CN102585842B

CN102585842B - Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device

Info

Publication number: CN102585842B
Application number: CN201110431724.8A
Authority: CN
Inventors: 小山贵由; 平井刚; 内山克博; 马场淳
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2010-12-17
Filing date: 2011-12-16
Publication date: 2015-12-09
Anticipated expiration: 2031-12-16
Also published as: KR101756786B1; TW201300451A; JP2012128372A; JP5720234B2; KR20120068697A; TWI504658B; CN102585842A

Abstract

The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.The invention provides the liquid crystal aligning agent for obtaining liquid crystal display device, even if this liquid crystal display device has the long durability carrying out life-time service and the orientation characteristic of liquid crystal also can be kept such.Described liquid crystal aligning agent contains polymkeric substance, this polymkeric substance has the repeating unit deriving from ethylene unsaturated monomer, aforementioned repeating unit has cyclic amine structure or phenol structure, two carbon atoms adjacent with nitrogen-atoms in this cyclic amine structure has respectively the substituting group that two following formula (S) represent, relative to the substituting group at least 1 carbon atom in the ortho position carbon atom of hydroxyl having following formula (S) and represent in this phenol structure.Formula (S):---R ¹¹---X---R ¹²

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device

Technical field

The present invention relates to liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device, specifically, be related to that obtain can the liquid crystal orientation film of life-time service and the liquid crystal aligning agent that uses, and the liquid crystal orientation film using this liquid crystal aligning agent to be formed and liquid crystal display device.

Background technology

As liquid crystal display device, horizontally oriented type and vertical orientating type is roughly divided into according to the differently-oriented directivity of liquid crystal molecule when not applying voltage, as horizontally oriented type known have TN (TwistedNematic, twisted-nematic) type element and IPS (In-PlaneSwitching, switch in face) type element etc., as vertical orientating type known have VA (VerticalAlignment, vertical orientated) type element etc.

Described when not applying voltage the tropism control of liquid crystal molecule adopt liquid crystal orientation film to carry out.Liquid crystal orientation film by being coated on substrate by the liquid crystal aligning agent containing polyimide or polyamic acid, then can carry out roasting to obtain to it.

In order to the display performance making liquid crystal display device reach good, need suitably to control by the orientation of liquid crystal orientation film to liquid crystal molecule, the liquid crystal aligning agent that can realize the liquid crystal orientation film of this purpose is made for being used for, propose various scheme (such as, see patent documentation 1 and patent documentation 2).

Patent Document 1 discloses the liquid crystal aligning agent containing polyamic acid, this polyamic acid has repeating unit main chain with phenylene, repeating unit main chain with groups such as biphenylenes.In addition, Patent Document 2 discloses the liquid crystal aligning agent containing the polyamic acid and polyimide side chain with bulky amine structure or sterically hindered phenol structure.In these patent documentations 1,2, by making containing polyamic acid and the polyimide with above-mentioned formation in liquid crystal aligning agent, make liquid crystal display device after long-time continuous uses, the orientation characteristic of liquid crystal still can be maintained, and has sought the raising of reliability.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2004-94179 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2010-244015 publication

Summary of the invention

Herein, liquid crystal display device is applied to the such high-quality watch-dog of LCD TV, for this high-quality watch-dog, require not only on long-time continuous uses, there is reliability, and when voltage carries out the life-time service of switch repeatedly, the long durability that the orientation characteristic of liquid crystal is so also can be kept.And this long durability required time is more and more longer.On the other hand, for the material recorded in the material recorded in above-mentioned patent documentation 1 and above-mentioned patent documentation 2, obviously Shortcomings in long durability as above.

The present invention makes in view of the foregoing, the liquid crystal orientation film that main purpose is to provide liquid crystal aligning agent, utilize this liquid crystal aligning agent to be formed and the liquid crystal display device with this liquid crystal orientation film, this liquid crystal aligning agent is for obtaining liquid crystal display device, even if this liquid crystal display device has the long durability carrying out life-time service and the orientation characteristic of liquid crystal also can be kept such.

In order to solve the problem of conventional art as above, present inventor has performed further investigation, found that by solving the problem containing a kind of polymkeric substance, described polymkeric substance is the polymkeric substance with the repeating unit deriving from ethylene unsaturated monomer, and the repeating unit with specific cyclic amine structure or particular phenol structure is as above-mentioned repeating unit, thus complete the present invention.Specifically, by the invention provides following liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.

According to the present invention, a kind of liquid crystal aligning agent is provided, it is characterized in that, containing polymkeric substance, this polymkeric substance has the repeating unit deriving from ethylene unsaturated monomer, aforementioned repeating unit has cyclic amine structure or phenol structure, two carbon atoms adjacent with nitrogen-atoms in this cyclic amine structure has respectively the substituting group that two following formula (S) represent, relative to the substituting group at least 1 carbon atom in the ortho position carbon atom of hydroxyl having following formula (S) and represent in this phenol structure

——R ¹¹——X——R ¹²(S)

In formula, R ¹¹for the alkyl that singly-bound maybe can be substituted, X is singly-bound, Sauerstoffatom, sulphur atom ,-CO-,-CO-O-or-O-CO-, R ¹²for the alkyl that can be substituted.Wherein, when X is not singly-bound, R ¹¹and R ¹²can be combined with each other formation ring structure.

According to liquid crystal aligning agent of the present invention, owing to deriving from ethylene unsaturated monomer containing having, and the polymkeric substance with the repeating unit of above-mentioned cyclic amine structure or above-mentioned phenol structure is (following, also referred to as polymkeric substance [A]), even if the liquid crystal display device that life-time service also can keep this long durability of liquid crystal aligning performance can be obtained.

In addition, as liquid crystal aligning agent, preferably also containing at least one polymkeric substance (hereinafter also referred to as polymkeric substance [B]) selected in the group be made up of polyamic acid and imide amination polymer thereof, this polyamic acid is obtained by tetracarboxylic dianhydride and diamine reactant.Thus, can expect that above-mentioned weather resistance is improved, can also expect that the electrical specifications such as voltage retention are improved further.

In the present invention, the liquid crystal aligning agent that can show above-mentioned long durability is obtained in order to suitable, preferred aforementioned repeating unit is the repeating unit that following formula (1-1) or (1-2) represent, be more preferably the repeating unit that following formula (1-1-1) or (1-2-1) represent

In formula (1-1) and formula (1-2), R is hydrogen atom or methyl, A ¹for singly-bound or divalent concatenating group, R ¹¹the alkyl that maybe can be substituted for singly-bound separately, X is singly-bound, Sauerstoffatom, sulphur atom ,-CO-,-CO-O-or-O-CO-, R separately ¹²alkyl separately for being substituted.Wherein, when X is not singly-bound, R ¹¹and R ¹²can be combined with each other formation ring structure.In formula (1-1), B ¹for hydrogen atom, Sauerstoffatom, halogen atom, hydroxyl or 1 valency organic group, m is the integer of 0 ~ 4.In formula (1-2), n is the integer of 0 ~ 3;

In formula (1-1-1) and formula (1-2-1), R is hydrogen atom or methyl, A ¹for singly-bound or divalent concatenating group, R ¹³be the alkyl of carbonatoms 1 ~ 5 separately, R ¹⁴for the alkyl of hydrogen atom or carbonatoms 1 ~ 5.In formula (1-1-1), B ¹for hydrogen atom, Sauerstoffatom, halogen atom, hydroxyl or 1 valency organic group.

In addition, in the present invention, preferred above-mentioned polymkeric substance [A] also has the repeating unit that following formula (2) represents,

In formula (2), R ²for hydrogen atom or methyl, A ²for singly-bound or divalent concatenating group, B ²for having the 1 valency organic group that 1 valency organic group of the carbonatoms 17 ~ 30 of steroid skeleton, the 1 valency organic group with tocopherol structure or following formula (B2) represent,

B ²¹for cyclohexylidene or substituted or unsubstituted phenylene, B ²²for the alkyl of hydrogen atom or carbonatoms 1 ~ 30, k is the integer of 0 ~ 3, wherein, and B ²²during for hydrogen atom, k is more than 1.In addition, when k is 2 or 3, multiple B ²¹there is above-mentioned definition independently of one another." * " represents and A ²in conjunction with connecting key.

In this case, the long life can seeking above-mentioned weather resistance can be formed, and the material that tilt angle is good.

In addition, according to the present invention, the liquid crystal orientation film utilizing the liquid crystal aligning agent of above-mentioned record to be formed and the liquid crystal display device with this liquid crystal orientation film can be provided.These liquid crystal orientation films and liquid crystal display device are suitable for being used to VA type liquid crystal display device especially.

Further, in this manual, " alkyl " comprises chain alkyl, ester ring type alkyl and aromatic hydrocarbyl.Should " alkyl " can be saturated hydrocarbyl, also can be unsaturated alkyl.

In addition, " chain alkyl " refers to the alkyl be only made up of chain-like structure, can be straight-chain, also can be branched." ester ring type alkyl " refers to and only comprises ester ring type hydrocarbon structure as ring structure, the alkyl not containing aromatic ring structure.But be not necessarily only made up of ester ring type hydrocarbon structure, chain-like structure can be contained in its local." aromatic hydrocarbyl " refers to containing the alkyl of aromatic ring structure as ring structure.But be not necessarily only made up of aromatic ring structure, chain-like structure and ester ring type hydrocarbon structure can be contained in its local.

In addition, in this manual, " (methyl) vinylformic acid " refers to vinylformic acid and methacrylic acid, and " (methyl) acryl " refers to acryl and methacryloyl.

Embodiment

Liquid crystal aligning agent of the present invention contains the polymkeric substance [A] with the repeating unit deriving from ethylene unsaturated monomer.Below liquid crystal aligning agent of the present invention is described in detail.

< polymkeric substance [A] >

[repeating unit (a1)]

Polymkeric substance [A] in the present invention has repeating unit (a1), and this repeating unit has:

Cyclic amine structure, in this cyclic amine structure, two carbon atoms adjoined has respectively the substituting group that two following formula (S) represent with nitrogen-atoms;

Or phenol structure, in this phenol structure, relative to the substituting group at least 1 carbon atom in the ortho position carbon atom of hydroxyl having following formula (S) and represent,

——R ¹¹——X——R ¹²(S)

As above-mentioned cyclic amine structure, the carbonatoms forming this ring structure is preferably two or more less than 7, is more preferably 5.In addition, as above-mentioned phenol structure, the position that hydroxyl combines on phenyl ring is arbitrary, but preferably relative to the para postion of the carbon atom that this phenyl ring is combined with main chain side.

As the preferred structure of repeating unit (a1), more particularly, when having cyclic amine structure, having bulky amine structural repeat unit, is the structure that following formula (1-1) represents.On the other hand, when having phenol structure, the repeating unit with sterically hindered phenol structure is the structure that following formula (1-2) represents,

In formula (1-1) and formula (1-2), R is hydrogen atom or methyl, A ¹for singly-bound or divalent concatenating group, in formula (1-1), B ¹for hydrogen atom, Sauerstoffatom, halogen atom, hydroxyl or 1 valency organic group, m is the integer of 0 ~ 4.In formula (1-2), n is the integer of 0 ~ 3.R ¹¹, X and R ¹²definition identical with above-mentioned formula (S).

As in above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2), R ¹¹alkyl specifically, the divalent chain alkyl of carbonatoms 1 ~ 10, the divalent ester ring type alkyl of carbonatoms 3 ~ 15 and the divalent aromatic hydrocarbyl of carbonatoms 6 ~ 20 can be enumerated.The alkylidene group of preferred methylene radical or carbonatoms 2 ~ 5 in these alkyl.As the alkylidene group of carbonatoms 2 ~ 5, can enumerate ethylidene, propylidene, butylidene, pentylidene etc. specifically, these groups can be any one in straight-chain and branched.In addition, this alkyl can have substituting group, such as, can enumerate halogen atom, the hydroxyl etc. such as fluorine atom or chlorine atom.

In above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2) ,-R ¹¹when-X-is not singly-bound, be preferably-CO-O-,-CH ₂-CO-or-CH ₂-CH (OH)-.

As the R in above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2) ¹², specifically, the alkyl of carbonatoms 1 ~ 6, the aryl of carbonatoms 6 ~ 12 or the aralkyl of carbonatoms 7 ~ 13 can be enumerated.In this case, the hydrogen atom of phenyl ring that aryl and aralkyl have can be replaced by the alkoxyl group of formyl radical or carbonatoms 1 ~ 4.

As R ¹²the alkyl of carbonatoms 1 ~ 6, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl etc. can be enumerated;

As the aryl as carbonatoms 6 ~ 12, such as phenyl, 4-Fonnylphenyl, 3,4,5-trimethoxyphenyls etc. can be enumerated;

As the aralkyl of carbonatoms 7 ~ 13, benzyl etc. can be enumerated.

As R ¹¹and R ¹²be combined with each other and the ring structure formed, can enumerate such as from the group that removing 1 hydrogen atom furans, thiophene, 2H-pyrans and 4H-pyrans etc. is formed.

In above-mentioned formula (S), above-mentioned formula (1-1) and above-mentioned formula (1-2), as-R ¹¹-X-R ¹²preferably can enumerate such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, phenyl, benzyl, benzoyl, 4-formylbenzoyl, 2-hydroxyl-2-phenylethyl, 2-oxo-2-(3; 4,5-trimethoxyphenyl) ethyl etc.In addition, as-R ¹¹-X-R ¹², the more preferably alkyl of carbonatoms 1 ~ 5, if above-mentioned formula (1-1) then particularly preferably methyl or ethyl, if above-mentioned formula (1-2) then particularly preferably methyl or the tertiary butyl.

In above-mentioned formula (1-1), m is preferably 0, and in above-mentioned formula (1-2), n is preferably 0 or 1.With the relation of these m and n and with above-mentioned-R ¹¹-X-R ¹²pass fasten, as above-mentioned formula (1-1) and above-mentioned formula (1-2), the structure preferably represented by following formula (1-1-1) and following formula (1-2-1),

In formula (1-1-1) and formula (1-2-1), R ¹³be the alkyl of carbonatoms 1 ~ 5 separately, in formula (1-2-1), R ¹⁴for the alkyl of hydrogen atom or carbonatoms 1 ~ 5.R, A ¹and B ¹definition identical with above-mentioned formula (1-1) and above-mentioned formula (1-2).

In above-mentioned formula (1-1), above-mentioned formula (1-2), above-mentioned formula (1-1-1) and above-mentioned formula (1-2-1), A ¹be preferably divalent concatenating group.As A ¹divalent concatenating group, the structure that following formula (A1) represents can be enumerated,

——A ¹¹——A ¹²——A ¹³——A ¹⁴——*1(A1)

In formula, A ¹¹for alkylidene group or the phenylene of singly-bound, methylene radical, carbonatoms 2 ~ 5, A ¹²for singly-bound ,-O-,-CO-,-CO-O-or-O-CO-, A ¹³for the alkylidene group of singly-bound or the methylene radical that can be substituted or carbonatoms 2 ~ 5, A ¹⁴for the alkyl that singly-bound ,-O-,-CO-,-CO-O-,-O-CO-,-NR ' or-NR '-CO-O-, R ' are hydrogen atom or carbonatoms 1 ~ 6.Wherein, A is got rid of ¹¹, A ¹², A ¹³and A ¹⁴it is all the situation of singly-bound.* 1 represents the connecting key be combined with the carbon atom of cyclic amine structure or the carbon atom of phenol structure.

In above-mentioned formula (A1), as A ¹¹and A ¹³the alkylidene group of carbonatoms 2 ~ 5, can enumerate as above-mentioned R ¹¹illustrative group.In addition, as A ¹³methylene radical or the alkylidene group of carbonatoms 2 ~ 5 substituting group that can have, can enumerate above-mentioned R ¹¹illustrative group.In addition, as the alkyl of the carbonatoms 1 ~ 6 of R ', can enumerate above-mentioned R ¹²illustrative group.

As the divalent concatenating group that above-mentioned formula (A1) represents, such as following structure can be enumerated,

In formula (A1-1) ~ formula (A1-17), * 1 represents the connecting key be combined with the carbon atom of cyclic amine structure or the carbon atom of phenol structure.

In order to seek the weather resistance improving the liquid crystal orientation film obtained better, in above-mentioned formula (A1-1) ~ formula (A1-17), as A ¹divalent concatenating group, the structure that in preferred formula (A1-2), formula (A1-5), formula (A1-8), formula (A1-10), formula (A1-11), formula (A1-16) and formula (A1-17), arbitrary formula represents, the structure that more preferably in formula (A1-2), formula (A1-5) and formula (A1-10), arbitrary formula represents.

In above-mentioned formula (1-1) and above-mentioned formula (1-1-1), as B ¹halogen atom, fluorine atom and chlorine atom etc. can be enumerated.

In above-mentioned formula (1-1) and above-mentioned formula (1-1-1), as B ¹1 valency organic group, the group that following formula (B1) represents can be enumerated.

——B ¹¹-B ¹²(B1)

In formula, B ¹¹for singly-bound ,-O-,-CO-,-CO-O-,-O-CO-,-O-CO-NR "-or-CO-NR "-, R " is the alkyl of hydrogen atom or carbonatoms 1 ~ 6.B ¹²for the ester ring type alkyl of the aryl of the alkyl of carbonatoms 1 ~ 15, carbonatoms 6 ~ 12, the aralkyl of carbonatoms 7 ~ 13,1 valency heterocyclic radical of carbonatoms 3 ~ 10 or carbonatoms 3 ~ 15, the hydrogen atom that these groups have can be substituted.

In above-mentioned formula (B1), as R " the alkyl of carbonatoms 1 ~ 6, can enumerate above-mentioned R ¹²illustrative group.

In above-mentioned formula (B1), as B ¹²the alkyl of carbonatoms 1 ~ 15, can be that straight-chain also for branched, such as, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl etc.;

As the aryl of carbonatoms 6 ~ 12, such as, can enumerate phenyl, tolyl, 4-ethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyls, naphthyl, anthryl etc.;

As the aralkyl of carbonatoms 7 ~ 13, such as, can enumerate benzyl, styroyl, α-methylbenzyl, menaphthyl etc.;

As 1 valency heterocyclic radical of carbonatoms 3 ~ 10, nitrogen-containing heterocycle compound can be enumerated, such as piperidines, morpholine, pyridine, pyrazine etc.;

As the ester ring type alkyl of carbonatoms 3 ~ 15, such as, can enumerate cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.

In addition, as B ¹²above-mentioned each group substituting group that can have, such as can enumerate the halogen atom such as fluorine atom and chlorine atom, hydroxyl, nitro, cyano group etc.

As 1 valency the organic group (-B that above-mentioned formula (B1) represents ¹¹-B ¹²), such as can enumerate methyl, normal-butyl, n-pentyl, tert-pentyl, n-octyl, benzyl, 4-ethylphenyl, 4-methylcyclohexyl, methoxyl group, octyloxy, cyclohexyloxy, ethanoyl, acetoxyl group, myristoyl, Alpha-Methyl benzyloxy, piperidino carbonyl, morpholinyl carbonyl, 2-hydroxy-2-methyl propoxy-,-O-CONH-C ₆h ₅deng.

In order to seek the raising of obtained liquid crystal orientation film weather resistance better, in above-mentioned formula (1-1) and above-mentioned formula (1-1-1), as B ¹be preferably any one in hydrogen atom, Sauerstoffatom, chlorine atom, methyl, normal-butyl, n-pentyl, tert-pentyl, benzyl, methoxyl group, octyloxy, ethanoyl, acetoxyl group, cyclohexyloxy, be more preferably any one in hydrogen atom, Sauerstoffatom, methyl, benzyl, octyloxy.

As the repeating unit (a1) with bulky amine structure, the repeating unit that following formula (a1-1-1) ~ (a1-1-20) represents can be enumerated specifically.

In formula, R is hydrogen atom or methyl.

There is provided the monomer of the repeating unit (a1) of above-mentioned bulky amine structure easily can be synthesized by the vitochemical ordinary method of combination.Such as, if provide the monomer of the repeating unit of above-mentioned formula (a1-1-1) ~ formula (a1-1-16), just can carry out reaction to obtain by known esterification by the compound making (methyl) acryloyl halide and following formula (C-1) represent.In addition, if provide the monomer of the repeating unit of above-mentioned formula (a1-1-17) or formula (a1-1-18), just can by making 2-halogen propenyl halogen or 9-halogen decane, the compound represented with following formula (C-1) is undertaken reacting obtaining by known etherification reaction.In addition, if provide the monomer of the repeating unit of above-mentioned formula (a1-1-19) or formula (a1-1-20), just can by making (methyl) acryloyl halide and by OH-A in following formula (C-1) ¹³-A ¹⁴-replace with NH ₂-compound carry out reacting obtaining with known amidate action,

In formula, A ¹³, A ¹⁴, B ¹and R ¹³definition with illustrate identical.

In addition, above-mentioned each monomer also can use commercially available prod, such as, and methacrylic acid 2,2,6,6-tetramethyl--4-piperidine ester and methacrylic acid 1,2,2,6,6-pentamethyl--4-piperidine ester is sold by Hitachi Chemical Co., Ltd. respectively as FA-712HM, FA-711MM.

As the repeating unit (a1) with sterically hindered phenol structure, specifically, the repeating unit that following formula (a1-2-1) ~ formula (a1-2-10) represents can be enumerated,

In formula, R is hydrogen atom or methyl.

There is provided the monomer of the repeating unit (a1) of above-mentioned sterically hindered phenol structure easily can be synthesized by the vitochemical ordinary method of combination.

As repeating unit (a1), in order to seek the raising of obtained liquid crystal orientation film weather resistance better, relative to the repeating unit with sterically hindered phenol structure, more preferably there is the repeating unit of bulky amine structure.

Polymkeric substance [A] only can have a kind of repeating unit (a1), also can have combination of more than two kinds.Although its structure is also indefinite, but can infer by making polymkeric substance [A] have repeating unit (a1), the ultraviolet irradiated from backlight etc. is absorbed by polymkeric substance [A] aptly, the at least one polymkeric substance that this ultraviolet is not easy selecting in subordinate group impacts, and this group is by making tetracarboxylic dianhydride and diamine reactant and the polyamic acid obtained and imide amination polymer thereof are formed.Thus, even if make the orientation characteristic that also can keep liquid crystal under life-time service, the liquid crystal display device with long durability can be obtained.In addition, in this effect of raising, as the repeating unit (a1) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a1)), be preferably more than 1 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 1 % by weight 50 % by weight, more preferably less than more than 1 % by weight 30 % by weight, be particularly preferably less than more than 1 % by weight 20 % by weight.

Other repeating unit of < >

For polymkeric substance [A], except above-mentioned repeating unit (a1), preferably containing repeating unit (a2) shown in following as other repeating unit, more preferably containing in repeating unit (a3) ~ (a7) shown in following at least any one as other repeating unit.

[repeating unit (a2)]

Repeating unit (a2) has at least one in cyclohexane structure and benzene ring structure.Specifically, as repeating unit (a2), the repeating unit that following general formula (2) represents can be enumerated,

B ²¹for cyclohexylidene or substituted or unsubstituted phenylene, B ²²for the alkyl of hydrogen atom or carbonatoms 1 ~ 30.K is the integer of 0 ~ 3.Wherein, B ²²during for hydrogen atom, k is more than 1.In addition, when k is 2 or 3, multiple B ²¹there is above-mentioned definition independently of one another." * " represents the connecting key be combined with A2.

In above-mentioned formula (2), as A ²divalent concatenating group, can enumerate any one of phenylene or following formula (A2-1) ~ formula (A2-6) represent group etc.,

P in above-mentioned formula be 0 or 2, q be 0 or 1, r and s be respectively 1 ~ 6 integer, " * 2 " represent and B ²in conjunction with connecting key.

As A2, be preferably singly-bound.

In above-mentioned formula (2), as B ²1 valency organic group of the carbonatoms 17 ~ 30 with steroid skeleton, such as cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base, lanostane-3-base etc. can be enumerated.

In above-mentioned formula (B2), as B ²¹the substituting group that has of phenylene, can enumerate for above-mentioned B ¹²the group enumerated, preferred fluorine atom.In addition, as B ²²the alkyl of carbonatoms 1 ~ 30, except as above-mentioned B ¹²the group cited by alkyl of carbonatoms 1 ~ 15, also can enumerate eicosyl, pentacosyl, triacontyl etc.

As the 1 valency organic group that above-mentioned formula (B2) represents, preferably enumerate the group etc. that the cyclohexyl of the alkyl with carbonatoms 4 ~ 8, the alkyl of carbonatoms 3 ~ 30, difluorophenyl, trifluoromethyl, Trifluoromethoxyphen-l or following formula (B2-1) represent

In formula, k1 is 1 or 2, B ²²definition identical with above-mentioned formula (B2).

In this case, as k1 preferably 2, as B ²²the alkyl of preferred carbonatoms 1 ~ 6.In addition, as the group that above-mentioned formula (B2-1) represents, particularly preferably 4-(4 '-amyl group dicyclohexyl-4-base) phenyl.

As B ², the group that the 1 valency organic group preferably with the carbonatoms 17 ~ 30 of steroid skeleton, the 1 valency organic group with tocopherol structure, the cyclohexyl with the alkyl of carbonatoms 4 ~ 8 or above-mentioned formula (B2-1) represent.

As repeating unit (a2), the repeating unit preferably obtained by the various monomers that methacrylic acid cholestane ester, methacrylic acid 4-(4 '-amyl group dicyclohexyl-4-base) phenyl ester, tocopherol methyl acrylate are such.

Further, as the monomer providing repeating unit (a2), can by making such as (methyl) acryloyl halide and compd B ²-A ²-OH carries out reaction to obtain by known esterification.

Polymkeric substance [A] only can have a kind of repeating unit (a2), also can have combination of more than two kinds.By making polymkeric substance [A] have repeating unit (a2), tilt angle stability can be improved, and can further improve liquid crystal aligning.In addition, in order to improve this effect, as repeating unit (a2) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a2)), be preferably less than 60 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 1 % by weight 60 % by weight, more preferably less than more than 2 % by weight 40 % by weight.

[repeating unit (a3)]

Repeating unit (a3) has the cyclic ether structure that can realize heat cross-linking reaction.Specifically, as repeating unit (a3), the repeating unit that following general formula (3) represents can be enumerated,

In formula (3), R ³for hydrogen atom or methyl, A ³for the alkylidene group of singly-bound, methylene radical or carbonatoms 2 ~ 10, B ³for having the group of the cyclic ether structure of carbonatoms 2 ~ 10.

As A in above-mentioned formula (3) ³the alkylidene group of carbonatoms 2 ~ 10, except to above-mentioned R ¹¹outside the group enumerated, also can enumerate hexylidene, sub-heptyl, sub-decyl etc.

As B in above-mentioned formula (3) ³the cyclic ether structure of carbonatoms 2 ~ 10, preferably there is reactive 1, the 2-epoxy construction of heat cross-linking or 1,3-epoxy construction, more preferably 1,2-epoxy construction in reactivity is excellent.

As repeating unit (a3), A in preferred above-mentioned formula (3) ³for the alkylidene group of methylene radical or carbonatoms 2 ~ 10 and B ³for having the repeating unit of the group of 1,2-epoxy construction, more preferably A ³for the alkylidene group of methylene radical or carbonatoms 2 or 5 and B ³for having the repeating unit of the group of 1,2-epoxy construction.

As repeating unit (a3), preferably by (methyl) glycidyl acrylate, (methyl) vinylformic acid-3,4-epoxybutyl, (methyl) vinylformic acid-6,7-epoxy heptyl ester, α-ethylacrylate-6, the repeating unit that the such various monomers of 7-epoxy heptyl ester obtain, in these repeating units, high from the viewpoint of the film density of the liquid crystal orientation film obtained, to present excellence electrical specification, the repeating unit more preferably obtained by (methyl) glycidyl acrylate.

Polymkeric substance [A] only can have a kind of repeating unit (a3), also can have combination of more than two kinds.By making polymkeric substance [A], there is repeating unit (a3), be coated with liquid crystal aligning agent of the present invention and after forming film, carry out heat cross-linking reaction by thermal treatment (curing afterwards), the thermotolerance of the liquid crystal orientation film obtained, resistance to liquid crystal liquid crystal property (solvent resistance), film density can be improved thus further.Foreign ion contained in liquid crystal can also be reduced in addition further spread in liquid crystal orientation film.And, owing to having these effects, even if apply thermal stresses to the liquid crystal display device that obtains or drive liquid crystal panel for a long time, still can obtain providing the liquid crystal aligning agent of the liquid crystal orientation film of the low and problem of burning screen of voltage retention by solving more effectively.In addition, in order to improve this effect, as repeating unit (a3) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a3)), be preferably less than 50 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 5 % by weight 50 % by weight, more preferably less than more than 15 % by weight 45 % by weight, be particularly preferably less than more than 20 % by weight 40 % by weight.

[repeating unit (a4)]

Repeating unit (a4) has carboxyl, can enumerate the repeating unit that following general formula (4) represents specifically,

In formula (4), R ⁴¹for hydrogen atom, methyl or carboxymethyl, R ⁴²for hydrogen atom, methyl or carboxyl.Wherein, R ⁴¹during for carboxymethyl, R ⁴²for hydrogen atom or methyl.

As repeating unit (a4), such as, can enumerate the repeating unit obtained by toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, various monomer such as (methyl) vinylformic acid, β-crotonic acid etc.In these repeating units, from improving the intermiscibility of polymkeric substance [A] to polyamic acid and imide amination polymer thereof, and improve the film density of the liquid crystal orientation film obtained, show in electrical specification in high reliability simultaneously and consider, the repeating unit preferably obtained by (methyl) vinylformic acid.

Polymkeric substance [A] only can have a kind of repeating unit (a4), also can have combination of more than two kinds.By making polymkeric substance [A], there is repeating unit (a4), in liquid crystal aligning agent containing at least one polymkeric substance selected in the group be made up of polyamic acid and imide amination polymer thereof, the intermiscibility of polymkeric substance [A] relative to this polymkeric substance can be improved.In addition, when polymkeric substance [A] has above-mentioned repeating unit (a3), by making it have repeating unit (a4) further, the crosslinking reaction of the cyclic ether structure of repeating unit (a3) can be promoted.In addition, in order to improve this effect, as repeating unit (a4) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a4)), be preferably less than 50 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 1 % by weight 40 % by weight, further preferably less than more than 1 % by weight 30 % by weight.

[repeating unit (a5)]

Repeating unit (a5) has maleimide structure, can enumerate the repeating unit that following general formula (5) represents specifically.

In formula (5), A ⁵for singly-bound, Sauerstoffatom or sulphur atom, or the divalent group containing Sauerstoffatom, sulphur atom, nitrogen-atoms or Siliciumatom, B ⁵for the aryl of carbonatoms 6 ~ 30 or the ester ring type group of carbonatoms 4 ~ 10.

In above-mentioned formula (5), as A ⁵preferred singly-bound.

In above-mentioned formula (5), as B ⁵the aryl of carbonatoms 6 ~ 30, such as phenyl, naphthyl, anthryl, fluorenyl etc. can be enumerated;

As the ester ring type base of carbonatoms 4 ~ 10, such as cyclopentyl, cyclohexyl etc. can be enumerated, particularly preferably phenyl or cyclohexyl.

As repeating unit (a5), the repeating unit such as obtained by various monomers such as N-phenylmaleimide, N-naphthyl maleimide, N-anthryl maleimide, N-fluorenyl maleimide, N-cyclopentylmaleimide, N-N-cyclohexylmaleimides can be enumerated, in these repeating units, the repeating unit more preferably obtained by N-phenylmaleimide or N-N-cyclohexylmaleimide.

Polymkeric substance [A] only can have a kind of repeating unit (a5), also can have combination of more than two kinds.By making polymkeric substance [A] have repeating unit (a5), the thermotolerance of the liquid crystal orientation film obtained can be improved further.In addition, in order to improve this effect, as repeating unit (a5) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a5)), be preferably less than 20 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 1 % by weight 15 % by weight, more preferably less than more than 1 % by weight 10 % by weight.

[repeating unit (a6)]

Repeating unit (a6) specifically represents with following general formula (6),

In formula (6), R ⁶for hydrogen atom or methyl, A ⁶for singly-bound, Sauerstoffatom or sulphur atom, or the divalent group containing Sauerstoffatom, sulphur atom, nitrogen-atoms or Siliciumatom, B ⁶for the alkyl of hydrogen atom, carbonatoms 1 ~ 20 or the aryl of carbonatoms 6 ~ 30.

In above-mentioned formula (6), as A ⁶, preferred singly-bound.

In above-mentioned formula (6), as B ⁶the alkyl of carbonatoms 1 ~ 20, such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl etc. can be enumerated;

As the aryl of carbonatoms 6 ~ 30, such as phenyl, 4-biphenyl, 2-biphenyl, 1-naphthyl, 2-naphthyl etc. can be enumerated, wherein preferred phenyl.

As repeating unit (a6), such as can enumerate the repeating unit obtained by various monomers such as the alpha-olefins such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, vinylbenzene, 4-vinyl biphenyl, 2-vinyl biphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, alpha-methyl styrenes, the wherein preferred repeating unit obtained by vinylbenzene.

Polymkeric substance [A] only can have a kind of repeating unit (a6), also can have combination of more than two kinds.By making polymkeric substance [A] have repeating unit (a6), the thermotolerance of the liquid crystal orientation film obtained can be improved further.In addition, in order to improve this effect, as repeating unit (a6) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a6)), be preferably less than 20 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 1 % by weight 15 % by weight, more preferably less than more than 1 % by weight 10 % by weight.

[repeating unit (a7)]

Repeating unit (a7) has hydroxyl, can enumerate the repeating unit that following general formula (7) represents specifically,

In formula (7), R ⁷for hydrogen atom or methyl, A ⁷for singly-bound or-COO-*3, (" * 3 " represent and B ⁷in conjunction with connecting key), B ⁷for the divalent ester ring type group of the alkylidene group of carbonatoms 2 ~ 10, the arylidene of carbonatoms 6 ~ 30 or carbonatoms 4 ~ 10.

In above-mentioned formula (7), as B ⁷the alkylidene group of carbonatoms 2 ~ 10, such as ethylidene, tetramethylene etc. can be enumerated;

As the arylidene of carbonatoms 6 ~ 30, such as phenylene etc. can be enumerated;

As the divalence ester ring type group of carbonatoms 4 ~ 10, such as hexanaphthene-Isosorbide-5-Nitrae-two base etc. can be enumerated.

As repeating unit (a7), can enumerate such as by isopropenyl phenol, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxybutyl, 1, the repeating unit that the various monomers such as 4-cyclohexanedimethanol mono acrylic ester obtain, the wherein preferred repeating unit obtained by 2-hydroxyethyl methacrylate.

Polymkeric substance [A] only can have a kind of repeating unit (a7), also can have combination of more than two kinds.By making polymkeric substance [A], there is repeating unit (a7), in liquid crystal aligning agent containing at least one polymkeric substance selected in the group be made up of polyamic acid and imide amination polymer thereof, the intermiscibility of polymkeric substance [A] relative to this polymkeric substance can be improved.In addition, in order to improve this effect, as repeating unit (a7) in polymkeric substance [A] containing proportional (or providing the copolymerization ratios of monomer of repeating unit (a7)), be preferably less than 50 % by weight in the gross weight (or the total weight of the monomer used time synthetic polymer [A]) of polymkeric substance [A], be more preferably less than more than 1 % by weight 40 % by weight, more preferably less than more than 1 % by weight 30 % by weight.

For polymkeric substance [A], the polystyrene conversion weight-average molecular weight (hereinafter referred to as " Mw ") using gel permeation chromatography (GPC) to measure is preferably 2 × 10 ³above 1 × 10 ⁶below, 5 × 10 are more preferably ³above 5 × 10 ⁵below, 1 × 10 is particularly preferably ⁴above 4 × 10 ⁵below.Be 2 × 10 by making Mw ³above, the precipitation of low molecular composition can be suppressed, and suppress the deterioration of panel characteristics (precipitation of low molecular composition is the major cause that the low of voltage retention and panel burn screen).On the other hand, by making Mw be 1 × 10 ⁶below, the soltion viscosity of the liquid crystal aligning agent obtained can be made to reach suitable degree, thus seek the raising of coating.In addition, molecular weight distribution is (hereinafter referred to as " Mw/Mn ".Mn is the number-average molecular weight of the polystyrene conversion using GPC to measure) be preferably less than 20.0, be more preferably less than 15.0, be particularly preferably less than 10.0.By reducing Mw/Mn, easily obtain coating excellent, and the liquid crystal aligning agent of the panel characteristics deterioration problem caused because of aforementioned low molecular composition precipitation etc. can not be produced.

[manufacture method of polymkeric substance [A]]

The method manufacturing above-mentioned polymkeric substance [A] has no particular limits, such as can, by under the existence of the initiator suitably selected and chain-transfer agent, in suitable polymer solvent, more than one corresponding free radical polymerization monomers be made to carry out the incompatible manufacture of radical polymerization.There is provided the usage ratio (copolymerization ratios) of the monomer of repeating unit (a1) ~ (a7) suitably can set according to polymkeric substance [A] composition of expection when carrying out described polymerization.

As above-mentioned polymer solvent, the alcohol such as such as methyl alcohol, ethanol, benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol can be enumerated;

The ethers such as tetrahydrofuran (THF), two n-amylethers; The glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether;

The ethylene glycol alkyl oxide acetic esters such as methyl glycol acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate;

The diethylene glycol alkyl ether such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;

The propylene-glycol monoalky lethers such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

The propylene glycol alkyl ether acetates such as 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester, propandiol butyl ether acetic ester;

The propylene glycol alkyl ether propionic esters such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester;

The aromatic hydrocarbons such as toluene, dimethylbenzene;

The ketone such as methylethylketone, pimelinketone, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone;

Ritalin, vinyl acetic monomer, propyl acetate, N-BUTYL ACETATE, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxacetic acid methyl esters, hydroxacetic acid ethyl ester, hydroxacetic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxypropionate, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl butane acid methyl esters, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid propyl ester, Methoxy acetic acid butyl ester, oxyethyl group ritalin, oxyethyl group vinyl acetic monomer, oxyethyl group propyl acetate, oxyethyl group N-BUTYL ACETATE, propoxy-ritalin, propoxy-vinyl acetic monomer, propoxy-propyl acetate, propoxy-N-BUTYL ACETATE, butoxy ritalin, butoxy vinyl acetic monomer, butoxy propyl acetate, butoxy N-BUTYL ACETATE, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, the esters etc. such as 3-butoxy butyl propionate.

In these solvents, preferred ethylene glycol alkyl oxide acetic ester, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetate, particularly preferably diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, 1-Methoxy-2-propyl acetate or 3-methoxy methyl propionate.

As above-mentioned polymerization starter, the known material usually used as radical polymerization initiator can be used.Such as 2 can be enumerated, 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile), 2, the azo-compounds such as 2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile); Benzoyl peroxide, lauroyl peroxide, tert-Butyl peroxypivalate, 1, organo-peroxide and the hydrogen peroxide such as 1 '-bis--(tert-butyl peroxide) hexanaphthene.When using superoxide as radical polymerization initiator, also superoxide can be used together with reductive agent, form redox type initiator.

Time synthetic polymer [A], the molecular weight regulator of the molecular weight for telomerized polymer [A] can be used.As its object lesson, the halon such as chloroform, carbon tetrabromide; The mercaptan such as n-hexyl mercaptan, n octylmercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, Thiovanic acid; Dimethyl thio xanthan essence, diisopropyl disulfide are for xanthan essence classes such as xanthan essences; Terpinolene, alpha-methyl styrene dimer etc.

Time synthetic polymer [A], preferably by suitably regulating polymerizing condition (kind of solvent species, solvent and monomer interpolation ratio, polymerization temperature, initiator type and addition thereof, molecular weight regulator and addition etc. thereof), control in above-mentioned molecular weight ranges.As the suitable polymerizing condition for realizing above-mentioned molecular weight ranges, those skilled in the art can easily be known by inference by a small amount of pilot study.

Just can obtain the polymers soln containing polymkeric substance [A] in a manner described.This polymers soln directly can be used to the preparation of liquid crystal aligning agent, also for the preparation of liquid crystal aligning agent after polymkeric substance [A] contained in polymers soln can being separated, for the preparation of liquid crystal aligning agent after maybe the polymkeric substance [A] after separation being refined.The separation of polymkeric substance [A] can by being injected in a large amount of poor solvent by above-mentioned polymers soln, by obtain precipitate carry out drying under reduced pressure method or by realizing the method that polymers soln carries out underpressure distillation with vaporizer.In addition, can by the polymkeric substance [A] be separated be dissolved in organic solvent again, then by the method that poor solvent is separated out, or the method for the operation of carrying out underpressure distillation with vaporizer being carried out one or many carrys out finished polymer [A].

As the content of polymkeric substance in liquid crystal aligning agent [A], relative to polymkeric substance described later [B] 100 weight part, be preferably below more than 3 weight parts 20 weight parts.Thus, even if the raising of the weather resistance that the orientation characteristic of liquid crystal also can be kept when life-time service such can be realized better.Be more preferably below more than 3 weight parts 15 weight part, particularly preferably below more than 3 weight parts 10 weight parts.

< polymkeric substance [B] >

As liquid crystal aligning agent of the present invention, except above-mentioned polymkeric substance [A], the polymkeric substance [B] of at least one material selected in the group formed as the polyamic acid making tetracarboxylic dianhydride and diamine reactant obtain and imide amination polymer thereof can also be contained.

[tetracarboxylic dianhydride]

As the tetracarboxylic dianhydride for the synthesis of above-mentioned polyamic acid, such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. can be enumerated.

For the tetracarboxylic dianhydride that these are various, specifically, as aliphatics tetracarboxylic dianhydride, such as butane tetracarboxylic acid dianhydride etc. can be enumerated;

As ester ring type tetracarboxylic dianhydride, such as 1 can be enumerated, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic acid anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl norbornane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2, 4, 6, 8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone etc.,

As aromatic tetracarboxylic acid's dianhydride, such as pyromellitic acid dianhydride etc. can be enumerated, in addition, the tetracarboxylic dianhydride recorded in Japanese Unexamined Patent Publication 2010-97188 publication can also be used.

As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, preferably containing ester ring type tetracarboxylic dianhydride wherein, more particularly, preferably containing 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride, particularly preferably containing 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride.

As the tetracarboxylic dianhydride for the synthesis of foregoing polyamides acid, preferably contain more than 10 % by mole 2 relative to whole tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride, more preferably containing more than 20 % by mole, most preferably only by 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride forms.

[diamines]

As the diamines for the synthesis of above-mentioned polyamic acid, such as aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc. can be enumerated.

As their object lesson, aliphatie diamine can enumerate such as m-xylene diamine, 1,3-propanediamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.;

Ester ring type diamines can enumerate such as Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine), 1,3-two (amino methyl) hexanaphthenes etc.;

Aromatic diamine can enumerate such as O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino-2,2 '-dimethyl diphenyl, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to benzene diisopropylidene) two (aniline), 4,4 '-(isophthalic diisopropylidene) two (aniline), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-benzidine, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl benzidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane ester, 3,5-diaminobenzoic acid cholestene ester, 3,5-diaminobenzoic acid lanostane ester, two (the 4-aminobenzoic acyl-oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine, 3-aminobenzyl amine, 1-(2,4-diamino-phenyl) piperazine-4-formic acid, 4-(morpholine-4-base) benzene-1,3-diamines, two (N-(4-aminophenyl) piperidyl) propane of 1,3-, the compound etc. that alpha-amino group-omega-amino-phenyl alkylene and following formula (D1) represent,

In formula (D1), X ⁱand X ^iIbe singly-bound ,-O-,-COO-or-OCO-separately, R ^d1for the alkylidene group of methylene radical or carbonatoms 2 or 3, a be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and d is 0 or 1.Wherein, be 0 when a and b is different.

Diamino organo-siloxane can enumerate such as 1,3-two (3-aminopropyl)-tetramethyl disiloxanes etc., in addition can also use the diamines recorded in Japanese Unexamined Patent Publication 2010-97188 publication.

As-X in above-mentioned formula (D1) ⁱ-(R ^d1-X ^iI) _d-divalent the group that represents, is preferably alkylidene group, * 4-O-, * 4-COO-or * 4-O-CH that methylene radical, carbonatoms are 2 or 3 ₂cH ₂-O-(wherein, being with the connecting key of " * 4 " to be combined with diamino-phenyl).As-C _ch _2c+1the object lesson of base, can enumerate such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.Two amino in diamino-phenyl are preferably in 2,4-position or 3,5-position relative to other group.

As the object lesson of the compound that above-mentioned formula (D1) represents, the compound etc. that such as following formula (D1-1) ~ (D1-3) represents respectively can be enumerated.

In the diamines enumerated above, as the diamines used time synthetic polymer [B], preferably contain by Ursol D, 4,4 '-diaminodiphenyl-methane, 2,7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino-2, at least one material in two (amino methyl) hexanaphthene of 2 '-dimethyl diphenyl and 1,3-.

As liquid crystal aligning agent of the present invention, by by polymkeric substance [A] in the composition of above-mentioned polymkeric substance [A] and liquid crystal aligning agent containing proportion adjustment in suitable scope, desired tilt angle can be presented, when liquid crystal aligning agent of the present invention is used to the liquid crystal display device of TN type, STN type, OCB type or VA type, as the diamines of the synthesis of the polymkeric substance being used to contain in liquid crystal aligning agent [B], by using the diamines with tilt angle performance position, the tilt angle of obtained liquid crystal orientation film can be controlled.

As the described diamines with tilt angle performance position, the compound etc. that such as following general formula (D2) or following general formula (D3) represent can be enumerated,

In formula (D2), R ^d2and R ^d3be hydrogen atom or methyl separately, R ^d4for the alkyl of the carbonatoms 1 ~ 20 of straight-chain or branched, R ^d5and R ^d6be divalent organic group separately;

In formula (D3), R ^d7for Sauerstoffatom, sulphur atom ,-CO-,-COO-,-OCO-,-NHCO-,-CONH-or methylene radical, R ^d8for have cholestane base skeleton or cholesteryl skeleton 1 valency group, there is 1 valency group of trifluoromethyl or Trifluoromethoxyphen-l or the alkyl of carbonatoms 1 ~ 22, R ^d9for the alkyl of carbonatoms 1 ~ 4, d is the integer of 0 ~ 3.

As the object lesson of the compound that above-mentioned formula (D2) represents, the compound etc. that such as following formula (D2-1) and (D2-2) represent respectively can be enumerated.

In above-mentioned formula (D3), as R ¹⁸the 1 valency group with cholestane base skeleton or cholesteryl skeleton, the group of preferred carbonatoms 17 ~ 30, can enumerate such as 3-cholestane base, 3-cholesteryl etc.In addition, R ¹⁹be preferably methyl, a3 is preferably 0 or 1, is more preferably 0.

As the object lesson of the compound that above-mentioned formula (D3) represents, the compound etc. that such as following formula (D3-1) ~ (D3-5) represents respectively can be enumerated.

The diamine compound as above with tilt angle performance position can be used alone a kind, also can combine two or more and use.

When liquid crystal aligning agent of the present invention is used to VA type liquid crystal display device, present excellent liquid crystal vertical-tropism, therefore the compound that the formula (D3) in the above-mentioned diamine compound with tilt angle performance position represents preferably is used, more preferably at least one be selected from compound that above-mentioned formula (D3-1) ~ (D3-5) represent respectively is used, at least one in the compound that the compound particularly preferably using above-mentioned formula (D3-1) to represent and above-mentioned formula (D3-2) represent.

As the usage ratio of diamines with tilt angle performance position, relative to whole diamines, be preferably more than 8 % by mole less than 60 % by mole, be more preferably more than 9 % by mole less than 50 % by mole, be particularly preferably more than 10 % by mole less than 40 % by mole.In this case, also can be used together the diamines and other diamines with tilt angle performance position, as the usage ratio of now other diamines above-mentioned, be preferably more than 1 % by mole less than 90 % by mole relative to whole diamines, be more preferably more than 10 % by mole less than 90 % by mole.

[molecular weight regulator]

During the acid of synthesis foregoing polyamides, while use tetracarboxylic dianhydride as above and diamines, suitable molecular weight regulator also can be used to synthesize the polymkeric substance of end modified type.By forming the polymkeric substance of described end modified type, the coating (printing) of liquid crystal aligning agent can be improved further when not damaging effect of the present invention.

As aforementioned molecular weight conditioning agent, such as sour single acid anhydride, monoamine compound, monoisocyanate compound etc. can be enumerated.For their object lesson, as acid list acid anhydride, such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, positive four decyl succinic anhydride, n-hexadecyl succinyl oxide etc. can be enumerated;

As monoamine compound, such as aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine etc. can be enumerated;

As monoisocyanate compound, such as phenyl isocyanate, naphthyl isocyanate etc. can be enumerated.

As the usage ratio of molecular weight regulator, relative to the tetracarboxylic dianhydride of use and total 100 weight part of diamines, be preferably below 20 weight parts, be more preferably below 10 weight parts.

[synthesis of polyamic acid]

As the tetracarboxylic dianhydride of building-up reactions and the usage ratio of diamines that are used to polyamic acid, preferably relative to amino 1 equivalent of diamines, the anhydride group of tetracarboxylic dianhydride is the ratio of 0.2 ~ 2 equivalent, is preferably the ratio of 0.3 ~ 1.2 equivalent further.

The building-up reactions of polyamic acid is preferably carried out in organic solvent.Temperature of reaction is now preferably-20 DEG C ~ 150 DEG C, is more preferably 0 ~ 100 DEG C.In addition, the reaction times is preferably 0.1 ~ 24 hour, is more preferably 0.5 ~ 12 hour.

Herein, as organic solvent, such as aprotic polar solvent, phenol and derivative thereof, alcohol, ketone, ester, ether, halon, hydrocarbon etc. can be enumerated.

As the object lesson of these organic solvents, above-mentioned aprotic polar solvent can enumerate such as METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.;

Above-mentioned amphyl can enumerate such as meta-cresol, xylenol, halogenation phenol etc.;

Above-mentioned alcohol can enumerate such as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol monomethyl ether etc.;

Above-mentioned ketone can enumerate such as acetone, methylethylketone, mibk, pimelinketone etc.;

Above-mentioned ester can enumerate such as ethyl lactate, n-Butyl lactate, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, methoxy methyl propionate, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc.;

Above-mentioned ether can enumerate such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol ether acetate alone, tetrahydrofuran (THF) etc.;

Above-mentioned halon can enumerate such as methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.;

Above-mentioned hydrocarbon can enumerate such as hexane, heptane, octane, benzene,toluene,xylene, isopentyl propionic ester, isopentyl isobutyrate, isoamyl ether etc.

In these organic solvents, preferred use more than a kind of selecting from the group's (first group of organic solvent) be made up of aprotic polar solvent and phenol and derivative thereof, or more than a kind that selects from aforementioned first group of organic solvent and the mixture of more than a kind solvent selected from the group be made up of alcohol, ketone, ester, ether, halon and hydrocarbon (second group of organic solvent).In the case of the latter, as the usage ratio of second group of organic solvent, relative to the total of first group of organic solvent and second group of organic solvent, be preferably less than 50 % by weight, be more preferably less than 40 % by weight, more preferably less than 30 % by weight.

For the usage quantity (a) of organic solvent, the total amount (b) of preferred tetracarboxylic dianhydride and diamines reaches the amount of 0.1 ~ 50 % by weight relative to the total amount (a+b) of reaction soln.

The reaction soln that dissolving polyamic acid is formed can be obtained as above.This reaction soln can be directly used in the preparation of liquid crystal aligning agent, is used for the preparation of liquid crystal aligning agent, or is used for the preparation of liquid crystal aligning agent after being refined by the polyamic acid of separation after also polyamic acid contained in reaction soln can being separated.When making polyamic acid dehydration closed-loop and form polyimide, above-mentioned reaction soln can be directly used in dehydration closed-loop reaction, also be used for dehydration closed-loop reaction after polyamic acid contained in reaction soln can being separated, or be used for dehydration closed-loop reaction after being refined by the polyamic acid of separation.The separation of polyamic acid and refiningly can be undertaken by known method.

[synthesis of polyimide]

Polyimide by making the polyamic acid dehydration closed-loop of synthesis as mentioned above, thus can carry out imidization to obtain.

Polyimide in the present invention can be the complete imide compound that the amido acid structure had as the polyamic acid of its precursor all carries out dehydration closed-loop formation, also can be only a part for amido acid structure is carried out dehydration closed-loop, amido acid structure and imide ring structure the part imide compound of depositing.As the polyimide in the present invention, preferably its imide rate is more than 30%, is more preferably less than more than 50% 99%, more preferably less than more than 65% 99%.This imide rate represents the total of amido acid structure number relative to polyimide and imide ring structure number, the ratio represented with percentage shared by imide ring structure number.At this, a part for imide ring can be different imide ring.

Polyamic acid preferably by the method heated polyamic acid, or dissolves in organic solvent by the dehydration closed-loop of polyamic acid, adds dewatering agent and dehydration closed-loop catalyzer and the method carrying out as required heating is carried out in this solution.Wherein, a kind of method after preferably adopting.

Add in the method for dewatering agent and dehydration closed-loop catalyzer above-mentioned in the solution of polyamic acid, as dewatering agent, the acid anhydrides such as such as acetic anhydride, propionic anhydride, trifluoro-acetic anhydride can be used.As the usage quantity of dewatering agent, relative to 1 mole, the amido acid structure of polyamic acid, be preferably 0.01 ~ 20 mole.As dehydration closed-loop catalyzer, the tertiary amines such as such as pyridine, trimethylpyridine, lutidine, triethylamine can be used.As the usage quantity of dehydration closed-loop catalyzer, preferably relative to use dewatering agent 1 mole be 0.01 ~ 10 mole.As dehydration closed-loop reaction in use organic solvent, can enumerate as polyamic acid synthesis in use solvent and illustrative organic solvent.The temperature of reaction of dehydration closed-loop reaction is preferably 0 ~ 180 DEG C, is more preferably 10 ~ 150 DEG C.Reaction times is preferably 1.0 ~ 120 hours, is more preferably 2.0 ~ 30 hours.

The reaction soln containing polyimide can be obtained in such a way.This reaction soln can be directly used in the preparation of liquid crystal aligning agent, also dewatering agent and dehydration closed-loop catalyzer can be removed from reaction soln, then for the preparation of liquid crystal aligning agent, for the preparation of liquid crystal aligning agent after being separated polyimide, or the preparation of liquid crystal aligning agent after being refined by the polyimide of separation, can be used for.These purification operations can be undertaken by known method.

[soltion viscosity of polymkeric substance [B]]

As the polymkeric substance obtained as above [B], when making it form the solution of concentration 10 % by weight, preferably there is the soltion viscosity of 20 ~ 800mPas, more preferably there is the soltion viscosity of 30 ~ 500mPas.

The soltion viscosity (mPas) of above-mentioned polymkeric substance [B] be for the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance [B] to prepare be 10 % by weight polymers soln, use the value that E type rotational viscosimeter measures at 25 DEG C.

Other additive of < >

As liquid crystal orientation film of the present invention, containing polymkeric substance as above [A] as required composition while, more preferably containing polymkeric substance [B], also can contain other composition as required.As other composition described, the compound (below, being called " epoxy compounds "), functional silanes compound etc. in such as other polymkeric substance, molecule with at least one epoxy group(ing) can be enumerated.

[epoxy compounds]

As above-mentioned epoxy compounds, such as ethylene glycol diglycidylether can be enumerated, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four Racemic glycidols-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-hexahydroaniline etc. are as preferred material.

As the mixing ratio of these epoxy compoundss, relative to total 100 weight part of polymkeric substance, be preferably below 40 weight parts, be more preferably 0.1 ~ 30 weight part.

[functional silanes compound]

As above-mentioned functional silanes compound, such as 3-TSL 8330 can be enumerated, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, 9-triethoxysilyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, glycidyl oxy methyl Trimethoxy silane, glycidyl oxy methyl triethoxyl silane, 2-glycidoxyethyl Trimethoxy silane, 2-glycidoxyethyl triethoxyl silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxyl silane etc.

As the mixing ratio of these functional silanes compounds, relative to total 100 weight part of polymkeric substance, be preferably below 2 weight parts, be more preferably 0.02 ~ 0.2 weight part.

< liquid crystal aligning agent >

Liquid crystal aligning agent of the present invention is by by above-mentioned polymkeric substance [A] and above-mentioned polymkeric substance [B], and other additive preferred dissolution coordinated arbitrarily if desired and comprise in organic solvent and form.

As the organic solvent used in liquid crystal aligning agent of the present invention, such as METHYLPYRROLIDONE can be enumerated, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, N-BUTYL ACETATE, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol ether acetate alone, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, Texacar PC etc.These solvents can be used alone, or are mixed with two or more.

Solids concentration (the total weight of the composition beyond the solvent of liquid crystal aligning agent accounts for the ratio of the gross weight of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention suitably can be selected from the viewpoint of viscosity, volatility etc., but preferably in the scope of 1 ~ 10 % by weight.That is, for liquid crystal aligning agent of the present invention, be coated with as following on the surface of the substrate, preferably by adding thermosetting as the film of liquid crystal orientation film or the film becoming liquid crystal orientation film, when solids concentration is less than 1 % by weight, the thickness of this film is too small, good liquid crystal orientation film can not be obtained, on the other hand, when solids concentration is more than 10 % by weight, the thickness of film is excessive, good liquid crystal orientation film can not be obtained, in addition, the viscosity of liquid crystal aligning agent increases, and coating characteristics is deteriorated.

The scope of particularly preferred solids concentration changes according to the method used during coating of liquid crystalline alignment agent on substrate.Such as, when adopting spinner method, particularly preferably solids concentration is in the scope of 1.5 ~ 4.5 % by weight.When adopting print process, particularly preferably solids concentration is set in the scope of 3 ~ 9 % by weight, makes soltion viscosity be in the scope of 12 ~ 50mPas thus.When adopting ink jet method, particularly preferably solids concentration is set in the scope of 1 ~ 5 % by weight, makes soltion viscosity be in the scope of 3 ~ 15mPas thus.

As temperature during preparation liquid crystal aligning agent of the present invention, be preferably 10 ~ 50 DEG C, be more preferably 20 ~ 30 DEG C.

< liquid crystal orientation film and liquid crystal display device >

Liquid crystal orientation film of the present invention is formed by above-mentioned liquid crystal aligning agent.In addition, liquid crystal display device of the present invention has this liquid crystal orientation film.About the operating mode of liquid crystal display device, be applicable to the horizontally oriented type that IPS type and TN type, STN type are such, be also applicable to the vertical orientating type as VA type.

Below the manufacture method of liquid crystal display device of the present invention is described, also the manufacture method of liquid crystal orientation film of the present invention is described in this explanation.Liquid crystal display device of the present invention can be manufactured by the operation of such as following (P1) ~ (P3).

[operation (P1): the formation of film]

First on substrate, liquid crystal aligning agent of the present invention is coated with, then by forming film to coated face heating on substrate.

(P1-1) when manufacturing TN type, STN type or VA type liquid crystal display device, to two plate bases of the nesa coating of patterning be provided with as a pair, formed on each face which form transparent conductive film, be coated with liquid crystal aligning agent of the present invention respectively preferably by adherography, spin-coating method, rolling method or ink jet printing method, then (preferably heat by preheating two steps that (prebake) and roasting (curing afterwards) form) by heating each coated face and form film.Herein, because the printing of liquid crystal aligning agent of the present invention is excellent, from the viewpoint of farthest playing excellent effect of the present invention, preferably adopt adherography as coating process.

As substrate, the transparency carrier be such as made up of the plastics such as the glass baseplate such as float glass, soda glass, Polyethylene Naphthalate, tri acetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polymeric amide, polyimide, polymethylmethacrylate, polycarbonate, poly-(ester ring type alkene) can be used.

As the nesa coating be arranged on a face of substrate, can use by stannic oxide (SnO ₂) form NESA film (PPG register of company of U.S. trade mark), by indium oxide-tin oxide (In ₂o ₃-SnO ₂) ito film etc. that forms, in order to obtain the nesa coating of patterning, can adopt after forming patternless nesa coating, such as utilize photolithography to form the method for pattern, using the method etc. of the mask with expection pattern when forming nesa coating.During coating of liquid crystalline alignment agent, in order to make substrate surface and nesa coating and film, there is better cementability, also can be embodied in substrate surface and should be formed on the surface of film, be coated with the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.

For the coated face after liquid crystal aligning agent coating, then carry out preheating (prebake), then carry out roasting (curing afterwards), thus form film.Prebake temperature is preferably 30 ~ 200 DEG C, is more preferably 40 ~ 150 DEG C, is particularly preferably 40 ~ 100 DEG C.The prebake time is preferably 0.25 ~ 10 minute, is more preferably 0.5 ~ 5 minute.Roasting (curing afterwards) temperature is preferably 80 ~ 300 DEG C, is more preferably 120 ~ 250 DEG C.After the time of curing be preferably 5 ~ 200 minutes, be more preferably 10 ~ 100 minutes.The thickness of the film formed in such a way is preferably 0.001 ~ 1 μm, is more preferably 0.005 ~ 0.5 μm.

(P1-2) on the other hand, when manufacturing IPS type liquid crystal display device, by be provided with interdigitated electrode structure patterning nesa coating substrate conducting film forming surface and do not arrange on a face of opposing substrate of conducting film, being coated with liquid crystal aligning agent of the present invention respectively, then forming film by carrying out heating to each coated face.About the preferred thickness of the film of the heating condition after the material of the substrate now used and nesa coating, coating process, coating, the patterning method of nesa coating, the pre-treatment of substrate and formation, identical with above-mentioned (P1-1).

In above-mentioned (P1-1) and (P1-2) in any one situation, on substrate after coating of liquid crystalline alignment agent, form by removing organic solvent the film becoming alignment films.In this case, dehydration closed-loop reaction can be carried out by again heating after formation film, forming the film through further imidization.

[operation (P2): friction treatment]

When manufacturing TN type, STN type or IPS type liquid crystal display device, for the film formed in a manner described, utilize the roller be rolled into by the such as fibrous cloth such as nylon, artificial silk, cotton to carry out wiping in certain direction, apply friction treatment.Thus, give film with liquid crystal molecular orientation energy, form liquid crystal orientation film.

In addition, for above-mentioned liquid crystal orientation film, by carrying out the process of the tilt angle changing liquid crystal orientation film subregion by a part for uviolizing liquid crystal orientation film, and carry out after a part of liquid crystal orientation film forms resist film on the surface, friction treatment is carried out according to the direction different from previous friction treatment, then removing the process of resist film, the visual field characteristic of the liquid crystal display device obtained can be improved by making liquid crystal orientation film have different liquid crystal aligning energy in each region.

Further, when manufacturing VA type liquid crystal display device, the film formed directly can be used as liquid crystal orientation film, but also can apply above-mentioned friction treatment by above-mentioned operation (1).

[operation (P3): the structure of liquid crystal cells]

In order to configure liquid crystal between substrate, such as following two kinds of methods can be enumerated.

First method is known method all the time.First, relatively configure two plate bases according to making the relative mode of each liquid crystal orientation film and make middle maintenance gap (box gap), sealing agent is used to fit the peripheral part of two plate bases, injection in the cell gap of being delimited by substrate surface and sealing agent, filling liquid crystal, then shutoff filling orifice, thus can liquid crystal cell be made.

Second method is called as ODF (OneDropFill, instil) method of mode, predetermined portion on a substrate in two plate bases defining liquid crystal orientation film is coated with such as ultraviolet light curable sealing material, liquid crystal is dripped on the surface again at liquid crystal orientation film, then to fit another substrate according to the mode making liquid crystal orientation film relative, then UV-irradiation is carried out to the whole face of substrate, make sealant cures, thus can liquid crystal cell be made.

When adopting any one method, for the liquid crystal cell manufactured in a manner described, preferably reheating the liquid crystal used and presenting the temperature of isotropic phase, then slowly cool to room temperature, thus flow orientation during removing Liquid crystal pour.

As sealing agent, the epoxy resin etc. such as containing solidifying agent and the alumina balls as spacer can be used.

As liquid crystal, nematic liquid crystal and smectic liquid crystal can be enumerated, wherein preferred nematic liquid crystal, such as, can use Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, biphenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In addition, in these liquid crystal, the cholesteryl liquid crystals such as such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate can be added; As that chiral agent that trade(brand)name " C-15 ", " CB-15 " (メルク Inc.) sell; To oxygen base benzylidene-use Ferroelectric liquid Crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.

By pasting Polarizer on the outer surface of liquid crystal cell, liquid crystal display device of the present invention can be obtained.As Polarizer, can enumerate with cellulose acetate protective membrane clamping stretch orientation polyvinyl alcohol while absorption iodine and Polarizer that the light polarizing film that is called as " H film " is formed or the Polarizer that is made up of H film itself.

Liquid crystal display device of the present invention can be effectively applied in various device, such as, can be used in the display unit such as clock and watch, pocket game machine, word processor, subnotebook PC, auto navigation class system, pick up camera, PDA, digital camera, portable phone, various watch-dog, LCD TV.

Embodiment

Below, by embodiment, the present invention will be described in more detail, but the present invention is not by the restriction of these examples.Further, for following each synthesis example, carry out repetition in following ratio if desired, guarantee the necessary amount in following polymerization example.

The synthesis > of < methacrylic acid cholestane ester

[synthesis example 1]

800g beta-cholestanol is dissolved in the dehydration tetrahydrofuran (THF) (THF) of 8,000mL, after adding triethylamine 270g, slowly adds 360g methacrylic chloride, at room temperature stir and react for 3 hours.After reaction terminates, filtering triethyl amine salt hydrochlorate by crossing, after staying removing THF by decompression steaming, adding 4,000mL chloroform.The solution obtained is washed, after dry over magnesium sulfate, stays removing chloroform by decompression steaming.Then, carry out weight recrystallize with ethanol, thus obtain the methacrylic acid cholestane ester (yield rate: 57.4%) of 540g white solid.

The synthesis > of < polymkeric substance [A]

Compound beyond above-mentioned methacrylic acid cholestane ester uses commercial goods respectively.Such as, as the methacrylic acid 2 of monomer providing repeating unit (a1), 2,6,6-tetramethyl--4-piperidine ester and methacrylic acid 1,2,2,6,6-pentamethyl--4-piperidine ester, directly uses commercial goods " FA-712HM " and " FA-711MM " of Hitachi Chemical Co., Ltd. respectively.

Also have, for weight-average molecular weight (Mw) and number-average molecular weight (Mn), the GPC post (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) using eastern ソ mono-Co., Ltd. to manufacture, by the analysis condition that flow 1.0 ml/min, precipitation solvent are tetrahydrofuran (THF), column temperature 40 DEG C, by measuring with the gel permeation chromatography (GPC) of monodisperse polystyrene as standard specimen.

[synthesis example 2: the synthesis of polymkeric substance [A-1]]

Stirring rod is being installed, in the four-hole boiling flask of T-valve and thermometer, add 5g (0.0222 mole) methacrylic acid 2 as monomer, 2, 6, 6-tetramethyl--4-piperidine ester, the methacrylic acid cholestane ester that 30.0g (0.0657 mole) is obtained by above-mentioned synthesis example 1, 25.0g (0.176 mole) glycidyl methacrylate, 10.0g (0.116 mole) methacrylic acid, 7.50g (0.0418 mole) N-N-cyclohexylmaleimide, 7.50g (0.0720 mole) vinylbenzene and 15.0g (0.115 mole) 2-hydroxyethyl methacrylate, add the diethylene glycol ethyl methyl ether of 200g as solvent again, 8.00g is as 2 of polymerization starter, 2 '-azo two (2, 4-methyl pentane nitrile) and 4.00g as the alpha-methyl styrene dimer of molecular weight regulator.By nitrogen gas stream, it is carried out to the bubbling of about 10 minutes, carry out nitrogen replacement in system, then react 5 hours at 70 DEG C under nitrogen atmosphere, thus obtain the solution containing 33.2 % by weight polymkeric substance [A-1].When measuring the molecular weight of polymkeric substance [A-1], Mw=10,000, Mw/Mn=2.4, can't see the peak that residual monomer causes.

[synthesis example 3 ~ 10, compare synthesis example 1 ~ 3]

For synthesis example 3 ~ 10 and compare synthesis example 1 and 3, except the kind of the monomer of use, outside ratio of components sets by following table 1, carry out the operation identical with synthesis example 1, preparation is respectively containing polymkeric substance [A-2] (containing 33.1 % by weight), polymkeric substance [A-3] (containing 33.2 % by weight), polymkeric substance [A-4] (containing 33.1 % by weight), polymkeric substance [A-5] (containing 33.1 % by weight), polymkeric substance [A-6] (containing 33.2 % by weight), polymkeric substance [A-7] (containing 33.2 % by weight), polymkeric substance [A-8] (containing 33.3 % by weight), polymkeric substance [A-9] (containing 33.0 % by weight), polymkeric substance [R-1] (containing 33.1 % by weight), the solution of polymkeric substance [R-3] (containing 33.3 % by weight).

In addition, for comparing the kind of monomer that synthesis example 2 uses, while ratio of components sets by following table 1, to as 2 of polymerization starter, 2 '-azo two (2,4-methyl pentane nitrile) add 4.50g to replace 8.00g, and 4.00g is replaced to the alpha-methyl styrene dimer interpolation 2.00g as molecular weight regulator, in addition, carry out identical operation with synthesis example 1, be mixed with the polymers soln containing 33.0 % by weight polymkeric substance [R-2].

In table 1, the abbreviation of each compound is as follows respectively.

[repeating unit (a1)]

A1-1: methacrylic acid 2,2,6,6-tetramethyl--4-piperidine ester

A1-2: methacrylic acid 1,2,2,6,6-pentamethyl--4-piperidine ester

A1-3:2-(methacryloxy)-ethyl-1,2,2,6,6-pentamethvl-4-manthanoate

A1-4: methacrylic acid 2,2,6,6-tetramethyl--1-octyloxy-4-piperidine ester

A1-5: methacrylic acid 2,2,6,6-tetramethyl--1-oxo-4-piperidine ester

A1-6: methacrylic acid 2,2,6,6-tetramethyl--1-benzyl-4-piperidine ester

A1-7:2-propenyloxy group-1,2,2,6,6-pentamethyl--4-piperidine ester

[repeating unit (a2)]

A2-1: methacrylic acid cholestane ester

A2-2: methacrylic acid 4-(4 '-amyl group dicyclohexyl-4-base) phenyl ester

[repeating unit (a3)]

A3-1: glycidyl methacrylate

[repeating unit (a4)]

A4-1: methacrylic acid

[repeating unit (a5)]

A5-1:N-N-cyclohexylmaleimide

[repeating unit (a6)]

A6-1: vinylbenzene

[repeating unit (a7)]

A7-1: 2-hydroxyethyl methacrylate

The synthesis > of < polymkeric substance [B]

In following polymerization example, the soltion viscosity of each polymers soln and the imide rate of polyimide measure by the following method.

[soltion viscosity of polymers soln]

As the soltion viscosity (mPas) of polymers soln, use the solvent of regulation, polymer concentration is deployed into the solution of 10 % by weight, use E type rotational viscosimeter to measure at 25 DEG C.

[the imide rate of polyimide]

The solution of polyimide is put in pure water, after at room temperature abundant drying under reduced pressure being carried out to the precipitation obtained, is dissolved in deuterated dimethyl sulfoxide, at room temperature carries out as reference material with tetramethylsilane ¹h-NMR measures.Based on what obtain ¹h-NMR composes, and obtains imide rate by following mathematical expression.

Imide rate (%)=(1-A ¹/ A ²× α) × 100

(A ¹for the peak area deriving from the proton of NH base occurred near chemical shift 10ppm, A ²the peak area being derived from other proton, α be NH base in the precursor (polyamic acid) relative to polymkeric substance 1 proton the number ratio of other proton)

[synthesis example 11: the synthesis of polymkeric substance [B-1]]

Using 112g (0.50 mole) as tetracarboxylic dianhydride's 2,3, the compound dissolution that 5-tricarboxylic cyclopentyl acetic acid dianhydride and 43g (0.40 mole) represent as Ursol D and the 52g (0.10 mole) above-mentioned formula (D3-1) of diamines is in 830gN-N-methyl-2-2-pyrrolidone N-(NMP), at 60 DEG C, react reaction in 6 hours, obtain polyamic acid solution.Take out a small amount of from the polyamic acid solution obtained, adding NMP and form the solution that polyamic acid concentration is 10 % by weight, is 60mPas when measuring its viscosity.

Then, in the polyamic acid solution obtained, add 1,900gNMP, add 40g pyridine and 51g acetic anhydride, at 110 DEG C, carry out the dehydration closed-loop reaction of 4 hours.After dehydration closed-loop reaction, (pyridine used in utilizing this operation to be reacted by dehydration closed-loop and acetic anhydride are rejected to outside system to carry out solvent replacing with new NMP to the solvent in system.Identical below), thus obtain the solution that imide rate that about Isosorbide-5-Nitrae 00g contains 15 % by weight is the imide amination polymer [B-1] of about 50%.Take a morsel this solution, and add NMP and form the solution that imide amination polymer concentration is 10 % by weight, the soltion viscosity of mensuration is 47mPas.

[synthesis example 12: the synthesis of polymkeric substance [B-2]]

Using 112g (0.50 mole) as tetracarboxylic dianhydride's 2,3, the compound dissolution that 5-tricarboxylic cyclopentyl acetic acid dianhydride and 43g (0.40 mole) represent as Ursol D and the 49g (0.10 mole) above-mentioned formula (D3-2) of diamines is in 820gNMP, react 6 hours at 60 DEG C, obtain polyamic acid solution.Take a morsel the polyamic acid solution obtained, and adding NMP and form the solution that polyamic acid concentration is 10 % by weight, is 60mPas during mensuration viscosity.

Then, in the polyamic acid solution obtained, add 1,900gNMP, add 40g pyridine and 51g acetic anhydride, carry out the dehydration closed-loop reaction of 4 hours at 110 DEG C.After dehydration closed-loop reaction, with new NMP, solvent replacing is carried out to the solvent in system, thus obtain the solution that about 1, the 300g imide rate containing 15 % by weight is the imide amination polymer [B-2] of about 50%.Take a morsel this solution, and add NMP and form the solution that imide amination polymer concentration is 10 % by weight, the soltion viscosity of mensuration is 47mPas.

[synthesis example 13: the synthesis of polymkeric substance [B-3]]

Using 112g (0.50 mole) as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 53g (0.35 mole) are as 3 of diamines, the compound that 5-diamino M-nitro benzoic acid, 52g (0.10 mole) above-mentioned formula (D3-1) represent and the compound dissolution that 25g (0.050 mole) above-mentioned formula (D3-2) represents are in 970gNMP, react 6 hours at 60 DEG C, obtain polyamic acid solution.Take a morsel the polyamic acid solution obtained, and adding NMP and form the solution that polyamic acid concentration is 10 % by weight, is 60mPas during mensuration viscosity.

Then, in the polyamic acid solution obtained, add 1,200gNMP, add 40g pyridine and 51g acetic anhydride, carry out the dehydration closed-loop reaction of 4 hours at 110 DEG C.After dehydration closed-loop reaction, with new NMP, solvent replacing is carried out to the solvent in system, thus obtain the solution that about 1, the 600g imide rate containing 15 % by weight is the imide amination polymer [B-3] of about 50%.Take a morsel this solution, and add NMP and form the solution that imide amination polymer concentration is 10 % by weight, the soltion viscosity of mensuration is 50mPas.

The preparation > of < liquid crystal aligning agent

[embodiment 1]

By the solution containing polymkeric substance [A-1] obtained by above-mentioned synthesis example 2 and the solution containing imide amination polymer [B-1] obtained by above-mentioned synthesis example 11, according to making polymkeric substance [A-1]: the weight ratio of imide amination polymer [B-1] be 1: 99 mode mix, add NMP and ethylene glycol butyl ether wherein, obtaining solvent composition is NMP: ethylene glycol butyl ether: diethylene glycol ethyl methyl ether=49.6: 50: 0.4 (weight ratios), solids concentration are the solution of 3.5 % by weight.After this solution is fully stirred, use the metre filter in 0.2 μm, aperture, thus be mixed with liquid crystal aligning agent.

[embodiment 2 ~ 13, comparative example 1 ~ 4]

Except setting kind and the weight ratio of polymkeric substance [A] and imide amination polymer [B] by following table 2, and outside the kind of solvent and weight ratio, carry out the operation identical with embodiment 1, the liquid crystal aligning agent of preparation embodiment 2 ~ 13 and comparative example 1 ~ 4.

[comparative example 5]

Add NMP and ethylene glycol butyl ether dilutes to what obtained by above-mentioned synthesis example 11 containing in the solution of imide amination polymer [B-1], forming solvent composition is NMP: ethylene glycol butyl ether=50: 50 (weight ratios), solids concentration are the solution of 3.5 % by weight.After this solution is fully stirred, use the metre filter in 0.2 μm, aperture, thus be mixed with liquid crystal aligning agent.

[comparative example 6 and 7]

In above-mentioned comparative example 5, use the solution containing the polymkeric substance recorded in following table 2 as polymers soln respectively, in addition, carry out the operation identical with comparative example 5, preparation liquid crystal aligning agent.

The manufacture > of < liquid crystal cell

Use liquid crystal orientation film printing press (Japan's description printing (strain) system), the embodiment 1 ~ 13 of preparation, each liquid crystal aligning agent of comparative example 1 ~ 7 are coated on the transparent electrical pole-face of the glass substrate of the band transparency electrode be made up of ito film, the hot-plate of 80 DEG C heats 1 minute (prebake) and removes desolventizing, then on the hot-plate of 200 DEG C, heat 10 minutes (curing afterwards), forming average film thickness is film.For this film, utilize the rubbing machine of the roller with winding artificial silk cloth, being pressed into length by roller revolution 500rpm, platform movement speed 3cm/ second, fine hair is that the condition of 0.4mm carries out friction treatment, gives liquid crystal aligning energy.Then, in ultrapure water, carry out the ultrasound washing of 1 minute, then in the baking oven of 100 DEG C dry 10 minutes, obtain the substrate with liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair (2) have liquid crystal orientation film.

Then, arbitrary in above-mentioned a pair substrate have on the outward flange of liquid crystal orientation film, coating adds the epoxy resin adhesive of the alumina balls of diameter 5.5 μm, then according to making the relative mode of liquid crystal aligning face superimposed and crimping, caking agent is solidified.Then, fill nematic liquid crystal (メルク Inc., MLC-6221) between from liquid crystal injecting port to a pair substrate, then close liquid crystal injecting port with acrylic acid or the like light-curing adhesive, thus make liquid crystal cell.

The evaluation > of < liquid crystal cell

[evaluation of vertical orientated property]

For the vertical alignment-type liquid crystal display device manufactured as mentioned above, the bonding strength determinator " OMS-J3 " utilizing central smart machine (strain) to manufacture measures tilt angle.When this tilt angle is more than 87 °, be considered as vertical orientated property " well ", during less than 87 °, be considered as vertical orientated property " defective ".

[evaluation of voltage retentivity]

For the vertical alignment-type liquid crystal display device manufactured as mentioned above, by the application time, 1 of 60 microseconds at 60 DEG C, the interval of 670 milliseconds applies the voltage of 5V, measure to remove under the atmosphere of 60 DEG C and to apply after voltage 1, voltage retention after 670 milliseconds, the determinator of voltage retention uses the VHR-1 of (strain) Dongyang テ Network ニカ manufacture.When the value of voltage retention is more than 97.5%, is considered as voltage retention " well ", is considered as " defective " during less than 97.5%.

[endurance test (whether having display defect) of liquid crystal display device]

Under hot and humid environment (temperature 70 C, relative humidity 80%), with the rectangular wave drive liquid crystal display device of 5V, 60Hz, with microscopic examination through 1, the display defect of whether adularescent stain shape after 500 hours.As a result, when there is not the display defect of white stains shape, be evaluated as weather resistance " well ", when there is the display defect of white stains shape, be evaluated as weather resistance " defective ".

[resistance to evaluation (mensuration of remanant DC voltages, accelerated test) of burning screen property]

For the liquid crystal display device manufactured as mentioned above, apply the volts DS of 17V under the atmosphere of 100 DEG C after, remove this voltage, under room temperature environment, leave standstill 15 minutes, then utilize flicker (Flicker) elimination method to obtain voltage (remanant DC voltages) residual in liquid crystal cell.Can judge that the value of remanant DC voltages is less, the long-term resistance to liquid crystal display device burning screen property excellence.Remanant DC voltages value is that the liquid crystal display device of below 200mV is considered as resistance to burning screen property " well ", is considered as resistance to burning screen property " defective " when remanant DC voltages value is greater than 200mV.

The evaluation result of embodiment 1 ~ 13 and comparative example 1 ~ 7 is shown in following table 2 together with various composition.

Table 2

As shown in table 2, in embodiment 1 ~ 13, vertical orientated property, voltage retentivity, weather resistance and resistance to burning screen property is good.On the other hand, not having weather resistance in the comparative example 1 ~ 7 of repeating unit (a1) is defective.Further, for comparative example 1 ~ 7, confirm to there is not display defect before the on-test of weather resistance.

In addition, as the repeating unit of polymkeric substance [A], not only do not have repeating unit (a1), also do not have the comparative example 2 of repeating unit (a2), not only weather resistance is defective, and vertical orientated property is also defective.In addition, as the repeating unit of polymkeric substance [A], not only do not have repeating unit (a1), also do not have the comparative example 3 of repeating unit (a3), not only weather resistance is defective, and voltage retentivity is also defective.In addition, not containing the comparative example 5 ~ 7 of polymkeric substance [A] as component of polymer, not only weather resistance is defective, and resistance to burning screen property is also defective.

Claims

1. liquid crystal aligning agent, it is characterized in that, containing polymkeric substance [A] and at least one polymkeric substance [B] selected from the group be made up of polyamic acid and imide amination polymer thereof, this polymkeric substance [A] has the repeating unit that following formula (1-1) represents, this polyamic acid is obtained by tetracarboxylic dianhydride and diamine reactant

In formula (1-1), R is hydrogen atom or methyl, A ¹for singly-bound or divalent concatenating group, R ¹¹the alkyl that maybe can be substituted for singly-bound separately, X is singly-bound, Sauerstoffatom, sulphur atom ,-CO-,-CO-O-or-O-CO-, R separately ¹²alkyl separately for being substituted, wherein, when X is not singly-bound, R ¹¹and R ¹²can be combined with each other formation ring structure, B ¹for hydrogen atom, halogen atom, hydroxyl or 1 valency organic group, m is the integer of 0 ~ 4,

And relative to polymkeric substance [B] 100 weight part, the content of polymkeric substance [A] is below below 3 weight parts 20 weight part.

2. liquid crystal aligning agent according to claim 1, is characterized in that, aforementioned repeating unit following formula (1-1-1) represents,

In formula (1-1-1), R is hydrogen atom or methyl, A ¹for singly-bound or divalent concatenating group, R ¹³be the alkyl of carbonatoms 1 ~ 5 separately, B ¹for hydrogen atom, halogen atom, hydroxyl or 1 valency organic group.

3. the liquid crystal aligning agent described in claim 1 or 2, is characterized in that, the polymkeric substance [A] with above-mentioned repeating unit also has the repeating unit that following formula (2) represents,

B ²¹for cyclohexylidene or substituted or unsubstituted phenylene, B ²²for the alkyl of hydrogen atom or carbonatoms 1 ~ 30, k is the integer of 0 ~ 3, wherein, and B ²²during for hydrogen atom, k is more than 1, in addition, when k is 2 or 3, and multiple B ²¹have above-mentioned definition independently of one another, " * " represents and A ²in conjunction with connecting key.

4. the liquid crystal orientation film that the liquid crystal aligning agent according to any one of claims 1 to 3 is formed.

5. there is the liquid crystal display device of liquid crystal orientation film according to claim 4.