl, phenyl styryl ketone base (カ Le コニ Le base), tonka bean camphor base, dimaleoyl imino, epoxy group(ing), vinyloxy group, acryloxies can be exemplified, alkyl that has been replaced by these photoreactive group such as these photoreactive group itself or hydrogen atom etc. can be exemplified.Substituted hydrogen atom is more than 1, better is 1.Consider the carbon number of the alkyl that hydrogen atom is replaced by photoreactive group preferably 1～30, more preferably 1～10, further more preferably 1～5 from the viewpoint of response speed and vertical orientated property.Obviously also can have two or more photoreactivity side chains.The photoreactivity side chain can be bonded directly to the main chain of the polymkeric substance such as polyimide precursor, polyimide or polysiloxane, and bonding perhaps also can be situated between with suitable concatenating group.As the photoreactivity side chain, can exemplify for example side chain shown in the following formula (b).

[changing 9]

(in the formula (b), R ⁸The expression singly-bound or-CH ₂-,-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-,-CH ₂O-,-N (CH ₃)-,-CON (CH ₃)-,-N (CH ₃) among the CO-any, R ⁹The alkylidene group of expression singly-bound or carbon number 1～20 non-substituted or that replaced by fluorine atom, alkylidene group-CH ₂-can be by-CF ₂-or-CH=CH-at random replaces, when the arbitrary group that below exemplifies is not adjacent one another are, also can be replaced by these groups :-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-, the carbocyclic ring of divalence, the heterocycle of divalence; R ¹⁰Expression vinyl, acryl, methacryloyl, allyl group, styryl ,-N (CH ₂CHCH ₂) ₂Or the structure shown in the following formula.)

[changing 10]

R in the following formula (b) ⁸Can form by the method for conventional organic synthesis, consider from the viewpoint of synthetic complexity, better be-CH ₂-,-O-,-COO-,-NHCO-,-NH-,-CH ₂O-.

As with R ⁹Arbitrarily-CH ₂Carbocyclic ring or the heterocycle of the carbocyclic ring of the divalence of-replacement or the heterocycle of divalence specifically can exemplify following structure, but be not limited to this.

[changing 11]

Consider R from photoreactive viewpoint ¹⁰Preferred vinyl, acryl, methacryloyl, allyl group, styryl ,-N (CH ₂CHCH ₂) ₂Or the structure shown in the following formula.

[changing 12]

Following formula (b) is following structure more preferably.

[changing 13]

The amount of photoreactivity side chain better is to form in the scope of response speed that covalent linkage improves liquid crystal reacting by ultraviolet irradiation, in order further to improve the response speed of liquid crystal, The more the better as far as possible in the scope that other characteristic is not impacted.

The polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism also can have side chain or photoreactivity side chain other side chain in addition that makes liquid crystal vertical-tropism.As other side chain, can exemplify hydrogen atom or can be by the alkyl of the carbon number 1～6 of heteroatoms, halogen atom, amino, glycidoxy, sulfydryl, isocyanate group or Carbamido substituted.If make the polysiloxane with these groups, then can improve the liquid crystal orientation film of gained and substrate adaptation and with the affinity of liquid crystal molecule.

Making this method that is used to form the polymkeric substance of the liquid crystal orientation film that makes liquid crystal vertical-tropism is not particularly limited, for example make when having the polyamic acid of the side chain that makes liquid crystal vertical-tropism, following method is very easy: the method is the method that obtains polyamic acid by diamines and tetracarboxylic dianhydride's reaction, is the method that makes the diamines with the side chain that makes liquid crystal vertical-tropism or have tetracarboxylic dianhydride's copolymerization of the side chain that makes liquid crystal vertical-tropism.When wanting to be used in the polymkeric substance that forms the liquid crystal orientation film that makes liquid crystal vertical-tropism and containing the photoreactivity side chain, as long as make the diamines with photoreactivity side chain or have tetracarboxylic dianhydride's copolymerization of photoreactivity side chain.

As the diamines with the side chain that makes liquid crystal vertical-tropism, can exemplify have chain alkyl, at alkyl such as the group that has ring structure or branched structure midway of chain alkyl, steroid radical, part or all of the hydrogen atom of these groups is substituted by the group of fluorine atom as the diamines of side chain, for example have the diamines of the side chain shown in the following formula (a).More specifically, can exemplify the diamines shown in the diamines of alkyl with carbon number 8～30 that hydrogen atom can replace by fluorine etc. or following formula (2), (3), (4), (5), but be not limited to this.

[changing 14]

(l, m, n, R in the formula (2) ³～R ⁷Definition identical with following formula (a).)

[changing 15]

(in formula (3) and the formula (4), A ₁₀Expression-COO-,-OCO-,-CONH-,-NHCO-,-CH ₂-,-O-,-CO-or-NH-, A ₁₁Expression singly-bound or phenylene, a represents the structure identical with the side chain that makes liquid crystal vertical-tropism shown in the following formula (a), and the divalent group of a structure behind the elements such as hydrogen is taken in a ' expression away from the structure identical with the side chain that makes liquid crystal vertical-tropism shown in the following formula (a).)

[changing 16]

(in the formula (5), A ₁₄The alkyl of the carbon number 3～20 that can be replaced by fluorine atom, A ₁₅Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, A ₁₆Be Sauerstoffatom or-COO-* (indicates key and the A of " * " here, ₁₅In conjunction with), A ₁₇Be Sauerstoffatom or-COO-* (key that indicates " * " here, and (CH ₂) a ₂In conjunction with).In addition, a ₁0 or 1 integer, a ₂2～10 integer, a ₃It is 0 or 1 integer.)

Two amino (NH in the formula (2) ₂) bonding position do not limit.Particularly, with respect to the concatenating group of side chain, can exemplify prosposition on the phenyl ring, 2,4,2,5,2,6,3,4,3,5.Reactive viewpoint during wherein, from synthesizing polyamides acid is considered preferred 2,4,2,5 or 3,5.If the complexity when adding synthetic diamines, then more preferably 2,4 or 3,5.

As the concrete structure of formula (2), can exemplify the diamines shown in following formula [A-1]～formula [A-24], but be not limited to this.

[changing 17]

(in formula [A-1]～formula [A-5], A ₁For the alkyl of carbon number 2～24 or contain fluoroalkyl.)

[changing 18]

(in formula [A-6] and the formula [A-7], A ₂Expression-O-,-OCH ₂-,-CH ₂O-,-COOCH ₂-or-CH ₂OCO-, A ₃Be carbon number 1～22 alkyl, alkoxyl group, contain fluoroalkyl or fluoroalkoxy.)

[changing 19]

(in formula [A-8]～formula [A-10], A ₄Expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH ₂-,-CH ₂OCO-,-CH ₂O-,-OCH ₂-or-CH ₂-, A ₅Be carbon number 1～22 alkyl, alkoxyl group, contain fluoroalkyl or fluoroalkoxy.)

[changing 20]

(in formula [A-11] and the formula [A-12], A ₆Expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH ₂-,-CH ₂OCO-,-CH ₂O-,-OCH ₂-,-CH ₂-,-O-or-NH-, A ₇Fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.)

[changing 21]

(in formula [A-13] and the formula [A-14], A ₈Be the alkyl of carbon number 3～12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer(ide).)

[changing 22]

(in formula [A-15] and the formula [A-16], A ₉Be the alkyl of carbon number 3～12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer(ide).)

[changing 23]

As the concrete example of the diamines shown in the formula (3), can exemplify the diamines shown in following formula [A-25]～formula [A-30], but be not limited to this.

[changing 24]

(in formula [A-25]～formula [A-30], A ₁₂Expression-COO-,-OCO-,-CONH-,-NHCO-,-CH ₂-,-O-,-CO-or-NH-, A ₁₃For the alkyl of carbon number 1～22 or contain fluoroalkyl.)

As the concrete example of the diamines shown in the formula (4), can exemplify the diamines shown in following formula [A-31]～formula [A-32], but be not limited to this.

[changing 25]

Wherein, consider the diamines of preferred [A-1], [A-2], [A-3], [A-4], [A-5], [A-25], [A-26], [A-27], [A-28], [A-29], [A-30] from the viewpoint of the response speed of the ability that makes liquid crystal vertical-tropism, liquid crystal.

Above-mentioned diamines can be when making liquid crystal orientation film liquid crystal aligning, tilt angle, voltage preserving property, accumulate the characteristic such as electric charge, use one or more to mix and use.

This consumption with diamines of the side chain that makes liquid crystal vertical-tropism better is 5～50 % by mole of two amine components that use in polyamic acid synthetic, 10～40 % by mole that are more preferably two amine components is the diamines with the side chain that makes liquid crystal vertical-tropism, particularly preferably 15～30 % by mole.If use the diamines with the side chain that makes liquid crystal vertical-tropism with 5～50 % by mole amount of two amine components that use in polyamic acid synthetic like this, then excellent especially aspect the orientation immobilization ability of the raising of response speed and liquid crystal.

As the diamines with photoreactivity side chain; can exemplify have vinyl, the photoreactive group such as acryl, methacryloyl, allyl group, styryl, cinnamoyl, phenyl styryl ketone base, tonka bean camphor base, dimaleoyl imino, epoxy group(ing), vinyloxy group, acryloxy is as the diamines of side chain, for example has the diamines of the side chain shown in the following formula (b).More specifically, can exemplify the diamines that for example represents with following general formula (6), but be not limited to this.

[changing 26]

(the R in the formula (6) ⁸, R ⁹And R ¹⁰Definition identical with following formula (b).)

Two amino (NH in the formula (6) ₂) bonding position do not limit.Particularly, with respect to the concatenating group of side chain, can exemplify prosposition on the phenyl ring, 2,4,2,5,2,6,3,4,3,5.Reactive viewpoint during wherein, from synthesizing polyamides acid is considered preferred 2,4,2,5 or 3,5.If the complexity when adding synthetic diamines, then more preferably 2,4 or 3,5.

As the diamines with photoreactivity side chain, specifically can exemplify following compound, but be not limited to this.

[changing 27]

(in the formula, X represents singly-bound or be selected from-O-,-COO-,-NHCO-,-concatenating group of NH-, Y represents the alkylidene group of singly-bound or carbon number 1～20 non-substituted or that replaced by fluorine atom.)

Above-mentioned diamines with photoreactive group can be when making liquid crystal orientation film liquid crystal aligning, tilt angle, voltage preserving property, accumulate the characteristic such as electric charge, the response speed of the liquid crystal during as liquid crystal display device etc., use one or more to mix and use.

This consumption with diamines of photoreactivity side chain better is 10～70 % by mole of two amine components that use in polyamic acid synthetic, is more preferably 20～60 % by mole, particularly preferably 30～50 % by mole.

Only otherwise damage effect of the present invention, may be used in the polyamic acid and above-mentionedly have the diamines of the side chain that makes liquid crystal vertical-tropism and have other diamines beyond the diamines of photoreactivity side chain as two amine components.Specifically can exemplify Ursol D, 2,3,5, the 6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, mphenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, the 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2, the 4-diaminophenol, 3,5-diaminophenol, 3,5-diamino benzylalcohol, 2,4-diamino benzylalcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-sulphonyl pentanoic, 3,3 '-sulphonyl pentanoic, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-two (4-aminophenyl) silane, dimethyl-two (3-aminophenyl) silane, 4,4 '-phenyl disulfide amine, 3,3 '-phenyl disulfide amine, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 1, the 4-diaminonaphthalene, 2,2 '-diamino benzophenone, 2,3 '-diamino benzophenone, 1,5-diaminonaphthalene, 1, the 6-diaminonaphthalene, 1, the 7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2, the 6-diaminonaphthalene, 2, the 7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, 1, two (3-aminophenyl) ethane of 2-, 1, two (4-aminophenyl) propane of 3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-two (4-aminophenyl) butane, 1, two (3-aminophenyl) butane of 4-, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 1, two (4-aminophenyl) benzene of 4-, 1, two (4-aminophenyl) benzene of 3-, Isosorbide-5-Nitrae-two (4-amino-benzene methyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[1,4-phenylene two (methylene radical)] pentanoic, 4,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,4 '-[1,4-phenylene two (methylene radical)] pentanoic, 3,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,3 '-[1,4-phenylene two (methylene radical)] pentanoic, 3,3 '-[1,3-phenylene two (methylene radical)] pentanoic, 1,4-phenylene two [(4-aminophenyl) ketone], 1,4-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], 1,4-phenylene two (PABA ester), 1,4-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(1, the 4-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamides), N, N '-(1, the 4-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-ABs), N, N '-two (4-aminophenyl) terephthalamide, N, N '-two (3-aminophenyl) terephthalamide, N, N '-two (4-aminophenyl) isophthaloyl amine, N, N '-two (3-aminophenyl) isophthaloyl amine, 9, two (4-aminophenyl) anthracenes of 10-, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-two (4-aminophenyl) HFC-236fa, 2,2 '-two (3-aminophenyl) HFC-236fa, 2,2 '-two (3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-two (4-aminophenyl) propane, 2,2 '-two (3-aminophenyl) propane, 2,2 '-two (3-amino-4-aminomethyl phenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1, two (4-amino-benzene oxygen) propane of 3-, 1, two (3-amino-benzene oxygen) propane of 3-, Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-two (3-amino-benzene oxygen) butane, 1, two (4-amino-benzene oxygen) pentanes of 5-, 1, two (3-amino-benzene oxygen) pentanes of 5-, two (4-amino-benzene oxygen) hexanes of 1,6-, two (3-amino-benzene oxygen) hexanes of 1,6-, 1, two (4-amino-benzene oxygen) heptane of 7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octanes of 1,8-, two (3-amino-benzene oxygen) octanes of 1,8-, 1, two (4-amino-benzene oxygen) nonanes of 9-, 1, two (3-amino-benzene oxygen) nonanes of 9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, the aromatic diamines such as 1,12-(3-amino-benzene oxygen) dodecane, two (4-aminocyclohexyl) methane, the alicyclic diamines such as two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1, the 5-1,5-DAP, 1, the 6-diamino hexane, 1,7-diamino heptane, 1,8-diamino-octane, 1,9-diamino nonane, 1, the 10-diamino decane, 1,11-diamino undecane, the aliphatie diamines such as 1,12-diamino dodecane

Above-mentioned other diamines can be when making liquid crystal orientation film liquid crystal aligning, tilt angle, voltage preserving property, accumulate the characteristic such as electric charge, use one or more to mix and use.

Tetracarboxylic dianhydride with above-mentioned two amine components reaction in polyamic acid synthetic is not particularly limited.Specifically can exemplify Pyromellitic Acid, 2,3,6, the 7-naphthalene tetracarboxylic acid, 1,2,5, the 6-naphthalene tetracarboxylic acid, Isosorbide-5-Nitrae, 5, the 8-naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', the 4-biphenyltetracarboxyacid acid, two (3,4-dicarboxyl phenyl) ether, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, two (3,4-dicarboxyl phenyl) sulfone, two (3,4-dicarboxyl phenyl) methane, two (3, the 4-dicarboxyl phenyl) propane of 2,2-, 1,1,1,3,3,3-hexafluoro-2,2-two (3,4-dicarboxyl phenyl) propane, two (3,4-dicarboxyl phenyl) dimethylsilane, two (3,4-dicarboxyl phenyl) diphenyl silane, 2,3,4,5-pyridine tetracarboxylic acid, 2, two (3, the 4-dicarboxyl phenyl) pyridines of 6-, 3,3 ', 4,4 '-diphenylsulfone acid, 3,4,9,10-perylene tetracarboxylic acid, 1,3-phenylbenzene-1,2,3,4-tetramethylene tetracarboxylic acid, the adjacent benzene tertacarbonic acid of bis oxide, 1,2,3,4-tetramethylene tetracarboxylic acid, 1,2,3,4-pentamethylene tetracarboxylic acid, 1,2,4,5-hexanaphthene tetracarboxylic acid, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid, 1,2,3,4-suberane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic acid, 3,4-dicarboxyl-1-cyclohexyl succsinic acid, 2,3,5-tricarboxylic basic ring amyl group acetic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic, dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, dicyclo [4,3,0] nonane-2,4,7, the 9-tetracarboxylic acid, dicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic acid, dicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, three rings [6.3.0.0＜2,6 〉] undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-BTCA, 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2,3,4-tetraline-1, the 2-dicarboxylic acid, dicyclo [2,2,2] suffering-7-alkene-2,3,5, the 6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-hexanaphthene-1, the 2-dicarboxylic acid, Fourth Ring [6,2,1,1,0,2,7] 12-4,5,9, the 10-tetracarboxylic acid, 3,5,6-, three carboxyl norbornane-2:3, the 5:6 dicarboxylic acid, 1,2,4,5-hexanaphthene tetracarboxylic acid etc.Obviously, liquid crystal aligning, the voltage preserving property that the tetracarboxylic dianhydride can be when making liquid crystal orientation film, accumulate the characteristic such as electric charge, use one or more and use.

When the reaction by two amine components and tetracarboxylic dianhydride obtains polyamic acid, can adopt known synthetic method.The method that two amine components and tetracarboxylic dianhydride are reacted in organic solvent.Two amine components and tetracarboxylic dianhydride's reaction is carried out than being easier in organic solvent, and is favourable not generating the by product this point.

As employed organic solvent in the above-mentioned reaction, so long as the organic solvent of the polyamic acid that dissolving generates gets final product, be not particularly limited.Also have, even the organic solvent of insoluble solution polyamic acid, so long as in the scope that the polyamic acid that generates can not be separated out, also can use with above-mentioned solvent.In addition, the moisture in the organic solvent can hinder polyreaction and then make the polyamic acid hydrolysis of generation, so organic solvent better is to dehydrate rear use.As used organic solvent in the reaction, can exemplify for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N, the N-diethylformamide, N-METHYLFORMAMIDE, METHYLPYRROLIDONE, the N-ethyl-2-pyrrolidone, 2-Pyrrolidone, 1, the 3-dimethyl-2-imidazolinone, 3-methoxyl group-N, N-dimethyl propylene acid amides, the N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, the pregnancy sulfoxide, gamma-butyrolactone, Virahol, the methoxymethyl amylalcohol, limonene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methylcyclohexane, ethyl cellosolve, methylcellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, the glycol tertiary butyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, Diethylene Glycol, the Diethylene Glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, hexyl ether, two Alkane, normal hexane, Skellysolve A, octane, diethyl ether, pimelinketone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diglyme, the 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol etc.These organic solvents can be used alone, but also also mix together.

When being reacted in organic solvent, two amine components and tetracarboxylic dianhydride's composition can exemplify: stir the solution that makes two amine components be dispersed or dissolved in organic solvent and get, then directly add tetracarboxylic dianhydride's composition or make tetracarboxylic dianhydride's composition be dispersed or dissolved in the method for adding again behind the organic solvent; Add the method for two amine components in the solution that gets tetracarboxylic dianhydride's composition is dispersed or dissolved in organic solvent on the contrary; Alternately add the method for tetracarboxylic dianhydride's composition and two amine components etc., can use any method wherein.In addition, when two amine components or tetracarboxylic dianhydride's composition comprise multiple compounds, can under the state that is pre-mixed, make its reaction, also can make its respectively successively reaction, can also make react respectively and lower molecular weight body hybrid reaction and obtain the high molecular body.

Make the temperature in two amine components and tetracarboxylic dianhydride's composition when reaction can select arbitrarily temperature, for example-20 ℃～150 ℃, preferred-5 ℃～100 ℃ scope.Reaction can be carrying out under the concentration arbitrarily, and for example with respect to reaction solution, the total amount of two amine components and tetracarboxylic dianhydride's composition is 1～50 quality %, is preferably 5～30 quality %.

In the above-mentioned polyreaction, the total mole number of tetracarboxylic dianhydride's composition can be selected arbitrarily value according to the molecular weight of the polyamic acid of wanting to obtain with respect to the ratio of the total mole number of two amine components.Identical with common polycondensation, this mol ratio is more close to 1.0, and the molecular weight of the polyamic acid of generation is larger.Saying preferred scope, can be 0.8～1.2.

The method of the synthesizing polyamides acid that the present invention uses is not limited to aforesaid method, same with the synthetic method of general polyamic acid, the tetracarboxylic acid derivatives such as the tetracarboxylic acid of use counter structure or tetracarboxylic acid two carboxylic acid halides replace above-mentioned tetracarboxylic dianhydride, make its reaction by known method, so also can obtain corresponding polyamic acid.

Make the method for polyimide as making above-mentioned polyamic acid imidization, can exemplify the hot-imide of the solution of direct heating polyamic acid, in the solution of polyamic acid, add the catalysis imidization of catalyzer.It must be 100% that imide rate from the polyamic acid to the polyimide there is no need.

Temperature when making the polyamic acid hot-imide in solution is 100 ℃～400 ℃, better is 120 ℃～250 ℃, better is to carry out when the water that will generate by imidization reaction is got rid of to system.

The catalysis imidization of polyamic acid can pass through to add basic catalyst and acid anhydrides in polyamic acid solution, and at-20～250 ℃, better is to carry out 0～180 ℃ of lower stirring.The amount of basic catalyst is counted 0.5～30 times of acid amides acidic group with mole, preferred 2～20 times, the amount of acid anhydrides is counted 1～50 times of acid amides acidic group, preferred 3～30 times with mole.As basic catalyst, can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc., wherein pyridine have for make reaction carry out for the alkalescence of appropriateness, therefore preferred.As acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc., wherein, be easy to react the purifying after the end when using diacetyl oxide, therefore preferred.Adopt the imide rate of catalysis imidization to control by adjusting catalytic amount and temperature of reaction, reaction times.

Poly amic acid ester can by tetracarboxylic acid diester diacid chloride and and the synthetic same diamines of above-mentioned polyamic acid between reaction or make by making the tetracarboxylic acid diester and reacting under existing of suitable condensing agent, alkali inferior condition with the synthetic same diamines of above-mentioned polyamic acid.In addition, by the pre-synthesis polyamic acid of aforesaid method, utilize high molecular weight reactive with the carboxylic esterification in the amido acid, also can obtain poly amic acid ester by this.Particularly, for example can make tetracarboxylic acid diester diacid chloride and diamines in the presence of alkali and organic solvent, and-20 ℃～150 ℃, preferred 0 ℃～50 ℃ lower reactions 30 minutes～24 hours, preferred 1 hour～4 hours, thereby the synthesizing polyamides acid esters.Then, poly amic acid ester is at high temperature heated, promote that dealcoholysis makes its closed loop, also can obtain polyimide by this.

When from the reaction soln of the polyimide precursor such as polyamic acid, poly amic acid ester or polyimide, reclaiming the polyimide precursor such as the polyamic acid that generates, poly amic acid ester or polyimide, reaction soln can be put into and make its precipitation in the Weak solvent.Weak solvent as being used for precipitation can exemplify methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc.Put in the Weak solvent and the polymkeric substance of precipitation can after filtered and recycled, carry out drying in normal temperature or heating under normal pressure or decompression.In addition, if the polymkeric substance that repeats to make precipitation to reclaim is dissolved in the operation 2～10 times that organic solvent and redeposition reclaim again, then can reduce the impurity in the polymkeric substance.Weak solvent as this moment can exemplify such as alcohols, ketone, hydro carbons etc., if use the Weak solvent more than 3 kinds that is selected from these solvents, then purification efficiency further improves, and is therefore desirable.

The method that manufacturing has the polysiloxane of the side chain that makes liquid crystal vertical-tropism is not particularly limited, and the method for condenses polycondensation that for example can be by making organoalkoxysilane or organoalkoxysilane is made.The condenses of organoalkoxysilane refers to the polymer of the organoalkoxysilanes such as dimer of organoalkoxysilane.If use the organoalkoxysilane with the side chain that makes liquid crystal vertical-tropism as this organoalkoxysilane, then can form the polysiloxane with the side chain that makes liquid crystal vertical-tropism.When making the polysiloxane of liquid crystal vertical-tropism contain the photoreactivity side chain, use organoalkoxysilane or its condenses with photoreactivity side chain to get final product.

As the organoalkoxysilane with the side chain that makes liquid crystal vertical-tropism, can exemplify have chain alkyl, at alkyl such as the group that has ring structure or branched structure midway of chain alkyl, steroid radical, part or all of the hydrogen atom of these groups is substituted by the group of fluorine atom as the organoalkoxysilane of side chain, the organoalkoxysilane shown in the following formula (7) for example.In the following formula (7), R ¹¹Preferred alkyl or fluoro-alkyl, particularly preferably alkyl.R ¹²The alkyl of preferred carbon number 1～5, the particularly preferably alkyl of carbon number 1～3.R ¹²More preferably methyl or ethyl.

Concrete example as the organoalkoxysilane shown in this following formula (7) can exemplify the octyl group Trimethoxy silane, octyltri-ethoxysilane, the decyl Trimethoxy silane, the decyl triethoxyl silane, dodecyltrimethoxysilane, the dodecyl triethoxyl silane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the heptadecyl Trimethoxy silane, the heptadecyl triethoxyl silane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, the nonadecyl Trimethoxy silane, the nonadecyl triethoxyl silane, the undecyl triethoxyl silane, the undecyl Trimethoxy silane, 21-docosene ethyl triethoxy silicane alkane, ten trifluoro octyl group Trimethoxy silanes, ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl Trimethoxy silanes, 17 fluorine decyl triethoxyl silanes, the iso-octyl triethoxyl silane, the styroyl triethoxyl silane, the pentafluorophenyl group propyl trimethoxy silicane, (1-naphthyl) triethoxyl silane, (1-naphthyl) Trimethoxy silane etc.Wherein, preferred octyl group Trimethoxy silane, octyltri-ethoxysilane, the decyl Trimethoxy silane, the decyl triethoxyl silane, dodecyltrimethoxysilane, the dodecyl triethoxyl silane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the heptadecyl Trimethoxy silane, the heptadecyl triethoxyl silane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, the nonadecyl Trimethoxy silane, the nonadecyl triethoxyl silane, the undecyl triethoxyl silane, or undecyl Trimethoxy silane, the triethoxy vinyl silanes, the trimethoxy vinyl silanes, the triethoxy allyl silicane, the trimethoxy allyl silicane, triethoxy styryl silane, the trimethoxy-benzene vinyl silanes.

Have the organoalkoxysilane of the side chain that makes liquid crystal vertical-tropism as other, can exemplify the organoalkoxysilane with the side chain shown in the following formula (a).

In order to obtain good liquid crystal aligning, be used for obtaining whole organoalkoxysilanes of polysiloxane, organoalkoxysilane shown in the following formula (7) or organoalkoxysilane with the side chain shown in the following formula (a) etc. have the organoalkoxysilane of the side chain that makes liquid crystal vertical-tropism preferably more than 0.1 % by mole, more preferably more than 0.5 % by mole, further more preferably more than 1 % by mole.In order to make formed liquid crystal orientation film obtain enough curing characteristicss, preferably below 30 % by mole, more preferably below 22 % by mole.

As the organoalkoxysilane with photoreactivity side chain; can exemplify have vinyl, the side chain of the photoreactive group such as acryl, methacryloyl, allyl group, styryl, cinnamoyl, phenyl styryl ketone base, tonka bean camphor base, dimaleoyl imino, epoxy group(ing), vinyloxy group, acryloxy; can exemplify and have alkyl of having been replaced by these photoreactive group such as these photoreactive group itself or hydrogen atom etc. as the organoalkoxysilane of side chain, specifically can exemplify the organoalkoxysilane shown in the following formula (8).In the following formula (8), by R ¹³The hydrogen atom that replaces is more than 1, better is 1.R ¹³The carbon number preferably 1～30 of alkyl, more preferably 1～10, further more preferably 1～5.R ¹⁴The alkyl of preferred carbon number 1～5, the particularly preferably alkyl of carbon number 1～3.R ¹⁴More preferably methyl or ethyl.

The concrete example of the organoalkoxysilane shown in this following formula (8) can exemplify such as 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, methacryloxy methyltrimethoxy silane, methacryloxy Union carbide A-162,3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-triethoxysilicane, acryloxy ethyl trimethoxy silane, acryloxy ethyl triethoxysilane etc.

Have the organoalkoxysilane of photoreactivity side chain as other, can exemplify the organoalkoxysilane with the side chain shown in the following formula (b).

For formed liquid crystal orientation film is fully solidified, be used for obtaining whole organoalkoxysilanes of polysiloxane, organoalkoxysilane shown in the following formula (8) or organoalkoxysilane with the side chain shown in the following formula (b) etc. have the organoalkoxysilane of photoreactivity side chain preferably below 60 % by mole, consider from the viewpoint of vertical orientated property, if content is more than 60 % by mole, worry that then vertical orientated property can reduce, therefore preferred 20～50 % by mole.

Also can use other organoalkoxysilane.As other organoalkoxysilane, can exemplify the organoalkoxysilane shown in the following formula (9).By using the organoalkoxysilane shown in one or more following formulas (9), can improve with the adaptation of substrate and with the affinity of liquid crystal molecule.

(R ¹⁵) _nSi(OR ¹⁶) _4-n (9)

(in the formula (9), R ¹⁵It is hydrogen atom or can be by the alkyl of the carbon number 1～6 of heteroatoms, halogen atom, amino, glycidoxy, sulfydryl, isocyanate group or Carbamido substituted, R ¹⁶Be the alkyl of carbonatoms 1～5, n represents 0～3 integer.)

In the organoalkoxysilane of following formula (9), as R ¹⁵Concrete example during for hydrogen atom can exemplify Trimethoxy silane, triethoxyl silane, tripropoxy silane, three butoxy silanes etc.

In the organoalkoxysilane of following formula (9), as R ¹⁵For can be by heteroatoms, halogen atom, amino, glycidoxy, sulfydryl, concrete example during the alkyl of the carbon number 1～6 of isocyanate group or Carbamido substituted, but exemplified by methyl Trimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl tripropoxy silane, the 3-TSL 8330, APTES, N-2 (amino-ethyl) APTES, N-2 (amino-ethyl) 3-TSL 8330,3-(2-aminoethylamino propyl group) Trimethoxy silane, 3-(2-aminoethylamino propyl group) triethoxyl silane, 2-aminoethylamino methyltrimethoxy silane, 2-(2-amino-ethyl ethylmercapto group) triethoxyl silane, 3-sulfydryl propyl-triethoxysilicane, the mercapto methyl Trimethoxy silane, 3-isocyanate group propyl-triethoxysilicane, the trifluoro propyl Trimethoxy silane, chloropropyl triethoxysilane, the bromopropyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, the diethyl diethoxy silane, diethyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl dimethylethoxysilane, trimethylethoxysilane, the trimethylammonium methoxy silane, γ-urea groups propyl-triethoxysilicane, γ-urea groups propyl trimethoxy silicane and γ-urea groups propyl group tripropoxy silane etc.

In the organoalkoxysilane shown in the following formula (9), n is that 0 organoalkoxysilane is tetraalkoxysilane.Tetraalkoxysilane easily with the organoalkoxysilane shown in the following formula (7) and the organoalkoxysilane polycondensation shown in the following formula (8), therefore preferred use.Be 0 organoalkoxysilane as the n in this following formula (9), preferred tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes, particularly preferably tetramethoxy-silicane or tetraethoxysilane.

When using the organoalkoxysilane shown in the following formula (9), the consumption of the organoalkoxysilane shown in the following formula (9) is preferably 10～99.8 % by mole of the whole organoalkoxysilanes that are used for the acquisition polysiloxane, more preferably 35～96.9 % by mole.

As the method that makes this organoalkoxysilane or its condenses polycondensation, can exemplify organoalkoxysilane or its condenses are hydrolyzed in alcohol or dibasic alcohol equal solvent-method of condensation.At this moment, the hydrolysis-condensation reaction can be any in partial hydrolysis and the complete hydrolysis.In the situation of complete hydrolysis, in theory as long as add the water of 0.5 times of mole of the whole alkoxyl groups in organoalkoxysilane or its condenses, but better be the water that adds the amount that surpasses 0.5 times of mole usually.Among the present invention, the amount of employed water can suitably be selected as required in the above-mentioned reaction, better is 0.5～2.5 times of mole of the whole alkoxyl groups in the organoalkoxysilane usually.

For facilitation of hydrolysis-condensation reaction, usually also use the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, toxilic acid, fumaric acid; The alkali such as ammonia, methylamine, ethamine, thanomin, triethylamine; The catalyzer such as metal-salt of hydrochloric acid, sulfuric acid, nitric acid etc.In addition, by the solution that is dissolved with organoalkoxysilane is heated generally also further facilitation of hydrolysis-condensation reaction.At this moment, can suitably select as required Heating temperature and heat-up time.For example can exemplify 50 ℃ of lower heating, stir 24 hours, heating under refluxing, the method such as stir 1 hour.

As other method, can exemplify the method for for example mixture heating up of organoalkoxysilane or its condenses, solvent and oxalic acid being carried out polycondensation.Particularly, the method is to be selected in advance to add oxalic acid in the alcohol, make the alcoholic solution of oxalic acid after, mixed oxyalkyl silane or its condenses under to this solution heating condition.At this moment, whole alkoxyl groups of having with respect to organoalkoxysilane or its condenses of the amount of employed oxalic acid are 1 mole preferably 0.2～2 mole.Heating in the method can be carried out under 50～180 ℃ of liquid temperatures.For the evaporation that do not cause liquid, wave loosely etc., better be the method for tens of minutes～ten a few hours of heating under refluxing.

When obtaining polysiloxane, use in the situation of multiple organoalkoxysilane or its condenses, both organoalkoxysilane or its condenses can be pre-mixed and make mixture, also multiple organoalkoxysilane or its condenses can be mixed successively.

The solvent that uses when making organoalkoxysilane or its condenses polycondensation (below be also referred to as polymer solvent) so long as the solvent of dissolvane TMOS or its condenses gets final product, is not particularly limited.Even do not dissolve in the situation of organoalkoxysilane or its condenses, as long as can be along with the carrying out of the polycondensation of organoalkoxysilane or its condenses and dissolve.In general, because generate alcohol by the polycondensation meeting of organoalkoxysilane or its condenses, use alcohols, di-alcohols, dibasic alcohol ethers or the organic solvent good with the consistency of alcohols.

Concrete example as such polycondensation solvent can exemplify the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, Pyranton; Ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-PD, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-PD, 2,4-pentanediol, 2,3-pentanediol, 1, the di-alcoholss such as 6-hexylene glycol; The glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, the ethylene glycol bisthioglycolate ethyl ether, the ethylene glycol bisthioglycolate propyl ether, the ethylene glycol bisthioglycolate butyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, the Diethylene Glycol single-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the Diethylene Glycol dipropyl ether, the Diethylene Glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, the propylene glycol dimethyl ether, the propylene glycol Anaesthetie Ether, the propylene glycol dipropyl ether, the dibasic alcohol ethers such as propylene glycol dibutyl ether; METHYLPYRROLIDONE, DMF, N,N-dimethylacetamide, gamma-butyrolactone, methyl-sulphoxide, tetramethyl-urea, HMPA, meta-cresol etc.Polymer solvent also can use in multiple mixing.

In the polymeric solution of the polysiloxane that obtains by aforesaid method (below be also referred to as polymeric solution), the Siliciumatom of whole organoalkoxysilanes that will use as raw material is converted into SiO ₂Concentration (hereinafter referred to as SiO ₂Conversion concentration) preferably below the 20 quality %, 5～15 quality % more preferably.By in this concentration range, selecting arbitrarily concentration, can suppress the generation of gel, obtain the solution of homogeneous.

Among the present invention, both can directly make the polymeric solution that obtains by aforesaid method be contained in liquid crystal aligning agent, polysiloxane is separated out, form with solid is contained in liquid crystal aligning agent, the solution that obtains by aforesaid method can also be concentrated, add solvent cut or be replaced as other solvent, then make it be contained in liquid crystal aligning agent.At this moment, employed solvent (below be also referred to as add solvent) can be identical with polymer solvent, also can be other solvent.As long as this interpolation solvent is not particularly limited so that polysiloxane can dissolve equably, both can be a kind of also can be multiple, choice for use at random.As this concrete example that adds solvent, except the solvent of enumerating as the example of above-mentioned polymer solvent, can exemplify the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); The ester classes such as methyl acetate, ethyl acetate, ethyl lactate.These solvents can be adjusted the viscosity of liquid crystal aligning agent, perhaps improve the coating when being coated on liquid crystal aligning agent on the substrate by methods such as spin coating, offset printing, ink-jets.

Liquid crystal aligning agent of the present invention as mentioned above, as long as comprise the polymerizable compound shown in the following formula (1), the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism, solvent, its proportioning is not particularly limited, the content of the polymerizable compound shown in the following formula (1) is with respect to polymkeric substance 100 mass parts that are used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism preferably 1～50 mass parts, more preferably 5～30 mass parts.The content of polymkeric substance contained, that be used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism preferably 1 quality %～20 quality %, more preferably 3 quality %～15 quality %, particularly preferably 3 quality %～10 quality % in the liquid crystal aligning agent.

Liquid crystal aligning agent of the present invention also can contain other polymkeric substance beyond the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism.At this moment, the content of this other polymkeric substance in whole compositions of polymkeric substance is 0.5 quality %～15 quality %, better is 1 quality %～10 quality %.

The molecular weight of the polymkeric substance that liquid crystal aligning agent has, considering the coating of liquid crystalline alignment agent the liquid crystal aligning film strength and the operability when forming of filming, the inhomogeneity situation of filming under, the weight-average molecular weight of utilizing GPC (gel permeation chromatography) method to measure better is 5000～1000000, is more preferably 10000～150000.

Solvent contained in the liquid crystal aligning agent is not particularly limited, as long as the polymkeric substance etc. that can dissolve or disperse the polymerizable compound shown in the following formula (1) or be used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism contains composition.Can exemplify the polymer solvent that exemplifies in the organic solvent that exemplifies in above-mentioned polyamic acid for example synthetic, polysiloxane synthetic or add solvent.Wherein, consider preferred METHYLPYRROLIDONE, gamma-butyrolactone, N-ethyl-2-pyrrolidone, DMI, 3-methoxyl group-N, N-dimethyl propylene acid amides from deliquescent viewpoint.Obviously also can use two or more mixed solvents.

Better be that homogeneity that raising is filmed and the solvent of smoothness are used in the high solvent of the solvability that contains composition of liquid crystal aligning agent, the homogeneity of filming as raising and the solvent of smoothness can exemplify for example Virahol, the methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, the ethyl carbitol acetic ester, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the propylene glycol single-butyl ether, the glycol tertiary butyl ether, DPGME, Diethylene Glycol, the Diethylene Glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, propylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol ester list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, the 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, the propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, the single ethyl ether of propylene glycol-1--2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol etc.These solvents also can multiplely mix.When using these solvents, better be 5～80 quality % that account for the solvent total amount that comprises in the liquid crystal aligning agent, be more preferably 20～60 quality %.

Liquid crystal aligning agent also can contain above-mentioned composition in addition.As its example, the compound of the adaptation of the film uniformity in the time of can exemplifying raising coating of liquid crystalline alignment agent or compound, raising liquid crystal orientation film and the substrate of surface smoothness etc.

As the homogeneity that improves thickness or the compound of surface smoothness, can exemplify fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc.More specifically, for example can exemplify ェ Off ト Star プ EF301, EF303, EF352 (illuminating product Co., Ltd. (ト one ケ system プロダ Network Star society) system), メガ Off ア Star Network F171, F173, R-30 (large Japanese ink Co., Ltd. (large Japanese ィ Application キ society) system), Off ロラ one De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリ one ェ system society) system), アサヒガ one De AG710, サ one Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.When using these tensio-active agents, its usage ratio better is 0.01～2 mass parts with respect to total amount 100 mass parts of the polymkeric substance that comprises in the liquid crystal aligning agent, is more preferably 0.01～1 mass parts.

Concrete example as the compound of the adaptation that improves liquid crystal orientation film and substrate can exemplify the compound that contains functional silanes, the compound that contains epoxy group(ing) etc.Can exemplify for example 3-TSL 8330, APTES, the 2-TSL 8330, the 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-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTESs of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N ',-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N ',-four glycidyl group-4,4 '-diaminodiphenyl-methane, 3-(N-allyl group-N-glycidyl) TSL 8330,3-(N, N-diglycidyl) TSL 8330 etc.In order further to improve the film toughness of liquid crystal orientation film, can also add the oxybenzene compounds such as 2,2 '-two (4-hydroxyl-3,5-dihydroxymethyl phenyl) propane, four (methoxymethyl) bis-phenol.When using these compounds, with respect to total amount 100 mass parts of the polymkeric substance that comprises in the liquid crystal aligning agent, its consumption better is 0.1～30 mass parts, is more preferably 1～20 mass parts.

Except above-mentioned substance, so long as in the scope of not damaging effect of the present invention, can also add dielectric medium and conducting material for electrical characteristic such as the specific inductivity that changes liquid crystal orientation film, electroconductibility in the liquid crystal aligning agent.

Also can contain inorganic particles, metal oxygen alkane (metalloxane) oligopolymer, metal oxygen alkane polymkeric substance, levelling agent, tensio-active agent etc. in the liquid crystal aligning agent.

As inorganic particles, better be the particulates such as silicon dioxide microparticle, alumina particulate, titanium dioxide fine particles or magnesium fluoride particulate, the particularly preferably state of colloidal solution.This colloidal solution can be with inorganic microparticle-dispersed in decomposition media and solution, also can be the colloidal solution of commercially available product.Among the present invention, by containing inorganic particles, can give surface shape and other function of formed curing tunicle.Preferred 0.001～0.2 μ m of the median size of inorganic particles, more preferably 0.001～0.1 μ m.When the median size of inorganic particles surpasses 0.2 μ m, sometimes use the coating fluid of preparing and the transparency reduction of the curing tunicle that forms.

As the dispersion medium of inorganic particles, can exemplify water and organic solvent.Form the viewpoint consideration of the stability of using coating fluid from tunicle, the pH of colloidal solution or pKa are adjusted to 1～10.Be more preferably 2～7.

Organic solvent as the dispersion medium that is used for colloidal solution can exemplify the alcohols such as methyl alcohol, propyl alcohol, butanols, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, Diethylene Glycol, dipropylene glycol, glycol monomethyl propyl ether; The ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The amidess such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; The ester classes such as ethyl acetate, butylacetate, gamma-butyrolactone; Tetrahydrofuran (THF), Isosorbide-5-Nitrae-two

The ethers such as alkane.Wherein, preferred alcohols or ketone.These organic solvents can be used as dispersion medium separately or after mixing more than 2 kinds.

As metal oxygen alkane oligopolymer, metal oxygen alkane polymkeric substance, can use the independent or precursor of compound oxide of silicon, titanium, aluminium, tantalum, antimony, bismuth, tin, indium, zinc etc.Metal oxygen alkane oligopolymer, metal oxygen alkane polymkeric substance can be commercially available products, also can be made by common methods such as hydrolysis by monomers such as metal alkoxide, nitrate, hydrochloride, carboxylate salts.

As the metal oxygen alkane oligopolymer of commercially available product, the concrete example of metal oxygen alkane polymkeric substance, but can exemplify youngster Kanggong department (コルコート society) methyl silicate 51 processed (メチ Le シリケート 51), methyl silicate 53A (メチ Le シリケート 53A), ethyl silicate 40 (エチ Le シリケート 40), tetraethyl silicate 48 (エチ Le シリケート 48), siloxane oligomer or the siloxane polymers such as EMS-485, SS-101; The (Off East of Northeast chemical company chemistry society) the titanoxane oligopolymer such as titanium n-butoxide tetramer of system.They can use separately or mix more than 2 kinds and use.

In addition, levelling agent and tensio-active agent etc. can use known reagent, and particularly commercially available product is preferred because easily obtaining.

The modulator approach of liquid crystal aligning agent of the present invention is not particularly limited.As long as make the polymerizable compound of following formula (1) expression, the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism, other one-tenth that other adds as required be divided into the state that mixes equably.For example, polysiloxane is as mentioned above polycondensation in solvent usually, and therefore easier is the solution that directly uses polysiloxane, perhaps adds as required other composition in the solution of polysiloxane.It is the easiest directly using the method for the polymeric solution of polysiloxane.

When adjusting the content of the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism in the liquid crystal aligning agent, can use the polymer solvent of the organic solvent that from above-mentioned polyamic acid synthetic, exemplifies, polysiloxane and add the solvent of selecting in the solvent.

Burn till by this liquid crystal aligning agent is coated on the substrate, can form the liquid crystal orientation film that makes liquid crystal vertical-tropism.Liquid crystal aligning agent of the present invention is owing to having a polymerizable compound shown in the following formula (1), therefore can accelerate the response speed of liquid crystal display device of the liquid crystal orientation film of use gained.

For example, can carry out as required drying behind the substrate by liquid crystal aligning agent of the present invention is coated, burn till, obtain cured film, with this cured film directly as liquid crystal orientation film.Also can rub or shine the light etc. of polarized light or specific wavelength or carry out the processing of ionic fluid etc. this cured film, perhaps shine UV with the liquid crystal display device of alignment films after to filling liquid crystal executing under the alive state as PSA.Be used as PSA particularly useful with alignment films.

At this moment; as employed substrate; so long as the high substrate of the transparency gets final product; be not particularly limited, can use the plastic bases such as sheet glass, polycarbonate, poly-(methyl) acrylate, polyethersulfone, polyarylester, urethane, polysulfones, polyethers, polyetherketone, 2,4,4-Trimethyl-1-pentene, polyolefine, polyethylene terephthalate, (methyl) vinyl cyanide, tri acetyl cellulose, diacetyl cellulose, cellulose acetate butyrate etc.In addition, from the viewpoint of work simplification, the preferred substrate that is formed with for the ITO electrode of liquid crystal drive etc. that uses.In addition, in the reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to the substrate of a side, the electrode of this moment can use the light reflecting materials such as aluminium.

The coating process of liquid crystal aligning agent is not particularly limited, and can exemplify the print processes such as silk screen printing, offset printing, flexographic printing, ink jet method, spray method, rolling method, dipping, roller coat, slot coated, turner etc.Consider that from the productivity aspect industrial extensive employing hectographic printing method is also preferably used among the present invention.

Drying process after the coating of liquid crystalline alignment agent is also nonessential, but the time till burn till all in the unfixed situation or in the situation that do not burn till immediately after the coating, preferably includes drying process for every substrate afterwards in coating.In this drying, solvent remove to the shape of filming not because the degree that carrying of substrate etc. is out of shape gets final product, be not particularly limited for this drying means.For example, can exemplify on 40 ℃～150 ℃ of temperature, preferred 60 ℃～100 ℃ hot-plate dry 0.5 minute～30 minutes, preferred 1 minute～5 minutes method.

Can burn till and make cured film with formed the filming of aforesaid method coating of liquid crystalline alignment agent.The firing temperature of filming that forms by the coating of liquid crystalline alignment agent is not particularly limited, and for example can carry out under 100～350 ℃ arbitrary temp.Liquid crystal aligning agent contain the polyimide precursor with the side chain that makes liquid crystal vertical-tropism or make this polyimide precursor imidization and polyimide the time, better be 120 ℃～300 ℃, be more preferably 150 ℃～250 ℃.When liquid crystal aligning agent contains the polysiloxane with the side chain that makes liquid crystal vertical-tropism, better be 140 ℃～300 ℃, be more preferably 150 ℃～230 ℃, further be more preferably 160 ℃～220 ℃.Firing time can be 5 minutes～240 minutes random time.Better be 10 minutes～90 minutes, be more preferably 20 minutes～90 minutes.Heating can be used generally well-known method, and such as hot-plate, heated air circulation type stove, IR stove, band oven etc. carried out.

Polysiloxane in the liquid crystal orientation film carries out polycondensation in this firing process.But, so long as do not damage effect of the present invention, need not complete polycondensation among the present invention.Better be to burn till than the high temperature more than 10 ℃ of thermal treatment temp of necessary sealant cures in the liquid crystal structure cell manufacturing processed etc.

The thickness of the liquid crystal orientation film that burns till and get is not particularly limited, because easily obtain the reliability of liquid crystal display device, so better be more than the 5nm, is more preferably more than the 10nm.In addition, because the current consumption of liquid crystal display device can extremely not increase, so the thickness of liquid crystal orientation film better is below the 300nm, be more preferably below the 150nm, further be more preferably below the 100nm.

After substrate forms liquid crystal orientation film, make liquid crystal structure cell by known method with aforesaid method, can obtain liquid crystal display device of the present invention by this.Concrete example as liquid crystal display device, the liquid crystal display device that vertical orientation mode with liquid crystal structure cell is arranged, this liquid crystal structure cell comprises: in opposite directions two substrates of configuration, be arranged at liquid crystal layer between substrate, be arranged at the above-mentioned liquid crystal orientation film that is formed by liquid crystal aligning agent of the present invention between substrate and the liquid crystal layer.Particularly, the liquid crystal display device with vertical orientation mode of the liquid crystal structure cell of making as described below: burn till to form liquid crystal orientation film by liquid crystal aligning agent of the present invention is coated on two substrates, two substrates are arranged so that this liquid crystal orientation film is opposed, to be clipped in by the liquid crystal layer that liquid crystal consists of between these two substrates, namely in the mode that contacts with liquid crystal orientation film liquid crystal layer is set, to liquid crystal orientation film and liquid crystal layer while applying the voltage irradiation ultraviolet radiation, thereby the liquid crystal structure cell of making.By using the liquid crystal orientation film that is formed by liquid crystal aligning agent of the present invention as mentioned above, to liquid crystal orientation film and liquid crystal layer while applying the voltage irradiation ultraviolet radiation, make the polymerizable compound polymerization shown in the following formula (1), thereby make the liquid crystal display device of response speed excellence.

As the substrate that is used for liquid crystal display device of the present invention, so long as the high substrate of the transparency get final product, be not particularly limited, normally be formed with substrate for the transparency electrode of driving liquid crystal at substrate.As concrete example, can exemplify with above-mentioned liquid crystal orientation film in the same substrate of the substrate put down in writing.Although also can use the existing substrate that is provided with electrode pattern or projection pattern, but in the liquid crystal display device of the present invention, because used the liquid crystal aligning agent of the present invention that contains the polymerizable compound shown in the following formula (1) as the liquid crystal aligning agent that forms liquid crystal orientation film, even so be formed with for example lines of 1～10 μ m/gap electrode pattern at the substrate of a side, the structure that does not form slit pattern or projection pattern on opposed substrate also can be worked, utilize the liquid crystal display device of this structure, the technique when making can be simplified, high-transmission rate can be obtained.

In addition, in the contour performance components of TFT type element, use the member that between the electrode that is used for liquid crystal drive and substrate, is formed with such as elements such as transistors.

For the liquid crystal display device of transmission-type, usually use aforesaid substrate, but for the liquid crystal display device of reflection-type, also can use the opaque substrates such as silicon wafer, but only limit to the substrate of a side.At this moment, the electrode that forms at substrate also can use catoptrical material, for example aluminium.

Liquid crystal orientation film forms by burning till behind this substrate coating liquid crystal aligning agent of the present invention, and its details as mentioned above.

The liquid crystal material that consists of the liquid crystal layer of liquid crystal display device of the present invention is not particularly limited, and can use the liquid crystal material that uses in the existing vertical orientation mode, negative liquid crystals such as the MLC-6608 of Merck ﹠ Co., Inc. (メ Le Network society) system or MLC-6609.

As this liquid crystal layer being clipped in two methods between the substrate, can exemplify known method.For example can exemplify following method: a pair of substrate of preparing to be formed with liquid crystal orientation film, liquid crystal orientation film at a substrate scatters uniformly-spaced thing of pearl, another piece substrate of fitting is in the inboard so that be formed with the face of a side of liquid crystal orientation film, and decompression seals after injecting liquid crystal.Also can make by the following method the liquid crystal structure cell: a pair of substrate of preparing to be formed with liquid crystal orientation film, scatter pearl uniformly-spaced behind the thing at the liquid crystal orientation film of a substrate, drip liquid crystal, then another piece substrate of fitting, be in the inboard so that be formed with the face of a side of liquid crystal orientation film, seal.At this moment, preferred 1～30 μ m of the thickness of spacer, more preferably 2～10 μ m.

By exemplifying for example following method to liquid crystal orientation film and liquid crystal layer while the operation that applies the voltage irradiation ultraviolet radiation and make the liquid crystal structure cell: by applying voltage to being arranged between the electrode on the substrate, thereby liquid crystal orientation film and liquid crystal layer are applied electric field, irradiation ultraviolet radiation under the state that keeps described electric field.Here, interelectrode voltage for example is 5～30Vp-p, preferred 5～20Vp-p.The ultraviolet irradiation amount for example is 1～60J, below the preferred 40J, when ultraviolet irradiation amount is few, can suppress the reliability decrease that the destruction by the member that consists of liquid crystal display device causes, and the minimizing ultraviolet irradiation time can improve manufacturing efficient thus, so comparatively suitable.

As mentioned above, if to liquid crystal orientation film and liquid crystal layer while applying the voltage irradiation ultraviolet radiation, then the reaction of the polymerizable compound shown in the following formula (1) forms polymkeric substance, remembered the vergence direction of liquid crystal molecule by this polymkeric substance, can accelerate by this response speed of the liquid crystal display device of gained.

The liquid crystal display device of above making for containing the polymerizable compound shown in the following formula (1) in the liquid crystal aligning agent that makes the formation liquid crystal orientation film is illustrated, but liquid crystal display device of the present invention also can be to make the liquid crystal display device that contains the polymerizable compound shown in the following formula (1) in the liquid crystal and make.Particularly, it is the liquid crystal display device with vertical orientation mode of liquid crystal structure cell, this liquid crystal structure cell comprises in opposite directions two substrates of configuration, be arranged at the liquid crystal layer between substrate, be arranged at the liquid crystal orientation film between substrate and the liquid crystal layer, this liquid crystal structure cell is made by the following method: liquid crystal aligning agent is coated on two substrates burns till, form by this liquid crystal orientation film, configure two substrates so that this liquid crystal orientation film is opposed, to be clipped between these two substrates, while liquid crystal layer is applied the voltage irradiation ultraviolet radiation by the liquid crystal layer that the liquid crystal that contains the polymerizable compound shown in the following formula (1) consists of.By as mentioned above the liquid crystal layer that contains the polymerizable compound shown in the following formula of the present invention (1) being made the polymerizable compound polymerization shown in the following formula (1) while applying the voltage irradiation ultraviolet radiation, make the liquid crystal indicator of response speed excellence.

Substrate with make the liquid crystal aligning agent that forms liquid crystal orientation film in contain the polymerizable compound shown in the following formula (1) and the above-mentioned liquid crystal display device made is identical.

Liquid crystal orientation film by coating from liquid crystal aligning agent of the present invention, remove liquid crystal aligning agent behind the polymerizable compound shown in the following formula (1), the method for for example burning till behind the existing liquid crystal aligning agent forms, can be by forming with the same operation of the manufacture method of above-mentioned liquid crystal orientation film.

As the liquid crystal that consists of liquid crystal layer, use the liquid crystal that contains the polymerizable compound shown in the following formula (1).The content of the polymerizable compound shown in the following formula (1) for example is 0.01 mass parts～0.10 mass parts with respect to liquid crystal 100 mass parts.As mentioned above, even the content of contained polymerizable compound is few in the liquid crystal, owing to having used the compound shown in the following formula (1) among the present invention, therefore also can improve fully the response speed of liquid crystal display device.Liquid crystal material is with above same, can use the liquid crystal material that uses in negative liquid crystals such as the MLC-6608 of Merck ﹠ Co., Inc.'s system or MLC-6609 etc., the existing vertical orientation mode.

This liquid crystal layer is clipped in two methods between the substrate and makes the above-mentioned liquid crystal display device that contains the polymerizable compound shown in the following formula (1) in the liquid crystal aligning agent that forms liquid crystal orientation film and make identical.

By exemplifying for example following method to liquid crystal layer while the operation that applies the voltage irradiation ultraviolet radiation and make the liquid crystal structure cell: by applying voltage to being arranged between the electrode on the substrate, thereby apply voltage to liquid crystal layer, irradiation ultraviolet radiation under the state that keeps described electric field.Here, interelectrode voltage for example is 5～30Vp-p, preferred 5～20Vp-p.The ultraviolet irradiation amount for example is 1～60J, below the preferred 40J, when ultraviolet irradiation amount is few, can suppress the reliability decrease that the destruction by the member that consists of liquid crystal display device causes, and the minimizing ultraviolet irradiation time can improve manufacturing efficient thus, so comparatively suitable.

As mentioned above, if to liquid crystal layer while applying the voltage irradiation ultraviolet radiation, then the reaction of the polymerizable compound shown in the following formula (1) forms polymkeric substance, is remembered the vergence direction of liquid crystal molecule by this polymkeric substance, can accelerate by this response speed of the liquid crystal display device of gained.

Also can be to make in the liquid crystal aligning agent that forms liquid crystal orientation film to contain the polymerizable compound shown in the following formula (1) and make the liquid crystal display device that contains the polymerizable compound shown in the following formula (1) in the liquid crystal and make.In addition, both can be that the liquid crystal orientation film that is formed at two substrates all is the liquid crystal orientation film that forms with the liquid crystal aligning agent that contains the polymerizable compound shown in the following formula (1), also can be that to only have a side liquid crystal orientation film be the liquid crystal orientation film that forms with the liquid crystal aligning agent that contains the polymerizable compound shown in the following formula (1), the opposing party's liquid crystal orientation film be the liquid crystal orientation film that forms with the liquid crystal aligning agent that does not contain the polymerizable compound shown in the following formula (1).

Above-mentioned liquid crystal aligning agent not only can be used as the liquid crystal aligning agent for the manufacture of the liquid crystal display device of the vertical orientation modes such as PSA type liquid-crystal display and SC-PVA type liquid-crystal display, also is suitable for the purposes of the liquid crystal orientation film made by friction treatment or light orientation process.

Embodiment

Below be described in more detail based on embodiment, but the present invention is not subjected to any restriction of this embodiment.

Synthesizing of＜polymerizable compound 〉

Synthesizing of (embodiment 1) polymerizable compound (RM1)

In the 300ml eggplant type flask with cooling tube, add 4,4 '-xenol 6.7g (35.9mmol), 2-(4-brombutyl)-1,3-dioxolane 15.0g (71.7mmol), salt of wormwood 19.8g (143mmol) and acetone 150ml make mixture, in 60 ℃ stirrings 48 hour on one side make its reaction on one side.After reaction finished, under reduced pressure steaming desolventized, and obtains yellow moistening solid.Then, this solid is mixed with water 200ml, add chloroform 80ml and extract.Extraction is carried out 3 times.

Add anhydrous magnesium sulfate in the organic layer that gets at separatory and carry out drying, under reduced pressure steaming desolventizes after the filtration, obtains yellow solid.By recrystallization (hexane/chloroform=4/1 (volume ratio)) this solid of purifying, thereby obtain white solid 14.6g.The result who measures the gained white solid with NMR is as follows.With the gained dissolution of solid in deuterate chloroform (CDCl ₃), use nuclear magnetic resonance device (dibasic alcohol company (ジオ one Le society) system) to measure with 300MHz.Can be confirmed by this result, this white solid is the midbody compound shown in the following reaction formula (RM1-A).Yield is 92%.

¹H-NMR(CDCl ₃)δ：1.65(m,4H),1.74(m,4H),1.87(m,4H),3.86(m,4H),3.97(m,8H),4.89(t,2H),6.92(m,4H),7.44(m,4H).

[changing 28]

Then, in with the 500ml eggplant type flask of cooling tube, add midbody compound (RM1-A) 13.3g (30mmol), 2-(brooethyl) the vinylformic acid 11.6g (70mmol), 10% hydrochloric acid (aq) 50ml, tetrahydrofuran (THF) (THF) 160ml, tin chloride (II) 13.2g (70mmol) that obtain as mentioned above and make mixture, stir in 70 ℃ and made its reaction in 20 hours.After reaction finished, with the reaction solution filtration under diminished pressure, 200ml mixed with pure water, adds therein chloroform 100ml and extracts.Extraction is carried out 3 times.

Add anhydrous magnesium sulfate in the organic layer that gets at separatory and carry out drying, steaming desolventizes the solution behind filtration under diminished pressure, obtains white solid.By recrystallization (hexane/chloroform=2/1) this solid of purifying, thereby obtain white solid 9.4g.Similarly measure the gained white solid with NMR with above-mentioned, results verification, this white solid are as the polymerizable compound (RM1) shown in the following formula of target.Yield is 64%.

¹H-NMR(CDCl ₃)δ：1.69(m,12H),2.61(m,2H),3.09(m,2H),4.00(t,4H),4.57(m,2H),5.64(m,2H),6.24(m,2H),6.92(d,4H),7.45(m,4H).

[changing 29]

Synthesizing of (embodiment 2) polymerizable compounds (RM2)

In the 300ml eggplant type flask with cooling tube, add 4,4 '-diphenyl-dimethanal 5.0g (23.8mmol), 2-(brooethyl) vinylformic acid 7.9g (47.6mmol), 10% hydrochloric acid (aq) 33ml, tetrahydrofuran (THF) (THF) 100ml, tin chloride (II) 9.5g (50mmol) make mixture, stir in 70 ℃ and make its reaction in 20 hours.Reaction is injected into pure water 300ml with reaction solution after finishing, and obtains white solid.Separating obtained solid behind recrystallization (hexane/chloroform=2/1) purifying, obtains white solid 3.5g.Measure this solid with NMR, results verification, this white solid are as the polymerizable compound (RM2) shown in the following formula of target.Yield is 72%.

¹H-NMR(CDCl ₃)δ：2.99(m,2H),3.42(m,2H),5.60(m,2H),5.74(m,2H),6.36(m,2H),7.42(m,4H),7.60(m,4H).

[changing 30]

(comparative example 1) polymerizable compound (RM3)

Polymerizable compound shown in the known following formula is denoted as RM3.

[changing 31]

Synthesizing of (embodiment 3) polymerizable compounds (RM4)

In the 500ml eggplant type flask with cooling tube, add 4,4 '-xenol 11.2g (60mmol), 2-(4-brombutyl)-1,3-dioxolane 25.0g (138mmol), salt of wormwood 35.9g (260mmol) and acetone 200ml make mixture, in 60 ℃ stirrings 48 hour on one side make its reaction on one side.After reaction finished, under reduced pressure steaming desolventized, and obtains yellow moistening solid.Then, this solid is mixed with water 200ml, add chloroform 100ml and extract.Extraction is carried out 3 times.

Add anhydrous magnesium sulfate in the organic layer that gets at separatory and carry out drying, under reduced pressure steaming desolventizes after the filtration, obtains yellow solid.This dissolution of solid in chloroform, after hexane (hexane/chloroform=2/1) precipitation, is obtained white solid 17.6g.The result who measures this solid with NMR is as follows.Can be confirmed by this result, this white solid is the compound shown in the following reaction formula (RM4-A).Yield is 76%.

¹H-NMR(CDCl ₃)δ：2.19(m,4H),3.89(m,4H),4.01(m,4H),4.16(m,4H),5.11(m,2H),6.95(m,4H),7.45(m,4H).

[changing 32]

Then, in with the 500ml eggplant type flask of cooling tube, add compound (RM4-A) 10.0g (26mmol), 2-(brooethyl) the vinylformic acid 10.0g (60.6mmol), 10%HCl (aq) 32ml, tetrahydrofuran (THF) (THF) 140ml, tin chloride (II) 11.4g (60.6mmol) that obtain as mentioned above and make mixture, stir in 70 ℃ and made its reaction in 20 hours.After reaction finished, with the reaction solution filtration under diminished pressure, 200ml mixed with pure water, adds therein chloroform 100ml and extracts.Extraction is carried out 3 times.

Add anhydrous magnesium sulfate in the organic layer after extraction and carry out drying, steaming desolventizes the solution behind filtration under diminished pressure, obtains white solid.This dissolution of solid in chloroform, with hexane (hexane/chloroform=2/1) precipitation, is obtained white solid.Behind this solid of methanol wash, obtain white solid 4.7g.The result who measures this solid with NMR is as follows.Can be confirmed by this result, this white solid is as the polymerizable compound (RM4) shown in the following reaction formula of target.Yield is 42%.

¹H-NMR(CDCl ₃)δ：2.18(m,4H),2.76(m,2H),3.16(m,2H),4.18(m,4H),4.84(m,2H),5.67(m,2H),6.27(m,2H),6.95(d,4H),7.46(m,4H).

[changing 33]

The preparation of＜liquid crystal aligning agent 〉

The abbreviation of using in the preparation of following liquid crystal aligning agent is as described below.

BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride

TCA: 2,3 shown in the following formula, 5-tricarboxylic basic ring amyl group acetic acid-Isosorbide-5-Nitrae: 2,3-dianhydride

[changing 34]

M-PDA: mphenylenediamine

P-PDA: Ursol D

PCH:1,3-diamino-4-[4-(4-heptyl cyclohexyl) phenoxy group] benzene

DBA:3, the 5-diaminobenzoic acid

DA-1: 3 shown in the following formula, 5-diaminobenzoic acid-2-(methacryloxy) ethyl ester

[changing 35]

DA-2: the N shown in the following formula ¹, N ¹-diallyl benzene-1,2, the 4-triamine

[changing 36]

DA-3: 3 shown in the following formula, 5-diaminobenzoic acid cholesterol ester

[changing 37]

The 3-AMP:3-aminomethyl pyridine

The NMP:N-N-methyl-2-2-pyrrolidone N-

BCS: ethylene glycol butyl ether

The molecule measuring fixed condition of polyimide is as described below.

Device: eternal lasting science Co., Ltd. (セ Application Star ュ one science society) normal temperature gel permeation chromatography processed (GPC) devices (SSC-7200)

Post: the post (KD-803, KD-805) of clear and electrician (Shodex) Co., Ltd. system

Column temperature: 50 ℃

Elutriant: N, and the N'-dimethyl formamide (as additive, lithiumbromide monohydrate (LiBrH ₂O) be that 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF) (THF))

Flow velocity: 1.0ml/ minute

Calibration curve is made and to be used standard test specimen: (East ソー society of eastern Cao company) TSK standard polyethylene oxide processed (molecular weight approximately 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リマーラボラトリー society) polyoxyethylene glycol processed (molecular weight approximately 12000,4000,1000).

The following mensuration of imide rate of polyimide.The polyimide powder of 20mg is joined NMR stopple coupon (the specification φ 5 of wasteland's science Co., Ltd. NMR stopple coupon processed), add the deuterate methyl-sulphoxide (DMSO-d of 1.0ml ₆, the 0.05%TMS mixture), make its dissolving fully with ultrasonic wave.For this solution, measured the proton N MR of 500MHz with the NMR determinator (JNW-ECA500) of NEC data Co., Ltd. (Japanese Hu デ one タ system society) system.The imide rate is following tries to achieve: will come from that the proton of unconverted structure is decided to be the benchmark proton before and after the imidization, and use the peak integrated value of this proton and the proton peak integrated value from the NH base of amido acid that occurs is tried to achieve by following formula near 9.5～10.0ppm.In the following formula, x is the proton peak integrated value from the NH base of amido acid, and y is the peak integrated value of benchmark proton, the number ratio with respect to the benchmark proton of NH matrix of an amido acid when α is polyamic acid (the imide rate is 0%).

Imide rate (%)=(1-α x/y) * 100

(embodiment 4)

BODA (28.15g, 112.5mmol), m-PDA (4.86g, 45mmol), PCH (11.42g, 30mmol), DBA (11.41g, 75mmol) are mixed in NMP (187.8g), in 80 ℃ the reaction 5 hours after, add CBDA (6.77g, 36mmol) and NMP (62.6g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (313g), add diacetyl oxide (79.1g) and pyridine (30.7g) as imidization catalyst, 100 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (4000ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (A) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 70%, and number-average molecular weight is 18000, and weight-average molecular weight is 59000.

Add NMP (40.2g) at the polyimide powder (A) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.The 5.0 % by weight nmp solutions (6.0g) (counting 0.3g with 3-AMP), NMP (27.9g) and the BCS (20.0g) that add 3-AMP in this solution in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (A1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (A1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (A2).Similarly, add the polymerizable compound RM10.18g that obtains among the embodiment 1 (be 30 quality %s with respect to solids component) with respect to liquid crystal aligning agent (A1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (A3).

(embodiment 5)

BODA (8.76g, 35.0mmol), p-PDA (3.78g, 35.0mmol), PCH (5.33g, 14.0mmol), DA-1 (5.55g, 21.0mmol) are mixed in NMP (90.0g), in 80 ℃ the reaction 5 hours after, add CBDA (6.59g, 33.6mmol) and NMP (30.0g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (140.0g), add diacetyl oxide (20.0g) and pyridine (25.8g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (1800ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (B) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 50%, and number-average molecular weight is 22000, and weight-average molecular weight is 77000.

Add NMP (74.0g) at the polyimide powder (B) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (B1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (B1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (B2).

(embodiment 6)

BODA (3.13g, 12.5mmol), p-PDA (1.08g, 10mmol), PCH (1.90g, 5mmol), DA-1 (2.64g, 10mmol) are mixed in NMP (33.3g), in 80 ℃ the reaction 5 hours after, add CBDA (2.35g, 12mmol) and NMP (11.1g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (55.5g), add diacetyl oxide (7.7g) and pyridine (9.9g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (710ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (C) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 48%, and number-average molecular weight is 26000, and weight-average molecular weight is 102000.

Add NMP (74.0g) at the polyimide powder (C) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (C1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (C1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (C2).

(embodiment 7)

BODA (3.13g, 12.5mmol), p-PDA (0.81g, 7.5mmol), PCH (1.90g, 5mmol), DA-1 (3.30g, 12.5mmol) are mixed in NMP (34.5g), in 80 ℃ the reaction 5 hours after, add CBDA (2.35g, 12mmol) and NMP (11.5g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (57.5g), add diacetyl oxide (7.7g) and pyridine (9.9g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (730ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (D) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 50%, and number-average molecular weight is 23000, and weight-average molecular weight is 63000.

Add NMP (74.0g) at the polyimide powder (D) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (D1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (D1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (D2).

(embodiment 8)

BODA (5.00g, 20mmol), p-PDA (0.87g, 8mmol), PCH (3.05g, 8mmol), DA-1 (6.34g, 24mmol) are mixed in NMP (57.1g), in 80 ℃ the reaction 5 hours after, add CBDA (3.77g, 19.2mmol) and NMP (19.0g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (95.5g), add diacetyl oxide (12.3g) and pyridine (15.9g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (1200ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (E) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 51%, and number-average molecular weight is 31000, and weight-average molecular weight is 111000.

Add NMP (74.0g) at the polyimide powder (E) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (E1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (E1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (E2).

(embodiment 9)

BODA (5.00g, 20.0mmol), p-PDA (2.16g, 20.0mmol), PCH (3.04g, 8.0mmol), DA-2 (2.44g, 12.0mmol) are mixed in NMP (49.2g), in 80 ℃ the reaction 5 hours after, add CBDA (3.77g, 19.2mmol) and NMP (16.4g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (75.0g), add diacetyl oxide (9.33g) and pyridine (14.6g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (950ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (F) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 47%, and number-average molecular weight is 20100, and weight-average molecular weight is 106000.

Add NMP (74.0g) at the polyimide powder (F) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (F1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (F1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (F2).

(embodiment 10)

BODA (5.00g, 20.0mmol), p-PDA (0.87g, 8.0mmol), PCH (3.04g, 8.0mmol), DA-2 (4.88g, 24.0mmol) are mixed in NMP (52.7g), in 80 ℃ the reaction 5 hours after, add CBDA (3.77g, 19.2mmol) and NMP (17.56g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (75g), add diacetyl oxide (8.7g) and pyridine (13.5g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (950ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (G) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 50%, and number-average molecular weight is 20000, and weight-average molecular weight is 86000.

Add NMP (74.0g) at the polyimide powder (G) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (G1).

Add the polymerizable compound RM10.06g that obtains among the embodiment 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (G1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (G2).

(embodiment 11)

TCA (3.36g, 15.0mmol), p-PDA (1.30g, 12.0mmol), DA-3 (3.14g, 6.0mmol), DA-1 (3.17g, 12.0mmol) are mixed in NMP (41.6g), in 60 ℃ the reaction 5 hours after, add CBDA (2.88g, 14.7mmol) and NMP (13.9g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (68g), add diacetyl oxide (6.0g) and pyridine (11.7g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (850ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (H) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 50%, and number-average molecular weight is 18000, and weight-average molecular weight is 58000.

Add NMP (74.0g) at the polyimide powder (H) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (H1).

Add RM10.06g (be 10wt% with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (H1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (H2).

(embodiment 12)

BODA (6.01g, 24.0mmol), p-PDA (2.60g, 24.0mmol), PCH (6.85g, 18.0mmol), DA-1 (4.76g, 18.0mmol) are dissolved among the NMP (81.5g), in 80 ℃ the reaction 5 hours after, add CBDA (6.94g, 35.4mmol) and NMP (27.2g), in 40 ℃ of reactions 10 hours, obtain polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (135g), add diacetyl oxide (18.3g) and pyridine (23.6g) as imidization catalyst, 50 ℃ of lower reactions 3 hours.This reaction soln is put in the methyl alcohol (1700ml) throw out that filtering separation obtains.With this throw out methanol wash, obtain polyimide powder (I) at 100 ℃ of lower drying under reduced pressure.The imide rate of this polyimide is 60%, and number-average molecular weight is 12000, and weight-average molecular weight is 39000.

Add NMP (74.0g) at the polyimide powder (I) of gained in (6.0g), stir in 50 ℃ and made its dissolving in 12 hours.In this solution, add BCS (20.0g), in 50 ℃ of stirrings 5 hours, thereby obtain liquid crystal aligning agent (I1).

Add polymerizable compound (RM4) 0.06g obtain as mentioned above (be 10 quality %s with respect to solids component) with respect to liquid crystal aligning agent (I1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (I2).

＜comprise the preparation of the liquid crystal of polymerizable compound 〉

Comprise the liquid crystal preparation as described below of polymerizable compound.Add the polymerizable compound RM10.0147g (3 * 10 that obtains among the embodiment 1 with respect to MLC-6608 (Merck ﹠ Co., Inc.'s trade(brand)name processed) 20g ^-5Mol), make its dissolving in 3 hours in 80 ℃ of stirrings, make liquid crystal 1.

Similarly, the MLC-6608 with respect to 20g adds the polymerizable compound RM20.0097g (3 * 10 that obtains among the embodiment 2 ^-5Mol), make its dissolving in 3 hours in 80 ℃ of stirrings, make liquid crystal 2.

In addition, the MLC-6608 with respect to 20g adds the polymerizable compound RM30.0097g (3 * 10 that obtains in the comparative example 1 ^-5Mol), make its dissolving in 3 hours in 80 ℃ of stirrings, make liquid crystal 3.

In liquid crystal 1, liquid crystal 2 and the liquid crystal 3, confirm that each polymerizable compound is dissolved among the liquid crystal material MLC-6608, even also can not separate out at 1 month post polymerization compound of stored refrigerated.

The making of＜liquid crystal structure cell 〉

(embodiment 13)

Use the liquid crystal aligning agent (A1) that obtains among the embodiment 4, carry out the manufacturing of liquid crystal structure cell with step as follows.The liquid crystal aligning agent (A1) that obtains among the embodiment 4 is spin-coated on is formed with on the ito surface of ITO electrode base board that Pixel Dimensions is 100 μ m * 300 μ m, the live width/spacing ITO electrode pattern that is respectively 5 μ m, with 80 ℃ hot-plates after dry 90 seconds, in 200 ℃ heated air circulation type stove, carry out 30 minutes burn till, form the liquid crystal orientation film of thickness 100nm.

In addition, liquid crystal aligning agent (A1) is spin-coated on the ito surface that does not form electrode pattern, with 80 ℃ hot-plates after dry 90 seconds, in 200 ℃ heated air circulation type stove, carries out 30 minutes burn till, form the liquid crystal orientation film of thickness 100nm.

For two aforesaid substrates, after the liquid crystal orientation film of a substrate scatters the pearl spacer of 6 μ m, printing and sealing agent thereon (Resins, epoxy of solvent type heat-curing type).Then, as the inboard, behind the former baseplate-laminating, make sealant cures with the face of the side that is formed with liquid crystal orientation film of another piece substrate, make the negative crystal born of the same parents.In this negative crystal born of the same parents, inject above-mentioned liquid crystal 1 by the decompression injection method, in 120 ℃ baking oven, carry out isotropy and process (utilizing the liquid crystal reorientation of heating to process), make the liquid crystal structure cell.

Measure the response speed after just the making of liquid crystal structure cell of gained by following method.Then, this liquid crystal structure cell is applied the voltage of 20Vp-p, passed through the UV of the bandpass filter of 313nm from the outside irradiation of this liquid crystal structure cell under this state, irradiation dose is 5J.Then, again measure response speed, relatively the response speed behind the UV pre-irradiation.After just the making of liquid crystal structure cell behind (initially) and the irradiation UV response speed of (UV shines afterwards) the results are shown in table 2.

" measuring method of response speed "

At first, the liquid crystal structure cell is configured between one group of polaroid in the determinator that a group of polaroid, light quantity detector by backlight, orthogonal thereto Nicol state consist of successively.At this moment, be formed with the pattern of ITO electrode at lines/interval and Nicol crossed angle at 45 °.Then, above-mentioned liquid crystal structure cell is applied the square wave of voltage ± 4V, frequency 1kHz, read variation till the brightness that is observed by light quantity detector reaches capacity with oscilloscope, brightness when not applying voltage is made as 0%, to apply ± saturated brightness value during the voltage of 4V is made as 100%, and brightness was changed to for 90% required time as response speed from 10%.

(embodiment 14)

Except replace liquid crystal 1 with liquid crystal 2, carry out operation similarly to Example 13, relatively the response speed behind the UV pre-irradiation.

(comparative example 2)

Except replace liquid crystal 1 with liquid crystal 3, carry out operation similarly to Example 13, relatively the response speed behind the UV pre-irradiation.

(embodiment 15)

Except using liquid crystal aligning agent (A2) to replace liquid crystal aligning agent (A1), replace the UV of liquid crystal 1, irradiation 20J to replace shining the UV of 5J with MLC-6608, carry out operation similarly to Example 13, relatively the response speed behind the UV pre-irradiation.

(embodiment 16)

Except use liquid crystal aligning agent (A3) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 3)

Except use liquid crystal aligning agent (A1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 17)

Except use liquid crystal aligning agent (B2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 4)

Except use liquid crystal aligning agent (B1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 18)

Except use liquid crystal aligning agent (C2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 5)

Except use liquid crystal aligning agent (C1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 19)

Except use liquid crystal aligning agent (D2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 6)

Except use liquid crystal aligning agent (D1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 20)

Except use liquid crystal aligning agent (E2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 7)

Except use liquid crystal aligning agent (E1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 21)

Except use liquid crystal aligning agent (F2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 8)

Except use liquid crystal aligning agent (F1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 22)

Except use liquid crystal aligning agent (G2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(comparative example 9)

Except use liquid crystal aligning agent (G1) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 23)

Except use liquid crystal aligning agent (H2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

Consequently, as shown in table 2, contain in the liquid crystal among the embodiment 13 and embodiment 14 of the polymerizable compound shown in the following formula (1), the increase rate of the response speed of the response speed after the uviolizing before with respect to uviolizing is compared with the comparative example 2 that contains existing polymerizable compound and is significantly improved.Therefore can confirm, contain the polymerizable compound shown in the following formula (1) in the liquid crystal by making, even the amount of the polymerizable compound that adds in the liquid crystal is few, also can significantly improve response speed.

And, use V and W in the following formula (1) to compare as the embodiment 14 of the polymerizable compound of singly-bound with W with V in using following formula (1) as the embodiment 13 of the polymerizable compound of oxyalkylene group, the increase rate of response speed is obviously higher.

In addition, the comparative example 3～9 that does not contain the polymerizable compound shown in the following formula (1) in the embodiment 15～23 that contains the polymerizable compound shown in the following formula (1) in the liquid crystal aligning agent and the liquid crystal aligning agent is compared, and the increase rate of the response speed before and after the uviolizing is obviously higher.Therefore can confirm, contain the polymerizable compound shown in the following formula (1) in the liquid crystal aligning agent by making, can significantly improve response speed.Can also confirm, the embodiment 15～23 that has changed the kind of polyimide compares with corresponding comparative example, and the increase rate of response speed is all higher.

In addition, the addition of the polymerizable compound shown in the following formula (1) is that embodiment 16 and the addition of 30 quality % is that the embodiment 15 of 10 quality % compares, and the increase rate of response speed is higher.Therefore can confirm, the addition of the polymerizable compound shown in the following formula (1) is more, and response speed improves.

And, the embodiment 17～23 that use has the polyimide of photoreactive group compares with the embodiment 15 that uses the polyimide that does not have photoreactive group, response speed significantly improves, can confirm that then response speed further improves if use the polyimide with photoreactive group.

[table 2]

(embodiment 24)

Add the polymerizable compound RM20.06g that obtains among the embodiment 2 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (D1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (D3).

(comparative example 10)

Add the polymerizable compound RM30.06g that obtains in the comparative example 1 (be 10 quality %s with respect to solids component) with respect to above-mentioned liquid crystal aligning agent (D1) 10.0g, at room temperature stir and made its dissolving in 3 hours, make liquid crystal aligning agent (D4).

(embodiment 25)

Except use liquid crystal aligning agent (D3) replaces liquid crystal aligning agent (D2), carry out operation similarly to Example 19, relatively the response speed behind the UV pre-irradiation.The results are shown in table 3.

(embodiment 26)

Burning till in the heated air circulation type stove do not adopted 200 ℃ of conditions of 30 minutes but adopted 160 ℃ of conditions of 30 minutes, carries out operation similarly to Example 25, relatively the response speed behind the UV pre-irradiation.

(comparative example 11)

Except use liquid crystal aligning agent (D4) replaces liquid crystal aligning agent (D3), carry out operation similarly to Example 25, relatively the response speed behind the UV pre-irradiation.

(comparative example 12)

Burning till in the heated air circulation type stove do not adopted 200 ℃ of conditions of 30 minutes but adopted 160 ℃ of conditions of 30 minutes, carries out the operation same with comparative example 11, relatively the response speed behind the UV pre-irradiation.

(embodiment 27)

Except use liquid crystal aligning agent (I2) replaces liquid crystal aligning agent (A2), carry out operation similarly to Example 15, relatively the response speed behind the UV pre-irradiation.

(embodiment 28)

Except firing temperature is changed into 140 ℃ from 200 ℃, carry out operation similarly to Example 27, relatively the response speed behind the UV pre-irradiation.

(comparative example 13)

Except use liquid crystal aligning agent (I1) replaces liquid crystal aligning agent (I2), carry out operation similarly to Example 27, relatively the response speed behind the UV pre-irradiation.

(comparative example 14)

Except firing temperature is changed into 140 ℃ from 200 ℃, carry out the operation same with comparative example 13, relatively the response speed behind the UV pre-irradiation.

Consequently, use among the embodiment 25～28 of the liquid crystal aligning agent contain the polymerizable compound shown in the following formula (1) and can confirm, irrelevant with firing temperature, can realize the abundant raising of response speed by the UV irradiation.On the other hand, use contains in the comparative example of liquid crystal aligning agent of existing polymerizable compound RM3, although be the abundant raising by UV irradiation visible response speed in 160 ℃ the comparative example 11 at firing temperature, but in firing temperature was 200 ℃ comparative example 12, the increase rate of response speed significantly reduced.In addition, use in the comparative example 13 and comparative example 14 of the liquid crystal aligning agent that does not add polymerizable compound, the response speed before and after the uviolizing is all almost constant under any firing temperature.

[table 3]

The abbreviation of hereinafter using is as described below.

TEOS: tetraethoxysilane

C18: octadecyltriethoxy silane

ACPS:3-acryloxy propyl trimethoxy silicane

UPS:3-urea groups propyl-triethoxysilicane

The MPMS:3-methacryloxypropyl trimethoxy silane

VTES: triethoxy vinyl silanes

The NMP:N-N-methyl-2-2-pyrrolidone N-

HG:2-methyl-2,4-pentanediol (another name: hexylene glycol)

The BCS:2-butyl cellosolve

The preparation of＜polysiloxane-based liquid crystal aligning agent 〉

(comparative example 15)

The C18 of TEOS, the 1.34g of BCS, the 32.4g of 24.5g is mixed in possessing the 100mL four-hole reaction flask of thermometer, return line, make the solution of organoalkoxysilane monomer.At room temperature drip in this solution in advance the water of BCS, the 8.65g of 12.3g and the solution that mixes as the oxalic acid 0.14g of catalyzer with time of 30 minutes.With this solution stirring after 30 minutes, it was refluxed 30 minutes, then add the mixed solution of the BCS of methanol solution 0.46g that ready-made UPS content is 92 quality % and 0.34g.After it was refluxed 30 minutes, let cool, obtain SiO ₂Conversion concentration is the polysiloxane solution of 12 quality %.

The NMP of BCS, the 49.6g of polysiloxane solution 38.0g, the 3.63g of gained is mixed, obtain SiO ₂Conversion concentration is the liquid crystal aligning agent (a) of 5 quality %.

(embodiment 29)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 15, obtains (a), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(embodiment 30)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 15, obtains (a), make it reach 20 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(embodiment 31)

Add polymerizable compound RM2 in the liquid crystal aligning agent that in comparative example 15, obtains (a), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(comparative example 16)

The C18 of TEOS, the 1.33g of BCS, the 25.7g of 24.5g and the VTES of 6.09g are mixed in possessing the 100mL four-hole reaction flask of thermometer, return line, make the solution of organoalkoxysilane monomer.At room temperature drip in this solution in advance the water of BCS, the 8.64g of 12.3g and the solution that mixes as the oxalic acid 0.72g of catalyzer with time of 30 minutes.With this solution stirring after 30 minutes, it was refluxed 30 minutes, then add the mixed solution of the BCS of methanol solution 0.46g that ready-made UPS content is 92 quality % and 0.34g.After it was refluxed 30 minutes, let cool, obtain SiO ₂Conversion concentration is the polysiloxane solution of 12 quality %.

The NMP of BCS, the 49.6g of polysiloxane solution 38.0g, the 3.63g of gained is mixed, obtain SiO ₂Conversion concentration is the liquid crystal aligning agent (b) of 5 quality %.

(embodiment 32)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 16, obtains (b), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(embodiment 33)

Add polymerizable compound RM2 in the liquid crystal aligning agent that in comparative example 16, obtains (b), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(comparative example 17)

The C18 of TEOS, the 1.33g of BCS, the 22.3g of 23.3g and the ACPS of 11.3g are mixed in possessing the 100mL four-hole reaction flask of thermometer, return line, make the solution of organoalkoxysilane monomer.At room temperature drip in this solution in advance the water of BCS, the 8.64g of 11.6g and the solution that mixes as the oxalic acid 0.72g of catalyzer with time of 30 minutes.With this solution stirring after 30 minutes, it was refluxed 30 minutes, then add the mixed solution of the BCS of methanol solution 0.46g that ready-made UPS content is 92 quality % and 0.34g.After it was refluxed 30 minutes, let cool, obtain SiO ₂Conversion concentration is the polysiloxane solution of 12 quality %.

The NMP of BCS, the 49.0g of polysiloxane solution 38.0g, the 4.24g of gained is mixed, obtain SiO ₂Conversion concentration is the liquid crystal aligning agent (c) of 5 quality %.

(embodiment 34)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 17, obtains (c), make it reach 5 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(embodiment 35)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 17, obtains (c), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(comparative example 18)

Add polymerizable compound RM3 in the liquid crystal aligning agent that in comparative example 17, obtains (c), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(comparative example 19)

The C18 of TEOS, the 1.33g of BCS, the 25.7g of 23.4g and the MPMS of 7.95g are mixed in possessing the 100mL four-hole reaction flask of thermometer, return line, make the solution of organoalkoxysilane monomer.At room temperature drip in this solution in advance the water of BCS, the 8.64g of 11.7g and the solution that mixes as the oxalic acid 0.58g of catalyzer with time of 30 minutes.With this solution stirring after 30 minutes, it was refluxed 30 minutes, then add the mixed solution of the BCS of methanol solution 0.46g that ready-made UPS content is 92 quality % and 0.34g.After it was refluxed 30 minutes, let cool, obtain SiO ₂Conversion concentration is the polysiloxane solution of 12 quality %.

The NMP of BCS, the 49.0g of polysiloxane solution 38.0g, the 4.20g of gained is mixed, obtain SiO ₂Conversion concentration is the liquid crystal aligning agent (d) of 5 quality %.

(embodiment 36)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 19, obtains (d), make it reach 5 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(embodiment 37)

Add polymerizable compound RM1 in the liquid crystal aligning agent that in comparative example 19, obtains (d), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

(comparative example 20)

Add polymerizable compound RM3 in the liquid crystal aligning agent that in comparative example 19, obtains (d), make it reach 10 quality %, at room temperature stirred 5 hours, make varnish (liquid crystal aligning agent).

The manufacturing of＜liquid crystal structure cell 〉

(embodiment 38)

Use the varnish (liquid crystal aligning agent) that obtains among the embodiment 29, carry out the manufacturing of liquid crystal structure cell with step as follows.At first, the varnish that obtains among the embodiment 29 is spin-coated on is formed with on the ito surface of ITO electrode base board that Pixel Dimensions is 100 μ m * 300 μ m, the live width/spacing ITO electrode pattern that is respectively 5 μ m, with 80 ℃ hot-plates after dry 5 seconds, in 200 ℃ heated air circulation type stove, carry out 30 minutes burn till, form the liquid crystal orientation film of thickness 100nm.

In addition, the liquid crystal aligning agent (a) that obtains in the comparative example 15 is spin-coated on the ito surface that does not form electrode pattern, with 80 ℃ hot-plates after dry 5 seconds, in 200 ℃ heated air circulation type stove, carry out 30 minutes burn till, form the liquid crystal orientation film of thickness 100nm.

For two aforesaid substrates, after the liquid crystal orientation film of a substrate scatters the pearl spacer of 6 μ m, printing and sealing agent thereon (Resins, epoxy of solvent type heat-curing type).Then, as the inboard, behind the former baseplate-laminating, make sealant cures with the face of the side that is formed with liquid crystal orientation film of another piece substrate, make the negative crystal born of the same parents.In this negative crystal born of the same parents, inject liquid crystal MLC-6608 (Merck ﹠ Co., Inc.'s trade(brand)name processed) by the decompression injection method, in 120 ℃ baking oven, carry out isotropy and process (utilizing the liquid crystal reorientation of heating to process), make the liquid crystal structure cell.

Measure the response speed after just the making of liquid crystal structure cell of gained by following method.Then, this liquid crystal structure cell is applied the voltage of 20Vp-p, passed through the UV of the bandpass filter of 313nm from the outside irradiation of this liquid crystal structure cell under this state, irradiation dose is 10J.Then, again measure response speed, relatively the response speed behind the UV pre-irradiation.After just the making of liquid crystal structure cell behind the UV of (initially), irradiation 5J (behind the UV5J) and shine the UV of 10J after (behind the UV10J) response speed the results are shown in table 4.

" measuring method of response speed "

At first, the liquid crystal structure cell is configured between one group of polaroid in the determinator that a group of polaroid, light quantity detector by backlight, orthogonal thereto Nicol state consist of successively.At this moment, be formed with the pattern of ITO electrode at lines/interval and cross Nicols angle at 45 °.Then, above-mentioned liquid crystal structure cell is applied the square wave of voltage ± 4V, frequency 1kHz, read variation till the brightness that is observed by light quantity detector reaches capacity with oscilloscope, brightness when not applying voltage is made as 0%, to apply ± saturated brightness value during the voltage of 4V is made as 100%, and brightness was changed to for 90% required time as response speed from 10%.

(embodiment 39)

Except the varnish that replaces obtaining among the embodiment 29 with the varnish that obtains among the embodiment 30, carry out the operation same with embodiment 38.

(embodiment 40)

Except the varnish that replaces obtaining among the embodiment 29 with the varnish that obtains among the embodiment 31, carry out the operation same with embodiment 38.

(embodiment 41)

Except the varnish that replaces obtaining among the embodiment 29 with the varnish that obtains among the embodiment 32, carry out the operation same with embodiment 38.

(embodiment 42)

Except the varnish that replaces obtaining among the embodiment 29 with the varnish that obtains among the embodiment 33, carry out the operation same with embodiment 38.

(embodiment 43)

Except the UV of the varnish that replaces with the varnish that obtains among the embodiment 34 obtaining among the embodiment 29 and irradiation 5J replaces shining the UV of 10J, carry out the operation same with embodiment 38.

(embodiment 44)

Except the UV of the varnish that replaces with the varnish that obtains among the embodiment 35 obtaining among the embodiment 29 and irradiation 5J replaces shining the UV of 10J, carry out the operation same with embodiment 38.

(embodiment 45)

Except the UV of the varnish that replaces with the varnish that obtains among the embodiment 36 obtaining among the embodiment 29 and irradiation 5J replaces shining the UV of 10J, carry out the operation same with embodiment 38.

(embodiment 46)

Except the UV of the varnish that replaces with the varnish that obtains among the embodiment 37 obtaining among the embodiment 29 and irradiation 5J replaces shining the UV of 10J, carry out the operation same with embodiment 38.

(comparative example 21)

The varnish that the liquid crystal aligning agent that obtains (a) replaces obtaining among the embodiment 29, carry out the operation same with embodiment 38 in usage comparison example 15.

(comparative example 22)

The varnish that the liquid crystal aligning agent that obtains (b) replaces obtaining among the embodiment 29, carry out the operation same with embodiment 38 in usage comparison example 16.

(comparative example 23)

The liquid crystal aligning agent that obtains in usage comparison example 17 (c) replaces the UV of the varnish that obtains among the embodiment 29 and irradiation 5J to replace shining the UV of 10J, carries out the operation same with embodiment 38.

(comparative example 24)

The varnish that obtains in usage comparison example 18 replaces the UV of the varnish that obtains among the embodiment 29 and irradiation 5J to replace shining the UV of 10J, carries out the operation same with embodiment 38.

(comparative example 25)

The liquid crystal aligning agent that obtains in usage comparison example 19 (d) replaces the UV of the varnish that obtains among the embodiment 29 and irradiation 5J to replace shining the UV of 10J, carries out the operation same with embodiment 38.

(comparative example 26)

The varnish that obtains in usage comparison example 20 replaces the UV of the varnish that obtains among the embodiment 29 and irradiation 5J to replace shining the UV of 10J, carries out the operation same with embodiment 38.

Consequently, as shown in table 4, use contains embodiment 38～46 and the comparative example 21～23 that uses the liquid crystal aligning agent do not contain polymerizable compound and 25 and use that to contain not be that the comparative example 24 of liquid crystal aligning agent of polymerizable compound of the polymerizable compound shown in the following formula (1) is compared with 26 of the liquid crystal aligning agent of the polymerizable compound shown in the following formula (1), and the increase rate of the response speed before and after the uviolizing is obviously higher.Therefore can confirm, contain the polymerizable compound shown in the following formula (1) in the liquid crystal aligning agent by making, can significantly improve response speed.Can also confirm, the embodiment 38～46 that has changed the kind of polysiloxane compares with corresponding comparative example, and the increase rate of response speed is all higher.

Can also confirm, the addition of the polymerizable compound shown in the following formula (1) is more, and response speed improves.

And, the embodiment 41～46 that use has the polysiloxane of photoreactive group compares with the embodiment 38～40 that uses the polysiloxane that does not have photoreactive group, response speed significantly improves, can confirm that then response speed further improves if use the polysiloxane with photoreactive group.

As mentioned above, the liquid crystal aligning agent of the present invention of the polymerizable compound shown in the following formula (1) can be confirmed to contain by use, even do not contain polymerizable compound in the liquid crystal, also response speed can be accelerated.And, even do not add in a large number polymerizable compound in this liquid crystal aligning agent of the present invention, and do not increase the ultraviolet irradiation amount, also can accelerate fully response speed.

[table 4]

The possibility of utilizing on the industry

Even the liquid crystal display device that uses liquid crystal aligning agent of the present invention to make does not add in the aligned middle use of PSA mode in the situation of liquid crystal of polymerizable compound, also can provide the liquid crystal display device that can obtain with the equal characteristic of PSA mode.TFT (thin film transistor) liquid crystal display device, TN (twisted-nematic) liquid crystal display device, VA liquid crystal display device etc. that consequently, can be used for the PSA mode.

Claims

1. a polymerizable compound is characterized in that, represents with following formula (1);

[changing 1]

2. a liquid crystal aligning agent is characterized in that, comprises: polymerizable compound claimed in claim 1, the polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism, solvent.

3. liquid crystal aligning agent as claimed in claim 2, it is characterized in that, the described polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism comprise be selected from the polyimide precursor with the side chain that makes liquid crystal vertical-tropism and make this polyimide precursor imidization and polyimide at least a.

4. liquid crystal aligning agent as claimed in claim 2 is characterized in that, the described polymkeric substance that is used to form the liquid crystal orientation film that makes liquid crystal vertical-tropism comprises the polysiloxane with the side chain that makes liquid crystal vertical-tropism.

5. liquid crystal aligning agent as claimed in claim 4 is characterized in that, described polysiloxane has the photoreactivity side chain.

6. such as claim 4 or 5 described liquid crystal aligning agent, it is characterized in that, described polysiloxane is to make at least a polysiloxane that carries out polycondensation and get that is selected from organoalkoxysilane and the condenses thereof.

7. liquid crystal aligning agent as claimed in claim 6 is characterized in that, described organoalkoxysilane comprises the organoalkoxysilane shown in the following formula (7);

R ¹¹Si(OR ¹²) ₃ (7)

8. such as claim 6 or 7 described liquid crystal aligning agent, it is characterized in that, described organoalkoxysilane comprises following formula (8);

R ¹³Si(OR ¹⁴) ₃ (8)

9. a liquid crystal orientation film is characterized in that, obtains by each described liquid crystal aligning agent in the claim 2～8 is coated substrate and burnt till.

10. a liquid crystal display device is characterized in that, has the liquid crystal structure cell, while this liquid crystal structure cell is to make in the liquid crystal or contain polymerizable compound claimed in claim 1 in the liquid crystal orientation film, it is applied the voltage irradiation ultraviolet radiation and the liquid crystal structure cell made.

11. the manufacture method of a liquid crystal indicator is characterized in that, makes in the liquid crystal or contains polymerizable compound claimed in claim 1 in the liquid crystal orientation film, makes the liquid crystal structure cell while it is applied the voltage irradiation ultraviolet radiation.