CN109952531A

CN109952531A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element

Info

Publication number: CN109952531A
Application number: CN201780070436.XA
Authority: CN
Inventors: 国见奈穗; 杉山崇明
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-11-18
Filing date: 2017-11-15
Publication date: 2019-06-28
Anticipated expiration: 2037-11-15
Also published as: WO2018092811A1; KR102483499B1; KR20190082293A; JP7259328B2; TWI745488B; CN109952531B; TW201831658A; JPWO2018092811A1

Abstract

The present invention provides a kind of aligning agent for liquid crystal that can obtain film hardness height and the liquid crystal orientation film with good image retention speciality etc..The aligning agent for liquid crystal contains following (A) ingredients, (B) ingredient and organic solvent.(A) ingredient: it is acid imide compound, that is, polyimides of polyimide precursor, and acid imide rate is 20%~80%, the polyimide precursor is the reaction product of tetracarboxylic acid derivatives ingredient with the diamine component of the diamines containing the structure with following formula (1).(in formula, * indicates the key with other atoms or group.) (B) ingredient: it is the compound containing 2 or more cross-linking functional groups.

Description

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

Technical field

The present invention relates to aligning agent for liquid crystal, the liquid crystal orientation film obtained by the aligning agent for liquid crystal and the liquid crystal is used to take Element is indicated to the liquid crystal of film.

Background technique

Liquid crystal orientation film is to be used in liquid crystal expression element, the phase difference board for having used polymerizable liquid crystal by liquid crystal molecule Tropism control constant direction film.For example, indicating to have the following structure in element: constituting the liquid crystal of liquid crystal layer in liquid crystal Molecule is sandwiched between the liquid crystal orientation film on the respective surface for being formed in a pair of of substrate.Then, liquid crystal molecule is taken by liquid crystal It is orientated in constant direction to film with pre-tilt angle, and by applying voltage to the electrode being arranged between substrate and liquid crystal orientation film To make a response.As a result, liquid crystal indicate element shown using change in orientation caused by the response due to liquid crystal molecule it is desired Image.Liquid crystal orientation film indicates to be formed together main composition part with liquid crystal molecule etc. in element in liquid crystal.

Liquid crystal orientation film needs various characteristics.Resistance to brushing treatability height is one of important feature therein.At known brushing Reason is the method for forming liquid crystal orientation film by the polymeric membrane being formed on substrate in the manufacturing process that liquid crystal indicates element, And it is still widely used in industry at present.In brushing processing, to polymeric membranes such as the polyimides being formed on substrate, into Row is rubbed the orientation process on its surface with cloth.

The brushing processing in, it is known that the problem of be, due to scrape liquid crystal orientation film and generate dust, be attached to liquid crystal Scratch in alignment films can reduce the expression quality for indicating element.It is therefore desirable to the resistance to brush that liquid crystal orientation film has film hardness big It grinds treatability (resistance to brushing).

As the method for being used to form the liquid crystal orientation film with high resistance to brushing, it is known that taken by using following liquid crystal To agent, regardless of brushing condition, the liquid crystal orientation film for showing constant pre-tilt angle can be obtained, the aligning agent for liquid crystal contains The polymer and/or its imide amination polymer and intramolecular for reacting tetracarboxylic dianhydride with amine compounds have 2 The compound of the above epoxy group (referring to patent document 1,2).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 07-234410 bulletin

Patent document 2: Japanese Unexamined Patent Publication 10-338880 bulletin

Summary of the invention

Problems to be solved by the invention

In recent years, towards the mobile purposes such as smart phone, mobile phone, the lightweight and slimming that liquid crystal indicates element are just It is rapidly developing.At the same time, in the manufacture of liquid crystal display panel, often implement to the glass substrate of the liquid crystal display panel after production into So-called " thinning process " of row grinding.In this process, exist using hydrofluoric acid etc. chemical method and using grinding agent into The method of row physical grinding.

In the case where carrying out physical grinding, since the device for grinding is different, the liquid crystal display panel of manufacture is curved sometimes It is bent, as a result, stress is applied to liquid crystal orientation film from all directions.Therefore, when the mechanical strength of liquid crystal orientation film is weak, especially The rupture of film can occur around column spacer, this may cause defect generation.Have at enough resistance to brushings so far The liquid crystal orientation film of rationality is usually insufficient to the tolerance of the thinning process.

The main purpose of the present invention is to provide a kind of aligning agent for liquid crystal, can obtain following liquid crystal orientation film: not only In brushing process, even if in thinning process, it may have it is able to suppress the abrasion of film, ruptures contour film hardness, and High yield rate in liquid crystal display panel manufacture, and electrical characteristics are excellent, can reduce the liquid crystal watch in IPS driving method, FFS driving method Show that the exchange occurred in element drives caused ghost.

The solution to the problem

In order to solve the above-mentioned technical problem the inventors of the present invention have made intensive studies, as a result complete the present invention.

That is, idea of the invention is that, the liquid crystal characterized by containing following (A) ingredients, (B) ingredient and organic solvent takes Element is indicated to agent, the liquid crystal orientation film obtained by the aligning agent for liquid crystal and the liquid crystal for having used the liquid crystal orientation film.

(A) ingredient: its be polyimide precursor acid imide compound, that is, polyimides, and acid imide rate be 20%~ 80%, the polyimide precursor is the diamines of tetracarboxylic acid derivatives ingredient with the diamines containing the structure with following formula (1) The reaction product of ingredient.

(in formula, * indicates the key with other atoms or group.)

(B) ingredient: the compound containing 2 or more cross-linking functional groups.

The effect of invention

Aligning agent for liquid crystal through the invention can obtain film hardness height and the liquid crystal aligning with good image retention speciality Film.Therefore, the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention can obtain following IPS driving method, FFS driving The liquid crystal of mode indicates element: the high yield rate in liquid crystal display panel manufacture, and image retention speciality is excellent, it is possible to reduce drives in IPS Flowing mode, FFS driving method liquid crystal indicate ghost caused by the exchange that occurs drives in element.

Specific embodiment

<(A) ingredient>

(A) ingredient contained in aligning agent for liquid crystal of the invention is that the acid imide compound i.e. polyamides of polyimide precursor is sub- Amine, and acid imide rate is 20%~80%, the polyimide precursor be tetracarboxylic acid derivatives ingredient with containing with above-mentioned The reaction product of the diamine component of the diamines of the structure of formula (1).

It as the diamines of the structure with formula (1), such as can enumerate: the both ends difference key of the phenyl ring in formula (1) Close the structure for having amino.In this case, in the amino of the both ends of phenyl ring bonding relative to-O-CH₂- O- is each independently It is bonded in ortho position, meta or para position.Wherein, preferably amino is relative to-O-CH₂- O- is bonded in contraposition.

In order to which the purpose of the present invention is better achieved, in all diamine components for being reacted with tetracarboxylic acid derivatives ingredient, The content ratio of the diamines of structure with formula (1) is preferably 10~80 moles of %, more preferably 20~60 moles of %, especially excellent It is selected as 20~50 moles of %.

In diamine component for obtaining polyimide precursor, in addition to the diamines of the structure with formula (1), it can also contain Other one kind or two or more diamines.Other described diamines can be indicated with following formula (6).

In above-mentioned formula (6), A₁And A₂Separately for hydrogen atom, the alkyl of carbon number 1~5, carbon number 2~5 alkenyl or The alkynyl of carbon number 2~5.From the angle of liquid crystal aligning, A₁And A₂Preferably hydrogen atom or methyl.

In addition, if illustrating the Y in formula (6)₁, (Y-1) below~(Y-168) can be enumerated.

Y from the angle of liquid crystal aligning, in above-mentioned formula (6)₁It is preferred that with High Linear structure, can exemplify by Structure shown in following formula (8) or following formula (9).

In above-mentioned formula (8), (9), A₁For the divalent organic group of singly-bound, ester bond, amido bond, thioester bond or carbon number 1~20.A₂ For 1 valence organic group of hydrogen atom, halogen atom, hydroxyl, amino, mercapto, nitro, phosphate or carbon number 1~20.A is 1 ~4 integer.When a is 2 or more, A₂Structure may be the same or different.B and c is separately 1~2 integer.

As the concrete example of above-mentioned formula (8) and above-mentioned formula (9), can enumerate: Y-7, Y-25, Y-26, Y-27, Y-43, Y- 44、Y-45、Y-46、Y-48、Y-71、Y-72、Y-73、Y-74、Y-75、Y-76、Y-82、Y-87、Y-88、Y-89、Y-90、Y- 92, Y-93, Y-94, Y-95, Y-96, Y-100, Y-101, Y-102, Y-103, Y-104, Y-105, Y-106, Y-110, Y-111, Y-112、Y-113、Y-115、Y-116、Y-121、Y-122、Y-126、Y-127、Y-128、Y-129、Y-132、Y-134、Y- 153, Y-156, Y-157, Y-158, Y-159, Y-160, Y-161, Y-162, Y-163, Y-164, Y-165, Y-166, Y-167 with And Y-168.

As for obtaining other above-mentioned diamines contained in the diamine component of polyimide precursor, wherein preferably have The heated diamines of heat leaving away property group as shown in following formula (7) for leaving away to can produce amino, preferably secondary amino group.

In above-mentioned formula (7), D be preferably leave away at 150~230 DEG C, the heat more preferably left away at 180~230 DEG C is left away Property group.From the angle for temperature of leaving away, D is particularly preferably tert-butoxycarbonyl or 9- fluorenylmethoxycarbonyl groups.

As the Y with heat the leaving away property group as shown in above-mentioned formula (7)₁Concrete example, can enumerate: Y-158, Y- 159, Y-160, Y-161, Y-162 or Y-163.

The diamines of structures in all diamine components reacted with tetracarboxylic acid derivatives ingredient, with above-mentioned formula (7) Content ratio is preferably 10~70 moles of %, more preferably 20~50 moles of %.

It reacts as with the diamine component of the diamines containing the structure with above-mentioned formula (1) for manufacture is of the invention The tetracarboxylic acid derivatives ingredient of (A) ingredient, not only can be used tetracarboxylic dianhydride contained in aligning agent for liquid crystal, can also use Tetrabasic carboxylic acid, tetracarboxylic acid acid ihalide, tetracarboxylic acid acid dialkyl ester or tetracarboxylic acid acid dialkyl ester dihalide.Wherein, as tetrabasic carboxylic acid Derivative, preferably tetracarboxylic dianhydride.

For tetracarboxylic acid derivatives, preferably with the tetracarboxylic acid derivatives of ester ring type structure, the tool as ester ring type structure Body example can enumerate following formula (X1-1)~(X1-10).

In formula (X1-1)~(X1-4), R₃~R₂₃Separately for hydrogen atom, halogen atom, carbon number 1~6 alkyl, The alkenyl of carbon number 2~6, the alkynyl of carbon number 2~6, carbon number 1~6 containing fluorine atom 1 valence organic group or phenyl.From liquid crystal The angle of orientation is set out, R₃~R₂₃Preferably hydrogen atom, halogen atom, methyl or ethyl, more preferably hydrogen atom or methyl.

As the specific structure of formula (X1-1), following structures can be enumerated.

In the present invention, in all full tetracarboxylic acid derivatives ingredients reacted with diamine component, with ester ring type structure The content ratio of above-mentioned tetracarboxylic acid derivatives is preferably 60~100 moles of %, more preferably 70~100 moles of %, particularly preferably It is 80~100%.

For tetracarboxylic acid derivatives used in the present invention, can be used with except the tetracarboxylic acid with above-mentioned ester ring type structure The tetracarboxylic acid derivatives of structure other than acid derivative.If enumerating concrete example, can enumerate with following formula (X-9)~(X-42) Structure tetracarboxylic acid derivatives.

Precursor, that is, the polyamic acid and poly amic acid ester of polyimides contained in aligning agent for liquid crystal of the invention pass through upper It states tetracarboxylic acid derivatives ingredient and reacts following manufacture with (polycondensation) of diamine component.

It specifically, can be by the presence of an organic, making tetracarboxylic acid at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C Acid dianhydride and diamine reactant 30 minutes~24 hours, preferably 1~12 hour manufacture polyamic acid.

Organic solvent for above-mentioned reaction is as long as the solvent for dissolving polyimide precursor generated without special It limits.Such as it can enumerate: n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, gamma-butyrolacton, N, N- dimethyl methyl Amide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,3- dimethyl-imidazol alkanone.

In addition, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4- hydroxyl -4- can be used when the dissolubility of polyamic acid is high Methyl -2 pentanone or the solvent as shown in following formula [D-1]~formula [D-3].

In formula [D-1]~formula [D-3], D¹Indicate the alkyl of carbon number 1~3, D²Indicate the alkyl of carbon number 1~3, D³Indicate carbon The alkyl of number 1~4.

These solvents can be used alone, and can also be used in mixed way.Further, even not dissolving the molten of polyamic acid Agent can also be used in mixed way in the range of polyamic acid generated is not precipitated with the solvent.In addition, due in solvent Water inhibits polymerization reaction, and leads to the polyamic acid generated hydrolysis, therefore it is preferable to use the solvents dehydrated.

From the angle being precipitated and be easy to get high molecular weight body for being difficult to happen polymer, the concentration of polyamic acid Preferably 1~30 mass %, more preferably 5~20 mass %.

It can make polyamide acid out by injecting reaction solution in poor solvent while reaction solution is sufficiently stirred Out to recycle the polyamic acid obtained as described above.In addition, being precipitated several times, after being washed with poor solvent, room temperature is carried out Or heat drying, so as to the powder of the polyamic acid purified.Poor solvent is not particularly limited, can be enumerated Water, methanol, ethyl alcohol, hexane, butyl cellosolve, acetone, toluene etc..

Poly amic acid ester can be manufactured by the method for (1) as shown below, (2) or (3).

(1) the case where being manufactured by polyamic acid

Poly amic acid ester can be manufactured by esterification by the polyamic acid that tetracarboxylic dianhydride and diamines obtain.It is specific and Speech, can be by the presence of an organic, at -20 DEG C~150 DEG C, preferably 0~50 DEG C, keeping polyamic acid and esterifying agent anti- Answer manufacture within 30 minutes~24 hours, preferably 1~4 hour.

As esterifying agent, can preferably be enumerated: N, N- dimethyl formyl by purifying the esterifying agent being readily removable Amine dimethylacetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N- dimethyl Formamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyl triazenes, 1- ethyl -3- p-methylphenyl triazenes, 1- propyl -3- p-methylphenyl triazenes, 4- (4,6- dimethoxy -1,3,5- triazine -2- Base) -4- methylmorpholinium chloride etc..Relative to 1 mole of repetitive unit, the dosage of esterifying agent is preferably 2~6 molar equivalents.

From the dissolubility of polymer, the solvent for above-mentioned reaction is preferably n,N-Dimethylformamide, N- methyl- 2-Pyrrolidone or gamma-butyrolacton, these can be used a kind or are mixed with two or more.From the analysis for being difficult to happen polymer Out and it is easy to get the angle of high molecular weight body and sets out, concentration when manufacture is preferably 1~30 mass %, more preferably 5~ 20 mass %.

(2) by tetracarboxylic acid acid diesters dichloride and diamine reactant come the case where manufacture

Poly amic acid ester can be manufactured by tetracarboxylic acid acid diesters dichloride and diamines.

Specifically, can be by the presence of alkali and organic solvent, at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C Under, manufacture tetracarboxylic acid acid diesters dichloride and diamine reactant 30 minutes~24 hours, preferably 1~4 hour.

Pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used in the alkali, but leniently carried out to react, It is preferred that pyridine.From for the amount easily removed and the angle of high molecular weight body is easily obtained, the dosage of alkali is relative to tetracarboxylic acid Acid diesters dichloride is preferably 2~4 times moles.

From the dissolubility of monomer and polymer, the solvent for above-mentioned reaction is preferably n-methyl-2-pyrrolidone Or gamma-butyrolacton, they can be used a kind or are mixed with two or more.From the precipitation for being difficult to happen polymer and it is easy The angle for obtaining high molecular weight body is set out, and polymer concentration when manufacture is preferably 1~30 mass %, more preferably 5~20 matter Measure %.In addition, the hydrolysis of tetracarboxylic acid acid diesters dichloride in order to prevent, for manufacturing the solvent of poly amic acid ester preferably as far as possible Dehydration, and preferably prevent outside air to be mixed into nitrogen atmosphere.

(3) by tetracarboxylic acid acid diesters and diamines come the case where manufacture

Poly amic acid ester can be manufactured by making tetracarboxylic acid acid diesters and diamines polycondensation.Specifically, can be by contracting In the presence of mixture, alkali and organic solvent, at 0 DEG C~150 DEG C, preferably 0 DEG C~100 DEG C, make tetracarboxylic acid acid diesters and diamines 30 minutes~24 hours, preferably 3~15 hours are reacted to manufacture.

Triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- diformazan ammonia can be used in the condensing agent Base propyl) carbodiimide hydrochloride, N, N'- carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5-methyl morpholine drone, O- (benzene And triazol-1-yl)-N, N, N', N'- tetramethylurea tetrafluoroborate, O- (benzotriazole -1- base)-N, N, N', N'- tetramethyl Urea hexafluorophosphate, diphenyl (thio -3- benzoxazolyl of 2,3- dihydro -2-) phosphonic acids etc..The dosage of condensing agent is relative to four Carboxylic acid diesters are preferably 2~3 times moles.

The tertiary amines such as pyridine, triethylamine can be used in the alkali.From for the amount easily removed and being easily obtained macromolecule The angle of amount body is set out, and the additive amount of alkali is preferably 2~4 times moles relative to diamine component.

In addition, reaction is effectively performed by the way that lewis acid is added in above-mentioned reaction.As lewis acid, preferably The lithium halides such as lithium chloride, lithium bromide.Lewis acidic additive amount is preferably 0~1.0 times mole relative to diamine component.

In the manufacturing method of above-mentioned 3 kinds of poly amic acid esters, the manufacturing method of above-mentioned (1) or above-mentioned (2) is due to that can obtain The poly amic acid ester of high molecular weight, therefore particularly preferably.

The solution of the poly amic acid ester obtained as described above can be sufficiently stirred by one side, inject poor solvent on one side In, polymer is precipitated.It is precipitated several times, after being washed with poor solvent, room temperature or heat drying is carried out, to be purified Poly amic acid ester powder.Poor solvent is not particularly limited, water outlet, methanol, ethyl alcohol, hexane, the molten fibre of butyl can be enumerated Agent, acetone, toluene etc..

Above-mentioned (A) ingredient, that is, polyimides can be by making the polyamic acid or poly amic acid ester imidizate It makes.When preparing polyimides by poly amic acid ester, in Xiang Suoshu polyamic acid ester solution or to by poly amic acid ester toner It is easy for being dissolved in polyamic acid solution obtained in organic solvent and adding the chemical imidization of basic catalyst.Chemistry Imidizate is due to being to carry out imidization reaction at relatively low temperature, and be less likely to occur to gather during imidizate The molecular weight and molecular weight of object is closed, therefore preferably.

Chemical imidization can by organic solvent, in the presence of basic catalyst, stirring will acid imide The polyamic acid or poly amic acid ester of change carries out.As organic solvent, what is used when above-mentioned polymerization reaction can be used is molten Agent.It as basic catalyst, can enumerate: pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc..Wherein, triethylamine has Enough alkalinity carries out so as to react, therefore preferably.

The temperature for carrying out imidization reaction is -20 DEG C~140 DEG C, and preferably 0 DEG C~100 DEG C, the reaction time can carry out 1 ~100 hours.The amount of basic catalyst is 0.5~30 mole times of polyamic acid or amic acid esters group, preferably 2~20 moles Times.The acid imide rate of resulting polymers can be controlled by adjusting catalytic amount, temperature, reaction time.Due to addition Catalyst etc. remains in the solution after imidization reaction, therefore preferably recycles obtained imide amination polymer, with having Solvent dissolves again, and aligning agent for liquid crystal is made.

The solution of the polyimides obtained as described above can be sufficiently stirred by one side, inject in poor solvent on one side, Polymer is precipitated.It is precipitated several times, after being washed with poor solvent, carries out room temperature or heat drying, it is pure so as to obtain The powder of the poly amic acid ester of change.

The poor solvent is not particularly limited, can be enumerated: methanol, acetone, hexane, butyl cellosolve, heptane, first Ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc..

(A) ingredient, that is, polyimides contained in aligning agent for liquid crystal of the invention, can be by making polyamides sub- as described above Amine precursor imidizate and obtain, acid imide rate at this time need to be 20~80%.When acid imide rate is excessive, it is significant to apply film property It reduces, and when acid imide rate is too small, then it may be unable to fully obtain the hardness of gained liquid crystal orientation film.Wherein, imidizate Rate is more preferably 50~70%.

In addition, for the molecular weight of polyimides, in terms of weight average molecular weight (Mw), preferably 2000~500000, it is more excellent It is selected as 5000~300000, further preferably 10000~100000.In addition, number-average molecular weight (Mn) be preferably 1000~ 250000, more preferably 2500~150000, further preferably 5000~50000.

<(B) ingredient>

(B) ingredient contained in aligning agent for liquid crystal of the invention is the compound with 2 or more cross-linking functional groups.From Acquired and effect angle is set out, and this cross-linking functional group is preferably selected from by hydroxyl, (methyl) is acrylate-based, blocks It is at least one kind of in the group of isocyanate group, oxetanyl and epoxy group composition.Wherein, preferred hydroxyl.As (B) at The compound divided can have 2 or more identical cross-linking functional groups, it is possible to have 2 or more two or more different Cross-linking functional group.The quantity of cross-linking functional group does not have the upper limit, but usually 8 hereinafter, preferably 6 or less.

Especially as the preferred compound with 2 or more hydroxyls, the chemical combination indicated by following formula (2) can be enumerated Object.

In above-mentioned formula (2), X₂Aliphatic alkyl for carbon number 1~20 or the n valence organic group comprising aromatic hydrocarbyl.n For 2~6 integer.Arbitrary carbon in above-mentioned aliphatic alkyl or aromatic hydrocarbyl is optionally replaced by nitrogen or oxygen.

R₂And R₃It is separately hydrogen atom, the alkyl of the optionally carbon number 1~4 with substituent group, optionally there is substituent group Carbon number 2~4 alkenyl or optionally with substituent group carbon number 2~4 alkynyl.In addition, R₂And R₃At least one of indicate The alkyl being optionally substituted by a hydroxyl group.

Wherein, from the X in the angle of liquid crystal aligning, formula (2)₂With the atom of carbonyl Direct Bonding preferably not Form the carbon atom of aromatic rings.In addition, from liquid crystal aligning and deliquescent angle, the X of formula (2)₂Preferably aliphatic Alkyl, more preferably carbon number 1~10.In formula (2), from deliquescent angle, n is preferably 2~4.

In formula (2), from reactive angle, R₂And R₃At least one of preferably tie shown in following formula (3) Structure shown in structure, more preferably following formula (4).

In formula (3), R₄~R₇It is separately hydrogen atom, alkyl or the alkyl being optionally substituted by a hydroxyl group.

The preference of compound as the group with 2 or more hydroxyls, can enumerate following substance.

(B) when ingredient is excessive, liquid crystal aligning, pre-tilt angle be will affect；When very few, effect of the invention cannot be obtained.Cause This, relative to (A) ingredient, the content of (B) ingredient is preferably 0.1~20 mass %, more preferably 1~10 mass %.

<(C) ingredient>

Aligning agent for liquid crystal of the invention can further contain polyimide precursor as ingredient (C), the polyimides Precursor is the reaction product of tetracarboxylic acid derivatives ingredient and diamine component.

As the polyimide precursor of (C) ingredient, can be used as the polyimides of (A) ingredient precursor i.e. The raw material of polyimide precursor and the tetracarboxylic acid derivatives and diamines recorded, but with (A) contained in same aligning agent for liquid crystal Except the identical polyimide precursor of the precursor of the polyimides of ingredient.As polyimide precursor, preferred polyamide acid.

Aligning agent for liquid crystal of the invention passes through containing (C) ingredient is somebody's turn to do, and can further increase resulting liquid crystal orientation film Film-strength.Relative to (A) ingredient, (C) ingredient in aligning agent for liquid crystal is preferably 20~80 moles of %, and more preferable 40~70 rub You are %.

Aligning agent for liquid crystal of the invention has aforementioned (A) ingredient and (B) ingredient and (C) ingredient dissolution as needed The form of the solution obtained from organic solvent.

The concentration of polymer in aligning agent for liquid crystal of the invention can suitably become according to the thickness of the film desirably formed Change, but from the angle for forming uniform and flawless film, preferably 1 mass % or more；From the storage stability of solution Angle set out, be preferably set to 10 mass % or less.Particularly preferably 3~6.5 mass %.

As long as organic solvent contained in aligning agent for liquid crystal of the invention can equably dissolve contained polymer Organic solvent be just not particularly limited.

Such as it can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- second Base -2-Pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-imidazol alkanone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4- hydroxy-4-methyl-2-pentanone etc..In particular it is preferred to using n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or Gamma-butyrolacton.

In the organic solvent contained in aligning agent for liquid crystal of the invention, the 1st solvent (I) and the 2nd solvent are preferably comprised (II), the 1st solvent (I) includes selected from by n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- amyl -2- pyrrole Pyrrolidone, gamma-butyrolacton, gamma-valerolactone, 1,3- dimethyl -2- imidazolidinone, 3- methoxyl group-N, N- dimethylpropionamide with And it is at least one kind of in the group of 3- butoxy-N, N- dimethylpropionamide composition,

2nd solvent (II) include selected from by butyl cellosolve, butyl cellosolve acetate, 1- butoxy -2- propyl alcohol, 2- butoxy -1- propyl alcohol, dimethyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, diisobutyl carbinol (DIBC), diisobutyl It is at least one kind of in the group that ketone, propylene carbonate, propylene-glycol diacetate and diisoamyl ether form.

Further, when the dissolubility of polymer of the invention in a solvent is high, it is preferable to use by previously described formula [D-1]~formula Solvent shown in [D-3].

Organic solvent in aligning agent for liquid crystal of the invention is preferably contained solvent is whole in aligning agent for liquid crystal 20~99 Quality %.Wherein, preferably 20~90 mass %.More preferably 30~80 mass %.

Painting film property, the table that liquid crystal orientation film is improved in coating of liquid crystalline alignment agent can be used in aligning agent for liquid crystal of the invention The solvent (also referred to as poor solvent) of face flatness.It is listed below the concrete example of poor solvent, but is not limited to these examples.

Such as it can enumerate: ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- Methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycol, dipropyl ether, butyl oxide, two hexyl ethers, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol two Butyl ether, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, two fourth of diethylene glycol Ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, acetic acid 3- Ethoxybutyl, acetic acid 1- methyl pentyl ester, acetic acid 2- Ethyl butyl ester, acetic acid 2- ethylhexyl, ethylene glycol acetate, ethylene acetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol monohexylether, 2- (hexyloxy) ethyl alcohol, Furfuryl alcohol, diethylene glycol (DEG), propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol methyl ether acetate, dipropyl Glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dimethyl ether, Tripropylene glycol monomethyl Ether, glycol monoethyl ether Acetic acid esters, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, ethylene acetate, two Ethylene glycol monoethylether acetate, butyl carbitol acetate, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol Acetic acid esters, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol list ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, N-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-c Sour methyl ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxyl group Butyl propionate, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, by previously described formula [D-1]~formula Solvent shown in [D-3] etc..

Wherein, preferably 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol monobutyl ether, ethylene glycol only son Ether or dimethyl ether.

Poor solvent is preferably 1~80 mass % of the entirety of solvent contained in aligning agent for liquid crystal, and further preferably 10 ~80 mass %, more preferably 20~70 mass %.

Apart from the above, it can be added in aligning agent for liquid crystal of the invention: poly- in addition to polymer of the present invention Close object；The dielectric or conductive materials of the electrical characteristics such as dielectric constant, electric conductivity for changing liquid crystal orientation film；For improving liquid The silane coupling agent of brilliant alignment films and the adaptation of substrate；For improving hardness, the consistency of film when liquid crystal orientation film is made Cross-linked compound；And when being burnt into film, for effectively facilitating through heating polyimide precursor to imidizate Imidizate promotor etc..

Liquid crystal orientation film of the invention is that above-mentioned aligning agent for liquid crystal is coated on substrate, obtained from drying and being burnt into Film.As the substrate for being coated with aligning agent for liquid crystal of the invention, it is not particularly limited, can be used as long as the high substrate of the transparency Plastic bases such as glass substrate, silicon nitride board, acrylic compounds substrate, polycarbonate substrate etc..In addition, the angle for the chemical industry skill that conforms to the principle of simplicity Degree sets out, it is preferable to use being formed with the substrate of ITO electrode for driving liquid crystal etc..In addition, indicating element in reflective liquid crystal In, if only single sided substrate, the opaque substance of silicon wafer etc. can be used, it is anti-that aluminium etc. also can be used in electrode at this time Penetrate the material of light.

As the coating method of aligning agent for liquid crystal of the invention, spin-coating method, print process, ink-jet method etc. can be enumerated.Coating In drying, firing process after aligning agent for liquid crystal of the invention, arbitrary temperature and time can choose.In general, in order to abundant Remove contained solvent, by its at 50~120 DEG C, preferably 60~100 DEG C it is 1~10 minute, preferably 2~5 minutes dry, then It is burnt into 5~120 minutes, preferably 10~30 minutes at 150~300 DEG C, preferably at 200~240 DEG C.Film after firing Thickness is not particularly limited, but if too thin, then liquid crystal indicates that the reliability of element may be decreased, therefore is 5~300nm, excellent It is selected as 10~200nm.

As the method for carrying out orientation process to gained liquid crystal orientation film, brushing method, light orientation position logos etc. can be enumerated.

Existing brushing device can be used and carry out brushing processing.As the material of brushing cloth at this time, can enumerate: Cotton, nylon, artificial silk etc..As the condition of brushing processing, usually using following condition: the rotation speed of 300~2000rpm, 5 The feed speed of~100mm/s, the pressing quantity of 0.1~1.0mm.Later, it using pure water, alcohol etc., is removed by ultrasonic washing The residue generated by brushing.

As the concrete example of light orientation position logos, can enumerate following method: Xiang Suoshu film coated surface is irradiated along certain Direction deflection radiation, according to circumstances further 150~250 DEG C at a temperature of heated, assign liquid crystal aligning Ability.As radiation, the ultraviolet light and luminous ray that wavelength is 100~800nm can be used.Wherein, optimal wavelength 100 The ultraviolet light of~400nm, particularly preferred wavelength are the ultraviolet light of 200~400nm.It, can be in addition, in order to improve liquid crystal aligning Illumination radiation line while heating applies ilm substrate at 50~250 DEG C.The exposure of the radiation is preferably 1~10000mJ/ cm², particularly preferably 100~5000mJ/cm².The liquid crystal orientation film prepared as described above can make liquid crystal molecule in a certain direction Steadily it is orientated.

The extinction ratio of polarized UV rays is higher, and the anisotropy that can be assigned is higher, therefore preferably.Specifically, straight line is inclined The extinction ratio of the ultraviolet light of vibration is preferably 10:1 or more, more preferably 20:1 or more.

It is then possible to at least one kind of solvent in the group comprising selecting Free water and organic solvent to form to above-mentioned through inclined The film of vibration irradiation with radiation carries out contact treatment.

It is not special as long as the solvent for dissolving the decomposition product generated by light irradiation as the solvent for contact treatment It does not limit.It as concrete example, can enumerate: water, methanol, ethyl alcohol, 2- propyl alcohol, acetone, methyl ethyl ketone, 1- methoxy-2-propanol, 1- Methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methoxy methyl propionate, 3- Ethoxyl ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate etc..Two or more can be applied in combination in these solvents.

From versatility, the angle of safety, it is more preferably selected from by water, 2- propyl alcohol, 1- methoxy-2-propanol and cream It is at least one kind of in the group of acetoacetic ester composition.The mixed solvent of particularly preferred water, 2- propyl alcohol or water and 2- propyl alcohol.

In the present invention, for the contact treatment of the film and the solvent-laden solution of packet that irradiate through polarized radiation line, leaching is utilized Method that stain processing, spraying (spray) processing etc., film and solution preferably come into full contact with carries out.Wherein, preferably including solvent Solution in impregnation method, preferably 10 seconds~1 hour, more preferable 1~30 minute.Contact treatment can be at normal temperature Progress can be heated, preferably 10~80 DEG C, it is 20~50 DEG C more preferable at carry out.Moreover, as needed, it is possible to implement ultrasonic wave The means of equal raisings contact.

After contact treatment, in order to remove the solvent in used solution, carry out with water, methanol, ethyl alcohol, 2- propyl alcohol, third The low boiling point solvents such as ketone, methyl ethyl ketone are rinsed any one of (flushing), dry, or both and are all carried out.

Further, in order to dry solvent and make the strand reorientation in film, can by the solution of included solvent into The film of row contact treatment 150 DEG C or more at a temperature of heat.

As heating temperature, preferably 150~300 DEG C.Temperature is higher, more the reorientation of promotion strand, but temperature mistake It may be with the decomposition of strand when high.Therefore, as heating temperature, more preferably 180~250 DEG C, particularly preferably 200~ 230℃。

When heating time is too short, the effect of strand reorientation possibly can not be obtained, when heating time is too long, strand can It can decompose, therefore preferably 10 seconds~30 minutes, more preferable 1~10 minute.

Liquid crystal of the invention indicates that element is characterized in that the liquid crystal orientation film for having of the invention.Liquid crystal of the invention indicates Element is as follows: obtaining the base with liquid crystal orientation film by aligning agent for liquid crystal of the invention by the manufacturing method of foregoing liquid crystal alignment films Then plate makes liquid crystal cells by well known method, and make liquid crystal using it to indicate element.

An example of production method as liquid crystal cells is said so that the liquid crystal of passive-matrix structure indicates element as an example It is bright.It should be noted that being also possible to be provided with TFT's (thin film transistor (TFT)) etc. on constituting each pixel portion that image is shown The liquid crystal of the active matrix structure of switch element indicates element.

Firstly, preparing transparent glass substrate of electrode, common electrode is set on one substrate, is arranged on another substrate Segment electrode.Such as ITO electrode can be made in these electrodes, and in order to realize that desired image is shown and is patterned (Patterning).Then, insulating film is set on each substrate, to cover common electrode and segment electrode.Insulating film can be made By sol-gel method formed, include SiO₂-TiO₂Film.

Then, liquid crystal orientation film of the invention is formed on each substrate.Next, overlapping another base on one substrate Plate keeps mutual orientation film surface opposite, and is bonded periphery with sealing material.For control base board gap, usually sealing Spacer is mixed into material.Additionally, it is preferred that in the face inner part for being not provided with sealing material, also dispersion is used for control base board in advance The spacer in gap.In a part of sealing material, presetting can be from the opening portion of external filling liquid crystal.

Then, liquid crystal material is injected by 2 substrates and sealing material packet by the opening portion of setting on the sealing material In the space enclosed.Later, the opening portion is sealed with bonding agent.For injection, vacuum impregnation can be used, also can be used The method of capillarity is utilized in atmosphere.Next, setting polarization plates.Specifically, in the opposite with liquid crystal layer of 2 substrates A pair of of polarization plates are pasted on the face of side.Obtaining liquid crystal of the invention by above-mentioned operation indicates element.

In the present invention, as sealant, such as using with epoxy group, acryloyl group, (methyl) acryloyl group, hydroxyl Base, allyl, acetyl group isoreactivity group, by ultraviolet light irradiation, heating to cured resin.Particularly preferably use The solidified resin class of reactive group with both epoxy group and (methyl) acryloyl group.

In sealant of the invention, for the purpose for improving cementability, moisture-proof, inorganic filler can be compounded.It can It is not particularly limited with the inorganic filler used, can specifically be enumerated: preparing spherical SiO 2, fused silica, crystalline substance Body silica, titanium oxide, titanium be black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, Talcum, clay, aluminium oxide, magnesia, zirconium oxide, aluminium hydroxide, calcium silicates, alumina silicate, lithium aluminosilicate, zirconium silicate, barium titanate, Glass fibre, carbon fiber, molybdenum disulfide, asbestos etc..Preferably, it can enumerate: preparing spherical SiO 2, fused silica, crystalline substance Body silica, titanium oxide, titanium be black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, oxidation Aluminium, aluminium hydroxide, calcium silicates or alumina silicate.The inorganic filler can be mixed with two or more.

Embodiment

It is exemplified below out embodiment, the present invention is more particularly described, but the present invention is not limited to these Examples.With Under compound abbreviation and each characteristic measuring method it is as described below.

NMP:N- N-methyl-2-2-pyrrolidone N, GBL: gamma-butyrolacton,

BCS: butyl cellosolve,

DA-1: bis- (4- amino-benzene oxygen) methane,

Bis- (4- amino-benzene oxygen) ethane of DA-2:1,2-,

DA-3:N- tert-butoxycarbonyl-N- (2- (4- aminophenyl) ethyl)-N- (4- aminobenzyl) amine,

DA-4: referring to following formula (DA-4),

DA-5:2- tertbutyloxycarbonylamino methyl-p-phenylenediamine (in formula, Boc indicates tert-butoxycarbonyl),

DA-6: referring to following formula (DA-6),

CA-1: referring to following formula (CA-1), CA-2: referring to following formula (CA-2),

CA-3: referring to following formula (CA-3), AD-1: referring to following formula (AD-1)

[viscosity]

The viscosity of solution uses E type viscosimeter TVE-22H (Dong Ji industry society system), in sample size 1.1mL, cone rotor TE-1 (1 ° of 34', R24), it measures at 25 DEG C of temperature.

[molecular weight]

Molecular weight is measured by GPC (room temperature gel permeation chromatography) device, with polyethylene glycol, polyethylene oxide scaled value Mode calculate number-average molecular weight (Mn) and weight average molecular weight (Mw).

GPC device: Shodex corporation (GPC-101), column: Shodex society system (series connection of KD803, KD805), column temperature: 50 DEG C, eluent: n,N-Dimethylformamide (as additive, lithium bromide-water and object (LiBrH₂O) 30 mMs/L, phosphorus 30 mMs/L of sour anhydrous crystalline (orthophosphoric acid), tetrahydrofuran (THF) 10ml/L), flow velocity: 1.0ml/ minutes

Be used to prepare the authentic specimen of standard curve: (weight average molecular weight (Mw) is about for Tosoh society TSK standard polyethylene oxide 900000,150000,100000,30000) and the polyethylene glycol (peak top molecular of Polymer Laboratories Ltd Measuring (Mp) is about 12000,4000,1000).In order to avoid overlap of peaks in measurement, to be mixed with 900000,100000,12000, 1000 this 4 kinds sample and 150000,30000,4000 this 3 kinds sample are mixed with, measure the two samples respectively.

Polyimide powder 20mg is added to NMR sample cell (NMR standard sample pipe, φ 5 (wasteland's scientific company system)), Deuterated dimethyl sulfoxide (DMSO-d6,0.05%TMS (tetramethylsilane) melange) 0.53ml is added, applying ultrasonic wave makes it It is completely dissolved.For the solution, utilize NMR measuring machine (JNW-ECA500) (JEOL DATUM LTD. system) measurement 500MHz's Proton NMR.Acid imide rate is found out as follows: the proton for being originated from the structure not changed before and after imidizate is determined as benchmark Proton, the proton of the NH base from amic acid occurred using the peak accumulated value of the proton and near 9.5ppm~10.0ppm Peak accumulated value, is found out using the following formula.

Acid imide rate (%)=(1- α x/y) × 100

In above-mentioned formula, x is for peak accumulated value, the α that proton peak accumulated value, the y of the NH base from amic acid are benchmark proton Number ratio of the reference proton relative to 1 NH matrix of amic acid in the case where polyamic acid (acid imide rate is 0%).

[preparations of liquid crystal cells]

The liquid crystal that preparation has fringing field switching (Fringe Field Switching:FFS) mode indicates the knot of element The liquid crystal cells of structure.

Prepare electroded substrate first.Substrate is the size of 30mm × 50mm and the glass substrate of thickness 0.7mm.In base It is formed on plate and to constitute opposite electrode, ITO electrode with solid pattern as the 1st layer.On the 1st layer of opposite electrode Form SiN (silicon nitride) film to form a film by CVD method as the 2nd layer.The film thickness of 2nd layer of SiN film is 500nm, as layer Between insulating film function.It configures on the 2nd layer of SiN film and ito film to be patterned to the comb teeth-shaped to be formed as the 3rd layer Pixel electrode forms the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is vertical 10mm, horizontal about 5mm.At this point, the 1st The opposite electrode of layer is electrically insulated with the 3rd layer of pixel electrode by the effect of the 2nd layer of SiN film.

3rd layer of pixel electrode has the multiple combs being arranged to make up of electrode member of curved " く word " shape of center portion The shape of dentation.The width of the width direction of each electrode member between 3 μm, electrode member between be divided into 6 μm.It is each due to being formed The pixel electrode of pixel be by curved " く word " shape of center portion electrode member it is multiple be arranged to make up, therefore each pixel Shape be not oblong-shaped, but have curved similar to runic " く word " in center portion in the same manner as electrode member Shape.And the bending part in each pixel using its center is divided up and down as boundary line, the 1st area of the upside with bending part 2nd region in domain and downside.

If the 1st region of each pixel and the 2nd region are compared, the electrode member of their pixel electrode is constituted It is different to form direction.That is, using the brushing direction of aftermentioned liquid crystal orientation film as benchmark in the case where, the 1st region of pixel with The mode for the angle (clockwise) that the electrode member of pixel electrode is+10 ° is formed, and the 2nd region of pixel is with the electricity of pixel electrode The mode for the angle (clockwise) that pole element is -10 ° is formed.That is, the 1st region and the 2nd region of each pixel are to pass through pixel electricity Voltage between pole and opposite electrode applies and the direction of the spinning movement (converting in face) in real estate of the liquid crystal of induction It is that the mode of mutual reverse direction is constituted.

Then, it after the filter filtering for being 1.0 μm by aligning agent for liquid crystal aperture, is coated on and is prepared using spin coating Above-mentioned electroded substrate and overleaf film forming have ito film and have height 4 μm column spacer glass substrate on. Drying after five minutes, utilizes 230 DEG C of heated air circulation type baking ovens be burnt within 20 minutes, forms film thickness in 80 DEG C of heating plate The film of 100nm.The ultraviolet of the wavelength 254nm of the linear polarization of extinction ratio 10:1 or more is irradiated to the coated surface by polarization plates Line.The substrate is impregnated 3 minutes at least one solvent selected from water and organic solvent, is then impregnated 1 minute in pure water, It is heated 5 minutes in 150~300 DEG C of heating plate, obtains the substrate with liquid crystal orientation film.Using above-mentioned 2 substrates as 1 group, Another substrate is pasted in the printing and sealing agent on substrate, make liquid crystal alignment film surface opposite to each other and 0 ° of differently- oriented directivity, then make close Envelope agent solidification is to prepare dummy cell.Liquid crystal MLC-3019 (Merck&Co. system) is injected into the dummy cell by decompression injection method In, and inlet is sealed, to obtain FFS driving liquid crystal cells.Later, it is small that obtained liquid crystal cells are heated to 1 at 110 DEG C When, each evaluation is used for after placing an evening.

[by exchanging driving evaluation ghost for a long time]

Prepare liquid crystal cells identical with the liquid crystal cell structure for the evaluation of above-mentioned ghost.

It is small with the alternating voltage 120 of frequency 60Hz application ± 5V under 60 DEG C of isoperibol using the liquid crystal cells When.Later, make short circuit between the pixel electrode of liquid crystal cells and opposite electrode, placed at room temperature one day with the state.

After placement, liquid crystal cells are arranged between 2 polarization plates configured in the orthogonal mode of polarizing axis, and is not having Have and open backlight in advance in the state of applying voltage, adjust the arrangement angles of liquid crystal cells, so that the brightness of transmitted light is minimum.So Afterwards, calculating makes liquid crystal cells from the 2nd region of the 1st pixel become most dark angle and rotate to the 1st region to become most dark angle When rotation angle as angle delta.Similarly, in the 2nd pixel, compare the 2nd region and the 1st region, and calculate same angle Spend Δ.

[evaluation of pencil hardness]

The sample of following production evaluating pencil hardness.Aligning agent for liquid crystal is coated on to the ITO of 30mm × 40mm using spin coating On substrate.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens are utilized be burnt within 14 minutes, shape At the film of film thickness 100nm.Implement the orientation process such as brushing, polarized UV rays irradiation to the coated surface, obtains band liquid crystal aligning The substrate of film.The substrate is impregnated 3 minutes at least one solvent selected from water and organic solvent, is then impregnated in pure water It 1 minute, is heated 14 minutes in 150 DEG C~300 DEG C of heating plate, obtains the substrate with liquid crystal orientation film.Pass through pencil hardness Test method(s) (JIS K5400) measures the liquid crystal alignment film surface of the substrate.

In the 100mL four-neck flask with agitating device and nitrogen ingress pipe measure DA-1 1.75g (7.60 mMs), NMP 46.9g is added in DA-2 4.64g (19.0 mMs) and DA-3 3.89g (11.4 mMs), while supplying nitrogen into Row stirring is allowed to dissolve.It is added while stirring the diamine solution CA-1 7.93g (35.3 mMs), and then NMP is added 36.1g makes 18 mass % of solid component concentration, stirs 24 hours at 40 DEG C, obtain polyamic acid solution (A) (viscosity: 800mPa·s).The Mn=10800 of polyamic acid, Mw=23600.

Obtained polyamic acid solution 30g is measured in the 100ml four-hole boiling flask with agitating device and nitrogen ingress pipe, NMP 37.5g is added, stirs 30 minutes.Acetic anhydride 3.39g, pyridine 0.88g are added in obtained polyamic acid solution, 55 It is heated 3 hours at DEG C, carries out chemical imidization.In the methanol for putting into 270ml while the reaction solution stirred to get, mistake The sediment being precipitated is collected in filter, is then washed 3 times with the methanol of 270ml.By obtained toner, drying 12 is small at 60 DEG C When, it is last (A) to obtain polyimide resin powder.

The acid imide rate at polyimide resin powder end is 67%, Mn=7500, Mw=1100.

In the 100mL four-neck flask with agitating device and nitrogen ingress pipe measure DA-1 3.50g (15.2 mMs), NMP 46.36g is added in DA-2 2.78g (11.4 mMs), DA-3 3.89g (11.4 mMs), while supplying nitrogen into Row stirring, dissolution.(35.3 mMs) of CA-1 7.92g additions are added while stirring the diamine solution, and then NMP is added 36.1g makes 18 mass % of solid component concentration, stirs 24 hours at 40 DEG C, obtain polyamic acid solution (C) (viscosity: 820mPa·s).Mn=11000, Mw=25200 of polyamic acid.

Obtained polyamic acid solution 30g is measured in the 100mL four-neck flask with agitating device and nitrogen ingress pipe, NMP 37.5g is added, stirs 30 minutes.Acetic anhydride 3.40g, pyridine 0.88g are added in obtained polyamic acid solution, 55 It is heated 3 hours at DEG C, carries out chemical imidization.In the methanol for putting into 270ml while the reaction solution stirred to get, mistake The sediment being precipitated is collected in filter, is then washed 3 times with the methanol of 270ml.By obtained toner, drying 12 is small at 60 DEG C When, it is last (B) to obtain polyimide resin powder.

The acid imide rate at polyimide resin powder end is 67%, Mn=8000, Mw=12500.

In the 50mL four-neck flask with agitating device and nitrogen ingress pipe measure DA-1 0.69g (3.00 mMs), NMP 32.3g is added in DA-4 1.60g (5.00 mMs), DA-3 0.68g (2.00 mMs), while supplying nitrogen into Row stirring is allowed to dissolve.It is added while stirring the diamine solution CA-1 2.17g (9.70 mMs), and then NMP is added 5.00g makes 18 mass % of solid component concentration, stirs 24 hours at 40 DEG C, obtain polyamic acid solution (C) (viscosity: 790mPa·s).The Mn=15500 of polyamic acid, Mw=40600.

Obtained polyamic acid solution 50g is measured in the 100mL four-neck flask with agitating device and nitrogen ingress pipe, NMP 62.5g is added, stirs 30 minutes.Acetic anhydride 5.39g, pyridine 1.39g are added in obtained polyamic acid solution, 55 It is heated 3 hours at DEG C, carries out chemical imidization.In the methanol for putting into 525ml while the reaction solution stirred to get, mistake The sediment being precipitated is collected in filter, is then washed 3 times with the methanol of 525ml.By obtained toner, drying 12 is small at 60 DEG C When, it is last (C) to obtain polyimide resin powder.

The acid imide rate at polyimide resin powder end is 63%, Mn=6000, Mw=9600.

DA-1 6.91g (30.0 mMs) are measured in the 100mL four-neck flask with agitating device and nitrogen ingress pipe, NMP 59.1g is added, supplying nitrogen while is stirred, is allowed to dissolve.CA-3 is added while stirring the diamine solution 1.50g (6.00 mMs) after being stirred at room temperature 3 hours, adds CA-2 6.62g (22.5 mMs), NMP is added 12.8gg makes 15 mass % of solid component concentration, be stirred at room temperature obtain within 24 hours polyamic acid solution (D) (viscosity: 870mPa·s).The Mn=13200 of polyamic acid, Mw=35700.

In the 100mL four-neck flask with agitating device and nitrogen ingress pipe measure DA-2 6.33g (25.9 mMs), NMP 73.1g is added in DA-3 3.79g (11.1 mMs), and supplying nitrogen while is stirred, is allowed to dissolve.It stirs on one side The diamine solution is added CA-1 7.73g (34.4 mMs) on one side, and then NMP 8.12g is added, and makes solid component concentration 18 Quality % is stirred 24 hours at 40 DEG C, obtains polyamic acid solution (E) (viscosity: 800mPas).The Mn=of polyamic acid 13500, Mw=23600.

Obtained polyamic acid solution 30g is measured in the 100mL four-neck flask with agitating device and nitrogen ingress pipe, NMP 15.0g is added, stirs 30 minutes.Acetic anhydride 3.37g, pyridine 0.44g are added in obtained polyamic acid solution, 55 It is heated 3 hours at DEG C, carries out chemical imidization.In the methanol for putting into 212ml while the reaction solution stirred to get, mistake The sediment being precipitated is collected in filter, is then washed 3 times with the methanol of 212ml.By obtained toner, drying 12 is small at 60 DEG C When, it is last (F) to obtain polyimide resin powder.The acid imide rate of polyimide resin is 68%, Mn=9400, Mw=23000.

In the 100mL four-neck flask with agitating device and nitrogen ingress pipe measure DA-2 4.40g (18.0 mMs), NMP 74.0g is added in DA-3 6.15g (18.0 mMs), and supplying nitrogen while is stirred, is allowed to dissolve.It stirs on one side The diamine solution is added CA-1 7.50g (33.4 mMs) on one side, and then NMP 8.22g is added, and makes solid component concentration 18 Quality % is stirred 24 hours at 40 DEG C, obtains polyamic acid solution (G) (viscosity: 820mPas).The Mn=of polyamic acid 11000, Mw=30700.

Obtained polyamic acid solution (A) is measured in the 100mL four-neck flask with agitating device and nitrogen ingress pipe NMP 14.29g is added in 20g, stirs 30 minutes.Acetic anhydride 1.48g, pyridine are added in obtained polyamic acid solution 0.38g is heated 3 hours at 60 DEG C, carries out chemical imidization.150ml is put into while the reaction solution stirred to get Methanol in, the sediment of precipitation is collected by filtration, is then washed 3 times with the methanol of 150ml.By obtained toner at 60 DEG C It is last (H) to obtain polyimide resin powder for lower drying 12 hours.The acid imide rate at polyimide resin powder end is 70%, Mn =9050, Mw=16600.

The end of polyimide resin powder obtained in synthesis example 1 (A) 1.80g is taken in 100ml conical flask, and NMP is added 10.2g makes solid component concentration 15%, stirs 24 hours at 70 DEG C and is allowed to dissolve, obtains polyimide solution (K).At this AD-1 0.09g, NMP 11.9g, BCS 6.00g are added in polyimide solution, are stirred at room temperature 3 hours, are obtained liquid crystal and take To agent (1).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

The end of polyimide resin powder obtained in synthesis example 2 (B) 1.80g is taken in 100ml conical flask, and NMP is added 10.2g makes solid component concentration 15%, stirs 24 hours at 70 DEG C and is allowed to dissolve, obtains polyimide solution (L).At this AD-1 0.09g, NMP 11.9g, BCS 6.00g are added in polyimide solution, are stirred at room temperature 3 hours, are obtained liquid crystal and take To agent (2).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

The end of polyimide resin powder obtained in synthesis example 2 (C) 1.80g is taken in 100ml conical flask, and NMP is added 22.11g makes solid component concentration 15%, stirs 24 hours at 70 DEG C and is allowed to dissolve, obtains polyimide solution (M).? AD-1 0.09g, NMP 11.9g, BCS 6.00g are added in the polyimide solution, are stirred at room temperature 3 hours, are obtained liquid crystal Alignment agent (3).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

The polyimide solution of polyamic acid (D) 7.80g and 15 mass % of 18 mass % are taken in 100mL conical flask (K) 5.20g adds AD-1 0.98g, NMP 4.34g, GBL 5.68g, BCS 6.00g, is stirred at room temperature 3 hours, obtains Aligning agent for liquid crystal (4).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

The polyimide solution of polyamic acid (D) 7.80g and 15 mass % of 18 mass % are taken in 100mL conical flask (L) 5.20g adds AD-1 0.98g, NMP 4.36g, GBL 5.66g, BCS 6.00g, is stirred at room temperature 3 hours, obtains Aligning agent for liquid crystal (5).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

The end of polyimide resin powder obtained in synthesis example 5 (F) 1.80g is taken in 100ml conical flask, and NMP is added 10.2g makes solid component concentration 15%, stirs 24 hours at 70 DEG C and is allowed to dissolve, obtains polyimide solution (N).At this AD-1 0.09g, NMP 11.9g, BCS 6.00g are added in polyimide solution, are stirred at room temperature 3 hours, are obtained liquid crystal and take To agent (6).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

The end of polyimide resin powder obtained in synthesis example 6 (H) 1.80g is taken in 100ml conical flask, and NMP is added 10.2g makes solid component concentration 15%, stirs 24 hours at 70 DEG C and is allowed to dissolve, obtains polyimide solution (O).At this AD-1 0.09g, NMP 11.9g, BCS 6.00g are added in polyimide solution, are stirred at room temperature 3 hours, are obtained liquid crystal and take To agent (7).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as homogeneous solution.

NMP 12.0g, BCS 6.00g are added in polyimide solution (K) 12g obtained in embodiment 1, at room temperature Stirring 3 hours, obtains aligning agent for liquid crystal (8).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as Even solution.

After the filter filtering for being 1.0 μm by above-mentioned aligning agent for liquid crystal aperture, it is coated on and is prepared using spin coating Above-mentioned electroded substrate and overleaf film forming have ito film and have height 4 μm column spacer glass substrate on. Drying after five minutes, utilizes 230 DEG C of heated air circulation type baking ovens be burnt within 20 minutes, forms film thickness in 80 DEG C of heating plate The film of 100nm.The ultraviolet light of the wavelength 254nm of the linear polarization of extinction ratio 26:1 is irradiated to the coated surface by polarization plates 0.25J/cm²Afterwards, in pure water: it impregnates in the mixed solution of propyl alcohol=1/1 2- 5 minutes, is then impregnated 1 minute in pure water, It is heated 14 minutes in 230 DEG C of heating plate, obtains the substrate with liquid crystal orientation film.Pass through pencil hardness test method (JIS K5400 the liquid crystal alignment film surface of the substrate, result 3H) are measured.

Other than replacing aligning agent for liquid crystal (1) using aligning agent for liquid crystal shown in table 1 respectively, with complete with embodiment 6 Exactly the same mode prepares pencil hardness test sample respectively.It is hard by pencil is carried out respectively including the result of embodiment 6 The result for spending test evaluation is shown in table 1.In table 1, " H&#60；" indicate pencil hardness less than 1.

[table 1]

	Aligning agent for liquid crystal	Pencil hardness test evaluation
			Embodiment 6	(1)	3H
Embodiment 7	(2)	H
			Embodiment 8	(3)	H
Embodiment 9	(4)	4H
			Embodiment 10	(5)	3H
Comparative example 4	(6)	H <
			Comparative example 5	(7)	H <
Comparative example 6	(8)	H <

It, will using spin coating after aligning agent for liquid crystal obtained in embodiment 1 (1) is filtered with the filter that aperture is 1.0 μm It is coated on the above-mentioned electroded substrate prepared and overleaf film forming has ito film and has the column spacer of 4 μm of height Glass substrate on.Drying after five minutes, utilizes 230 DEG C of heated air circulation type baking ovens to carry out 20 minutes in 80 DEG C of heating plate Firing forms the film of film thickness 100nm.The wavelength of the linear polarization of extinction ratio 26:1 is irradiated to the coated surface by polarization plates The ultraviolet light 0.25J/cm of 254nm².Impregnate the substrate in pure water 3 minutes, it is 14 minutes dry in 230 DEG C of heating plate, Obtain the substrate with liquid crystal orientation film.

Using obtained above-mentioned 2 substrates as 1 group, the printing and sealing agent on substrate pastes another substrate, makes liquid crystal aligning Film surface is opposite to each other and differently- oriented directivity is 0 °, makes sealant cures then to prepare dummy cell.By depressurizing injection method for liquid Brilliant MLC-3019 (Merck&Co. system) is injected in the dummy cell, and seals inlet, to obtain FFS driving liquid crystal cells.It Afterwards, obtained liquid crystal cells are heated 1 hour at 110 DEG C, places an evening, implement ghost evaluation by exchanging driving for a long time. The value of the angle delta of the liquid crystal cells after long-term exchange driving is 0.10 degree.

In addition to aligning agent for liquid crystal (1) is replaced using aligning agent for liquid crystal shown in table 2 respectively, and by ultraviolet irradiation Amount is set as except measuring shown in table 2, to drive liquid crystal cells with the identical method of embodiment 11 preparation FFS, and passes through Ghost evaluation is implemented in long-term exchange driving.The value and embodiment 11 of the angle delta of the liquid crystal cells after each long-term exchange driving As a result it is shown in table 2 together.

[table 2]

Industrial availability

Aligning agent for liquid crystal through the invention can obtain film hardness height and the liquid crystal aligning with good image retention speciality Film.Therefore, the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention can obtain the high yield rate in liquid crystal display panel manufacture, And the liquid crystal of the excellent IPS driving method of image retention speciality, FFS driving method indicates element, it is possible to reduce in the driving side IPS Formula, FFS driving method liquid crystal indicate ghost caused by the exchange that occurs drives in element.Therefore, can be used for pursuing high table Show that the liquid crystal of quality indicates in element.

It should be noted that by Japanese patent application 2016-225395 specification filed on November 18th, 2016, Claims, drawings and abstract full content be incorporated in this, draw the disclosure as specification of the invention.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that containing following (A) ingredients, (B) ingredient and organic solvent,

(A) ingredient: it is acid imide compound, that is, polyimides of polyimide precursor, and acid imide rate is 20%~80%, The polyimide precursor is tetracarboxylic acid derivatives ingredient and the diamine component of the diamines containing the structure with following formula (1) Reaction product,

In formula, * indicates the key with other atoms or group；

(B) ingredient: it is the compound containing 2 or more cross-linking functional groups.

2. aligning agent for liquid crystal according to claim 1, wherein the diamine component contain 20~50 moles of % have formula (1) diamines of structure.

3. aligning agent for liquid crystal according to claim 1 or 2, wherein the diamine component also contain have it is heated leave away from And generate the diamines of the structure of amino.

4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein the tetracarboxylic acid derivatives ingredient has At least one kind of structure in group consisting of the following,

5. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein the cross-linking functional group be selected from by The group of hydroxyl, containing the group of (methyl) acrylate, the group containing blocked isocyanate, oxygen heterocycle butane group, And it is at least one kind of in the group of the group composition containing epoxy group.

6. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein the cross-linking functional group is hydroxyl Group.

7. aligning agent for liquid crystal described according to claim 1~any one of 6, wherein described to contain 2 or more bridging property functions Formula (2) expression of group,

X₂Aliphatic alkyl for carbon number 1~20 or the n valence organic group comprising aromatic hydrocarbyl, the integer that n is 2~6 are described Arbitrary carbon in aliphatic alkyl or aromatic hydrocarbyl is optionally replaced by nitrogen or oxygen, R₂And R₃It is separately hydrogen atom, appoints Select the alkynyl of the alkyl of carbon number 1~4 with substituent group, the alkenyl of carbon number 2~4 or carbon number 2~4, R₂And R₃In at least one Person indicates the alkyl being optionally substituted by a hydroxyl group.

8. aligning agent for liquid crystal according to claim 7, wherein the R in the formula (2)₂And R₃At least one of by formula (3) it indicates,

R₄~R₇Separately indicate any one of hydrogen atom, alkyl or the alkyl being optionally substituted by a hydroxyl group.

9. aligning agent for liquid crystal described according to claim 1~any one of 8, wherein described to contain 2 or more bridging property functions The compound of group is formula (5) compound represented,

10. aligning agent for liquid crystal described according to claim 1~any one of 9, wherein relative to (A) ingredient, contain (B) ingredient of 0.1~20 mass %.

11. aligning agent for liquid crystal described according to claim 1~any one of 10, wherein also contain following (C) ingredients,

(C) ingredient: its be tetracarboxylic acid derivatives ingredient and diamine component reaction product, that is, polyimide precursor, but do not include with The identical polyimide precursor of polyimide precursor of (A) ingredient.

12. aligning agent for liquid crystal described according to claim 1~any one of 11, wherein the organic solvent contains the 1st solvent (I) and the 2nd solvent (II), the 1st solvent (I) include selected from by n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- amyl -2-Pyrrolidone, gamma-butyrolacton, gamma-valerolactone, 1,3- dimethyl -2- imidazolidinone, 3- methoxyl group-N, N- diformazan At least one kind of in the group of base propionamide and 3- butoxy-N, N- dimethylpropionamide composition, the 2nd solvent (II) includes choosing Free butyl cellosolve, butyl cellosolve acetate, 1- butoxy -2- propyl alcohol, 2- butoxy -1- propyl alcohol, dipropylene glycol diformazan Ether, dipropylene glycol monomethyl ether, diacetone alcohol, diisobutyl carbinol (DIBC), diisobutyl ketone, propylene carbonate, propylene-glycol diacetate, It is at least one kind of in the group of diisoamyl ether composition.

13. a kind of liquid crystal orientation film, the aligning agent for liquid crystal as described in any one of claim 1~12 is obtained.

14. a kind of manufacturing method of liquid crystal orientation film, wherein liquid crystal aligning described in any one of coating claim 1~12 Agent is simultaneously burnt into, and polarized UV rays are further irradiated.

15. a kind of liquid crystal indicates element, with the liquid crystal orientation film described in claim 13.