CN105814478B

CN105814478B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Info

Publication number: CN105814478B
Application number: CN201480066711.7A
Authority: CN
Inventors: 芦泽亮一; 后藤耕平; 南悟志; 森内正人; 川野勇太
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-10-07
Filing date: 2014-10-06
Publication date: 2019-09-17
Anticipated expiration: 2034-10-06
Also published as: JPWO2015053232A1; WO2015053232A1; KR20160067156A; TWI659063B; JP6418401B2; KR102351459B1; TW201529726A; CN105814478A

Abstract

Aligning agent for liquid crystal contains polymer, polymerizable compound and solvent, the aromatic rings that polymerizable compound has polyunsaturated bond conjunction group, forms the functional group of hydrogen bond and at least one near functional group or more, functional group is by forming mesomorphic structure in intermolecular formation hydrogen bond.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Technical field

The present invention relates to the aligning agent for liquid crystal used when production liquid crystal orientation film, the liquid crystal aligning obtained by aligning agent for liquid crystal Film and liquid crystal indicate element.

Background technique

Liquid crystal used in LCD TV, liquid crystal display etc. indicates that element is usually provided in element for controlling liquid The liquid crystal orientation film of brilliant ordered state.

Now, according to industrial most popular method, liquid crystal orientation film be by with the cloth of cotton, nylon, polyester etc. along What one direction friction was formed on the electrode substrate carries out polyimides shape made of imidizate as polyamic acid and/or to it At film surface, carry out so-called brushing processing and make, handled by the brushing, liquid crystal orientation film assigned and is orientated Property.

However, the requirement for the high performance of liquid crystal expression element, high-definition, enlargement is gradually increased, pass through brush Mill processing and generate the surface scratch of liquid crystal orientation film, dust, influenced by mechanical external force and/or electrostatic bring, Yi Jiqu The various problems such as the inhomogeneities into process face become obvious.

As one of the technology for not implementing brushing processing, it is known to optical alignment method (referring for example to patent document 1).Light orientation In method, by irradiating polarized UV rays to liquid crystal orientation film, make the polymer contained in liquid crystal orientation film that photoisomerization occur anti- Answer, photodimerizationization reaction etc., thus to liquid crystal orientation film assign alignment capability.For liquid crystal indicate element high-definition, In the case that the requirement of high-quality is gradually increased, optical alignment method is applied to IPS mode (plane conversion, In-Plane Switching), the liquid crystal of FFS mode (boundary electric field switching, Fringe Field Switching) indicates that element (such as is joined According to patent document 2).In addition, about IPS mode, in recent years in order to further increase alignment capability, develop by its with use The PSA mode (Polymer sustained Alignment, polymer stabilizing orientation) of liquid crystal containing polymerizable compound carries out Combined method.

On the other hand, as the other technologies for not implementing brushing processing, it is known to VA (vertical) mode.In VA mode, Know just like under type: forming MVA obtained from the protrusion for controlling liquid crystal toppling direction on TFT substrate, filter substrate (Multi Vertical Alignment, more quadrants are vertically oriented) mode；So that the ITO electrode of substrate is formed slit and passes through electricity Control PVA (Patterned Vertical Alignment) mode, PSA mode of liquid crystal toppling direction.VA mode it In, PSA mode is the technology being concerned in recent years.

In PSA mode, into liquid crystal, the polymerizable compound of photopolymerization or thermal polymerization occurs for addition, makes liquid crystal cells Afterwards, exist while applying electric field and irradiate UV in the state of making LC tilt.Make polymerizable compound that polymerization occur or hand over as a result, Connection, is orientated liquid crystal along inclined direction.According to the PSA mode, even to the single-sided electrode system for constituting liquid crystal cells Make slit and oncoming lane electrode pattern be not provided with the protrusion of MVA etc, PVA etc slit structure, can also operate (referring for example to patent document 3).

In addition it reporting: by adding above-mentioned polymerizable compound in liquid crystal orientation film, rather than adding in liquid crystal group It closes in object, liquid crystal indicates that the response speed of element can also become faster (referring for example to non-patent literature 1).

However, the dissolubility of the polymerizable compound added in aligning agent for liquid crystal is low, there is the preservation in aligning agent for liquid crystal The problem of storage stabilities such as precipitation aspect, occurs for polymerizable compound in the process.

In addition, unreacted polymerizable compound remains in liquid crystal in the form of impurity when indicating in element, it is easy to happen Afterimage etc., it is desirable to which when reducing unreacted polymerizable compound, if increasing ultraviolet irradiation amount, there are the following problems: purple Outside line is damaged caused by liquid crystal, component to become larger, it is possible to liquid crystal be caused to indicate that the reliability of element reduces.Therefore, in order into One step improves luminous sensitivity, it is desirable to make to end when all having absorption until the long wavelength side of ultraviolet light, need further to extend The conjugation of polymerizable compound creates the problem that mesomorphic structure becomes much larger, alternatively, the upright and outspoken structure because of ring structure etc. increases The dissolubility for adding and causing it in aligning agent for liquid crystal gradually decreases.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2004-163646 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2013-080193 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2004-302061 bulletin

Non-patent literature

Non-patent literature 1:K.H Y.-J, Lee, SID 09DIGEST, P666-668

Summary of the invention

Problems to be solved by the invention

It is an object of the present invention to which in light of this situation, providing improves the dissolubility of polymerizable compound, has Gao Ling The aligning agent for liquid crystal of the orientation immobilization ability of sensitivity, the liquid crystal orientation film obtained by aligning agent for liquid crystal and liquid crystal indicate element.

The solution to the problem

Present inventor has performed further investigations, as a result, it has been found that: the aligning agent for liquid crystal containing following polymerizable compound for Realize above-mentioned purpose be it is extremely effective, the polymerizable compound contains polyunsaturated bond and closes group, forms hydrogen bond Aromatic rings more than at least one near functional group and functional group, functional group is by forming Jie in intermolecular formation hydrogen bond Crystal structure, so as to complete the present invention.

The present invention is using following technical proposals as purport.

(1) a kind of aligning agent for liquid crystal, which is characterized in that it contains polymer, polymerizable compound and solvent, aforementioned polymeric Property compound have polyunsaturated bond close group, formed hydrogen bond functional group and near aforementioned functional groups at least 1 A above aromatic rings, aforementioned functional groups are by forming mesomorphic structure in intermolecular formation hydrogen bond.

(2) aligning agent for liquid crystal according to above-mentioned (1), which is characterized in that aforementioned functional groups are carboxyl.

(3) aligning agent for liquid crystal according to above-mentioned (1) or (2), which is characterized in that aforementioned polymeric compound be selected from It is at least one kind of in following formula [1-1]~[1-4].

(T be ehter bond, ester bond, amido bond, S be carbon atom number 2~11 alkylidene, R be hydrogen atom or methyl, n=1 or 2)

(4) aligning agent for liquid crystal according to any one of (1)~(3), which is characterized in that aforementioned polymeric compound is It is at least one kind of in following formula [2-1]~[2-6].

(5) aligning agent for liquid crystal according to any one of above-mentioned (1)~(4), which is characterized in that the side of aforementioned polymer Chain has the group for making liquid crystal vertical-tropism.

(6) aligning agent for liquid crystal according to above-mentioned (5), which is characterized in that the side chain of aforementioned polymer is also poly- with light Conjunction property group.

(7) aligning agent for liquid crystal according to above-mentioned (6), which is characterized in that foregoing photo-polymerization group is selected from following It is at least one kind of in formula [3-1]~[3-7].

(in formula, Me indicates methyl.)

(8) aligning agent for liquid crystal according to any one of above-mentioned (1)~(4), which is characterized in that aforementioned polymer has Photoreactive group.

(9) aligning agent for liquid crystal according to above-mentioned (8), which is characterized in that aforementioned photoreactive group is selected from following It is at least one kind of in formula [4-1]~[4-5].

(10) aligning agent for liquid crystal according to any one of above-mentioned (1)~(9), which is characterized in that aforementioned polymer packet Containing selected from polyimide precursor and being carried out at least one kind of, polysiloxanes in polyimides obtained from imidizate or poly- (methyl) acrylate.

(11) a kind of liquid crystal orientation film, which is characterized in that it is using liquid crystal described in any one of above-mentioned (5)~(7) Alignment agent and make, obtained via the process for irradiating ultraviolet light while applying voltage.

(12) a kind of liquid crystal indicates element, which is characterized in that it has liquid crystal orientation film described in above-mentioned (11).

(13) a kind of liquid crystal orientation film, which is characterized in that its be using aligning agent for liquid crystal described in above-mentioned (8) or (9) and Production, it is obtained via the process of irradiation polarized UV rays.

(14) a kind of liquid crystal indicates element, which is characterized in that it has liquid crystal orientation film described in above-mentioned (13).

The effect of invention

According to the present invention, by the inclusion of the polymerizable compound with the functional group for forming mesomorphic structure because of hydrogen bond, energy The dissolubility for enough improving polymerizable compound realizes the aligning agent for liquid crystal with highly sensitive orientation immobilization ability, by liquid The liquid crystal orientation film and liquid crystal that brilliant alignment agent obtains indicate element.

Specific embodiment

Hereinafter, the present invention is described in detail for needle.

Aligning agent for liquid crystal of the invention contains polymerizable compound.There is polymerizable compound polyunsaturated bond to close base The aromatic rings of the functional group of hydrogen bond and at least one near functional group or more is rolled into a ball, is formed, the functional group for forming hydrogen bond passes through Mesomorphic structure is formed in intermolecular formation hydrogen bond.

Polyunsaturated bond conjunction group, which refers to, facilitates photopolymerization or photo-crosslinking because of the stimulation of heat, ultraviolet light etc. Ethylenical unsaturated double bonds group.Specifically, can enumerate vinyl, (methyl) acryloyl group and isopropenyl, allyl, The radically polymerizable groups groups such as styryl, alpha-methylene-gamma-butyrolactone base.

In addition, hydrogen bond of the invention refers to: because the hydrogen atom in functional group and the electronegativity for being adjacent to the hydrogen atom are high Electronegativity difference between atom and the offset for generating electronics, therefore, in the solvent of aligning agent for liquid crystal or in liquid crystal orientation film, The interaction of gravitation, the intermolecular key formed by hydrogen atom are generated between hydrogen atom and the high other atoms of electronegativity. The functional group for forming hydrogen bond refers in liquid crystal orientation film, in the solvent of aligning agent for liquid crystal in the intermolecular group for forming hydrogen bond. This functional group for forming hydrogen bond primarily forms dimer in liquid crystal orientation film, in the solvent of aligning agent for liquid crystal intermolecular. This polymerizable compound has carboxyl, the contour polar group of hydroxyl, therefore, compared with common polymerizable compound etc., Dissolubility is high.Therefore, the dissolubility of polymerizable compound in a solvent improves, when saving aligning agent for liquid crystal (such as freeze and protect Deposit) polymerizable compound is also not easy to be precipitated.

In turn, the functional group of hydrogen bond is formed by forming mesomorphic structure in intermolecular formation hydrogen bond.Mesomorphic structure refers to For showing the upright and outspoken structure of liquid crystal liquid crystal property.By forming mesomorphic structure by this hydrogen bond, forming upright and outspoken structure, in liquid While the luminous sensitivity of brilliant alignment films is got higher, the orientation immobilization ability of liquid crystal orientation film is also improved.

It should be noted that being not particularly limited as the functional group for forming hydrogen bond, carboxyl, hydroxyl, urea can be enumerated Base, amide groups and imide etc..Among these, in view of the easness for forming dimer, preferably carboxyl.

In addition, aromatic rings more than at least one that polymerizable compound has be it is upright and outspoken, therefore, by be located at formed Mesomorphic structure is formed together with the functional group near the functional group of hydrogen bond.It presents to the doubtful property of these mesomorphic structures huge Mesomorphic structure, therefore it is conjugated diffusion, absorption is all had until the ultraviolet region of long wavelength side (such as until 365nm).Cause This, even if the ultraviolet light relative to long wavelength irradiates, sensitivity is also got higher, can irradiation energy weaker ultraviolet light Realize orientation immobilization.As aromatic rings, the hydrocarbon aromatic rings such as phenyl ring, naphthalene nucleus and anthracene nucleus can be enumerated；Pyridine ring, pyridine ring and pyrrole Cough up the miscellaneous aromatic rings such as ring.The quantity of aromatic rings is not particularly limited, and preferably 1~4.It should be noted that these aromatic rings are appointed Choosing has substituent group.

As an example of above-mentioned polymerizable compound, above-mentioned formula [1-1]~[1-4] with carboxyl, above-mentioned can be enumerated Polymerizable compound shown in formula [2-1]~[2-6].Electricity between the hydrogen atom of carboxyl and the oxygen atom for being adjacent to the hydrogen atom Negativity differs greatly, and therefore, by using these polymerizable compounds, forms dimer by stronger hydrogen bond intermolecular. The molecule of this polymerizable compound is very small, and therefore, each molecule of dimer is also very small.Polymerizable compound as a result, Dissolubility in a solvent further increases, and the luminous sensitivity of liquid crystal orientation film becomes higher.In addition, above-mentioned formula [1-1]~[1- 4], polymerizable compound shown in above-mentioned formula [2-1]~[2-6] has near carboxyl is formed together mesomorphic knot with the carboxyl More than two aromatic rings of structure.The luminous sensitivity of liquid crystal orientation film further becomes higher as a result, orientation immobilization ability into One step improves.

It should be noted that the adding proportion about the polymerizable compound being added in aligning agent for liquid crystal, for example, polymerization Property compound reaches 0.1~30 (quality) % relative to aligning agent for liquid crystal.

Aligning agent for liquid crystal includes above-mentioned polymerizable compound, polymer and solvent for making liquid crystal orientation film.The present invention Aligning agent for liquid crystal be used for following liquid crystal and indicate element: 1) and liquid crystal cells are irradiated with ultraviolet light when applying voltage The liquid crystal expression element of the vertical orientation mode of production, i.e. longitudinal electric field driving method；Alternatively, 2) via irradiation polarized UV rays After the process of (ultraviolet light polarized), liquid crystal cells are made, the IPS mode made to liquid crystal cells irradiation ultraviolet light Horizontal alignment mode, the i.e. transverse electric field such as (In-Plane Switching), FFS mode (Fringe Field Switching) The liquid crystal of driving method indicates element.

For vertical orientation mode liquid crystal indicate element when aligning agent for liquid crystal in, contain as polymer in side chain Polymer with the group for making liquid crystal vertical-tropism.In addition, these polymer optionally have photoreactive group, light in side chain Free radical generates group.Using these when side chain has photoreactive group, optical free radical generates the polymer of group, more hold Photopolymerization or photo-crosslinking easily occurs by irradiating ultraviolet light, orientation immobilization ability improves.

For the mode of being horizontally oriented liquid crystal indicate element when aligning agent for liquid crystal in, as polymer optionally have light Reactive group.By the way that the light reactions such as photoisomerization reaction occur because of the irradiation of polarized UV rays with photoreactive group, Without brushing processing horizontal alignment ability (so-called light orientation) can be assigned to liquid crystal orientation film.Hereinafter, for liquid is made Brilliant vertically oriented group, polymerism group and photoreactive group are illustrated.

The polymer contained when liquid crystal indicates that element is vertical orientation mode, in aligning agent for liquid crystal has in its side chain and makes liquid Brilliant vertically oriented group.The group of liquid crystal vertical-tropism is set to refer to have the energy for making liquid crystal molecule relative to substrate vertical orientation The group of power, as long as having the ability, structure is not particularly limited.As the group for making liquid crystal vertical-tropism, can enumerate The fluoroalkyl of the alkyl of straight chain, straight chain out, end have the cyclic group of alkyl, fluoroalkyl, steroid radical etc..As specific Example, can enumerate group shown in following formula [5].

R¹Indicate the alkylidene of carbon number 2~6, preferably 2~4 ,-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- or carbon The alkylidene of number 1~3-ether (- C-C-O-).Among these, from the viewpoint of synthesizing easiness, preferably-O- ,- Alkylidene-ether of COO- ,-CONH- or carbon number 1~3.Above-mentioned R²、R³、R⁴Separately indicate phenylene or sub- cycloalkanes Base.From the viewpoint of synthesis easiness and making the ability of liquid crystal vertical-tropism, preferably a, b, c, R shown in table 1²、R³And R⁴ Combination.

[table 1]

a	b	c	R²	R³	R⁴
						1	1	1	Phenylene	Phenylene	Cyclohexylene
1	1	1	Phenylene	Cyclohexylene	Ring inferior hexyl
						1	1	1	Cyclohexylene	Cyclohexylene	Cyclohexylene
1	1	0	Phenylene	Phenylene	-
						1	1	0	Phenylene	Cyclohexylene	-

Above-mentioned R⁵Indicate hydrogen atom, the alkyl of carbon number 2~24, preferably 5~8 or contain fluoroalkyl, aromatic rings, aliphatic ring, Heterocycle or big cyclic group comprising them.A, when at least one of b and c are 1, as R⁵Structure, preferably expression hydrogen Atom, the alkyl of carbon number 2~14 or carbon number 2~14 contain fluoroalkyl, more preferably expression hydrogen atom, and carbon number 2~12, preferably 2~ 10 alkyl contains fluoroalkyl.

In addition, when a, b and c are 0, as R⁵Structure, preferably the alkyl of carbon number 12~22, preferably 12~20 or contain Fluoroalkyl, aromatic rings, aliphatic ring, heterocycle or the big cyclic group comprising them, more preferably carbon number 12~20, preferably 12~18 alkyl contains fluoroalkyl.

It should be noted that alloing the side chain of the group of liquid crystal vertical-tropism to be bonded directly to the main chain of polymer, separately Outside, it can also be bonded by binding groups appropriate.Like this, the side for making the group of liquid crystal vertical-tropism is imported to side chain Method is not particularly limited.

In addition, the amount of the group of liquid crystal vertical-tropism is made to be preferably capable making being orientated the range of immobilization, in order into One step improves luminous sensitivity and orientation immobilization ability, preferably as more as possible in the range of not influencing other characteristics.

The side chain of the polymer contained in aligning agent for liquid crystal of the invention can also have polymerism group.Optical polymerism Group is the group that polymerization reaction occurs because of light such as ultraviolet lights, as long as the group polymerizeing such as the light because of ultraviolet light (hereinafter also referred to photopolymerizable group), the group (hereinafter also referred to photo-crosslinking group) that photo-crosslinking occurs, there is no particular limitation, It is at least one kind of in polymerism group shown in above-mentioned formula [3-1]~[3-7] it is preferable to use being selected from.

Contain polymerism group in liquid crystal orientation film using obtained from the aligning agent for liquid crystal containing this polymer.It is right When liquid crystal in liquid crystal orientation film containing polymerism group indicates the light such as element irradiation ultraviolet light, it is located at liquid crystal orientation film and liquid Polymerism group, the polyunsaturated bond of above-mentioned polymerizable compound of crystalline substance contact one side close group and photopolymerization or light occur Cross-linking reaction, the orientation positioned at the liquid crystal of liquid crystal aligning film surface can be more effectively fixed.

The polymerism group (hereinafter also referred to optical polymerism side chain) preferably imported in the side chain of polymer includes In methylacryloyl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base extremely A kind of few side chain.

This optical polymerism side chain can be bonded directly to the main chain of polymer, alternatively, it is also possible to by bonding appropriate Group is bonded.Like this, the method for importing optical polymerism side chain is not particularly limited.As optical polymerism side chain, can arrange Enumerate side chain shown in such as following formula [6].

-R⁶-R⁷-R⁸ [6]

In formula [6], R⁶Indicate singly-bound or-CH₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、-N (CH₃)-、-CON(CH₃)-、-N(CH₃Any one of) CO-；R⁷Indicate singly-bound or carbon that is unsubstituted or being replaced by fluorine atoms The alkylidene of number 1~20；- the CH of alkylidene₂- CF can be arbitrarily replaced as₂Or-CH=CH-, it is any what is next enumerated In the case that group is not adjacent to each other, optionally replaced by these groups :-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, Divalent carbocyclic ring, bivalent heterocyclic.R⁸Indicate methylacryloyl, acryloyl group, vinyl, allyl, styryl and α-methylene Base-gamma-butyrolacton base.

It should be noted that the R in above-mentioned formula [6]⁶It can be formed by common methodology of organic synthesis, but held from synthesis From the perspective of easy property, preferably-CH₂-、-O-、-COO-、-NHCO-、-NH-、-CH₂O-。

In addition, as replacing R⁷In any-CH₂Divalent carbocyclic ring, bivalent heterocyclic carbocyclic ring, heterocycle, it is specific and Speech can enumerate following such structures, and but not limited thereto.

From the viewpoint of optical polymerism, R⁸Preferably methylacryloyl, acryloyl group, vinyl or alpha-methylene- Gamma-butyrolacton base.

The amount of optical polymerism side chain react preferably by irradiation ultraviolet light etc. light, form covalent bond thus Range that can be fixed by orientation is not influencing other characteristics to further increase luminous sensitivity and orientation immobilization ability In the range of, it is preferably as more as possible.

The horizontal alignments modes such as IPS mode, the FFS mode made and indicating element irradiation polarized UV rays to liquid crystal In the case where, the polymer contained in aligning agent for liquid crystal has imported preferably by polarized UV rays and has shown liquid crystal aligning The photoreactive group of ability.

By shining the liquid crystal orientation film obtained by the aligning agent for liquid crystal containing the polymer for having imported photoreactive group Penetrate polarized UV rays, light reaction promotes, to direction identical with polarization direction or perpendicular to the direction of polarization direction assign it is each to The opposite sex, liquid crystal are orientated.There are photodimerization, photoisomerizations etc. in light reaction.As photoreactive group, preferably have not Saturated bond particularly preferably has double bond, can enumerate acryloyl group, vinyl, methylacryloyl, anthryl, chalcone base, perfume (or spice) Legumin base, Stilbene base, dimaleoyl imino and cinnamoyl etc..

If enumerating concrete example, as the structure for promoting photodimerizationization reaction, above-mentioned formula [4-1]~[4-3] can be enumerated Shown in structure.In addition, can enumerate and be tied shown in above-mentioned formula [4-4], [4-5] as the structure for promoting photoisomerization reaction Structure.It should be noted that having the photoreactive group of the structure in above-mentioned formula [4-1]~[4-5] to refer to: from these formulas Removed in the structure of [4-1]~[4-5] group obtained from any number of H, in above-mentioned formula [4-1] O be connecting key group, The group that these structures are bonded with other structures (such as alkylidene etc.).

It should be noted that this photoreactive group can be fed to the main chain of polymer, side can also be directed into Chain.Like this, the method for importing photoreactive group is not particularly limited.In addition, polymer can have photoreactivity simultaneously Group and the above-mentioned group for making liquid crystal vertical-tropism.

In addition, the amount of photoreactive group is preferably that light reaction occurs and is capable of fixing the range of orientation, in order into One step improves luminous sensitivity and orientation immobilization ability, preferably as more as possible in the range of not influencing other characteristics.

The polymer contained in aligning agent for liquid crystal of the invention is in addition to using polyimide precursor, being carried out imidizate Obtained from except polyimides, further preferably use polysiloxanes, poly- (methyl) acrylate.Herein, polyimide precursor is Refer to polyamic acid (also referred to as poly- AMIC acid), poly amic acid ester.In addition, can be different containing these simultaneously in aligning agent for liquid crystal Polymer, their containing ratio can indicate the characteristic of element according to liquid crystal and make various selections.Contain in aligning agent for liquid crystal The total amount of polymer be preferably 0.1~20 (quality) %.It should be noted that is contained in aligning agent for liquid crystal of the invention is poly- The polymer such as imide precursor, polyimides, polysiloxanes, poly- (methyl) acrylate are required to be dissolved in aligning agent for liquid crystal Contained solvent.Hereinafter, being illustrated for each polymer.

When the polymer contained in aligning agent for liquid crystal of the invention includes polyimide precursor, polyimide precursor for example has There is repetitive unit (structural unit) shown in following formula [7].

In formula [7], R₁For hydrogen atom or the alkyl of carbon number 1~4.From the viewpoint of the easness by heating imidizate It sets out, particularly preferably hydrogen atom or methyl.X₂For quadrivalent organic radical group, structure is not particularly limited.If enumerating specific Example, then can enumerate following formula [X-1]~[X-43].From the viewpoint of liquid crystal aligning, X₂Preferably [X-1]~[X- 10], [X-26]~[X-28], [X-31]~[X-37].

In formula [X-1], R₂、R₃、R₄And R₅Be each independently hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 2~ 6 alkenyl, alkenyl or phenyl.From the viewpoint of liquid crystal aligning, R₂、R₃、R₄And R₅Preferably hydrogen atom, halogen atom, Methyl or ethyl, more preferably hydrogen atom or methyl, further preferably selected from by being tied shown in following formula [X1-1]~[X1-2] It is at least one kind of in the group of structure composition.

When being used for aligning agent for liquid crystal of the invention to indicate element by irradiating the liquid crystal that polarized UV rays make, as X₂Preferred structure, can enumerate [X1-1], [X1-2], [X-2], [X-3], [X-5], [X-6], [X-7], [X-8], [X-9], [X-10], particularly preferably [X1-1], [X1-2] and [X-6].

In above-mentioned formula [7], Y₂For bivalent organic group, structure is not particularly limited.If enumerating Y₂Concrete example, then Following formula [Y-1]~[Y-73] can be enumerated.

(in formula, Me indicates methyl.)

Since it can be expected that improving the dissolubility in organic solvent such as polyimide precursor, polyimides, preferably there is tool The structural unit of standby [Y-8], [Y-20], [Y-21], [Y-22], [Y-28], [Y-29] or [Y-30] structure.

The polyimide precursor contained in aligning agent for liquid crystal of the invention can by diamine component (for example, it is aftermentioned have make The diamines such as the diamines of the side chain of liquid crystal vertical-tropism, the diamines with optical polymerism side chain, the diamines with photoreactive group) With reacting for tetracarboxylic dianhydride's ingredient (for example, aftermentioned tetracarboxylic dianhydride, tetracarboxylic acid acid diesters dichloride, tetracarboxylic acid acid diesters etc.) To obtain.As polyimide precursor, such as polyamic acid, poly amic acid ester can be enumerated.Specifically, polyamic acid can lead to Cross the reacting to obtain of diamine component and tetracarboxylic dianhydride.Poly amic acid ester can be by making diamine component and tetracarboxylic acid acid diesters dichloro Compound reacts to obtain in the presence of base, or can by make diamine component and tetracarboxylic acid acid diesters appropriate condensing agent, It is reacted in the presence of alkali to obtain.In addition, polyimides can be obtained by making the polyamic acid carry out dehydration closed-loop, or Person can be obtained by making poly amic acid ester carry out heating closed loop.The polyamic acid, poly amic acid ester and polyimides conduct Polymer for obtaining liquid crystal orientation film is useful.

As the diamines with the side chain for making liquid crystal vertical-tropism, it can enumerate: there is chain alkyl, length as side chain The midway of alkyl group has a part or complete of the alkyl such as group, the steroid radical of ring structure and/or apparatus derivatorius, these groups The diamines for the group that portion's hydrogen atom is replaced by fluorine atoms, such as the diamines with side chain shown in above-mentioned formula [5].More specifically, It can enumerate such as with the hydrogen atom optionally diamines by the alkyl of fluorine-substituted carbon number 8~30, following formula [8]~[11] institute The diamines shown, but not limited thereto.

(a, b, c, R in formula [8]¹~R⁵Definition it is identical as above-mentioned formula [5].)

(in formula [9] and formula [10], A₁₀Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂,-O- ,-CO- or- NH-, A₁₁Indicate singly-bound or phenylene, a₁₀Indicate knot identical with the side chain of liquid crystal vertical-tropism is made shown in above-mentioned formula [5] Structure, a₁₀' indicate to remove the elements such as 1 hydrogen from structure identical with the side chain of liquid crystal vertical-tropism is made shown in above-mentioned formula [5] Obtained from structure, that is, bivalent group.)

(in formula [11], A₁₄For the alkyl for the carbon number 3~20 being optionally replaced by fluorine atoms, A₁₅For 1,4- cyclohexylene or 1, 4- phenylene, A₁₆For oxygen atom or-COO-* (wherein, the key and A of subsidiary " * "₁₅It is bonded), A₁₇For oxygen atom or-COO-* (wherein, the key and (CH of subsidiary " * "₂)a₂It is bonded.).In addition, a₁For 0 or 1 integer, a₂For 2~10 integer, a₃It is 0 Or 1 integer.)

Two amino (- NH in formula [8]₂) bonding position do not limit.Specifically, the bonding base relative to side chain Group, can enumerate 2 on phenyl ring, 3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position It sets.Wherein, reactivity when synthesizing polyamides acid, preferably 2,4 position, 2,5 position or 3,5 position It sets.When the easiness being additionally contemplates that when synthesizing diamines, more preferably 2,4 position or 3,5 position.

As the specific structure of formula [8], diamines shown in following formula [A-1]~formula [A-24] can be exemplified, but is not limited In this.

(in formula [A-1]~formula [A-5], A₁For the alkyl of carbon number 2~24 or containing fluoroalkyl.)

(in formula [A-6] and formula [A-7], A₂Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂Or-CH₂OCO-, A₃For carbon number 1~22 alkyl, contains fluoroalkyl or fluoroalkoxy at alkoxy.)

(in formula [A-8]~formula [A-10], A₄Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂Or-CH₂, A₅For the alkyl of carbon number 1~22, alkoxy, contain fluoroalkyl or fluoroalkoxy.)

(in formula [A-11] and formula [A-12], A₆Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂,-O- or-NH-, A₇For fluorine-based, cyano, fluoroform alkyl, nitro, azo group, formyl Base, acetyl group, acetoxyl group or hydroxyl.)

(in formula [A-13] and formula [A-14], A₈For the alkyl of carbon number 3~12, Isosorbide-5-Nitrae-cyclohexylene cis-trans isomerization difference For transisomer.)

(in formula [A-15] and formula [A-16], A₉For the alkyl of carbon number 3~12, Isosorbide-5-Nitrae-cyclohexylene cis-trans isomerization difference For transisomer.)

As the concrete example of diamines shown in formula [9], diamines shown in following formula [A-25]~formula [A-30] can be enumerated, But not limited thereto.

(in formula [A-25]~formula [A-30], A₁₂Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、-CO- Or-NH-, A₁₃It indicates the alkyl of carbon number 1~22 or contains fluoroalkyl.)

As the concrete example of diamines shown in formula [10], can enumerate two shown in following formula [A-31]~formula [A-32] Amine, but not limited thereto.

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

Above-mentioned diamines can also according to when being made liquid crystal orientation film liquid crystal aligning, pre-tilt angle, voltage retention performance, store The characteristics such as accumulated charge and using a kind or mix two or more use.

When the liquid crystal that aligning agent for liquid crystal of the invention is used for vertical orientation mode indicates element, become in aligning agent for liquid crystal The diamine component of the raw material of the polyimide precursor contained has preferably imported optical polymerism side chain.Two with optical polymerism side chain Amine can enumerate: comprising being selected from methylacryloyl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-γ- At least one of butyrolactone base, the diamines for example with side chain shown in above-mentioned formula [6].More specifically, it can enumerate for example Diamines shown in the following general formula [12], but not limited thereto.

(the R in formula [12]⁶、R⁷And R⁸Definition it is identical as above-mentioned formula [6].)

Two amino (- NH in formula [12]₂) bonding position do not limit.Specifically, the bonding relative to side chain Group, can enumerate 2 on phenyl ring, 3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 Position.Wherein, reactivity when synthesizing polyamides acid, preferably 2,4 position, 2,5 position or 3,5 Position.When the easiness being additionally contemplates that when synthesizing diamines, more preferably 2,4 position or 3,5 position.

As with comprising being selected from methylacryloyl, acryloyl group, vinyl, allyl, styryl and α-methylene The diamines of the optical polymerism side chain of at least one of base-gamma-butyrolacton base, specifically, following suchization can be enumerated Object is closed, but not limited thereto.

(in formula, R₆It indicates to be selected from-CH₂,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH-, the group in-CO-. R₇For the alkylidene, divalent carbocyclic ring or heterocycle formed by 1~carbon number of carbon number 30,1 in the alkylidene, divalent carbocyclic ring or heterocycle Or multiple hydrogen atoms are optionally replaced by fluorine atom or organic group.In addition, not adjacent to each other in any group next enumerated In the case where, R₇In-CH₂Optionally replaced by these groups :-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,- NHCONH-、-CO-。R₈Expression-CH₂,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- ,-CO-, any in singly-bound Person.R₉Indicate cinnamoyl.R₁₀For singly-bound or the alkylidene formed by 1~carbon number of carbon number 30, divalent carbocyclic ring or heterocycle, the Asia One or more hydrogen atoms in alkyl, divalent carbocyclic ring or heterocycle are optionally replaced by fluorine atom or organic group.In addition, in the case where connecing Come any group for enumerating it is not adjacent to each other in the case where, R₁₀In-CH₂Optionally replaced by these groups :-O- ,-NHCO- ,- CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。R₁₁Indicate any in acryloyl group, methylacryloyl The polymerism group of person.)

(X is that binding groups Y of the singly-bound perhaps in-O- ,-COO- ,-NHCO- ,-NH- indicates singly-bound or unsubstituted Or the alkylidene for the carbon number 1~20 being replaced by fluorine atoms.)

It is above-mentioned to have comprising being selected from methylacryloyl, acryloyl group, vinyl, allyl, styryl and α-methylene The diamines of the optical polymerism side chain of at least one of base-gamma-butyrolacton base can also be according to liquid crystal when being made liquid crystal orientation film The characteristics such as orientation, luminous sensitivity, pre-tilt angle, voltage retention performance, accumulated charge, the liquid crystal sound that liquid crystal is made when indicating element It answers speed etc. and using a kind or mixes two or more use.

In addition, this have comprising being selected from methylacryloyl, acryloyl group, vinyl, allyl, styryl and α- In synthesis of the diamines of the optical polymerism side chain of at least one of methylene-y-butyrolactone base preferably to reach polyamic acid The mode of the amount of 10~70 moles of % of the diamine component total amount used uses, more preferably 20~60 moles of %, especially excellent It is selected as 30~50 moles of %.

When the liquid crystal that aligning agent for liquid crystal of the invention is used by irradiation polarized UV rays and makes indicates element, become The diamine component of the raw material of the polyimide precursor contained in aligning agent for liquid crystal has preferably imported photoreactive group.

It promotes photodimerization reaction, photoisomerization to react using by irradiating polarized UV rays and generates anisotropic When method for orientation treatment, above-mentioned formula [4-1]~[4-5] structure can be directed into the main chain or side chain of polymer.

Polyimide precursor is used as the polymer contained in aligning agent for liquid crystal and is carried out imidizate and obtained When the polyimides arrived, exists and contain above-mentioned formula [4-1]~[4-5] structure tetracarboxylic dianhydride or diamines using main chain or side chain Method, but, it is preferable to use side chain contains above-mentioned formula [4-1]~[4-5] structure diamines from the viewpoint of synthesizing easiness. It should be noted that the side chain of diamines refers to the structure gone out from the structure branch of two amino of connection of diamines.As this two The concrete example of amine can enumerate following formula compound represented, and but not limited thereto.

(in formula, X indicates singly-bound or the binding groups in-O- ,-COO- ,-NHCO- ,-NH-, Y indicate singly-bound or Person is unsubstituted or the alkylidene of carbon number 1~20 that is replaced by fluorine atoms.R indicates hydrogen atom or unsubstituted or be replaced by fluorine atoms Carbon number 1~5 alkyl or alkylether radicals.)

In order to obtain the polyimide precursor contained in aligning agent for liquid crystal of the invention i.e. polyamic acid, and diamine component The tetracarboxylic dianhydride to react is not particularly limited.It is exemplified below out its concrete example.

As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, 1,2,3,4- cyclobutane tetracarboxylic acids can be enumerated Acid dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid two Acid anhydride, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,4,5- Tetrahydrofuran tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride, 3,4- dicarboxyl -1- cyclohexyl amber acid dianhydride, 3, 4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydride, bicyclic [3,3,0] octane - It is 2,4,6,8- tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydrides, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, suitable Formula -3,7- dibutyl ring octyl- 1,5- diene -1,2,5,6- tetracarboxylic dianhydride, tricyclic [4.2.1.0^2,5] nonane -3,4,7,8- four Carboxylic acid -3,4:7,8- dianhydride, six ring [6.6.0.1^2,7.0^3,6.1^9,14.0^10,13] hexadecane -4,5,11,12- tetrabasic carboxylic acid -4,5: 11,12- dianhydride, 4- (2,5- dioxotetrahydrol furans -3- base) -1,2,3,4- naphthane -1,2- dicarboxylic anhydride etc..

In turn, on the basis of the above-mentioned tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, aromatic series is used When tetracarboxylic dianhydride, liquid crystal aligning improves and can reduce the accumulated charge of liquid crystal cells, so it is preferred that.As aromatic series four Carboxylic acid dianhydride can enumerate benzenetetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 2,2 ', 3,3 '-biphenyltetracarboxyacid acids two Acid anhydride, 2,3,3 ', 4- biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3,3 ', 4- benzophenone tetracarboxylic acid Acid dianhydride, bis- (3,4- dicarboxyphenyi) ether dianhydrides, bis- (3,4- dicarboxyphenyi) sulfone dianhydrides, 1,2,5,6- naphthalene tetracarboxylic acid two Acid anhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride etc..

Tetracarboxylic dianhydride can also protect according to liquid crystal aligning, luminous sensitivity, pre-tilt angle, the voltage when liquid crystal orientation film is made It holds the characteristics such as characteristic, accumulated charge and using a kind or is used in combination of two or more.

In order to obtain the polyimide precursor contained in aligning agent for liquid crystal of the invention i.e. poly amic acid ester, with diamines at The tetracarboxylic acid acid dialkyl ester to react is divided to be not particularly limited.It is exemplified below out its concrete example.

As the concrete example of aliphatic tetracarboxylic acid acid diesters, 1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl esters, 1 can be enumerated, 2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl ester, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl Ester, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl ester, 1,2,3,4- pentamethylene tetracarboxylic acid acid dialkyl ester, 2,3,4,5- tetrahydrofuran tetracarboxylic acid acid dialkyl ester, 1,2,4,5- cyclopentanetetracarboxylic dialkyl ester, 3,4- dicarboxyl -1- hexamethylene Base dialkyl succinate, 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dialkyl ester, 1,2,3,4- butane tetracarboxylic Acid dialkyl ester, bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic acid acid dialkyl ester, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acids two Arrcostab, 2,3,5- tricarboxylic cyclopentyl acetic acid dialkyl ester, cis- -3,7- dibutyl ring octyl- 1,5- diene -1,2,5,6- four Carboxylic acid dialkyl esters, tricyclic [4.2.1.0^2,5] nonane -3,4,7,8- tetrabasic carboxylic acid -3,4:7,8- dialkyl ester, six rings [6.6.0.^12,7.0^3,6.1^9,14.0^10,13] hexadecane -4,5,11,12- tetrabasic carboxylic acid -4,5:11,12- dialkyl ester, 4- (2,5- bis- Oxa- tetrahydrofuran -3- base) -1,2,3,4- naphthane -1,2- dicarboxylic acid dialkyl esters etc..

As aromatic tetracarboxylic acid's dialkyl ester, pyromellitic acid dialkyl ester, 3,3 ', 4,4 '-biphenyl tetracarboxylic acids can be enumerated Acid dialkyl ester, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl esters, 2,3,3 ', 4- biphenyltetracarboxyacid acid dialkyl ester, 3,3 ', 4, 4 '-benzophenone tetracarboxylic acid acid dialkyl esters, 2,3,3 ', 4- benzophenone tetracarboxylic acid acid dialkyl ester, bis- (3,4- dicarboxyphenyis) Ether dialkyl ester, bis- (3,4- dicarboxyphenyi) sulfone dialkyl esters, 1,2,5,6- naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7- naphthalene four Carboxylic acid dialkyl esters etc..

When the polymer contained in aligning agent for liquid crystal includes polysiloxanes, polysiloxanes can be by making alkoxy silane ingredient React (such as polycondensation reaction) in organic solvent to obtain.Alkoxy silane ingredient refers to that intramolecular has 1~4 alkane The alkoxy silane of oxygroup.For example, can be by gathering alkoxy silane ingredient shown in following formula [14] and reacting Siloxanes.

R¹¹Si(OR¹²)₃ [14]

In formula [14], R¹¹Indicate 1 valence organic group, R¹²For the alkyl of carbon number 1~5, preferably 1~3.R¹²More preferably first Base or ethyl.

As the alkoxy silane with the side chain for making liquid crystal vertical-tropism, it can enumerate: there is formula as side chain [14] R in¹¹There are the hydrocarbon such as group, steroid radical of ring structure and/or apparatus derivatorius for the midway of chain alkyl, chain alkyl The alkoxy silane for the group that part or all of hydrogen atom of base, these groups is replaced by fluorine atoms, such as with above-mentioned formula [5] diamines of side chain shown in.More specifically, it can enumerate for example with hydrogen atom optionally by fluorine-substituted carbon number 8~30 Alkoxy silane shown in the diamines of alkyl etc., following formula [15], but not limited thereto.

(a, b, c, R in formula [15]¹~R⁵Definition it is identical as above-mentioned formula [5].In formula [15], R⁹Indicate singly-bound or- (CH₂)_nO- (alkyl that n is carbon atom number 0~5), R¹²Indicate the alkyl of carbon number 1~5, preferably 1~3.)

Herein, the concrete example as the alkoxy silane for having vertical orientation side-chain structure shown in formula [14] below, Formula [14-1]~[14-13] can be enumerated, but not limited thereto.It should be noted that in following formula [14-1]~[14-13] R¹²With the R in formula [14]¹²It is identical, R⁹With the R in formula [15]⁹It is identical.

(in formula [14-7]~formula [14-9], R¹³For the alkyl of carbon number 1~22, alkoxy, contain fluoroalkyl or fluorine-containing alcoxyl Base.)

(in formula [14-10] and formula [14-11], R¹⁴For fluorine-based, cyano, fluoroform alkyl, nitro, azo group, formoxyl, Acetyl group, acetoxyl group or hydroxyl.)

(in formula [14-12] and formula [14-13], R¹⁵For the alkyl of carbon number 3~12, Isosorbide-5-Nitrae-cyclohexylene cis-trans isomerization point It Wei not transisomer.)

Alkoxy silane shown in formula [14] can be according in a solvent molten when being made siloxane polymer (polysiloxanes) The spies such as Xie Xing, liquid crystal aligning, luminous sensitivity, pre-tilt angle, voltage retention performance, accumulated charge when being made liquid crystal orientation film Property, liquid crystal is made indicates liquid crystal response speed etc. when element and using a kind or mix two or more use.Alternatively, it is also possible to The alkoxy silane of chain alkyl containing carbon number 10~18 is combined use.

Like this, alkoxy silane shown in formula [14] can be for example, by remembering in Japanese Unexamined Patent Application 61-286393 bulletin The known method of load manufactures.

In addition, such as following formula [16] institute also can be used as the alkoxy silane ingredient for obtaining polysiloxanes Show such alkoxy silane with polymerism group.

R²¹Si(OR²²)₃ [16]

In formula [16], R²¹It is hydrogen atom by acryloyl group, acryloxy, methylacryloyl, methacryloxy Or the alkyl that styryl replaces.Substituted hydrogen atom is 1 or more, preferably 1.The carbon number of alkyl is preferably 1~30, More preferably 1~20.Further preferably 1~10.R²²For the alkyl of carbon number 1~5, preferably carbon number 1~3, particularly preferably Carbon number 1~2.

The concrete example of alkoxy silane shown in formula [16] is enumerated, but is not limited to these.For example, 3- metering system Acryloxypropylethoxysilane trimethoxy silane, 3- methacryloxypropyl, methacryloxymethyl three Methoxy silane, methacryloxymethyl triethoxysilane, 3- acryloyloxypropyltrimethoxysilane, 3- propylene Acryloxypropylethoxysilane triethoxysilane, acryloyl-oxyethyl trimethoxy silane, acryloyl-oxyethyl triethoxysilane, Styryl ethyl trimethoxy silane, styryl ethyl triethoxysilane, 3- (N- styrylmethyl -2- amino second Base amino) propyl trimethoxy silicane.

It in turn, can be with use example such as following formula [17] institute as the alkoxy silane ingredient for obtaining polysiloxanes The alkoxy silane shown.

(R²³)_n2Si(OR²⁴)_4-n2 [17]

The R of alkoxy silane shown in formula [17]²³It is hydrogen atom or hydrogen atom optionally by hetero atom, halogen atom, ammonia Base, glycidoxy, sulfydryl, isocyanate group, Carbamido substituted carbon number 1~10 alkyl, preferably amino, glycidol Base, urea groups.R²⁴For the alkyl of carbon number 1~5, preferably 1~3, n2 indicates 0~3, preferably 0~2 integer.

The concrete example of alkoxy silane shown in this formula [17] is enumerated, but not limited thereto.Such as 3- can be enumerated (2- aminoethylaminopropyl) trimethoxy silane, 3- (2- aminoethylaminopropyl) triethoxysilane, 2- amino second Base amino methyl trimethoxy silane, 2- (2- amino-ethyl sulfenyl ethyl) triethoxysilane, 3- mercaptopropyi triethoxy Silane, mercapto methyl trimethoxy silane, vinyltriethoxysilane, 3- isocyanate propyl triethoxysilane, trifluoro Propyl trimethoxy silicane, chloropropyl triethoxysilane, bromopropyl triethoxysilane, 3- mercaptopropyi trimethoxy silicon Alkane, dimethyl diethoxysilane, dimethyldimethoxysil,ne, diethyldiethoxysilane, diethyl dimethoxy silicon Alkane, dimethoxydiphenylsilane, diphenyl diethoxy silane, 3-amino propyl methyl diethoxy silane, 3- aminopropan Base dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-urea propyl-triethoxysilicane, γ-urea propyl trimethoxy silicane and γ-urea propyl tripropoxy silane etc..

In alkoxy silane shown in formula [17], the alkoxy silane that n2 is 0 is tetraalkoxysilane.Tetraalkoxysilane It is easy that polycondensation reaction occurs with alkoxy silane shown in above-mentioned formula [14]~formula [16], therefore for obtaining polysiloxanes It is preferred.

The alkoxy silane for being 0 as the n2 in this formula [17], more preferably tetramethoxy-silicane, tetraethoxy-silicane Alkane, tetrapropoxysilane or four butoxy silanes, particularly preferably tetramethoxy-silicane or tetraethoxysilane.

The method for obtaining the polysiloxanes contained in aligning agent for liquid crystal is not particularly limited, such as can make containing above-mentioned formula [14] the alkoxy silane ingredient of alkoxy silane shown in~formula [17] reacts in organic solvent, and (such as polycondensation is anti- Answer) it obtains.In general, polysiloxanes is by by this alkoxy silane ingredient polycondensation and being made uniform dissolution in organic solvent Solution obtains.It should be noted that in the alkoxy silane ingredient of the alkoxy silane containing above-mentioned formula [14]~[17] etc. The compounding ratio of alkoxy silane be not particularly limited.

As the method that alkoxy silane is carried out polycondensation in order to obtain polysiloxanes, can enumerate for example makes alkoxy The method that condensation is hydrolyzed in silane in the organic solvents such as alcohol or glycol.At this point, hydrolysis-condensation reaction can be part Any one of hydrolysis and complete hydrolysis.

When the liquid crystal that aligning agent for liquid crystal is used for vertical orientation mode indicates element, the side chain of polysiloxanes described above It can have the group for making liquid crystal vertical-tropism, side chain can also have polymerism group.In addition, aligning agent for liquid crystal is used for When the liquid crystal of horizontal alignment mode indicates element, polysiloxanes described above can have photoreactive group.Therefore, for For the alkoxy silane ingredient of monomer, it is preferred that import group, the optical polymerism for making liquid crystal vertical-tropism to side chain Group, chain linked to owner or side chain import photoreactive group.It is this have make the group of liquid crystal vertical-tropism, polymerism group or The polysiloxanes of photoreactive group is as the polymerization for obtaining the liquid crystal orientation film for showing liquid crystal aligning immobilization ability Object is useful.

<poly- (methyl) acrylate>

When the polymer contained in aligning agent for liquid crystal includes poly- (methyl) acrylate, poly- (methyl) acrylate can pass through Make monomer and polymerization initiator of acrylate compounds, methacrylate compound etc. etc. that polymerization reaction occur to obtain.

As acrylate compounds, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, third can be enumerated Olefin(e) acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2- trifluoro second Ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxy triethylene Acrylate, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- ethyl -8- tricyclic Last of the ten Heavenly stems ester etc..

As methacrylate compound, such as methyl methacrylate, ethyl methacrylate, methyl can be enumerated Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, Phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, first Base isobornyl acrylate, methacrylic acid 2- methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, methacrylic acid 2- methyl -2- gold Rigid alkyl ester, methacrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, methacrylic acid 8- methyl -8- tricyclodecyl and methacrylic acid 8- Ethyl -8- tricyclodecyl etc..

About poly- (methyl) acrylate described above, the liquid crystal that aligning agent for liquid crystal is used for vertical orientation mode is indicated When element, side chain can have the group for making liquid crystal vertical-tropism, and side chain can also have polymerism group.In addition, liquid crystal When the liquid crystal that alignment agent is used for the mode of being horizontally oriented indicates element, photoreactive group can have.Therefore, for as list For acrylate compounds, methacrylate compound of body etc., it is preferred that make liquid crystal vertical-tropism to side chain importing Group, polymerism group, chain linked to owner or side chain import photoreactive group.It is this that there is the base for making liquid crystal vertical-tropism Group, polymerism group or photoreactive group poly- (methyl) acrylate be used as and show liquid crystal aligning for obtaining and fix The polymer of the liquid crystal orientation film of change ability is useful.

Herein, as the acrylate compounds with side chain, methacrylate compound, can enumerate for example with The acrylate compounds of side chain shown in above-mentioned formula [5], methacrylate compound.More specifically, it can enumerate for example Acrylate compounds, methacrylate compound shown in following formula [18] and following formula [19-1]~[19-3], but not It is defined in this.

(a, b, c, R in formula [18]¹~R⁵Definition it is identical as above-mentioned formula [5].R is hydrogen atom or methyl, and S is carbon atom The alkylidene of number 2~11.)

(R is hydrogen atom or methyl, and S is the alkylidene of carbon atom number 2~11, and X is ehter bond, ester bond, amido bond, R¹⁰For hydrogen Atom or the alkyl of carbon number 1~5 that is unsubstituted or being replaced by fluorine atoms.)

As long as what is contained in the solvent uniform dissolution aligning agent for liquid crystal contained in aligning agent for liquid crystal of the invention is above-mentioned poly- Close object, the solvent of above-mentioned polymerizable compound is just not particularly limited.If enumerating its concrete example, used as polymer poly- When imide precursor, polyimides, n,N-Dimethylformamide, N, N- diethylformamide, N, N- dimethyl second can be enumerated Amide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- methyl caprolactam, 2-Pyrrolidone, N- vinyl- 2-Pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3- dimethyl-imidazolinone, 3- methoxyl group-N, N- diformazan Base propionamide etc..In addition, as polymer and when using polysiloxanes, and enumerate more such as ethylene glycol, 1,2-PD First alcoholic compound, amide compounds such as N-METHYLFORMAMIDE, n,N-Dimethylformamide etc..In addition, being used as polymer When poly- (methyl) acrylate, can enumerate such as alcoholic compound, ketone compound, amide compound or ester compounds or its Its aprotic compound etc..They can be used a kind or are mixed with two or more.Even in addition, when individualism Can not uniform dissolution polymer, polymerizable compound solvent, as long as the range that will not be precipitated in polymer, polymerizable compound It is interior, then it can also mix into above-mentioned organic solvent.

It, can be with other than the solvent for dissolving polymer, polymerizable compound in aligning agent for liquid crystal of the invention Solvent containing painting film uniformity when aligning agent for liquid crystal being coated on substrate for improving.Table usually can be used in the solvent The low solvent of the above-mentioned organic solvent of face warp tension ratio.If enumerating its concrete example, the molten fibre of ethyl cellosolve, butyl can be enumerated Agent, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1- methoxy-2-propanol, 1- ethyoxyl -2- Propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- Monomethyl ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2- (2- ethoxy Base propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..These solvents can It is two or more to be applied in combination.

In aligning agent for liquid crystal of the invention, in addition to that mentioned above, as long as within the scope of the effect of the invention, it can also To add the electrical characteristics such as the polymer other than aforementioned polymer, the dielectric constant for changing liquid crystal orientation film and/or electric conductivity Dielectric substance or conductive materials, the silane coupling agent of adaptation for improving liquid crystal orientation film and substrate, in coating fluid The compound of film thickness uniformity and/or surface smoothness is improved when brilliant alignment agent, for improving film when liquid crystal orientation film is made The cross-linked compound of hardness and/or consistency and for efficiently promoting the acyl of polyimide precursor sub- when being burnt into film Imidizate promotor of amination etc..

As the compound for improving film thickness uniformity, surface smoothness, fluorine system surfactant, organic silicon-type can be enumerated Surfactant, nonionic surfactants etc..More specifically, can enumerate such as Eftop EF301, EF303, EF352 (Tohkem products Corporation system), Megafac F171, F173, R-30 (big Japanese ink strain formula meeting Society's system), Fluorad FC430, FC431 (Sumitomo 3M Limited system), AsahiGuard AG710, Surflon S- 382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's system) etc..Use these surface-actives When agent, use ratio is preferably 0.01~2 mass relative to 100 mass parts of total amount of the polymer contained in aligning agent for liquid crystal Part, more preferably 0.01~1 mass parts.

As the concrete example for the compound for improving the adaptation of liquid crystal orientation film and substrate, silicon containing functionality can be enumerated The compound of alkane, compound containing epoxy group etc..Such as 3- TSL 8330,3- aminopropyl three can be enumerated Ethoxysilane, 2- TSL 8330,2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- ammonia Base propyl trimethoxy silicane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- urea propyl trimethoxy Silane, 3- urea propyl-triethoxysilicane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3- Aminopropyltriethoxywerene werene, N- triethoxysilylpropyltetrasulfide diethylenetriamine, N- trimethoxysilyl third Base diethylenetriamine, three azepine decane of 10- trimethoxysilyl -1,4,7-, triethoxysilyl -1,4 10-, Tri- azepine decane of 7-, 9- trimethoxysilyl -3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- Diaza nonyl acetic acid esters, N- benzyl -3- TSL 8330, N- benzyl -3-aminopropyltriethoxysilane, Bis- (oxygen the ethylidene) -3- of N- phenyl -3- TSL 8330, N- phenyl -3-aminopropyltriethoxysilane, N- TSL 8330, N- bis- (oxygen ethylidene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl Ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol two contract Water glycerin ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- bis- Bromine neopentylglycol diglycidyl ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N ', N '-four glycidyl group M-xylene diamine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', four glycidyl group -4 N ' -, (N, N- bis- contracts by 4 '-diaminodiphenyl-methanes, 3- (N- allyl-N- glycidyl) TSL 8330,3- Water glyceryl) TSL 8330 etc..In addition, in order to further increase the film-strength of liquid crystal orientation film, Ke Yitian Add the oxybenzene compounds such as 2,2 '-bis- (4- hydroxyl -3,5- bishydroxymethyl phenyl) propane, four (methoxy) bis-phenols.It uses When these compounds, relative to 100 mass parts of total amount of the polymer contained in aligning agent for liquid crystal, preferably 0.1~30 mass Part, more preferably 1~20 mass parts.

Liquid crystal of the invention indicates that liquid crystal orientation film used in element can be by being coated on base for above-mentioned aligning agent for liquid crystal Plate after being dried as needed, carries out orientation process to coated surface obtained from firing to obtain.

As the substrate of coating of liquid crystalline alignment agent, it is not particularly limited, can be used as long as the high substrate of the transparency The viewpoint of plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc., the chemical industry skill that conforms to the principle of simplicity goes out Hair is, it is preferable to use be formed with the substrate of ITO (tin indium oxide, Indium Tin Oxide) electrode for driving liquid crystal etc..Separately Outside, it indicates, if being only single sided substrate, the opaque substance such as silicon wafer also to can be used in element in the liquid crystal of reflection-type, The material of the meeting reflected light such as aluminium also can be used in electrode at this time.

The coating method of aligning agent for liquid crystal is not particularly limited, and industrial is usually to utilize silk-screen printing, hectographic printing, soft Property printing or the progress such as ink-jet method method.As other coating methods, have infusion process, rolling method, slot coated method, Spin-coating method or spray coating method etc. can use these methods according to purpose.

Aligning agent for liquid crystal is coated on substrate, hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven are then utilized Etc. heating meanss, the solvent according to used in aligning agent for liquid crystal make solvent with 30~300 DEG C, preferably with 30~250 DEG C of temperature Evaporation, so as to which liquid crystal orientation film is made.When the thickness of liquid crystal orientation film after firing is blocked up, the consumption of element is indicated in liquid crystal Electric aspect becomes unfavorable, and when thickness is excessively thin, liquid crystal indicates that the reliability of element reduces sometimes, it is therefore preferable that for 5~300nm, More preferably 10~100nm.

The liquid crystal of vertical orientation mode of the invention indicates that element can be by obtaining liquid of the band containing polymerizable compound After the substrate of brilliant alignment films, liquid crystal cells are made by known method to obtain.Specifically, by the way that aligning agent for liquid crystal is coated with It on 2 plate bases and is burnt into form liquid crystal orientation film, 2 plate bases is configured in the opposite mode of the liquid crystal orientation film, to this 2 Injection includes the liquid-crystal composition of liquid crystal between substrate, to form liquid crystal layer.Also, by liquid crystal layer and liquid crystal orientation film Ultraviolet light is irradiated while applying voltage, indicates member so as to obtain the liquid crystal for the vertical orientation mode for having liquid crystal cells Part.It should be noted that liquid-crystal composition can contain polymerizable compound.

Process by irradiating ultraviolet light while applying voltage, polymerism possessed by polymerizable compound are unsaturated Photopolymerization or photo-crosslinking occur for binding groups, to control the molecularly oriented state of liquid crystal layer.It is located at liquid crystal aligning as a result, Even if the orientation of the liquid crystal of film surface can also be consolidated without brushing processing in the state of being slightly slanted from vertical direction It is fixed.

The liquid crystal of horizontal alignment mode indicate element refer to relative to substrate along horizontal direction (transverse direction) application electric field from And element is indicated to the liquid crystal for the mode that liquid crystal molecule is converted.The horizontal alignments sides such as IPS mode of the invention, FFS mode The liquid crystal of formula indicates that element can obtain as follows: after obtaining substrate of the band containing the liquid crystal orientation film of polymer compound, with known Method production liquid crystal cells obtain.Specifically, by the way that aligning agent for liquid crystal to be coated on 2 plate bases and be burnt into, according to After needing to carry out brushing processing, polarized UV rays are irradiated, to form liquid crystal orientation film.Then, opposite with liquid crystal orientation film Mode configures 2 plate bases, includes the liquid-crystal composition of liquid crystal to injection between 2 plate base, to form liquid crystal layer.Also, By irradiating polarized UV rays to liquid crystal layer and liquid crystal orientation film, the liquid for the horizontal alignment mode for having liquid crystal cells can be obtained Crystalline substance indicates element.It should be noted that liquid-crystal composition can contain polymerizable compound.

By irradiating the process of ultraviolet light to liquid crystal layer and liquid crystal orientation film, making after element from the irradiation of the outside of element The process of ultraviolet light, the polyunsaturated bond having in polymerizable compound, which closes group, can occur the light such as photopolymerization, photo-crosslinking Reaction.It is fixed under conditions of being orientated along horizontal direction positioned at the liquid crystal of liquid crystal aligning film surface as a result,.

The vertical orientation mode of aforementioned present invention, the liquid crystal of horizontal alignment mode indicate that element has by containing polymerism Close the liquid crystal orientation film that the aligning agent for liquid crystal of object obtains.Polymerizable compound in aligning agent for liquid crystal has to form hydrogen as described above Therefore the functional group of key forms dimer in liquid crystal orientation film, in aligning agent for liquid crystal by hydrogen bond.In turn, it is used in the present invention Polymerizable compound there is upright and outspoken aromatic rings, therefore, form the functional group of hydrogen bond by hydrogen bond and form mesomorphic structure.Jie Huge mesomorphic structure is presented by hydrogen bond doubtfully for crystal structure, and the long wavelength side of ultraviolet region, which has, to be absorbed, therefore, light spirit Sensitivity improves.Therefore, shown in embodiment as be described hereinafter like that, the liquid crystal for having this liquid crystal orientation film indicates the luminous sensitivity of element It improves, even the ultraviolet light of long wavelength side, response speed also sufficiently becomes faster, and orientation immobilization ability becomes excellent.

Embodiment

Hereinafter, being described in detail based on embodiment further progress, but the present invention is not limited to the embodiment completely.

It is referred to as follows used in the preparation of following aligning agent for liquid crystal.

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

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

DBA:3,5- diaminobenzoic acid

M-PCH7: 1,3- diamino -5- shown in following formula ((4- (4- heptyl cyclohexyl) phenoxy group) methyl) benzene

PCH7: 1,3- diamino -4- shown in following formula [4- (4- heptyl cyclohexyl) phenoxy group] benzene

BEM-S: 2- shown in following formula (methacryloxy) ethyl -3,5- diaminobenzoic acid ester

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

BCS: butyl cellosolve

3AMP:3- picolyl amine

Polymerizable compound [RM1]~[RM7] being added in aligning agent for liquid crystal is structure below.It needs to illustrate It is that polymerizable compound [RM1]~[RM6] is identical as above-mentioned formula [the 2-1]~polymerizable compound of [2-6].

The synthesis of polymerizable compound [RM1]

The bromo- 4 '-xenol [A] (150g, 0.60mol) of 4-, tert-butyl acrylate [B] are added into 3L four-hole boiling flask (162g, 1.3mol), palladium acetate (2.7g, 12mmol), three (o-tolyl) phosphines (7.3g, 24mmol), tri-n-butylamine (334g, 1.8mol), n,N-dimethylacetamide (hereinafter referred to as DMAc) (750g), with 100 DEG C of progress heating stirrings.It is carried out with HPLC Reactive tracing near confirmation is cooled to room temperature after reaction, by reaction solution, and injects 1M aqueous hydrochloric acid solution 1.8L.Xiang Qi Middle addition ethyl acetate (1L) operates removal water layer by liquid separation.Organic layer is cleaned 2 times with 10% aqueous hydrochloric acid solution 1L, and It is after cleaning 3 times with saturated salt solution 1L, organic layer is dry with magnesium sulfate.Thereafter, it filters and distills removal solvent with evaporator, To obtain compound [C] 174g (yield 98%) of oily compound form.

The measurement result of the nuclear magnetic resonance (NMR) of compound [C] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 9.68 (1H, s), 7.72 (2H, d), 7.63 (2H, d), 7.59- 7.55(9H,m),6.87-6.85(2H,m),1.44(9H,s).

Added into the 2L four-hole boiling flask for having mechanical agitator, stirring blade compound obtained above [C] (174g, 0.59mol), the chloro- 1- hexanol (96.7g, 0.71mol) of 6-, potassium carbonate (163g, 1.2mol), potassium iodide (9.8g, 59mmol), N,N-Dimethylformamide (hereinafter referred to as DMF) (1600g), with 80 DEG C of progress heating stirrings.Reactive tracing is carried out with HPLC, Confirmation after reaction, by reaction solution be cooled to room temperature nearby, into reaction solution injection distilled water 2L.To the solid of precipitation After being filtered, it is injected into methanol/distilled water (1:1) solution, is filtered again.By being dried under reduced pressure to obtained solid, from And obtain compound [D] 221g (yield 95%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [D] is as follows.

¹H-NMR(400MHz,CDCl₃, δ ppm): 7.61 (1H, d), 7.56-7.52 (6H, m), 6.98-6.95 (2H, m), 6.38(1H,d),4.02(2H,t),3.67(2H,t),1.84-1.44(17H,m).

Added into 3L four-hole boiling flask compound obtained above [D] (221g, 0.56mol), triethylamine (67.7g, 0.67mol), tetrahydrofuran (hereinafter referred to as THF) (1800g), reaction solution is cooling.Pay attention to not making internal temperature super on one side 10 DEG C are crossed, THF (200g) solution of methacrylic chloride (70.0g, 0.67mmol) is added dropwise thereto on one side.After completion of dropwise addition, Make 23 DEG C of reaction solution and further progress reaction.Reactive tracing is carried out with HPLC, is confirmed after reaction, to reaction solution Middle injection distilled water 6L adds ethyl acetate 2L, operates removal water layer with liquid separation.Thereafter, successively water-soluble with 5% potassium hydroxide Liquid, 1M aqueous hydrochloric acid solution, saturated salt solution clean organic layer, and organic layer is dried with magnesium sulfate.Thereafter, filter and with steaming Device distillation removal solvent is sent out, to obtain crude product.Gained crude product is carried out clearly with 2- propyl alcohol (hereinafter referred to as IPA) 100g It washes, filter and dries, to obtain compound [E] 127g (yield 49%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [E] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 7.73 (2H, d), 7.70-7.63 (4H, m), 7.58 (1H, d), 7.02-7.00(2H,m),6.53(1H,d),6.03-6.02(1H,m),5.67-5.66(1H,m),4.11(2H,t),4.00 (2H,t),1.88-1.87(3H,m),1.79-1.25(17H,m).

Compound obtained above [E] (81g, 0.17mol), formic acid (400g) are added, into 1L four-hole boiling flask with 40 DEG C Carry out heating stirring.Reactive tracing is carried out with HPLC, confirmation after reaction, distilled water 3L and mistake is injected into reaction solution Filter.Obtained solid is cleaned, and it is dry to make solid with methanol 200g, (is received to obtain polymerizable compound [RM1] 56g 79%) rate is.

The measurement result of the nuclear magnetic resonance (NMR) of polymerizable compound [RM1] is as follows.

¹H-NMR(400MHz,CDCl₃, δ ppm): 7.81 (1H, d), 7.60 (4H, s), 7.55 (2H, d), 6.97 (2H, d), 6.47(2H,d),6.11-6.10(1H,m),5.56-5.52(1H,m),4.17(2H,t),4.00(2H,t),1.95-1.94 (2H,m),1.85-1.82(3H,m),1.75-1.71(2H,m),1.55-1.48(4H,m).

The synthesis of polymerizable compound [RM2]

The chloro- 1- hexanol of 6- used when by intermediate, that is, compound [D] of synthesized polymer compound [RM1] is altered to 8- In addition to this chloro- 1- hexanol carries out operation same as Example 1, to obtain polymerizable compound [RM2] 40.82g.

The measurement result of the nuclear magnetic resonance (NMR) of polymerizable compound [RM2] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 7.70-7.56 (7H, m), 6.97 (2H, d), 6.51 (1H, d), 5.98(1H,s),5.62(1H,s),4.04(2H,t),3.94(2H,t),1.83(3H,s),1.70-1.10(12H).

The synthesis of polymerizable compound [RM3]

Into 2L four-hole boiling flask add the bromo- beta naphthal of 6- [H] (150g, 672mol), tert-butyl acrylate [B] (103.4g, 807mmol), palladium acetate (3.02g, 13.5mmol), three (o-tolyl) phosphines (8.19g, 26.9mmol), tripropyl amine (TPA) (289.0g, 2.02mol), DMAc (700g), with 100 DEG C of progress heating stirrings.Reactive tracing is carried out with HPLC, confirmation after reaction, will Near reaction solution is cooled to room temperature, and it is injected into 1M aqueous hydrochloric acid solution 3L.Ethyl acetate (2L) is added thereto, passes through liquid separation Operation removal water layer.Organic layer is cleaned 2 times with 10% aqueous hydrochloric acid solution 1L, and after cleaning 3 times with saturated salt solution 1L, will be had Machine layer is dry with magnesium sulfate.Thereafter, filtering and removal solvent is distilled with evaporator, (yield is to obtain compound [I] 181g 99%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [I] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 10.01 (1H, s), 8.04 (1H, s), 7.81-7.74 (2H, m), 7.70-7.63(2H,m),7.14-7.10(2H,m),6.54(1H,d),1.51-1.48(9H,m).

Added into the 2L four-hole boiling flask for having mechanical agitator, stirring blade compound obtained above [I] (181g, 672mmol), the chloro- 1- hexanol (110.2g, 806mol) of 6-, potassium carbonate (111.5g, 806mmol), potassium iodide (1.12g, 6.7mmol), DMF (900g), with 80 DEG C of progress heating stirrings.Carry out reactive tracing with HPLC, confirmation after reaction, to anti- Injection distilled water 2L in solution is answered, is added ethyl acetate (2L), removal water layer is operated by liquid separation.Thereafter, organic layer is used full It is cleaned 2 times with saline solution (1L), distillation removal solvent after drying, filtering organic layer with magnesium sulfate, to obtain crude product.It will Gained crude product is recrystallized with ethyl acetate/hexane mixed solvent, to obtain compound [J] 185g, (yield is 74%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [J] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 8.06 (1H, s), 7.80 (1H, d), 7.77-7.76 (2H, m), 7.62(1H,d),7.34(1H,d),7.15(1H,dd),6.53(1H,d),4.34(1H,t),4.05(2H,t),3.39-3.33 (2H,m),1.73(2H,t),1.46-1.31(15H,m).

Added into 3L four-hole boiling flask compound obtained above [J] (130.5g, 352mmol), triethylamine (42.76g, 423mmol), THF (950g), cooled reaction solution.Pay attention to that internal temperature is not made to be more than 10 DEG C on one side, first is added dropwise thereto on one side THF (100g) solution of base acryloyl chloride (44.2g, 423mmol).After completion of dropwise addition, keep 23 DEG C of reaction solution simultaneously further It is reacted.Reactive tracing is carried out with HPLC, confirmation after reaction, distilled water 6L is injected into reaction solution, adds acetic acid Ethyl ester 2L operates removal water layer with liquid separation.Thereafter, successively with 5% potassium hydroxide aqueous solution, 1M aqueous hydrochloric acid solution, saturated common salt Water cleans organic layer, and organic layer is dried with magnesium sulfate.Thereafter, it filters and distills removal solvent with evaporator, thus To compound [K] 140.9g (yield 92%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [K] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 8.09 (1H, s), 7.83 (1H, d), 7.80-7.79 (2H, m), 7.66(1H,d),7.33(1H,d),7.18(1H,dd),6.57(1H,d),6.02-6.01(1H,m),5.66-5.65(1H,m), 4.12-4.06(4H,m),1.88-1.87(3H,m),1.84-1.42(15H,m).

Compound obtained above [K] (140.9g, 321mmol), formic acid (700g) are added, into 3L four-hole boiling flask with 40 DEG C carry out heating stirring.Reactive tracing is carried out with HPLC, confirmation after reaction, injects distilled water 4.5L simultaneously into reaction solution Filtering.Obtained solid is cleaned with IPA/ hexane mixed solvent, and keeps solid dry, to obtain polymerizable compound [RM3] 95.9g (yield 78%).

The measurement result of the nuclear magnetic resonance (NMR) of polymerizable compound [RM3] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 12.4 (1H, brs), 8.10 (1H, s), 7.84 (1H, d), 7.81- 7.80(2H,m),7.70(1H,d),7.35(1H,d),7.19(1H,dd),6.59(1H,d),6.03-6.02(1H,m),5.67- 5.65(1H,m),4.13-4.07(4H,m),1.88-1.87(3H,m),1.83-1.41(8H,m).

The synthesis of polymerizable compound [RM4]

The chloro- 1- hexanol of 6- used when by intermediate, that is, compound [J] of synthesized polymer compound [RM3] is altered to 8- In addition to this chloro- 1- hexanol carries out operation same as Example 1, to obtain polymerizable compound [RM4] 171g.

The measurement result of the nuclear magnetic resonance (NMR) of polymerizable compound [RM4] is as follows.

¹H-NMR (400MHz, CDCl3, δ ppm): 12.4 (1H, brs), 7.94-7.88 (2H, m), 7.77-7.71 (2H, m),7.70-7.63(1H,m),7.17(1H,dd),7.12-7.11(1H,m),6.51(1H,d),6.11-6.10(1H,m), 5.55-5.54(1H,m),4.17-4.06(4H,m),1.95-1.94(3Hm),1.87-1.40(12H,m).

Using polymerizable compound shown in well known following formula as polymerizable compound [RM5].

The synthesis of polymerizable compound [RM6]

Into 2L four-hole boiling flask add 6- hydroxyl -2- naphthalene-carboxylic acid [N] (300g, 1.59mol), potassium hydroxide (205g, 3.66mol), distilled water (1200g), with 100 DEG C of progress heating stirrings.Thereto be added dropwise the chloro- 1- hexanol of 6- (261g, 1.91mol).After completion of dropwise addition, reactive tracing is carried out with HPLC, confirmation after reaction, reaction solution is cooled to room temperature attached Closely, reaction solution is then injected into ice water (3L), 35% hydrochloric acid of addition is neutralized.Thereafter, the solid being precipitated is carried out Filtering, after being cleaned with distilled water, is dried under reduced pressure solid, to obtain compound [O] 275g (yield 60%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [O] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 8.53-8.52 (1H, m), 8.06-7.87 (3H, m), 7.40 (1H, d),7.27-7.23(1H,m),4.32(1H,t),4.12(2H,m),3.44-3.33(2H,m),1.82-1.76(2H,m), 1.51-1.3(6H).

Compound obtained above [O] (50.00g, 173mmol), dimethyl p-aminophenol are added into 2L four-hole boiling flask (46.23g, 382mmol), nitrobenzene (2.13g, 17.3mmol), THF (500g) and after being replaced with nitrogen, in the case where being heated to reflux It is stirred.THF (100g) solution of methacrylic chloride (38.1g, 361mmol) is slowly added dropwise thereto.After completion of dropwise addition, Reactive tracing is carried out with HPLC, after reaction, reaction solution is cooled to room temperature for confirmation.Thereafter, to 1M aqueous hydrochloric acid solution 3L Middle injection reaction solution, is filtered the solid being precipitated, to obtain crude product.Then, by gained crude product with ethyl alcohol/ Hexane mixed solvent cleaning, is then cleaned with acetone, is then dried under reduced pressure, to obtain polymerizable compound [RM6] 38.4g (yield 62%).

The measurement result of the nuclear magnetic resonance (NMR) of polymerizable compound [RM6] is as follows.

¹H-NMR (400MHz, DMSO-d6, δ ppm): 8.63 (1H, s), 8.08 (1H, dd), 7.87 (1H, d), 7.76 (1H,d),7.22-7.19(1H,m),7.16-7.15(1H,m),6.11-6.10(1H,m),5.56-5.54(1H,m),4.20- 4.10(4H,m),1.97-1.95(3H,m),1.92-1.85(2H,m),1.78-1.71(2H,m),1.60-1.47(4HH,m).

The synthesis of polymerizable compound [RM7]

Xenol 14.9g (80.0mmol), 5- bromine pentaacetic acid ester are added into the 500ml eggplant type beaker of subsidiary condenser pipe 35g (167.0mmol), potassium carbonate 41.5g (300mmol) and acetone 250ml and mixture is made, stirred on one side with 60 DEG C of temperature Mix 48 hours makes its reaction on one side.After reaction, reaction solution is injected into pure water 600ml, obtains the chemical combination of white solid Object [P] 33.6g (yield 95%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [P] is as follows.

¹H-NMR(CDCl₃) δ: 1.57 (m, 4H), 1.74 (m, 4H), 1.86 (m, 4H), 2.06 (s, 6H), 4.02 (t, 4H), 4.12(t,4H),6.95(d,4H),7.47(d,4H).

Ethyl alcohol 250ml, compound obtained above [P] 18.0g are added into the 1l eggplant type beaker of subsidiary condenser pipe (41mmol) and 10% sodium hydrate aqueous solution 100ml and mixture is made, make while being stirred 5 hours with 85 DEG C of temperature It is reacted.After reaction, water 500ml and reaction solution are added into the beaker of 1000ml, after being stirred at room temperature 30 minutes, drop Add 10%HCl aqueous solution 80ml, be then filtered, (yield is to obtain compound [Q] 12.2g of white solid 83%).

The measurement result of the nuclear magnetic resonance (NMR) of compound [Q] is as follows.

¹H-NMR(DMSO-d6)δ:1.46(m,8H),1.71(m,4H),3.41(m,4H),3.98(m,4H),4.39(m, 2H),6.96(m,4H),7.51(m,4H).

Make compound obtained above [Q] 5.0g (14.0mmol) and triethylamine 3.2g and a small amount of 2,6- di-t-butyl pair Cresols (BHT) is dissolved in THF 30ml together, is stirred at room temperature, under conditions of carrying out cooling using water-bath, expends The solution that methacrylic chloride 3.3g (32mmol) is dissolved in 20ml THF is added dropwise within 15 minutes.After dropwise addition, stir 30 minutes, It removes water-bath and restores to room temperature, and the stirring that lasts through the night.After reaction, reaction solution is injected into pure water 200ml, is passed through White solid is obtained after filter.So that the solid is dissolved in chloroform, after being precipitated using hexane (hexane/chloroform=2/1), obtains white Polymerizable compound [RM7] 2.6g (yield 38%) of color solid.

The measurement result of the nuclear magnetic resonance (NMR) of polymerizable compound [RM7] is as follows.

¹H-NMR(CDCl₃) δ: 1.56 (m, 4H), 1.74 (m, 4H), 1.82 (m, 4H), 1.97 (s, 6H), 4.03 (m, 4H), 4.20(m,4H),5.55(m,2H),6.10(m,2H),6.94(d,4H),7.45(d,4H).

The molecule measuring fixed condition of polyimides is as follows.

Device: Senshu Scientific co., ltd. room temperature gel permeation chromatography (GPC) device (SSC-7200),

Column: the column (KD-803, KD-805) of Shodex company manufacture

Column temperature: 50 DEG C

Eluent: N, N '-dimethyl formamide is (as additive, lithium bromide monohydrate (LiBrH₂O) it is 30mmol/L, phosphoric acid anhydrous crystal (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L

Flow velocity: 1.0ml/ minutes

Standard curve making standard sample: (molecular weight is about for the TSK standard polyethylene oxide that TOSOH Co., Ltd manufactures 9000,000,150,000,100,000,30,000) and the polyethylene glycol of Polymer Laboratories Ltd. manufacture (point Son amount about 12,000,4,000,1,000).

In addition, the acid imide rate of polyimides is operated as follows to measure.Polyimide powder 20mg is put into NMR sample Quality control (wasteland's science Co. Ltd. system, NMR sample cell specification φ 5) adds deuterated dimethyl sulfoxide (DMSO-d₆, 0.05% TMS melange) 1.0ml, apply ultrasonic wave and makes it completely dissolved.The solution is utilized to the NMR of JEOL DATUM company manufacture The proton NMR of analyzer (JNW-ECA500) measurement 500MHz.About acid imide rate, imidizate front and back will be originated from and do not occurred The proton of the structure of variation is determined as reference proton, the source nearby occurred using the peak integrating value of the proton and 9.5~10.0ppm From the proton peak integrating value of the NH base of amic acid, found out using following formula.It should be noted that x is from amide in following formula The proton peak integrating value of NH base of acid, the peak integrating value that y is benchmark proton, α are in polyamic acid (acid imide rate is 0%) In the case of ratio of the reference proton number relative to NH matrix of 1 amic acid.

Acid imide rate (%)=(1- α x/y) × 100

(embodiment 1)

By BODA (10.0g, 40.0mmol), DBA (6.09g, 40.0mmol), PCH7 (11.5g, 30.0mmol), BEM-S (7.93g, 30.0mmol) is dissolved in NMP (140.7g), after being reacted 5 hours with 60 DEG C, addition CBDA (11.37g, 58.0mmol) with NMP (46.9g), reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To the polyamic acid solution Addition NMP in (200g) and after being diluted to 6 mass %, acetic anhydride (17.4g) and pyridine are added as imidization catalyst (67.6g) is reacted 3 hours with 50 DEG C.The reaction solution is put into methanol (3000ml), and leaching gained sediment.It should Sediment is cleaned with methanol, is dried under reduced pressure at 60 DEG C, to obtain polyimide powder (A).The acyl of the polyimides Amination rate is 60%, number-average molecular weight 12,000, weight average molecular weight 26,000.

NMP (44.0g) is added in gained polyimide powder (A) (6.0g), with 50 DEG C are stirred 5 hours and keep its molten Solution.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, and it is small to be stirred at room temperature 5 When, to obtain liquid crystal aligning composition (B).

In addition, adding polymerizable compound obtained in synthesis example 1 relative to above-mentioned liquid crystal aligning composition (B) 10.0g RM1 0.06g (being 10 mass % relative to solid component), is stirred at room temperature 3 hours and makes it dissolve, to prepare liquid crystal Alignment agent (B1).

(embodiment 2)

Relative to liquid crystal aligning composition (B), polymerizable compound is replaced using [RM2] obtained in synthesis example 2 [RM1] in addition to this carries out operation same as Example 1, to prepare aligning agent for liquid crystal (B2).

(embodiment 3)

Relative to liquid crystal aligning composition (B), polymerizable compound is replaced using [RM3] obtained in synthesis example 3 [RM1] in addition to this carries out operation same as Example 1, to prepare aligning agent for liquid crystal (B3).

(embodiment 4)

Relative to liquid crystal aligning composition (B), polymerizable compound is replaced using [RM4] obtained in synthesis example 4 [RM1] in addition to this carries out operation same as Example 1, to prepare aligning agent for liquid crystal (B4).

(embodiment 5)

Relative to liquid crystal aligning composition (B), polymerizable compound is replaced using [RM5] obtained in synthesis example 5 [RM1] in addition to this carries out operation same as Example 1, to prepare aligning agent for liquid crystal (B5).

(embodiment 6)

Relative to liquid crystal aligning composition (B), polymerizable compound is replaced using [RM6] obtained in synthesis example 6 [RM1] in addition to this carries out operation same as Example 1, to prepare aligning agent for liquid crystal (B6).

(comparative example 1)

Relative to liquid crystal aligning composition (B), polymerizable compound is replaced using [RM7] obtained in synthesis example 7 [RM1] in addition to this carries out operation same as Example 1, to prepare aligning agent for liquid crystal (B7).

(embodiment 7)

By BODA (10.0g, 40.0mmol), DBA (5.3g, 35.0mmol), m-PCH7 (12.0g, 30.0mmol), BEM- S (9.2g, 35.0mmol) is dissolved in NMP (144.5g), after being reacted 5 hours with 60 DEG C, addition CBDA (11.5g, 58.5mmol) with NMP (48.2g), reacted 10 hours with 40 DEG C, to obtain polyamic acid solution.To the polyamic acid solution Addition NMP in (200g) and after being diluted to 6 mass %, acetic anhydride (17.0g) and pyridine are added as imidization catalyst (65.8g) is reacted 3 hours with 50 DEG C.The reaction solution is put into methanol (3000ml), and leaching gained sediment.It should Sediment is cleaned with methanol, is dried under reduced pressure at 60 DEG C, to obtain polyimide powder (C).The acyl of the polyimides Amination rate is 60%, number-average molecular weight 14,000, weight average molecular weight 47,000.

NMP (44.0g) is added in gained polyimide powder (C) (6.0g), with 50 DEG C are stirred 5 hours and keep its molten Solution.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, and it is small to be stirred at room temperature 5 When, to obtain liquid crystal aligning composition (D).

In addition, adding polymerizable compound obtained in synthesis example 1 relative to above-mentioned liquid crystal aligning composition (D) 10.0g [RM1] 0.06g (being 10 mass % relative to solid component), is stirred at room temperature 3 hours and makes it dissolve, to prepare liquid crystal Alignment agent (D1).

(embodiment 8)

Relative to liquid crystal aligning composition (D), polymerizable compound is replaced using [RM2] obtained in synthesis example 2 [RM1] in addition to this carries out operation same as Example 7, to prepare aligning agent for liquid crystal (D2).

(embodiment 9)

Relative to liquid crystal aligning composition (D), polymerizable compound is replaced using [RM3] obtained in synthesis example 3 [RM1] in addition to this carries out operation same as Example 7, to prepare aligning agent for liquid crystal (D3).

(embodiment 10)

Relative to liquid crystal aligning composition (D), polymerizable compound is replaced using [RM4] obtained in synthesis example 4 [RM1] in addition to this carries out operation same as Example 7, to prepare aligning agent for liquid crystal (D4).

(comparative example 2)

Relative to liquid crystal aligning composition (D), polymerizable compound is replaced using [RM7] obtained in synthesis example 7 [RM1] in addition to this carries out operation same as Example 7, to prepare aligning agent for liquid crystal (D5).

By aligning agent for liquid crystal obtained in 1~embodiment of embodiment 10, comparative example 1 and comparative example 2 in -20 DEG C of freezer After 1 week of keeping, whether visual confirmation has precipitate etc..Absolutely not precipitate etc. whens to be regarded as storage stability good.Table 2 shows The result of the composition of aligning agent for liquid crystal and storage stability test out.

As shown in Table 2 it is found that containing the embodiment of polymerizable compound [RM1]~[RM6] in liquid crystal aligning composition (B) The aligning agent for liquid crystal (B1) of 1~embodiment 6~(B6) absolutely not precipitate etc., therefore, storage stability is good.Another party Face produces in the aligning agent for liquid crystal (B7) of the comparative example 1 in liquid crystal aligning composition (B) containing polymerizable compound [RM7] Precipitate.

Similarly, embodiment 7~implementation of polymerizable compound [RM1]~[RM4] is contained in liquid crystal aligning composition (D) The aligning agent for liquid crystal (D1) of example 10~(D4) absolutely not precipitate etc., but contain polymerizable compound in aligning agent for liquid crystal (D) Precipitate is produced in the aligning agent for liquid crystal (D5) of the comparative example 2 of [RM7].

According to the above results it is believed that: the aligning agent for liquid crystal of 1~embodiment of embodiment 10 contains the function to form hydrogen bond Group, polymerizable compound [RM1]~[RM6] with carboxyl, therefore dissolubility in a solvent is high, even if at -20 DEG C Freezer in took care of for 1 week after, also absolutely not generate precipitate etc..It may thus be appreciated that: by will be used in aligning agent for liquid crystal Polymerizable compound is set as the polymerizable compound for the functional group that there is carboxyl etc. to form hydrogen bond, can make the guarantor of aligning agent for liquid crystal It deposits and has good stability.

Can be additionally considered to: polymerizable compound [RM1]~[RM6] with carboxyl is formed in intermolecular formation hydrogen bond Huge mesomorphic structure, therefore until absorbing the long wavelength side for extending to ultraviolet region, the sensitivity of ultraviolet light is improved, because This, in the measurement of aftermentioned response speed, response speed becomes faster.

[table 2]

(embodiment 11)

Using aligning agent for liquid crystal obtained in embodiment 1 (B1), the system of liquid crystal cells is carried out according to following shown steps Make.

Aligning agent for liquid crystal obtained in embodiment 1 (B1) is spun on be formed with Pixel Dimensions be 300 μm of 100 μ m and Line/interval is respectively on the ito surface of the ITO electrode substrate of 5 μm of ITO electrode pattern, after press drying 90 seconds of 80 DEG C, Be burnt within 30 minutes with 200 DEG C of heated air circulation type baking oven, to form the liquid crystal orientation film that film thickness is 100nm.

In addition, aligning agent for liquid crystal (B1) to be spun on to the ito surface of not formed electrode pattern, with press drying 90 seconds of 80 DEG C Afterwards, be burnt within 30 minutes with 200 DEG C of heated air circulation type baking oven, to form the liquid crystal orientation film that film thickness is 100nm.

For above-mentioned 2 plate base, after 4 μm of pearl spacer is spread on the liquid crystal orientation film of a plate base, printed from thereon Brush sealant (epoxy resin of solvent type heat-curing class).Then, there is liquid crystal orientation film side with the formation of another plate base Surface is towards inside, after being pasted with substrate before, makes sealant cures to make dummy cell.Normal direction is injected by decompression Liquid crystal MLC-6608 (MERCK CORPORATION system, trade name) is injected in the dummy cell, to make liquid crystal cells.

(embodiment 12)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (B2) Make, to make liquid crystal cells.

(embodiment 13)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (B3) Make, to make liquid crystal cells.

(embodiment 14)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (B4) Make, to make liquid crystal cells.

(embodiment 15)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (B5) Make, to make liquid crystal cells.

(embodiment 16)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (B6) Make, to make liquid crystal cells.

(embodiment 17)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (D1) Make, to make liquid crystal cells.

(embodiment 18)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (D2) Make, to make liquid crystal cells.

(embodiment 19)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (D3) Make, to make liquid crystal cells.

(embodiment 20)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (D4) Make, to make liquid crystal cells.

(comparative example 3)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (B7) Make, to make liquid crystal cells.

(comparative example 4)

Other than replacing aligning agent for liquid crystal (B1), behaviour identical with embodiment 11 is carried out in addition to using aligning agent for liquid crystal (D5) Make, to make liquid crystal cells.

Liquid crystal cells obtained in 11~embodiment of embodiment 20, comparative example 3 and comparative example 4 are measured by following methods For UV irradiation response speed.

Firstly, by backlight, the measurement that one group of polarization plates, the sequence of light quantity detector of crossed nicols state are constituted be made filling In setting, liquid crystal cells are configured between one group of polarization plates.At this point, making the pattern to form the ITO electrode at wired/interval relative to friendship Pitch prism angle at 45 °.Also, the rectangular wave that above-mentioned liquid crystal cells are applied with voltage ± 6V, frequency 1kHz, is read with oscillograph The variation until reaching saturation using the brightness that light quantity detector observes is taken, brightness when by no applied voltage is set as 0%, and The brightness value that the voltage of application ± 4V is saturated is set as 100%, by brightness from 10% be changed to 90% needed for the time be denoted as Response speed.

Thereafter, it in the state that the liquid crystal cells are applied with the D/C voltage of 10V, is irradiated from the outside of the liquid crystal cells saturating Cross the UV 10J of the bandpass filter of 365nm.Thereafter, response speed is measured again, and compares the response speed of UV irradiation front and back. Table 3 shows the measurement result of response speed.

For liquid crystal cells obtained in 11~embodiment of embodiment 20, comparative example 3 and comparative example 4, after measuring UV irradiation Pixel portion pre-tilt angle.The LCD analyzer that measurement device has used MEIRYO TECHNICA CORPORATION to manufacture LCA-LUV42A.Table 3 shows the measurement result of pre-tilt angle.

[table 3]

As shown in table 3 like that, the liquid crystal cells of 11~embodiment of embodiment 20 are by comprising having the function for forming hydrogen bond It rolls into a ball, i.e. obtained from polymerizable compound [RM1]~[RM6] aligning agent for liquid crystal of carboxyl.It is considered that: these liquid crystal cells Hydrogen bond by being originated from carboxyl is formed with huge mesomorphic structure in liquid crystal orientation film.The liquid of 11~embodiment of embodiment 20 Brilliant unit also has sensitivity in the ultraviolet light (365nm) of long wavelength side due to the influence of the huge mesomorphic structure, even if according to The ultraviolet light of 365nm is penetrated, also can fully realize faster response speed (17~35 milliseconds).Known to and then: embodiment 11 The liquid crystal cells of~embodiment 20 can obtain high pre-tilt angle, therefore, for making the aligning agent for liquid crystal of these liquid crystal cells Excellent orientation immobilization ability can be assigned.

On the other hand, the liquid crystal cells of comparative example 3 and comparative example 4 are by being added to the functional group for not having and forming hydrogen bond Obtained from the aligning agent for liquid crystal of polymerizable compound [RM7].Mesomorphic position about these liquid crystal cells, in liquid crystal orientation film Therefore do not have sensitivity substantially for simple biphenyl structural to the ultraviolet light (365nm) of long wavelength side, irradiate the purple of 365nm Sufficient response speed is unable to get when outside line.

In turn, the intramolecular of polymerizable compound [RM7], which does not have, forms the functional group of hydrogen bond, therefore in a solvent molten Solution property is low, and polymerizable compound [RM7] can be precipitated when freezing.

As can be known from the above results: by the inclusion of polymerizable compound [RM1]~[RM6] with carboxyl, it can be achieved that i.e. Make to be that the ultraviolet light of long wavelength side also can sufficiently realize faster response speed and can assign excellent orientation immobilization ability Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element.

In turn, with polymerizable compound [RM1]~[RM6] noresidue in a solvent of carboxyl, therefore, by containing this A little polymerizable compounds can make the storage stability of aligning agent for liquid crystal good, and can be improved ultraviolet line sensitivity.

Industrial availability

Aligning agent for liquid crystal of the invention contains the polymerizable compound of highly dissoluble, therefore, can obtain sensitive with light Spend the liquid crystal orientation film of excellent orientation immobilization ability.Thus, have and is taken by the liquid crystal that aligning agent for liquid crystal of the invention obtains The excellent in reliability of element is indicated to the liquid crystal of film, the LCD TV etc. of big picture and high-resolution can be suitably employed in, for adopting With longitudinal electric field driving method (VA mode, TN mode, OCB mode etc.), transverse electric field driving method (IPS mode, FFS mode) Various liquid crystal indicate element be useful.Especially, liquid is controlled for having through irradiation ultraviolet light or polarized UV rays The liquid crystal of the liquid crystal orientation film of crystalline substance orientation indicates that element is useful.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that it contains polymer, polymerizable compound and solvent,

The polymer include selected from polyimide precursor and carried out in polyimides obtained from imidizate at least 1 Kind, polysiloxanes or poly- (methyl) acrylate,

The functional group and the functional group that there is the polymerizable compound polyunsaturated bond to close group, form hydrogen bond Near at least one more than aromatic rings, the functional group is by forming mesomorphic structure in intermolecular formation hydrogen bond.

2. aligning agent for liquid crystal according to claim 1, which is characterized in that the functional group is carboxyl.

3. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, which is characterized in that the polymerizable compound is It is at least one kind of in following formula [1-1]~[1-4],

T is ehter bond, ester bond, amido bond, and S is the alkylidene of carbon atom number 2~11, and R is hydrogen atom or methyl, n=1 or 2.

4. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, which is characterized in that the polymerizable compound is It is at least one kind of in following formula [2-1]~[2-6]:

5. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, which is characterized in that the side chain of the polymer has There is the group for making liquid crystal vertical-tropism.

6. aligning agent for liquid crystal according to claim 5, which is characterized in that the side chain of the polymer also has optical polymerism Group.

7. aligning agent for liquid crystal according to claim 6, which is characterized in that the polymerism group is selected from following formula It is at least one kind of in [3-1]~[3-7],

In formula [3-1], Me indicates methyl.

8. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, which is characterized in that the polymer has light anti- Answering property group.

9. aligning agent for liquid crystal according to claim 8, which is characterized in that the photoreactive group is selected from following formula It is at least one kind of in [4-1]~[4-5]:

10. a kind of liquid crystal orientation film, which is characterized in that it is using aligning agent for liquid crystal described in any one of claim 5~7 And make, it is obtained via the process for irradiating ultraviolet light while applying voltage.

11. a kind of liquid crystal indicates element, which is characterized in that it has liquid crystal orientation film described in any one of claim 10.

12. a kind of liquid crystal orientation film, which is characterized in that it is using claim 8 or aligning agent for liquid crystal as claimed in claim 9 And make, it is obtained via the process of irradiation polarized UV rays.

13. a kind of liquid crystal indicates element, which is characterized in that it has liquid crystal orientation film described in claim 12.