CN105315463A - Diamin, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents
Diamin, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element Download PDFInfo
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- CN105315463A CN105315463A CN201510370134.7A CN201510370134A CN105315463A CN 105315463 A CN105315463 A CN 105315463A CN 201510370134 A CN201510370134 A CN 201510370134A CN 105315463 A CN105315463 A CN 105315463A
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- 0 C*CCCCCCN Chemical compound C*CCCCCCN 0.000 description 16
- ZPZDVOAWPQVPEC-UHFFFAOYSA-N CC(C)CCCC(C)C(CC1)C(C)(CC2)C1C1C2C(C)(CCC(C2)OC(c3cc(N)cc(N)c3)=O)C2=CC1 Chemical compound CC(C)CCCC(C)C(CC1)C(C)(CC2)C1C1C2C(C)(CCC(C2)OC(c3cc(N)cc(N)c3)=O)C2=CC1 ZPZDVOAWPQVPEC-UHFFFAOYSA-N 0.000 description 1
- VELVHOCYCCQQIZ-UHFFFAOYSA-N NC(CC1)=CC=C1N Chemical compound NC(CC1)=CC=C1N VELVHOCYCCQQIZ-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N NC(CC1)CCC1N Chemical compound NC(CC1)CCC1N VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N Nc1cc(C(O)=O)cc(N)c1 Chemical compound Nc1cc(C(O)=O)cc(N)c1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N Nc1cc(N)ccc1 Chemical compound Nc1cc(N)ccc1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ARZJOVRCBIGEOL-WPLRKUEPSA-N OC(C(C1)C(C2)C(C3OC3O3)[C@H]1C3=O)OC2=O Chemical compound OC(C(C1)C(C2)C(C3OC3O3)[C@H]1C3=O)OC2=O ARZJOVRCBIGEOL-WPLRKUEPSA-N 0.000 description 1
- PTJDVJPLDIISFE-UHFFFAOYSA-N OC(CC(c1c2)=O)c1ccc2OCc(cc1)ccc1Oc(cc1C(O2)=O)ccc1C2=O Chemical compound OC(CC(c1c2)=O)c1ccc2OCc(cc1)ccc1Oc(cc1C(O2)=O)ccc1C2=O PTJDVJPLDIISFE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a liquid crystal aligning agent of polyamic acid or a derivative thereof obtained by reaction between at least one kind of diamin and tetracarboxylic dianhydride, a liquid crystal aligning film forming by the liquid crystal aligning agent, and a liquid crystal display element with the liquid crystal aligning film. The liquid crystal display element is characterized in that the quality does not decreased even if the liquid crystal display element is exposed to strong light for a long time. And when liquid crystal aligning agent is in use, the liquid crystal aligning film capable of realizing the performance of the liquid crystal display element even under high-temperature calcining is provided. In a formular (1), R1 is hydrogen or methyl, and R2 is hydrogen, -OH, alkyl with a carbon number 1-6 or alkoxy with a carbon number 1-6.
Description
Technical field
The present invention relates to a kind of the polyamic acid or derivatives thereof, the liquid crystal aligning agent containing described polyamic acid and derivative thereof, liquid crystal orientation film, the liquid crystal display device that diamines represented by formula (1) are used for raw material.
Background technology
Nowadays commercialization and the main flow of the liquid crystal display device generally circulated are the display elements using nematic liquid crystal.What the display mode of nematic liquid crystal display element was widely known by the people is twisted nematic (TwistedNematic, TN) pattern, STN Super TN (SuperTwistedNematic, STN) pattern.In order to one of problem improving these patterns, namely visual angle is narrow and small in recent years, propose there is the TN type liquid crystal display device using optical compensation films, and with vertical orientated (Multi-domainVerticalAlignment vertical orientated with the multizone of the technology of pop-up structure thing, MVA) the coplanar switching (In-PlaneSwitching of pattern or Transverse electric-field type, IPS) pattern, fringing field switch (FringeFieldSwitching, FFS) pattern, and practical (with reference to patent documentation 1 ~ patent documentation 3).
The development of the technology of liquid crystal display device is not only realized by the improvement of these type of drive or component structure, but also is realized by the improvement of member of formation that uses in element.In the member of formation used in liquid crystal display device, particularly liquid crystal orientation film is one of important materials being related to display quality, along with the high-quality of liquid crystal display device, the performance of alignment films is improved and becomes important.
At present, the liquid crystal orientation film of main use is coated on after on substrate by the solution (varnish) that the polyimide of polyamic acid or solubility is dissolved in organic solvent, carried out the polyimide system liquid crystal orientation film of film forming by methods such as heating.Usually, use in liquid crystal display device orientation process is implemented to the described polyimide system liquid crystal orientation film through masking.Some orientation process known, the rubbing manipulation can carrying out big area high speed processing in industrialness is easily used widely by as orientation process method.Rubbing manipulation uses the cloth having transplanted the fibers such as nylon, artificial silk, polyester, in the process that the surface of a direction to liquid crystal orientation film rubs, can obtain the consistent orientation of liquid crystal molecule thus.
The purposes of liquid crystal display device across and the watch-dog (monitor) of Personal Computer (personalcomputer), LCD TV, mobile telephone, the display part of smart mobile phone, multiple fields of liquid crystal projection apparatus.In recent years, consider display quality raising or for outdoor, also there is the purposes increased before becoming the luminance factor of the backlight of light source, even if thus require a kind of liquid crystal display device being exposed to display quality under strong light for a long time and also can not declining.
In order to tackle this kind of requirement, also various research is carried out to liquid crystal orientation film, such as there will be a known following method: make in raw material containing the diamines with the structure of hindered amine or hindered phenol structure, in polyimide chain, import the method (with reference to patent documentation 4) of described structure, maybe the antioxidant with the structure of hindered amine or hindered phenol structure is added into the method (with reference to patent documentation 5) in liquid crystal aligning agent.But, even if use these technology, because of the manufacturing process of liquid crystal display device difference, wherein have because making liquid crystal orientation film be formed at the calcining temperature of the operation on substrate problems such as not showing required performance.
And, in order to suppress the generation of " burning trace " in vertical alignment-type liquid crystal display device, carry out the trial (with reference to patent documentation 6) importing the structure of hindered amine at the side chain position of side chain type diamines, but described Technological expression goes out the tilt angle of liquid crystal molecule, be not suitable as IPS pattern or the FFS mode of lateral electric field mode.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 6-194646
[patent documentation 2] Japanese Patent Laid-Open 2001-117083
[patent documentation 3] Japanese Patent Laid-Open 6-160878
[patent documentation 4] Japanese Patent Laid-Open 2010-244015
[patent documentation 5] Japanese Patent Laid-Open 2012-194537
[patent documentation 6] International Publication 2008/078629
Summary of the invention
[inventing problem to be solved]
Even if problem of the present invention is to provide a kind of liquid crystal display device being exposed to display quality under strong light for a long time and also can not declining, even if provide simultaneously a kind of manufacturing process at liquid crystal display device, wherein make liquid crystal orientation film be formed on substrate operation in select high calcining temperature also can show the liquid crystal display device of required performance.And then problem of the present invention is to provide a kind of liquid crystal aligning agent and the liquid crystal orientation film that can provide this kind of display element.
[in order to solve the technique means of problem]
The people such as the present inventor carry out effort research, result is by the compound of use formula (1), a kind of liquid crystal display device and can not by the liquid crystal aligning agent of different impacts of the calcining temperature of manufacturing process, the particularly liquid crystal orientation film of described liquid crystal display device and liquid crystal orientation film of can stably providing is provided, even if under described liquid crystal display device is exposed to strong light for a long time, display quality also can not decline.Particularly in IPS pattern and FFS mode, effect of the present invention is played further.
The present invention comprises following formation.
[1] a polyamic acid or derivatives thereof, it makes at least one of the diamines represented by formula (1) and at least one of tetracarboxylic dianhydride react and obtain:
In formula (1), R
1hydrogen or methyl; And
R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
[2] the polyamic acid or derivatives thereof Gen Ju [1] item, at least one of the diamines of the diamines represented by its Chinese style (1) represented by formula (1-1):
In formula (1-1), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
[3] the polyamic acid or derivatives thereof Gen Ju [1] item, at least one of the diamines of the diamines represented by its Chinese style (1) represented by formula (1-2):
In formula (1-2), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
[4] the polyamic acid or derivatives thereof Gen Ju [2] item, the diamines represented by its Chinese style (1) is for being selected from least one in the group of the compound represented by formula (1-1-1) ~ formula (1-1-28):
[5] the polyamic acid or derivatives thereof Gen Ju [3] item, the diamines represented by its Chinese style (1) is for being selected from least one in the group of the compound represented by formula (1-2-1) ~ formula (1-2-28):
[6] according to polyamic acid or derivatives thereof according to any one of [1] item to [5] item, it is that at least one of diamines represented by formula (1) and the mixture of at least one of other diamines and at least one of tetracarboxylic dianhydride are carried out reacting and obtained.
[7] according to the polyamic acid or derivatives thereof according to any one of [1] item to [6] item, wherein tetracarboxylic dianhydride is for being selected from least one in the group of the tetracarboxylic dianhydride represented by following formula (AN-I) ~ formula (AN-VII):
In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently singly-bound or-CH
2-;
In formula (AN-II), G is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-;
In formula (AN-II) ~ formula (AN-IV), Y is independent of being selected from the one in the group of the base of following trivalent,
At least one hydrogen of described base can be replaced by methyl, ethyl or phenyl;
In formula (AN-III) ~ formula (AN-V), ring A
10for the base of carbon number to be the base of the monocyclic hydrocarbon of 3 ~ 10 or carbon number the be condensation polycyclic formula hydrocarbon of 6 ~ 30, at least one hydrogen of described base can be replaced by methyl, ethyl or phenyl, the associative key be connected on ring links with the arbitrary carbon forming ring, and 2 associative keys can link with same carbon;
In formula (AN-VI), X
10for carbon number is the alkylidene group of 2 ~ 6, Me represents methyl, and Ph represents phenyl,
In formula (AN-VII), G
10independent is-O-,-COO-or-OCO-; And r is independently 0 or 1.
[8] the polyamic acid or derivatives thereof Gen Ju [7] item, wherein tetracarboxylic dianhydride is for being selected from following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-11-3), formula (AN-16-3), and at least one in formula (AN-16-4):
In formula (AN-1-2) and formula (AN-4-17), m is the integer of 1 ~ 12.
[9] the polyamic acid or derivatives thereof Gen Ju [6] item, wherein other diamines are for being selected from least one in the group that is made up of following formula (DI-1) ~ formula (DI-16), formula (DIH-1) ~ formula (DIH-3) and formula (DI-31) ~ formula (DI-35):
In formula (DI-1), G
20for-CH
2-, at least one-CH
2-can be replaced by-NH-,-O-, m is the integer of 1 ~ 12, and at least one hydrogen of alkylidene group can be replaced by-OH;
In formula (DI-3) and formula (DI-5) ~ formula (DI-7), G
21independent is singly-bound ,-NH-,-NCH
3-,-O-,-S-,-S-S-,-SO
2-,-CO-,-COO-,-CONH-,-CONCH
3-,-C (CH
3)
2-,-C (CF
3)
2-,-(CH
2)
m'-,-O-(CH
2)
m'-O-,-N (CH
3)-(CH
2)
k-N (CH
3)-,-(O-C
2h
4)
m'-O-,-O-CH
2-C (CF
3)
2-CH
2-O-,-O-CO-(CH
2)
m'-CO-O-,-CO-O-(CH
2)
m'-O-CO-,-(CH
2)
m'-NH-(CH
2)
m'-,-CO-(CH
2)
k-NH-(CH
2)
k-,-(NH-(CH
2)
m')
k-NH-,-CO-C
3h
6-(NH-C
3h
6)
n-CO-or-S-(CH
2)
m'-S-, m' are independently the integer of 1 ~ 12, and k is the integer of 1 ~ 5, and n is 1 or 2;
In formula (DI-4), s is independently the integer of 0 ~ 2;
In formula (DI-6) and formula (DI-7), G
22independent is singly-bound ,-O-,-S-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-or carbon number be the alkylidene group of 1 ~ 10;
In formula (DI-2) ~ formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can be the alkyl ,-OCH of 1 ~ 3 by-F ,-Cl, carbon number
3,-OH ,-CF
3,-CO
2h ,-CONH
2,-NHC
6h
5, phenyl or benzyl replace, in addition, in formula (DI-4), at least one hydrogen of phenyl ring can by a replacement in the group of the base be selected from represented by following formula (DI-4-a) ~ formula (DI-4-e);
In formula (DI-4-a) and (DI-4-b), R
20independent is hydrogen or-CH
3;
The basis representation binding site on which ring that binding site is not fixed on the carbon atom forming ring is any ,-NH
2binding site on cyclohexane ring or phenyl ring is for removing G
21or G
22binding site beyond arbitrary position;
In formula (DI-11), r is 0 or 1;
In formula (DI-8) ~ formula (DI-11) ,-NH of bond on ring
2binding site be arbitrary position;
In formula (DI-12), R
21and R
22independently for carbon number is the alkyl or phenyl of 1 ~ 3, G
23independent for carbon number be 1 ~ 6 alkylidene group, phenylene or the phenylene through alkyl replacement, w is the integer of 1 ~ 10;
In formula (DI-13), R
23independent for carbon number be 1 ~ 5 alkyl, carbon number be 1 ~ 5 alkoxyl group or-Cl, p be independently 0 ~ 3 integer, q is the integer of 0 ~ 4;
In formula (DI-14), ring B is monocyclic heteroaromatic, R
24the thiazolinyl, the carbon number that are 2 ~ 6 for hydrogen ,-F ,-Cl, the carbon number alkyl that is 1 ~ 6, the carbon number alkoxyl group that is 1 ~ 6, carbon number are the alkynyl of 1 ~ 6, and q is independently the integer of 0 ~ 4;
In formula (DI-15), ring C is for containing heteroatomic monocycle;
In formula (DI-16), G
24for alkylidene group or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2 ~ 6, r is 0 or 1;
In formula (DI-13) ~ formula (DI-16), the basis representation binding site on which ring that binding site is not fixed on the carbon atom forming ring is any;
In formula (DIH-1), G
25for singly-bound, carbon number are alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-;
In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl;
In formula (DIH-3), ring E is independently cyclohexane ring or phenyl ring, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl, and Y is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-;
In formula (DIH-2) and formula (DIH-3) ,-CONHNH of bond on ring
2binding site be arbitrary position;
In formula (DI-31), G
26for singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-or-(CH
2)
m'-, m' is the integer of 1 ~ 12, R
25for carbon number be 3 ~ 30 alkyl, phenyl, have the base of steroid skeleton or the base represented by following formula (DI-31-a), in described alkyl, at least one hydrogen can be replaced by-F, at least one-CH
2-can be replaced by-O-,-CH=CH-or-C ≡ C-, the hydrogen of described phenyl can by-F ,-CH
3,-OCH
3,-OCH
2f ,-OCHF
2,-OCF
3, carbon number be 3 ~ 30 alkyl or carbon number be 3 ~ 30 alkoxyl group replace ,-the NH of bond on phenyl ring
2binding site represent for arbitrary position in described ring,
In formula (DI-31-a), G
27, G
28and G
29for bond base, they are independently singly-bound or carbon number is the alkylidene group of 1 ~ 12, the more than one-CH of described alkylidene group
2-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-, ring B
21, ring B
22, ring B
23and ring B
24independent is Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, ring B
21, ring B
22, ring B
23and ring B
24in, at least one hydrogen can by-F or-CH
3replace, s, t and u are independently the integer of 0 ~ 2, they add up to 1 ~ 5, when s, t or u are 2,2 bond bases in each bracket can be identical, also can be different, and 2 rings can be identical, also can be different,
R
26for hydrogen ,-F ,-OH, the carbon number alkyl that is 1 ~ 30, the carbon number fluorine substituted alkyl that is 1 ~ 30, carbon number are alkoxyl group ,-the CN ,-OCH of 1 ~ 30
2f ,-OCHF
2or-OCF
3, described carbon number is at least one-CH of the alkyl of 1 ~ 30
2-can replace by with the base of the divalence represented by following formula (DI-31-b),
In formula (DI-31-b), R
27and R
28independently for carbon number is the alkyl of 1 ~ 3, v is the integer of 1 ~ 6;
In formula (DI-32) and formula (DI-33), G
30independent is singly-bound ,-CO-or-CH
2-, R
29independent is hydrogen or-CH
3, R
30for hydrogen, carbon number be 1 ~ 20 alkyl or carbon number be the thiazolinyl of 2 ~ 20;
The alkyl or phenyl that a hydrogen of the phenyl ring in formula (DI-33) can be 1 ~ 20 by carbon number replaces, and,
In formula (DI-32) and formula (DI-33), the basis representation binding site on which ring that binding site is not fixed on any one carbon atom forming ring is any;
In formula (DI-34) and formula (DI-35), G
31independently for-O-or carbon number are the alkylidene group of 1 ~ 6, G
32for singly-bound or carbon number are the alkylidene group of 1 ~ 3,
R
31for at least one-CH that hydrogen or carbon number are the alkyl of 1 ~ 20, described alkyl
2-can be replaced by-O-,-CH=CH-or-C ≡ C-, R
32for carbon number is the alkyl of 6 ~ 22, R
33for hydrogen or carbon number are the alkyl of 1 ~ 22, ring B
25for Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1, and ,-the NH of bond on phenyl ring
2represent that binding site is on which ring any.
[10] the polyamic acid or derivatives thereof Gen Ju [6] item, wherein other diamines are for being selected from by following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-13-1), formula (DI-16-1), and at least one in the group that forms of formula (DIH-2-1):
In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13) and formula (DI-7-3), m is the integer of 1 ~ 12;
In formula (DI-5-30), k is the integer of 1 ~ 5; And
In formula (DI-7-3), n is 1 or 2.
[11] liquid crystal aligning agent, it is containing the polyamic acid or derivatives thereof according to any one of with good grounds [1] item to [10] item.
[12] liquid crystal aligning agent, it is containing the polyamic acid or derivatives thereof according to any one of with good grounds [1] item to [10] item and the polymkeric substance except them.
[13] according to [11] item or the liquid crystal aligning agent described in [12] item, it is also containing at least one be selected from the compound group that is made up of alkenyl substituted Na Dike imide compound, the compound with free-radical polymerised unsaturated double-bond, oxazine compounds, oxazoline compound and epoxy compounds.
[14] a kind of according to the liquid crystal aligning agent according to any one of [11] item to [13] item, it is for lateral electric-field type liquid crystal display device.
[15] liquid crystal orientation film, it is formed by the liquid crystal aligning agent according to any one of [11] item to [14] item.
[16] liquid crystal display device, it comprises the liquid crystal orientation film Gen Ju [15] item.
[17] diamines, it is represented by formula (1-2):
In formula (1-2), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
[effect of invention]
The liquid crystal orientation film formed by liquid crystal aligning agent of the present invention excellent in reliability, described liquid crystal aligning agent contains the polyamic acid or derivatives thereof diamines represented by formula (1) being used for raw material.And have nothing to do in manufacturing process difference and certain performance can be played.Even if the liquid crystal display device comprising described liquid crystal orientation film uses for a long time, display quality also can not decline.Further, when reducing image retention further for giving, improving other characteristics such as the printings of substrate, also can pass through other polymkeric substance of fusion, or also provide the liquid crystal display device with required characteristic with additive.
Embodiment
In diamines represented by formula (1), R
1hydrogen or methyl, R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.The position of substitution in 2 amino phenyl ring is not particularly limited, and in order to be set to the liquid crystal aligning agent arranging liquid crystal molecule more well, it is desirable to the position of substitution relative to amide group and being 3,5 or 2,5.
Diamines represented by formula (1) is classified into R
1diamines represented by the formula (1-1) of hydrogen and R
1for the diamines represented by the formula (1-2) of methyl.
In formula (1-1) and formula (1-2), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
When the liquid crystal aligning agent needing the solvability in solvent higher, preferably use the diamines of formula (1-1).And, when the liquid crystal orientation film needing reliability higher, preferably use R in formula (1-1) and formula (1-2)
2for the compound of hydrogen or-OH.
The concrete example of the diamines represented by formula (1-1) is for the compound represented by following formula (1-1-1) ~ formula (1-1-28).
The concrete example of the diamines represented by formula (1-2) is for the compound represented by following formula (1-2-1) ~ formula (1-2-28).
One of raw material diamines represented by formula (1-1-1) ~ formula (1-1-4), formula (1-2-1) and formula (1-2-2) being used as the polymkeric substance forming liquid crystal aligning agent of the present invention can be passed through, even if obtain the high liquid crystal orientation film of the long-time liquid crystal aligning using display quality also can not decline.
By one of raw material being used as the polymkeric substance forming liquid crystal aligning agent of the present invention by the diamines represented by formula (1-2-1) ~ formula (1-2-6), even and if with other diamines beyond the diamines represented by formula (1), also gelation can be suppressed when Macroscopic single crystal.Think that its reason is: the hydrogen of amide group is by methyl substituted, so the intermolecular interaction that hydrogen bond is formed disappears.
The synthetic method > of the diamines represented by < formula (1)
Diamines represented by formula (1) synthesizes by following flow process.
The position of substitution of < amino is 3,5-position, R
1for the compound > of hydrogen
Under the existence of the alkali such as triethylamine, make 3,5-dinitrobenzoyl chloride and commercially available 4-amino-2,2,6,6-tetramethyl piperidine derivatives reaction, then under the existence of palladium-carbon catalyst, under hydrogen environment, carry out the reduction of nitro, obtaining amino the position of substitution is thus 3,5-position, R
1for the diamines of the formula (1) of hydrogen.
The position of substitution of < amino is 3,5-position, R
1for the compound > of methyl
Make commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative and iodomethane reaction, obtain 4-methylamino-2,2,6,6-tetramethyl piperidine derivative.The position of substitution according to amino is 3,5-position, R
1for the synthesis of the compound of hydrogen carry out after reaction, obtaining amino the position of substitution is thus 3,5-position, R
1for the diamines represented by the formula (1) of methyl.
The position of substitution of < amino is 2,5-position, R
1for the compound > of hydrogen
The bromo-5-nitrobenzoic acid of commercially available 2-and thionyl chloride is made to react and obtain 2-bromo-5-oil of mirbane acyl chlorides.Under the existence of the alkali such as triethylamine, make the 2-of acquisition bromo-5-oil of mirbane acyl chlorides and commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivatives reaction, and obtain acid amides body.Buchwald (Buchwald) is utilized to react the compound obtaining the bromine replacing described acid amides body with benzophenone imine.Change benzophenone imine position into amino with acid such as hydrochloric acid, then under the existence of palladium-carbon catalyst, carry out the reduction of nitro under hydrogen environment, obtaining amino the position of substitution is thus 2,5-positions, R
1for the diamines represented by the formula (1) of hydrogen.
The position of substitution of < amino is 2,5-position, R
1for the compound > of methyl
Make commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative and iodomethane reaction, obtain 4-methylamino-2,2,6,6-tetramethyl piperidine derivative.The position of substitution according to amino is 2,5-position, R
1for the synthesis of the compound of hydrogen carry out after reaction, obtaining amino the position of substitution is thus 2,5-position, R
1for the diamines represented by the formula (1) of methyl.
Polyamic acid of the present invention and derivative thereof are described.
Polyamic acid of the present invention and derivative thereof are tetracarboxylic dianhydride and the reaction product of the diamines containing the diamines represented by formula (1).The derivative of described polyamic acid refers to the composition be dissolved in when making the liquid crystal aligning agent described later containing solvent in solvent, and refer to when this liquid crystal aligning agent is made liquid crystal orientation film, the composition of the liquid crystal orientation film being principal constituent can be formed with polyimide.As the derivative of this kind of polyamic acid, include, for example soluble polyimide, poly amic acid ester, and polyamic acid acid amides etc., more specifically, can enumerate: 1) all amino of polyamic acid and carboxyl carry out the polyimide that dehydration closed-loop reacts, 2) the part polyimide of dehydration closed-loop reaction is partly carried out, 3) carboxyl of polyamic acid is transformed into the poly amic acid ester of ester, 4) part for acid dianhydride contained in tetracarboxylic dianhydride's compound is replaced to organic dicarboxylic acid and the polyamic acid-polyamide copolymer carrying out reacting and obtain, and 5) make this polyamic acid-polyamide copolymer part or all carry out the polyamidoimide of dehydration closed-loop reaction.Described polyamic acid and derivative thereof can be a kind of compound, also can be two or more.As long as and described polyamic acid and derivative thereof are for having the compound of the structure of the reaction product of tetracarboxylic dianhydride and diamines, other raw materials also can be used and containing other reaction product of reacting beyond the reaction of tetracarboxylic dianhydride and diamines.
Tetracarboxylic dianhydride for the manufacture of polyamic acid of the present invention and derivative thereof is described.
The tetracarboxylic dianhydride used in the present invention can unrestrictedly select from known tetracarboxylic dianhydride.This kind of tetracarboxylic dianhydride can be the tetracarboxylic dianhydride in the arbitrary group belonging to the fragrant family of the direct bond of dicarboxylic anhydride on aromatic nucleus (comprising assorted aromatic ring) and the not direct fatty family of bond on aromatic nucleus (comprising heterocycle system) of dicarboxylic anhydride.
As the suitable example of this kind of tetracarboxylic dianhydride, with regard to the viewpoint of the easiness when easiness obtained with regard to raw material or polymer polymerizing, the electrical characteristic of film, the tetracarboxylic dianhydride represented by formula (AN-I) ~ formula (AN-VII) can be enumerated.
In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently singly-bound or-CH
2-.In formula (AN-II), G is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-.In formula (AN-II) ~ formula (AN-IV), Y is independent of being selected from a kind in the group of the base of following trivalent, and bond key and arbitrary carbon link, and at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl.
In formula (AN-III) ~ formula (AN-V), ring A
10for the base of carbon number to be the base of the monocyclic hydrocarbon of 3 ~ 10 or carbon number the be condensation polycyclic formula hydrocarbon of 6 ~ 30, at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl, the associative key be connected on ring links with the arbitrary carbon forming ring, and 2 associative keys can link with same carbon.In formula (AN-VI), X
10for carbon number is the alkylidene group of 2 ~ 6, Me represents methyl, and Ph represents phenyl.In formula (AN-VII), G
10independent is-O-,-COO-or-OCO-, and r is independently 0 or 1.
More specifically, the tetracarboxylic dianhydride represented by the formula of following formula (AN-1) ~ formula (AN-16-14) can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-1)]
In formula (AN-1), G
11for alkylidene group, Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene that singly-bound, carbon number are 1 ~ 12.X
11independent is singly-bound or-CH
2-.G
12independent is any one of the base of following trivalent.
Work as G
12during for > CH-, the hydrogen of > CH-can by-CH
3replace.Work as G
12during for > N-, G
11be not singly-bound and-CH
2-, X
11it is not singly-bound.And, R
11for hydrogen or-CH
3.
As the example of the tetracarboxylic dianhydride represented by formula (AN-1), the compound represented by following formula can be enumerated.
In formula (AN-1-2) and formula (AN-1-14), m is the integer of 1 ~ 12.
[tetracarboxylic dianhydride represented by formula (AN-2)]
In formula (AN-2), R
12independent is hydrogen ,-CH
3,-CH
2cH
3or phenyl.
As the example of the tetracarboxylic dianhydride represented by formula (AN-2), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-3)]
In formula (AN-3), ring A
11for cyclohexane ring or phenyl ring.
As the example of the tetracarboxylic dianhydride represented by formula (AN-3), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-4)]
In formula (AN-4), G
13for singly-bound ,-(CH
2)
m-,-O-,-S-,-C (CH
3)
2-,-SO
2-,-CO-,-C (CF
3)
2-or the base of divalence represented by following formula (G13-1), m is the integer of 1 ~ 12.Ring A
11be independently cyclohexane ring or phenyl ring.G
13ring A can be binding on
11arbitrary position.
In formula (G13-1), G
13aand G
13bit is independently the base of singly-bound ,-O-or the divalence represented by-NHCO-.Preferred Isosorbide-5-Nitrae-the phenylene of phenylene and 1,3-phenylene.
As the example of the tetracarboxylic dianhydride represented by formula (AN-4), the compound represented by following formula can be enumerated.
In formula (AN-4-17), m is the integer of 1 ~ 12.
[tetracarboxylic dianhydride represented by formula (AN-5)]
In formula (AN-5), R
11for hydrogen or-CH
3.Binding site is not fixed on the R on the carbon atom forming phenyl ring
11represent that the binding site in phenyl ring is any.
As the example of the tetracarboxylic dianhydride represented by formula (AN-5), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-6)]
In formula (AN-6), X
11independent is singly-bound or-CH
2-.X
12for-CH
2-,-CH
2cH
2-or-CH=CH-.N is 1 or 2.As the example of the tetracarboxylic dianhydride represented by formula (AN-6), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-7)]
In formula (AN-7), X
11for singly-bound or-CH
2-.
As the example of the tetracarboxylic dianhydride represented by formula (AN-7), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-8)]
In formula (AN-8), X
11for singly-bound or-CH
2-.R
12for hydrogen ,-CH
3,-CH
2cH
3or phenyl, ring A
12for cyclohexane ring or cyclohexene ring.
As the example of the tetracarboxylic dianhydride represented by formula (AN-8), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-9)]
In formula (AN-9), r is independently 0 or 1.
As the example of the tetracarboxylic dianhydride represented by formula (AN-9), the compound represented by following formula can be enumerated.
[formula (AN-10-1) and the tetracarboxylic dianhydride represented by formula (AN-10-2)]
[tetracarboxylic dianhydride represented by formula (AN-11)]
In formula (AN-11), ring A
11independent is cyclohexane ring or phenyl ring.
As the example of the tetracarboxylic dianhydride represented by formula (AN-11), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-12)]
In formula (AN-12), ring A
11be independently cyclohexane ring or phenyl ring.
As the example of the tetracarboxylic dianhydride represented by formula (AN-12), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-13)]
In formula (AN-13), X
13for carbon number is the alkylidene group of 2 ~ 6, Ph represents phenyl.
As the example of the tetracarboxylic dianhydride represented by formula (AN-13), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-14)]
In formula (AN-14), G
14independent is-O-,-COO-or-OCO-, and r is independently 0 or 1.
As the example of the tetracarboxylic dianhydride represented by formula (AN-14), the compound represented by following formula can be enumerated.
[tetracarboxylic dianhydride represented by formula (AN-15)]
In formula (AN-15), w is the integer of 1 ~ 10.
As the example of the tetracarboxylic dianhydride represented by formula (AN-15), the compound represented by following formula can be enumerated.
As the tetracarboxylic dianhydride beyond described, following compound can be enumerated.
Carry out describing to the appropriate materials improving each characteristic in described acid dianhydride.When paying attention to the orientation promoting liquid crystal, compound preferably represented by formula (AN-1), formula (AN-3) and formula (AN-4), compound particularly preferably represented by formula (AN-1-2), formula (AN-1-13), formula (AN-3-2), formula (AN-4-17) and formula (AN-4-29), wherein in formula (AN-1-2), preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
When paying attention to the transmitance promoting liquid crystal display device, in described acid dianhydride, compound preferably represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and formula (AN-16-4), wherein in formula (AN-1-2), preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
Paying attention to the voltage retention (voltageholdingratio promoting liquid crystal display device, VHR) when, in described acid dianhydride, preferably by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-3), and the compound represented by formula (AN-16-4), wherein in formula (AN-1-2), preferred m=4 or 8, in formula (AN-4-17), preferred m=4, or 8, particularly preferably m=8.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (remnant dc electricity (DirectCurrent, DC)) in alignment films is improved.When paying attention to this object, in described acid dianhydride, the compound preferably represented by formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3).
Be described for the manufacture of the diamines of polyamic acid of the present invention and derivative thereof and two hydrazides.When manufacturing polyamic acid or derivatives thereof of the present invention, unrestrictedly diamines and two hydrazides can be selected from known diamines and two hydrazides.
Diamines can be divided into 2 kinds according to its structure.That is, have the diamines of side chain radical and do not have the diamines of side chain radical, described side chain radical is when regarding skeleton amino for link 2 as main chain, the base of branch from main chain.This side chain radical is the base with the effect increasing tilt angle.The side chain radical with this kind of effect must to be carbon number be more than 3 base, as concrete example, can enumerate: the alkoxyl group that the alkyl that carbon number is more than 3, carbon number are more than 3, carbon number are the alkoxyalkyl of more than 3 and have the base of steroid skeleton.There is the ring of more than 1 and the ring of its end have carbon number be more than 1 alkyl, carbon number be more than 1 alkoxyl group and carbon number be the effect that the base of any one alternatively base of the alkoxyalkyl of more than 2 also has as side chain radical.In the following description, sometimes the diamines with this kind of side chain radical is called side chain type diamines.And, sometimes the diamines without this kind of side chain radical is called non-side chain type diamines.
Use by non-side chain type diamines is suitably separated with side chain type diamines, may correspond in tilt angle required separately.Side chain type diamines preferably comes with the degree of harmless characteristic of the present invention and uses.In addition, about side chain type diamines and non-side chain type diamines, preferably carry out choice selection to use for for the purpose of the vertical orientated property of liquid crystal, voltage retention, burning trace characteristic and orientation to promote.
Non-side chain type diamines is described.As the known diamines without side chain, the diamines of following formula (DI-1) ~ formula (DI-16) can be enumerated.
In described formula (DI-1), G
20for-CH
2-, at least one-CH
2-can be replaced by-NH-,-O-, m is the integer of 1 ~ 12, and at least one hydrogen of alkylidene group can be replaced by-OH.In formula (DI-3) and formula (DI-5) ~ formula (DI-7), G
21independent is singly-bound ,-NH-,-NCH
3-,-O-,-S-,-S-S-,-SO
2-,-CO-,-COO-,-CONCH
3-,-CONH-,-C (CH
3)
2-,-C (CF
3)
2-,-(CH
2)
m-,-O-(CH
2)
m-O-,-N (CH
3)-(CH
2)
k-N (CH
3)-,-(O-C
2h
4)
m-O-,-O-CH
2-C (CF
3)
2-CH
2-O-,-O-CO-(CH
2)
m-CO-O-,-CO-O-(CH
2)
m-O-CO-,-(CH
2)
m-NH-(CH
2)
m-,-CO-(CH
2)
k-NH-(CH
2)
k-,-(NH-(CH
2)
m)
k-NH-,-CO-C
3h
6-(NH-C
3h
6)
n-CO-or-S-(CH
2)
m-S-, m are independently the integer of 1 ~ 12, and k is the integer of 1 ~ 5, and n is 1 or 2.In formula (DI-4), s is independently the integer of 0 ~ 2.In formula (DI-6) and formula (DI-7), G
22independent is singly-bound ,-O-,-S-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-or carbon number be the alkylidene group of 1 ~ 10.Cyclohexane ring in formula (DI-2) ~ formula (DI-7) and at least one hydrogen of phenyl ring can be the alkyl ,-OCH of 1 ~ 3 by-F ,-Cl, carbon number
3,-OH ,-CF
3,-CO
2h ,-CONH
2,-NHC
6h
5, phenyl or benzyl replace, in addition, in formula (DI-4), at least one hydrogen of cyclohexane ring and phenyl ring can by a replacement in the group of the base be selected from represented by following formula (DI-4-a) ~ formula (DI-4-e).The binding site of basis representation on this ring that binding site is not fixed on the carbon atom forming ring is any.And ,-NH
2binding site on cyclohexane ring or phenyl ring is for removing G
21or G
22binding site beyond arbitrary position.
In formula (DI-4-a) and formula (DI-4-b), R
20independent is hydrogen or-CH
3.
In formula (DI-11), r is 0 or 1.In formula (DI-8) ~ formula (DI-11) ,-NH of bond on ring
2binding site be arbitrary position.
In formula (DI-12), R
21and R
22independently for carbon number is the alkyl or phenyl of 1 ~ 3, G
23independent for carbon number be 1 ~ 6 alkylidene group, phenylene or the phenylene through alkyl replacement, w is the integer of 1 ~ 10.In formula (DI-13), R
23independent for carbon number be 1 ~ 5 alkyl, carbon number be 1 ~ 5 alkoxyl group or-Cl, p be independently 0 ~ 3 integer, q is the integer of 0 ~ 4.In formula (DI-14), ring B is the hetero ring type aromatic series base of monocycle, R
24for alkyl, alkoxyl group, vinyl, alkynyl that hydrogen ,-F ,-Cl, carbon number are 1 ~ 6, q is independently the integer of 0 ~ 4.In formula (DI-15), ring C is hetero ring type aromatic series base or hetero ring type fatty group.In formula (DI-16), G
24for alkylidene group or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2 ~ 6, r is 0 or 1.And the binding site of basis representation on this ring that binding site is not fixed on the carbon atom forming ring is any.In formula (DI-13) ~ formula (DI-16) ,-NH of bond on ring
2binding site be arbitrary position.
As the diamines without side chain of described formula (DI-1) ~ formula (DI-16), the concrete example of following formula (DI-1-1) ~ formula (DI-16-1) can be enumerated.
Below represent the example of the diamines represented by formula (DI-1).
In formula (DI-1-7) and formula (DI-1-8), k is independently the integer of 1 ~ 3.
Below represent the example of the diamines represented by formula (DI-2) ~ formula (DI-3).
Below represent the example of the diamines represented by formula (DI-4).
Below represent the example of the diamines represented by formula (DI-5).
In formula (DI-5-1), m is the integer of 1 ~ 12.
In formula (DI-5-12) and formula (DI-5-13), m is the integer of 1 ~ 12.
In formula (DI-5-16), v is the integer of 1 ~ 6.
In formula (DI-5-30), k is the integer of 1 ~ 5.
In formula (DI-5-35) ~ formula (DI-5-37) and formula (DI-5-39), m is the integer of 1 ~ 12, in formula (DI-5-38) and formula (DI-5-39), k is the integer of 1 ~ 5, in formula (DI-5-40), n is the integer of 1 or 2.
Below represent the example of the diamines represented by formula (DI-6).
Below represent the example of the diamines represented by formula (DI-7).
In formula (DI-7-3) and formula (DI-7-4), m is the integer of 1 ~ 12, and n is independently 1 or 2.
Below represent the example of the diamines represented by formula (DI-8).
Below represent the example of the diamines represented by formula (DI-9).
Below represent the example of the diamines represented by formula (DI-10).
Below represent the example of the diamines represented by formula (DI-11).
Below represent the example of the diamines represented by formula (DI-12).
Below represent the example of the diamines represented by formula (DI-13).
Below represent the example of the diamines represented by formula (DI-14).
Below represent the example of the diamines represented by formula (DI-15).
Below represent the example of the diamines represented by formula (DI-16).
Two hydrazides are described.As known two hydrazides without side chain, following formula (DIH-1) ~ formula (DIH-3) can be enumerated.
In formula (DIH-1), G
25for singly-bound, carbon number are alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-.
In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl.In formula (DIH-3), ring E is independently cyclohexane ring or phenyl ring, and at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl, and Y is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-.In formula (DIH-2) and formula (DIH-3) ,-CONHNH of bond on ring
2binding site be arbitrary position.
The example of following expression (DIH-1) ~ formula (DIH-3).
In formula (DIH-1-2), m is the integer of 1 ~ 12.
This kind of non-side chain type diamines and two hydrazides have the effect making the ion density reduction etc. of liquid crystal display device improve electrical characteristic.When using non-side chain type diamines and/or two hydrazides as diamines in order to be manufactured on the polyamic acid or derivatives thereof used in liquid crystal aligning agent of the present invention, its preferably shared in the total amount of diamines and two hydrazides ratio is set to 0mol% (molar percentage) ~ 90mol%, is more preferably set to 0mol% ~ 50mol%
Side chain type diamines is described.As the side chain radical of side chain type diamines, following base can be enumerated.
As side chain radical, first can enumerate: alkyl, alkoxyl group, alkoxyalkyl, alkyl-carbonyl, alkyl carbonyl oxy, alkoxy carbonyl, alkyl amino-carbonyl, thiazolinyl, alkene oxygen base, alkenyl carbonyl, thiazolinyl carbonyl oxygen base, allyloxycarbonyl, alkenyl amino carbonyl, alkynyl, alkynyloxy group, alkynylcarbonyl groups, alkynyl carbonyl oxygen base, alkynyloxycar bonyl, alkynylaminocarbonyl etc.Alkyl in these bases, thiazolinyl and alkynyl to be all carbon numbers be more than 3 base.But, in alkoxyalkyl, as long as the carbon number of whole base is more than 3.These bases can be straight-chain, also can be branched.
Secondly, with the ring of end, there is the alkyl that carbon number is more than 1, carbon number be more than 1 alkoxyl group or carbon number be more than 2 alkoxyalkyl alternatively base be condition, can enumerate: phenyl, phenylalkyl, phenyl alkoxyl group, phenoxy group, phenylcarbonyl group, phenyl carbonyl oxygen base, phenyloxycarbonyl, phenyl amino carbonyl, benzyl ring hexyloxy, carbon number is the cycloalkyl of more than 3, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxy carbonyl, cyclohexyl phenyl, cyclohexyl phenyl alkyl, cyclohexyl phenoxy group, two (cyclohexyl) oxygen base, two (cyclohexyl) alkyl, two (cyclohexyl) phenyl, two (cyclohexyl) phenylalkyl, two (cyclohexyl) oxygen base carbonyl, two (cyclohexyl) phenyloxycarbonyl, and the base of the ring structure such as two (phenyl) oxygen base carbonyls of cyclohexyl.
And then, the ring set base that can be listed below, it is the base of more than the base of the phenyl ring with more than 2, the base with the cyclohexane ring of more than 2 or 2 rings comprising phenyl ring and cyclohexane ring, and bond base is independently for singly-bound ,-O-,-COO-,-OCO-,-CONH-or carbon number are the alkylidene group of 1 ~ 3, the ring of end have carbon number be more than 1 alkyl, carbon number be more than 1 fluorine substituted alkyl, carbon number be more than 1 alkoxyl group or carbon number be more than 2 alkoxyalkyl alternatively base.The base with steroid skeleton is also effective as side chain radical.
As the diamines with side chain, the compound represented by following formula (DI-31) ~ formula (DI-35) can be enumerated.
In formula (DI-31), G
26for singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-or-(CH
2)
m'-, m' is the integer of 1 ~ 12.G
26preferred example be singly-bound ,-O-,-COO-,-OCO-,-CH
2o-and carbon number are the alkylidene group of 1 ~ 3, and example is particularly preferably singly-bound ,-O-,-COO-,-OCO-,-CH
2o-,-CH
2-and-CH
2cH
2-.R
25for carbon number be 3 ~ 30 alkyl, phenyl, there is the base of steroid skeleton or the base represented by following formula (DI-31-a).In this alkyl, at least one hydrogen can be replaced by-F, and at least one-CH
2-can be replaced by-O-,-CH=CH-or-C ≡ C-.The hydrogen of this phenyl can by-F ,-CH
3,-OCH
3,-OCH
2f ,-OCHF
2,-OCF
3, carbon number be 3 ~ 30 alkyl or carbon number be 3 ~ 30 alkoxyl group replace.-the NH of bond on phenyl ring
2binding site represent for arbitrary position in this ring, this binding site preferably between position or contraposition.That is, when by base " R
25-G
26-" binding site when being set to 1,2 binding site preferably 3 with 5 or 2 with 5.
In formula (DI-31-a), G
27, G
28and G
29for bond base, they are independently singly-bound or carbon number is the alkylidene group of 1 ~ 12, the more than one-CH of this alkylidene group
2-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-.Ring B
21, ring B
22, ring B
23and ring B
24independent is Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, ring B
21, ring B
22, ring B
23and ring B
24in, at least one hydrogen can by-F or-CH
3replace, s, t and u are independently the integer of 0 ~ 2, they add up to 1 ~ 5, when s, t or u are 2,2 bond bases in each bracket can be identical, also can be different, and 2 rings can be identical, also can be different.R
26for hydrogen ,-F ,-OH, the carbon number alkyl that is 1 ~ 30, the carbon number fluorine substituted alkyl that is 1 ~ 30, carbon number are alkoxyl group ,-the CN ,-OCH of 1 ~ 30
2f ,-OCHF
2or-OCF
3, this carbon number is at least one-CH of the alkyl of 1 ~ 30
2-can replace by with the base of the divalence represented by following formula (DI-31-b).
In formula (DI-31-b), R
27and R
28independently for carbon number is the alkyl of 1 ~ 3, v is the integer of 1 ~ 6.R
26preferred example to be carbon number be 1 ~ 30 alkyl and carbon number be the alkoxyl group of 1 ~ 30.
In formula (DI-32) and formula (DI-33), G
30independent is singly-bound ,-CO-or-CH
2-, R
29independent is hydrogen or-CH
3, R
30for hydrogen, carbon number be 1 ~ 20 alkyl or carbon number be the thiazolinyl of 2 ~ 20.The alkyl or phenyl that at least one hydrogen of phenyl ring in formula (DI-33) can be 1 ~ 20 by carbon number replaces.And the binding site of basis representation in this ring that binding site is not fixed on any one carbon atom forming ring is any.2 base "-phenylene-G in preferred formula (DI-32)
30-O-" a bond 3 of steroid core, another bond is at 6 of steroid core.2 base "-phenylene-G in formula (DI-33)
30-O-" binding site on phenyl ring preferably relative to the binding site of steroid core, position or contraposition between being respectively.In formula (DI-32) and formula (DI-33) ,-NH of bond on phenyl ring
2represent that the binding site in this ring is any.
In formula (DI-34) and formula (DI-35), G
31independently for-O-or carbon number are the alkylidene group of 1 ~ 6, G
32for singly-bound or carbon number are the alkylidene group of 1 ~ 3.R
31for at least one-CH that hydrogen or carbon number are the alkyl of 1 ~ 20, this alkyl
2-can be replaced by-O-,-CH=CH-or-C ≡ C-.R
32for carbon number is the alkyl of 6 ~ 22, R
33for hydrogen or carbon number are the alkyl of 1 ~ 22.Ring B
25for Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1.And ,-the NH of bond on phenyl ring
2represent that binding site on this ring be arbitrarily, but preferred independence and relative to G
31binding site be between position or contraposition.
The concrete example of following Exemplary sidechain type diamines.As the diamines with side chain of described formula (DI-31) ~ formula (DI-35), the compound represented by following formula (DI-31-1) ~ formula (DI-35-3) can be enumerated.
Below represent the example of the compound represented by formula (DI-31).
In formula (DI-31-1) ~ formula (DI-31-11), R
34for carbon number be 1 ~ 30 alkyl or carbon number be the alkoxyl group of 1 ~ 30, preferred carbon number be 5 ~ 25 alkyl or carbon number be the alkoxyl group of 5 ~ 25.R
35for carbon number be 1 ~ 30 alkyl or carbon number be the alkoxyl group of 1 ~ 30, preferred carbon number be 3 ~ 25 alkyl or carbon number be the alkoxyl group of 3 ~ 25.
In formula (DI-31-12) ~ formula (DI-31-17), R
36for carbon number is the alkyl of 4 ~ 30, preferred carbon number is the alkyl of 6 ~ 25.R
37for carbon number is the alkyl of 6 ~ 30, preferred carbon number is the alkyl of 8 ~ 25.
In formula (DI-31-18) ~ formula (DI-31-43), R
38for carbon number be 1 ~ 20 alkyl or carbon number be the alkoxyl group of 1 ~ 20, preferred carbon number be 3 ~ 20 alkyl or carbon number be the alkoxyl group of 3 ~ 20.R
39the alkyl, the carbon number that are 1 ~ 30 for hydrogen ,-F, carbon number are alkoxyl group ,-the CN ,-OCH of 1 ~ 30
2f ,-OCHF
2or-OCF
3, preferred carbon number be 3 ~ 25 alkyl or carbon number be the alkoxyl group of 3 ~ 25.And, G
33for carbon number is the alkylidene group of 1 ~ 20.
Below represent the example of the compound represented by formula (DI-32).
Below represent the example of the compound represented by formula (DI-33).
Below represent the example of the compound represented by formula (DI-34).
In formula (DI-34-1) ~ formula (DI-34-12), R
40for hydrogen or carbon number are the alkyl of 1 ~ 20, preferred hydrogen or carbon number are the alkyl of 1 ~ 10, and, R
41for hydrogen or carbon number are the alkyl of 1 ~ 12.
Below represent the example of the compound represented by formula (DI-35).
In formula (DI-35-1) ~ formula (DI-35-3), R
37for carbon number is the alkyl of 6 ~ 30, R
41for hydrogen or carbon number are the alkyl of 1 ~ 12.
As the diamines in the present invention, the diamines beyond the diamines represented by formula (DI-1-1) ~ formula (DI-16-1), formula (DIH-1-1) ~ formula (DIH-3-6) and formula (DI-31-1) ~ formula (DI-35-3) also can be used.As this kind of diamines, include, for example the compound represented by following formula (DI-36-1) ~ formula (DI-36-13).
In formula (DI-36-1) ~ formula (DI-36-8), R
42separately represent that carbon number is the alkyl of 3 ~ 30.
In formula (DI-36-9) ~ formula (DI-36-11), e is the integer of 2 ~ 10, in formula (DI-36-12), and R
43be independently hydrogen ,-NHBoc or-N (Boc)
2, R
43at least one be-NHBoc or-N (Boc)
2, in formula (DI-36-13), R
44for-NHBoc or-N (Boc)
2, and m is the integer of 1 ~ 12.Herein, Boc is tert-butoxycarbonyl.
When paying attention to the orientation promoting liquid crystal further, in described diamines and two hydrazides, preferred use is by formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3), and the diamines represented by formula (DI-11-2), wherein in formula (DI-5-1), preferred m=2, 4 or 6, particularly preferably m=4, in formula (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in formula (DI-5-13), preferred m=1, or 2, particularly preferably m=1.
When paying attention to promoting transmitance, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), formula (DI-5-24) and formula (DI-7-3), the diamines particularly preferably represented by formula (DI-2-1).In formula (DI-5-1), preferred m=2,4 or 6, particularly preferably m=4, in formula (DI-7-3), preferred m=2 or 3, n=1 or 2, particularly preferably m=1.
When paying attention to the VHR promoting liquid crystal display device, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1), the diamines particularly preferably represented by formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1).Wherein in formula (DI-5-1), particularly preferably m=1, in formula (DI-5-30), particularly preferably k=2.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28) and formula (DI-16-1), the diamines particularly preferably represented by formula (DI-4-1), formula (DI-5-1) and formula (DI-5-13).Wherein in formula (DI-5-1), preferred m=2,4 or 6, particularly preferably m=4, in formula (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in formula (DI-5-13), preferred m=1 or 2, particularly preferably m=1.
In each diamines, also in the scope that the ratio of the monoamine relative to diamines is below 40mol%, a part for diamines can be replaced to monoamine.This kind of replacement can cause the termination of polyreaction when generating polyamic acid, can suppress further carrying out of polyreaction.Therefore, replaced by this kind, easily can control the molecular weight of obtained polymkeric substance (polyamic acid or derivatives thereof), such as, can can't harm effect of the present invention and improve the coating characteristics of liquid crystal aligning agent.As long as harmless effect of the present invention, then the diamines being replaced to monoamine can be a kind of, also can be two or more.As described monoamine, include, for example: aniline, 4-hydroxyanilines, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, hexadecylamine, positive heptadecyl-amine, octadecyl amine and positive 20 amine.
Polyamic acid or derivatives thereof of the present invention can in monomer whose and then containing monoisocyanate compound.By containing monoisocyanate compound in monomer, the end of the polyamic acid or derivatives thereof obtained is modified, and molecular weight is adjusted.By using the polyamic acid or derivatives thereof of this end modified type, such as, can can't harm effect of the present invention and improve the coating characteristics of liquid crystal aligning agent.With regard to described viewpoint, relative to the total amount of the diamines in monomer and tetracarboxylic dianhydride, the preferred 1mol% ~ 10mol% of content of the monoisocyanate compound in monomer.As described monoisocyanate compound, include, for example: phenylcarbimide and naphthyl isocyanate.
Polyamic acid of the present invention and derivative thereof obtain by making the mixture of described acid anhydrides and diamines carry out in a solvent reacting.In this building-up reactions, except the selection of raw material, without the need to special condition, the condition in the synthesis of common polyamic acid directly can be applied.The solvent used is by aftermentioned.
Other compositions that liquid crystal aligning agent of the present invention can and then contain beyond polyamic acid or derivatives thereof.Other compositions can be a kind, also can be two or more.As other compositions, include, for example other polymkeric substance or compounds etc. described later.
Other polymkeric substance that liquid crystal aligning agent of the present invention can and then contain beyond polyamic acid or derivatives thereof of the present invention.As other polymkeric substance, can enumerate: make tetracarboxylic dianhydride and the diamines that comprises diamines of the present invention carry out reacting and polymkeric substance beyond the polyamic acid or derivatives thereof that obtains, namely, make tetracarboxylic dianhydride and do not carry out reacting containing the diamines of diamines of the present invention and the polyamic acid or derivatives thereof that obtains is (following, be called " other polyamic acid or derivatives thereofs "), polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.Can be a kind, also can be two or more.In these polymkeric substance, preferably other polyamic acid or derivatives thereof and polysiloxane, more preferably other polyamic acid or derivatives thereofs.
By in the alignment agent of polyamic acid or derivatives thereof of the present invention and other polyamic acid or derivatives thereof fusion, control structure or the molecular weight of each polymkeric substance, then as described later, be coated on substrate, and carry out predrying, polyamic acid or derivatives thereof composition [A] of the present invention can be separated into upper strata thus, other polyamic acid or derivatives thereof compositions [B] are separated into lower floor.It is by utilizing following phenomenon to control: in the polymkeric substance that mixing exists, the polymkeric substance that surface energy is little is separated into upper strata, and the polymkeric substance that surface energy is large is separated into lower floor.Layer is separated approves that the surface energy passing through formed alignment films is that the value identical or close with the surface energy of the film formed by the liquid crystal aligning agent only containing [A] composition confirms really.
As the tetracarboxylic dianhydride for the synthesis of other polyamic acid or derivatives thereofs, unrestrictedly can select from as the synthesis of the required composition of liquid crystal aligning agent of the present invention and the known tetracarboxylic dianhydride of the tetracarboxylic dianhydride of polyamic acid or derivatives thereof, can enumerate identical with described illustrative tetracarboxylic dianhydride.
Wherein, in described acid dianhydride, under attention promotes layer situation separatory, preferred formula (AN-3-2), formula (AN-1-13) and formula (AN-4-30).
When paying attention to the transmitance promoting liquid crystal display device, in described acid dianhydride, preferably by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-10-2), formula (AN-16-3), and the compound represented by formula (AN-16-4), wherein, in formula (AN-1-2), preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
When paying attention to the VHR promoting liquid crystal display device, in described acid dianhydride, compound preferably represented by formula (AN-1-2), formula (AN-2-1), formula (AN-7-2), formula (AN-10-1), formula (AN-10-2), formula (AN-16-3) and formula (AN-16-4), wherein, in formula (AN-1-2), preferred m=4 or 8.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, in described acid dianhydride, the compound preferably represented by formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3).
As the tetracarboxylic dianhydride for the synthesis of other polyamic acid or derivatives thereofs, the aromatic tetracarboxylic acid's dianhydride preferably relative to all tetracarboxylic dianhydrides containing more than 10mol%, the aromatic tetracarboxylic acid's dianhydride more preferably containing more than 30mol%.
As for the synthesis of the diamines of other polyamic acid or derivatives thereofs and two hydrazides, can enumerate with above as the required composition and polyamic acid or derivatives thereof that can be used for synthesizing liquid crystal aligning agent of the present invention other diamines illustrated in diamines and two hydrazides identical.
Wherein, layer separation property is promoted further in attention, when the orientation of i.e. liquid crystal, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28) and formula (DIH-2-1) and two hydrazides, wherein, in formula (DI-5-1), preferred m=1,2 or 4, particularly preferably m=1 or 2.
When paying attention to promoting transmitance, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-1-2), formula (DI-2-1), formula (DI-5-1) and formula (DI-7-3), the diamines particularly preferably represented by (DI-2-1).In formula (DI-5-1), preferred m=1,2 or 4, particularly preferably m=1 or 2, in formula (DI-7-3), preferred m=2 or 3, n=1 or 2, particularly preferably m=1.
When paying attention to the VHR promoting liquid crystal display device, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1), the diamines particularly preferably represented by formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1).Wherein, in (DI-5-1), particularly preferably m=1 or 2, in (DI-5-30), particularly preferably k=2.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, in described diamines and two hydrazides, the diamines of preferred use represented by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30) and formula (DI-16-1), the diamines particularly preferably represented by formula (DI-4-1), formula (DI-5-1) and formula (DI-5-12).Wherein, in formula (DI-5-1), preferred m=1 or 2, in (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in (DI-5-13), preferred m=1 or 2, particularly preferably m=1, in (DI-5-30), particularly preferably k=2.
As the diamines for the synthesis of other polyamic acid or derivatives thereofs, the aromatic diamine preferably relative to all diamines containing more than 30mol%, the aromatic diamine more preferably containing more than 50mol%.
Other polyamic acid or derivatives thereofs can synthesize as the method described in the required composition of liquid crystal aligning agent of the present invention and the synthetic method of polyamic acid or derivatives thereof according to following respectively.
As the ratio of [A] composition relative to the total amount of polyamic acid or derivatives thereof of the present invention (described [A] composition) and other polyamic acid or derivatives thereofs (described [B] composition), preferred 10wt% (weight percent) ~ 100wt%, more preferably 20wt% ~ 100wt%.
And then Japanese Patent Laid-Open 2009-036966 can be contained, Japanese Patent Laid-Open 2010-185001, Japanese Patent Laid-Open 2011-102963, Japanese Patent Laid-Open 2011-253175, Japanese Patent Laid-Open 2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, the polysiloxane disclosed in International Publication 2012/165354 grade is as described polysiloxane.
< alkenyl substituted Na Dike imide compound >
Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can contain alkenyl substituted Na Dike imide compound further.Alkenyl substituted Na Dike imide compound can use a kind, and also two or more kinds may be used.With regard to described object, relative to polyamic acid or derivatives thereof, the preferred 1wt% ~ 100wt% of content of alkenyl substituted Na Dike imide compound, more preferably 1wt% ~ 70wt%, and then more preferably 1wt% ~ 50wt%.
Below Na Dike imide compound is specifically described.
Alkenyl substituted Na Dike imide compound preferably may be dissolved in the compound in the solvent dissolving the polyamic acid or derivatives thereof used in the present invention.The example of this kind of alkenyl substituted Na Dike imide compound can enumerate the compound represented by following formula (NA).
In formula (NA), L
1and L
2aryl or benzyl that the cycloalkyl that the thiazolinyl that the alkyl that independence is hydrogen, carbon number is 1 ~ 12, carbon number are 3 ~ 6, carbon number are 5 ~ 8, carbon number are 6 ~ 12, n is 1 or 2.
In formula (NA), as n=1, W to be carbon number be 1 ~ 12 alkyl, the carbon number thiazolinyl that is 2 ~ 6, the carbon number cycloalkyl that is 5 ~ 8, carbon number be 6 ~ 12 aryl, benzyl, by-Z
1-(O)
r-(Z
2o)
k-Z
3-H (herein, Z
1, Z
2and Z
3independent for carbon number be the alkylidene group of 2 ~ 6, r is 0 or 1, and, the integer that k is 1 ~ 30) represented by base, by-(Z
4)
r-B-Z
5-H (herein, Z
4and Z
5independent for carbon number be 1 ~ 4 alkylidene group or carbon number be the cycloalkylidene of 5 ~ 8, B is phenylene, and r is 0 or 1) represented by base, by-B-T-B-H, (herein, B is phenylene, and T is-CH
2-,-C (CH
3)
2-,-O-,-CO-,-S-or-SO
2-) represented by base or the base that replaces through-OH of 1 hydrogen ~ 3 hydrogen of these bases.
Now, preferred W to be carbon number be 1 ~ 8 alkyl, carbon number be 3 ~ 4 thiazolinyl, cyclohexyl, phenyl, benzyl, carbon number be the base that 1 hydrogen of poly-(inferior ethoxyl) ethyl, Phenoxyphenyl, phenyl methyl phenyl, phenyl isopropylidene phenyl and these bases of 4 ~ 10 or 2 hydrogen replace through-OH.
In formula (NA), as n=2, W to be carbon number be 2 ~ 20 alkylidene group, the carbon number cycloalkylidene that is 5 ~ 8, the carbon number arylidene that is 6 ~ 12, by-Z
1-O-(Z
2o)
k-Z
3-(herein, Z
1~ Z
3, and the definition of k described above) represented by base, by-Z
4-B-Z
5-(herein, Z
4, Z
5and the definition of B is described above) represented by base, by-B-(O-B)
r-T-(B-O)
r-B-(herein, B is phenylene, T to be carbon number be 1 ~ 3 alkylidene group ,-O-or-SO
2-, the definition of r is described above) represented by base or the base that replaces through-OH of 1 hydrogen ~ 3 hydrogen of these bases.
Now, preferred W to be carbon number be 2 ~ 12 alkylidene group, cyclohexylidene, phenylene, tolylene, xylylene, by-C
3h
6-O-(Z
2-O)
n-O-C
3h
6-(herein, Z
2for carbon number is the alkylidene group of 2 ~ 6, n is 1 or 2) represented by base, by-B-T-B-, (herein, B is phenylene, and T is-CH
2-,-O-or-SO
2-) represented by base, by-B-O-B-C
3h
6the base of the base represented by-B-O-B-(herein, B is phenylene) and 1 hydrogen of these bases or 2 hydrogen warp-OH replacement.
This kind of alkenyl substituted Na Dike imide compound can use such as described in Japanese Patent No. 2729565 publications, the compound obtained by alkenyl substituted carbic anhydride derivative and diamines are kept 0.5 hour ~ 20 hours to carry out synthesizing at the temperature of 80 DEG C ~ 220 DEG C or commercially available compound.As the concrete example of alkenyl substituted Na Dike imide compound, compound shown below can be enumerated.
N-methyl-allyl dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-allyl methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-(2-ethylhexyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide,
N-(2-ethylhexyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-allyl group-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-allyl group-allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Allyl-methyl allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pseudoallyl-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pseudoallyl-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pseudoallyl-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-cyclohexyl-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-cyclohexyl-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Cyclohexyl-methyl allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Phenyl-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-Phenyl-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-methyl allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-hydroxyethyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-hydroxyethyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-hydroxyethyl)-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-(2, 2-dimethyl-3-hydroxypropyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 2-dimethyl-3-hydroxypropyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 3-dihydroxypropyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 3-dihydroxypropyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyl-1-propenyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxy-cyclohexyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-(4-hydroxyphenyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxyphenyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxyphenyl)-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxyphenyl)-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyphenyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyphenyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(to hydroxybenzyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-{2-(2-hydroxyl-oxethyl) ethyl }-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl]-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl]-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl]-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxyphenyl isopropylidene) phenyl }-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxyphenyl isopropylidene) phenyl }-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxyphenyl isopropylidene) phenyl }-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, and their oligomer,
N, N'-ethylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-trimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
1, two { 3'-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxy-} ethane, 1, two { 3'-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxy-} ethane, 1, two { 3'-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxy-} ethane, two [2'-{3'-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) propoxy-} ethyl] ether, two [2'-{3'-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) propoxy-} ethyl] ether, 1, two { 3'-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide) propoxy-} butane, 1, two { 3'-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide) propoxy-} butane,
N, N'-is to phenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-{ (1-methyl)-2, 4-phenylene }-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde base-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xylylene between N'--bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xylylene between N'--bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane,
Two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone,
Two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, 1, two (allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 6-, 3-dicarboximide)-3-hydroxy-hexane, 1, two (methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 12-, 3-dicarboximide)-3, 6-dihydroxyl-dodecane, 1, two (allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 3-, 3-dicarboximide)-5-hydroxy-cyclohexan alkane, 1, two { 3'-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 5-, 3-dicarboximide) propoxy-}-3-hydroxyl-pentane, 1, two (allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide)-2-hydroxyl-benzene,
1, two (allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide)-2, 5-dihydroxyl-benzene, N, N'-is to (2-hydroxyl) xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to (2-hydroxyl) xylylene-bis-(allyl methyl ring [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, (2-hydroxyl) xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, (2-hydroxyl) xylylene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, N'-is to (2, 3-dihydroxyl) xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide)-2-Hydroxy-phenoxy } phenyl] propane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-2-hydroxy-pheny } methane, two { 3-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-4-hydroxy-pheny } ether, two { 3-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-5-hydroxy-pheny } sulfone, 1, 1, 1-tri-{ 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) } phenoxymethyl propane, N, N', N "-three (ethylidene methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) isocyanuric acid ester, and their oligomer etc.
And then the alkenyl substituted Na Dike imide compound used in the present invention can be the compound represented by following formula containing asymmetrical alkylidene group phenylene.
Below represent the preferred compound in alkenyl substituted Na Dike imide compound.
N, N'-ethylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-trimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
N, N'-is to phenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-{ (1-methyl)-2, 4-phenylene }-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde base-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xylylene between N'--bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xylylene between N'--bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), 2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane.
Two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone.
Below represent preferred alkenyl substituted Na Dike imide compound.
N, N'-ethylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-trimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide).
N, N'-is to phenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-{ (1-methyl)-2, 4-phenylene }-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde base-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xylylene between N'--bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xylylene between N'--bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide).
2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane.
And, as alkenyl substituted Na Dike imide compound particularly preferably, can enumerate: two { 4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 represented by following formula (NA-1), 3-dicarboximide) phenyl methane, N represented by formula (NA-2), xylylene between N'--bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide) and N represented by formula (NA-3), N'-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide).
< has the compound > of free-radical polymerised unsaturated double-bond
Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can further containing the compound with free-radical polymerised unsaturated double-bond.The compound with free-radical polymerised unsaturated double-bond can be a kind of compound, also can be compound of more than two kinds.Moreover, not containing alkenyl substituted Na Dike imide compound in the compound with free-radical polymerised unsaturated double-bond.With regard to described object, relative to polyamic acid or derivatives thereof, there is the preferred 1wt% ~ 100wt% of content of the compound of free-radical polymerised unsaturated double-bond, more preferably 1wt% ~ 70wt%, and then more preferably 1wt% ~ 50wt%.
Moreover, about the ratio with the compound of free-radical polymerised unsaturated double-bond relative to alkenyl substituted Na Dike imide compound, in order to reduce liquid crystal display device ion density, suppress ion density through time increase so that suppress the generation of image retention, compound/alkenyl substituted Na Dike the imide compound with free-radical polymerised unsaturated double-bond with mass ratio range preferably 0.1 ~ 10, more preferably 0.5 ~ 5.
Below the compound with free-radical polymerised unsaturated double-bond is specifically described.
As the compound with free-radical polymerised unsaturated double-bond, can enumerate: (methyl) acrylic acid derivative and two maleimides such as (methyl) acrylate, (methyl) acrylamide.The compound with free-radical polymerised unsaturated double-bond more preferably has (methyl) acrylic acid derivative of the free-radical polymerised unsaturated double-bond of more than 2.
As the concrete example of (methyl) acrylate, include, for example: (methyl) cyclohexyl acrylate, (methyl) vinylformic acid-2-methyl cyclohexyl, (methyl) vinylformic acid two ring pentyl ester, (methyl) vinylformic acid two cyclopentyloxy ethyl ester, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate and (methyl) 2-hydroxypropyl acrylate.
As the concrete example of two senses (methyl) acrylate, include, for example: ethylenebis acrylate, as sieve's Ah Knicks M-210 (AronixM-210) of the goods of East Asia synthetic chemical industry (share), AronixM-240 and AronixM-6200, as card Ya De HDDA (KAYARADHDDA) of the goods of Japanese chemical drug (share), KAYARADHX-220, KAYARADR-604 and KAYARADR-684, as the V260 of the goods of Osaka Organic Chemical Industry (share), V312 and V335HP, and the light acrylate BA-4EA (LightAcrylateBA-4EA) of goods as common prosperity society oil chemical industry (share), LightAcrylateBP-4PA and LightAcrylateBP-2PA.
As the concrete example of multifunctional (methyl) acrylate more than trifunctional, include, for example: 4, 4'-methylene-bis (N, N-dihydroxyl ethylidene acrylate aniline), as the AronixM-400 of the goods of East Asia synthetic chemical industry (share), AronixM-405, AronixM-450, AronixM-7100, AronixM-8030, AronixM-8060, as the KAYARADTMPTA of the goods of Japanese chemical drug (share), KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120, and the VGPT of goods as Osaka Organic Chemical Industry (share).
As the concrete example of (methyl) acrylamide derivative, include, for example: NIPA, N-isopropyl acrylamide, N-n-propyl acrylamide, N-n-propyl Methacrylamide, N-cyclopropyl acrylamide, N-Cvclopropvlmethvl acrylamide, N-ethoxyethyl group acrylamide, N-ethoxyethyl group Methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl Methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloylpiperidine, N-acryl tetramethyleneimine, N, N'-methylene-bisacrylamide, N, N'-ethylenebisacrylamide, N, N'-dihydroxyl ethylenebisacrylamide, N-(4-hydroxyphenyl) Methacrylamide, N-phenyl methacrylamide, N-butyl methyl acrylamide, N-(isobutoxymethyl) Methacrylamide, N-[2-(N, N-dimethylamino) ethyl] Methacrylamide, N, N-dimethylmethacryl amide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-(methoxymethyl) Methacrylamide, N-(methylol)-2-Methacrylamide, N-benzyl-2-Methacrylamide, and N, N'-methylenebismethacrylamide.
Among described (methyl) acrylic acid derivative, particularly preferably N, N'-methylene-bisacrylamide, N, N'-dihydroxyl ethylidene-bisacrylamide, ethylenebis acrylate and 4,4'-methylene-bis (N, N-dihydroxyl ethylidene acrylate aniline).
As two maleimide, include, for example: BMI-70 and BMI-80 that KI changes into (share) manufactures and large and change into BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 that industry (share) manufactures.
< oxazine compounds >
Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can Han You oxazine compounds further.Oxazine compounds can be a kind of compound, also can be compound of more than two kinds.With regard to described object, relative to the preferred 0.1wt% ~ 50wt% of content of polyamic acid or derivatives thereof ， oxazine compounds, more preferably 1wt% ~ 40wt%, and then more preferably 1wt% ~ 20wt%.
Yi Xia paroxazine compound is specifically described.
Oxazine compounds preferably to dissolve in the solvent that polyamic acid or derivatives thereof is dissolved and has ring-opening polymerization oxazine compounds.
The quantity of Ling Wai ， oxazine compounds Zhong oxazine structure is not particularly limited.
The structure of oxazine there will be a known various structure.The structure of Zhong ， oxazine of the present invention is not particularly limited in ， oxazine compounds Zhong oxazine structure, can enumerate the structure that benzoxazine or Nai Bing oxazine etc. have the aromatic series Ji oxazine containing fused-ring aromatic base.
Zuo is oxazine compounds, include, for example the compound shown in following formula (OX-1) ~ formula (OX-6).Moreover, in following formula, show that bond is at formation ring and can on bond any one carbon substituent towards the key table represented by Ring current distribution.
In formula (OX-1) ~ formula (OX-3), L
3and L
4for carbon number is the organic radical of 1 ~ 30, in formula (OX-1) ~ formula (OX-6), L
5~ L
8for hydrogen or carbon number are the alkyl of 1 ~ 6, in formula (OX-3), formula (OX-4) and formula (OX-6), Q
1for singly-bound ,-O-,-S-,-S-S-,-SO
2-,-CO-,-CONH-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-(CH
2)
v-,-O-(CH
2)
v-O-,-S-(CH
2)
v-S-, herein, v is the integer of 1 ~ 6, in formula (OX-5) and formula (OX-6), Q
2independent is singly-bound ,-O-,-S-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-or carbon number be the alkylidene group of 1 ~ 3, Q
2in phenyl ring, the hydrogen of institute's bond is independent and can by-F ,-CH on naphthalene nucleus
3,-OH ,-COOH ,-SO
3h ,-PO
3h
2replace.
Ling Wai ， oxazine compounds comprises oligomer or the polymkeric substance of Ju You oxazine structure in the oligomer of Ju You oxazine structure on side chain or polymkeric substance, main chain.
As oxazine compounds represented by formula (OX-1), include, for example oxazine compounds Xia Yi.
In formula (OX-1-2), L
3preferred carbon number is the alkyl of 1 ~ 30, and more preferably carbon number is the alkyl of 1 ~ 20.
As oxazine compounds represented by formula (OX-2), include, for example oxazine compounds Xia Yi.
In formula, L
3preferred carbon number is the alkyl of 1 ~ 30, and more preferably carbon number is the alkyl of 1 ~ 20.
As oxazine compounds represented by formula (OX-3), oxazine compounds represented by following formula (OX-3-I) can be enumerated.
In formula (OX-3-I), L
3and L
4for carbon number is the organic radical of 1 ~ 30, L
5~ L
8for hydrogen or carbon number are the alkyl of 1 ~ 6, Q
1for singly-bound ,-CH
2-,-C (CH
3)
2-,-CO-,-O-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-.As oxazine compounds represented by formula (OX-3-I), include, for example oxazine compounds Xia Yi.
In formula, L
3and L
4preferred carbon number is the alkyl of 1 ~ 30, and more preferably carbon number is the alkyl of 1 ~ 20.
As oxazine compounds represented by formula (OX-4), include, for example oxazine compounds Xia Yi.
As oxazine compounds represented by formula (OX-5), include, for example oxazine compounds Xia Yi.
As oxazine compounds represented by formula (OX-6), include, for example oxazine compounds Xia Yi.
Among these, more preferably can enumerate oxazine compounds represented by formula (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3-7), formula (OX-3-9), formula (OX-4-1) ~ formula (OX-4-6), formula (OX-5-3), formula (OX-5-4) and formula (OX-6-2) ~ formula (OX-6-4).
Oxazine compounds manufactures by the method identical with method described in International Publication 2004/009708, Japanese Patent Laid-Open 11-12258, Japanese Patent Laid-Open 2004-352670.
Represented by formula (OX-1), oxazine compounds obtains by making phenolic compound and primary amine and aldehyde carry out reacting (with reference to International Publication 2004/009708).
Oxazine compounds represented by formula (OX-2) is by such as under type acquisition: after being reacted by the method for adding primary amine in formaldehyde lentamente, adds the compound with naphthols system hydroxyl and carries out reacting (with reference to International Publication 2004/009708).
Oxazine compounds represented by formula (OX-3) obtains by such as under type: under the existence of secondary fatty race amine, three grades of fatty amines or alkaline nitrogen-containing heterocycle compound, make phenolic compound 1 mole, be at least the aldehyde of more than 2 moles relative to 1 phenolic hydroxyl group of this phenolic compound and the primary amine of 1 mole carries out reacting (reference International Publication 2004/009708 and Japanese Patent Laid-Open 11-12258) in organic solvent.
Oxazine compounds represented by formula (OX-4) ~ formula (OX-6) is by such as under type acquisition: at the temperature more than 90 DEG C, make 4,4'-diaminodiphenyl-methane etc. have multiple phenyl ring and in propyl carbinol, carry out dehydration condensation (with reference to Japanese Patent Laid-Open 2004-352670) with the aldehyde such as diamines, formaldehyde of the organic radical of these phenyl ring bonds and phenol.
< oxazoline compound >
Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can Han You oxazoline compound further.Oxazoline compound is the compound of Ju You oxazoline structure.Oxazoline compound can be a kind of compound, also can be compound of more than two kinds.With regard to described object, relative to the preferred 0.1wt% ~ 50wt% of content of polyamic acid or derivatives thereof ， oxazoline compound, more preferably 1wt% ~ 40wt%, and then more preferably 1wt% ~ 20wt%.Or, when Jiang oxazoline compound Zhong oxazoline structure Huan Suan oxazoline, with regard to described object, relative to the preferred 0.1wt% ~ 40wt% of content of polyamic acid or derivatives thereof ， oxazoline compound.
Yi Xia Dui oxazoline compound is specifically described.
Oxazoline compound only can have 1 Zhong oxazoline structure in a kind of compound, also can have two or more.As long as Ling Wai ， oxazoline compound has 1 Ge oxazoline structure in a kind of compound, but preferably has more than 2.Ling Wai ， oxazoline compound can be the polymkeric substance of Ju You oxazoline structure on side chain, also can be multipolymer.On side chain, the polymkeric substance of Ju You oxazoline structure can be the homopolymer of the monomer of Ju You oxazoline structure on side chain, also can be the multipolymer of the monomer of Ju You oxazoline structure on side chain and the monomer of Bu Ju You oxazoline structure.On side chain, the multipolymer of Ju You oxazoline structure can be the multipolymer of the monomer of more than two kinds of Ju You oxazoline structure on side chain, also can be the multipolymer of the monomer of more than two kinds of Ju You oxazoline structure on side chain and the monomer of Bu Ju You oxazoline structure.
The carbonyl of one or two and polyamic acid of the oxygen in oxazoline structure optimization Yi oxazoline structure and nitrogen can carry out the structure in the mode Cun Yu oxazoline compound reacted.
Zuo is oxazoline compound, include, for example: 2, 2'-two (2-oxazoline), 1, 2, 4-tri--(2-oxazolinyl-2)-benzene, 4-furans-2-methylene-2-phenyl-4H-oxazole-5-ketone, 1, 4-two (4, 5-dihydro-2-oxazolyl) benzene, 1, 3-two (4, 5-dihydro-2-oxazolyl) benzene, 2, two (4-pseudoallyl-2-oxazoline-2-base) butane of 3-, 2, two-4-benzyl-2-the oxazoline of 2'-, 2, two (sec.-propyl-2-oxazoline-2-base) pyridine of 6-, 2, 2'-isopropylidene two (4-tributyl-2-oxazoline), 2, 2'-isopropylidene two (4-phenyl-2-oxazoline), 2, 2'-methylene-bis (4-tributyl-2-oxazoline), and 2, 2'-methylene-bis (4-phenyl-2-oxazoline).Except this little oxazoline compound, also can enumerate as Ai Bo Kroes (Epocros) (trade(brand)name, Japanese catalyst (share) manufacture) such tool has polymkeric substance or the oligomer of oxazolyl.Among Zhe Xie oxazoline compound, more preferably can enumerate two (4, the 5-dihydro-2-oxazolyl) benzene of 1,3-.
< epoxy compounds >
Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can contain epoxy compounds further.Epoxy compounds can be a kind of compound, also can be compound of more than two kinds.With regard to described object, relative to polyamic acid or derivatives thereof, the preferred 0.1wt% ~ 50wt% of content of epoxy compounds, more preferably 1wt% ~ 40wt%, and then more preferably 1wt% ~ 20wt%.
Below epoxy compounds is specifically described.
As epoxy compounds, the various compounds of the oxirane ring with more than 1 or 2 can be enumerated in molecule.As the compound in molecule with 1 oxirane ring, include, for example: phenyl glycidyl ether, butylglycidyl ether, 3, 3, 3-trifluoromethyl propylene oxide, Styrene oxide 98min., Propylene oxide hexafluoride, epoxy cyclohexane (cyclohexaneoxide), 3-glycidoxypropyltrimewasxysilane, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, N-glycidyl phthalic imidine, (nine fluoro-N-butyl) epoxide, perfluoro-ethyl glycidyl ether, Epicholorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3-[2-(perfluoro hexyl) oxyethyl group]-1, 2-epoxy group(ing) propane.
As the compound in molecule with 2 oxirane rings, include, for example: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 3,4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester and 3-(N, N-diglycidyl) TSL 8330.
As the compound in molecule with 3 oxirane rings, include, for example: 2-[4-(2,3-epoxy group(ing) propoxy-) phenyl]-2-[4-[1, two [the 4-([2 of 1-, 3-epoxy group(ing) propoxy-] phenyl)] ethyl] phenyl] propane (trade(brand)name " iron Ke Moya VG3101L (TechmoreVG3101L) ", (Mitsui Chemicals (share) manufacture)).
As the compound in molecule with 4 oxirane rings, include, for example: 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N', N'-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane and 3-(N-allyl group-N-glycidyl) TSL 8330.
Except described, also can enumerate the oligomer with oxirane ring or polymkeric substance as the example of compound in molecule with oxirane ring.As the monomer with oxirane ring, include, for example: (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxycyclohexyethylSiOi ester and (methyl) vinylformic acid methylglycidyl esters.
Other monomers of copolymerization are carried out as with the monomer with oxirane ring, include, for example: (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, vinylbenzene, vinyl toluene, 1-chloro-4-methyl-benzene, (methyl) vinylformic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, N-cyclohexylmaleimide and N-phenylmaleimide.
As the preferred concrete example of polymkeric substance of monomer with oxirane ring, poly (glycidyl methacrylate) etc. can be enumerated.In addition, as the preferred concrete example of the multipolymer of the monomer and other monomers with oxirane ring, can enumerate: N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl esters-glycidyl methacrylate copolymer, and styrene-t glycidyl ester copolymer.
Among these examples, particularly preferably N, N, N', N'-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane, trade(brand)name " TechmoreVG3101L ", 3,4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane.
More systematically say, as epoxy compounds, include, for example: glycidyl ether, glycidyl ester, glycidyl amine, acrylic resin, glycidyl acid amides, isocyanuric acid Racemic glycidol fat, chain fatty race type epoxy compounds and annular aliphatic type epoxy compounds containing epoxy group(ing).Moreover epoxy compounds refers to the compound with epoxy group(ing), epoxy resin refers to the resin with epoxy group(ing).
As epoxy compounds, include, for example: glycidyl ether, Racemic glycidol fat, glycidyl amine, acrylic resin, glycidyl acid amides, isocyanuric acid glycidyl ester, chain fatty race type epoxy compounds and annular aliphatic type epoxy compounds containing epoxy group(ing).
As glycidyl ether, include, for example: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenol type epoxy compound, A Hydrogenated Bisphenol A-A type epoxy compounds, A Hydrogenated Bisphenol A-F type epoxy compounds, A Hydrogenated Bisphenol A-S type epoxy compounds, A Hydrogenated Bisphenol A type epoxy compounds, brominated bisphenol-A type epoxy compounds, brominated bisphenol-F type epoxy compounds, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compounds, bromination cresol novolak type epoxy compound, bisphenol A novolac type epoxy compounds, epoxy compounds containing naphthalene skeleton, aromatic series poly epihydric alcohol ether compound, dicyclopentadiene phenol epoxy compounds, ester ring type 2-glycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type 2-glycidyl ether compound, and biphenyl phenolic epoxy compounds.
As glycidyl ester, include, for example: 2-glycidyl ester cpds and glycidyl ester epoxy compound.
As glycidyl amine, include, for example: poly epihydric alcohol amine compound and glycidyl amine type epoxy resin.
As the acrylic compounds containing epoxy group(ing), include, for example: homopolymer and the multipolymer with the monomer of Oxyranyle (oxiranyl).
As glycidyl acid amides, include, for example: glycidyl acid amide type epoxy compounds.
As chain fatty race type epoxy compounds, include, for example: the compound containing epoxy group(ing) that the oxidation of the carbon-to-carbon double bond of olefin(e) compound is obtained.
As annular aliphatic type epoxy compounds, include, for example: the compound containing epoxy group(ing) that the oxidation of the carbon-to-carbon double bond of cyclic olefins is obtained.
As bisphenol A type epoxy compound, include, for example: jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (is trade(brand)name, Mitsubishi Chemical's (share) manufactures), the appropriate YD-128 of Ai Putuo (EpotohtoYD-128) (Dongdu changes into (share) manufactures), DER-331, DER-332, DER-324 (being Dow Chemical (TheDowChemicalCompany) to manufacture), Chinese mugwort clone 840 (Epiclon840), Epiclon850, Epiclon1050 (is trade(brand)name, Di Aisheng (DIC) (share) manufactures), Ai Bo Mick R-140 (EpomikR-140), EpomikR-301, and EpomikR-304 (is trade(brand)name, Mitsui Chemicals (company) manufactures).
As bisphenol F type epoxy compound, include, for example: jER806, jER807, jER4004P (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), EpotohtoYDF-170, EpotohtoYDF-175S, EpotohtoYDF-2001 (be trade(brand)name, Dongdu change into (share) manufacture), DER-354 (trade(brand)name, Dow Chemical manufacture), Epiclon830 and Epiclon835 (be trade(brand)name, Di Aisheng (share) manufactures).
As biphenol type epoxy compound, include, for example: the epoxide of 2,2-two (4-hydroxyphenyl)-1,1,1,3,3,3-HFC-236fa.
As A Hydrogenated Bisphenol A-A type epoxy compounds, include, for example: business holds in the palm appropriate ST-3000 (SuntohtoST-3000) (trade(brand)name, Dongdu change into (share) and manufacture), Li Kaleixin HBE-100 (RikaresinHBE-100) (trade(brand)name, new Japan Chemical (share) manufacture) and Dai Nakeer EX-252 (DenacolEX-252) (trade(brand)name, Chang Lai change into (NagasechemteX) (share) manufacture).
As A Hydrogenated Bisphenol A type epoxy compounds, include, for example: the epoxide of hydrogenation 2,2-two (4-hydroxyphenyl)-1,1,1,3,3,3-HFC-236fa.
As brominated bisphenol-A type epoxy compounds, include, for example: jER5050, jER5051 (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), EpotohtoYDB-360, EpotohtoYDB-400 (be trade(brand)name, Dongdu change into (share) manufacture), DER-530, DER-538 (be trade(brand)name, Dow Chemical manufactures), Epiclon152 and Epiclon153 (be trade(brand)name, Di Aisheng (share) manufactures).
As phenol novolak-type epoxy compound, include, for example: jER152, jER154 (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), YDPN-638 (trade(brand)name, Dongdu change into company and manufacture), DEN431, DEN438 (be trade(brand)name, Dow Chemical manufactures), EpiclonN-770 (trade(brand)name, Di Aisheng (share) manufacture), EPPN-201 and EPPN-202 (be trade(brand)name, Japanese chemical drug (share) manufactures).
As cresol novolak type epoxy compound, include, for example: jER180S75 (trade(brand)name, Mitsubishi Chemical's (share) manufacture), YDCN-701, YDCN-702 (be trade(brand)name, Dongdu change into company manufacture), EpiclonN-665, EpiclonN-695 (be trade(brand)name, Di Aisheng (share) manufactures), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (be trade(brand)name, Japanese chemical drug (share) manufactures).
As bisphenol A novolac type epoxy compounds, include, for example: jER157S70 (trade(brand)name, Mitsubishi Chemical's (share) manufacture) and EpiclonN-880 (trade(brand)name, Di Aisheng (share) manufacture).
As the epoxy compounds containing naphthalene skeleton, include, for example: EpiclonHP-4032, EpiclonHP-4700, EpiclonHP-4770 (be trade(brand)name, Di Aisheng (share) manufactures), and NC-7000 (trade(brand)name, Japanese chemical drug Inc. make).
As aromatic series poly epihydric alcohol ether compound, include, for example: Resorcinol diglycidylether (following formula EP-1), DGEC (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2-[4-(2, 3-epoxy group(ing) propoxy-) phenyl]-2-[4-[1, two [the 4-([2 of 1-, 3-epoxy group(ing) propoxy-] phenyl)] ethyl] phenyl] propane (following formula EP-4), three (4-glycidoxypropyl phenyl) methane (following formula EP-5), jER1031S, jER1032H60 (is trade(brand)name, Mitsubishi Chemical's (share) manufactures), Plutarch is for Ke Si-742 (TACTIX-742) (trade(brand)name, Dow Chemical manufactures), DenacolEX-201 (trade(brand)name, long rapids change into (share) manufactures), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (is trade(brand)name, Japan's chemical drug (share) manufactures), TechmoreVG3101L (trade(brand)name, Mitsui Chemicals (share) manufactures), compound represented by following formula EP-6, and the compound represented by following formula EP-7.
As dicyclopentadiene phenol epoxy compounds, include, for example: TACTIX-556 (trade(brand)name, Dow Chemical manufacture) and EpiclonHP-7200 (trade(brand)name, Di Aisheng (share) manufacture).
As ester ring type 2-glycidyl ether compound, include, for example: cyclohexanedimethanodiglycidyl diglycidyl ether compound and RikaresinDME-100 (trade(brand)name, new Japan Chemical (share) manufacture).
As aliphatic polyglycidyl ether compound, include, for example: ethylene glycol diglycidylether (following formula EP-8), diethylene glycol diglycidyl glyceryl ether (following formula EP-9), polyethyleneglycol diglycidylether, propylene glycol diglycidylether (following formula EP-10), tripropyleneglycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether (following formula EP-12), 1, 4-butanediol diglycidyl ether (following formula EP-13), 1, 6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidylether (following formula EP-15), DenacolEX-810, DenacolEX-851, DenacolEX-8301, DenacolEX-911, DenacolEX-920, DenacolEX-931, DenacolEX-211, DenacolEX-212, DenacolEX-313 (is trade(brand)name, long rapids change into (share) manufactures), DD-503 (trade(brand)name, Ai Dike (ADEKA) (share) manufactures), RikaresinW-100 (trade(brand)name, new Japan Chemical (share) manufactures), 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol (following formula EP-16), glycerine polyglycidyl ether, sorbyl alcohol polyglycidyl ether, TriMethylolPropane(TMP) polyglycidyl ether, tetramethylolmethane polyglycidyl ether, DenacolEX-313, DenacolEX-611, DenacolEX-321, and DenacolEX-411 (is trade(brand)name, long rapids change into (share) manufactures).
As polysulfide type 2-glycidyl ether compound, include, for example: FLDP-50 and FLDP-60 (be trade(brand)name, beautiful skilful solid happy (TorayThiokol) (share) in east manufactures).
As biphenyl phenolic epoxy compounds, include, for example: YX-4000, YL-6121H (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), NC-3000P and NC-3000S (be trade(brand)name, Japanese chemical drug (share) manufactures).
As 2-glycidyl ester cpds, include, for example: two (the 2-methyl oxirane ylmethyl) ester (following formula EP-19) of terephthalic acid diglycidyl ester (following formula EP-17), o-phthalic acid diglycidyl ester (following formula EP-18), phthalic acid, hexahydrophthalic acid 2-glycidyl ester (following formula EP-20), compound, the compound represented by following formula EP-22 and the compound represented by following formula EP-23 represented by following formula EP-21.
As glycidyl ester epoxy compound, include, for example: jER871, jER872 (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), Epiclon200, Epiclon400 (be trade(brand)name, Di Aisheng (share) manufacture), DenacolEX-711 and DenacolEX-721 (be trade(brand)name, Chang Lai change into (share) and manufacture).
As poly epihydric alcohol amine compound, include, for example: N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-Ortho Toluidine (following formula EP-25), N, N-diglycidyl-meta-aminotoluene (following formula EP-26), N, N-diglycidyl-2,4,6-bromamide (following formula EP-27), 3-(N, N-diglycidyl) TSL 8330 (following formula EP-28), N, N, O-triglycidyl group-p-aminophenol (following formula EP-29), N, N, O-triglycidyl group-Metha Amino Phenon (following formula EP-30), N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane (following formula EP-31), N, N, N', N'-four glycidyl group-m-xylene diamine (iron Te Lade-X (TETRAD-X) (trade(brand)name, Mitsubishi's gas chemistry (share) manufactures), following formula EP-32), two (N, the N-diglycidyl amino methyl) hexanaphthene (TETRAD-C (trade(brand)name of 1,3-, Mitsubishi's gas chemistry (share) manufactures), following formula EP-33), Isosorbide-5-Nitrae-bis-(N, N-diglycidyl amino methyl) hexanaphthene (following formula EP-34), 1,3-two (N, N-diglycidyl is amino) hexanaphthene (following formula EP-35), Isosorbide-5-Nitrae-bis-(N, N-diglycidyl is amino) hexanaphthene (following formula EP-36), 1,3-two (N, N-diglycidyl is amino) benzene (following formula EP-37), Isosorbide-5-Nitrae-bis-(N, N-diglycidyl is amino) benzene (following formula EP-38), two (N, N-diglycidyl amino methyl) dicyclo [2.2.1] heptane (following formula EP-39) of 2,6-, N, N, N', N'-four glycidyl group-4,4'-diamino-dicyclohexyl methane (following formula EP-40), 2,2'-dimethyl-(N, N, N', N'-four glycidyl group)-4,4'-benzidines (following formula EP-41), N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl oxide (following formula EP-42), 1,3,5-tri-(4-(N, N-diglycidyl) amino-benzene oxygen) benzene (following formula EP-43), 2,4,4'-tri-(N, N-diglycidyl is amino) phenyl ether (following formula EP-44), three (4-(N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3', 4'-tetra-(N, N-diglycidyl is amino) biphenyl (following formula EP-46), 3,4,3', 4'-tetra-(N, N-diglycidyl is amino) phenyl ether (following formula EP-47), compound represented by following formula EP-48, and the compound represented by following formula EP-49.
As the homopolymer of monomer with Oxyranyle, include, for example poly (glycidyl methacrylate).As the multipolymer of monomer with Oxyranyle, include, for example: N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-methyl propenoic acid glycidyl resin copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl esters-methyl propenoic acid glycidyl resin copolymer, and styrene-t Racemic glycidol resin copolymer.
As the monomer with Oxyranyle, include, for example: (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxycyclohexyethylSiOi ester and (methyl) vinylformic acid methylglycidyl esters.
As have Oxyranyle monomer multipolymer in the monomer with Oxyranyle beyond other monomers, include, for example: (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, vinylbenzene, vinyl toluene, 1-chloro-4-methyl-benzene, (methyl) vinylformic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, N-cyclohexylmaleimide, and N-phenylmaleimide.
As isocyanuric acid glycidyl ester, include, for example: 1,3,5-triglycidyl group-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-50), 1,3-diglycidyl-5-allyl group-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-51) and isocyanuric acid glycidyl ester type epoxy resin.
As chain fatty race type epoxy compounds, include, for example: epoxidized polybutadiene and Ai Bo Reed PB3600 (EpoleadPB3600) (trade(brand)name, Daicel (Daicel) (share) manufacture).
As annular aliphatic type epoxy compounds, include, for example: 3, 4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester (silicon Luo Ji Saden 2021 (Celloxide2021) (Daicel (share) manufacture), following formula EP-52), 2-methyl-3, 4-epoxycyclohexylmethyl-2'-methyl-3', 4'-expoxycyclohexyl carboxylicesters (following formula EP-53), 2, 3-epoxy group(ing) pentamethylene-2', 3'-epoxy group(ing) pentamethylene ether (following formula EP-54), 6-caprolactone upgrading 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane carboxylate, 1, 2:8, 9-bicyclic oxygen limonene (Celloxide3000 (trade(brand)name, Daicel (share) manufactures), following formula EP-55), compound represented by following formula EP-56, CY-175, CY-177, CY-179 (is trade(brand)name, Ciba-Geigy Chemical Company (TheCiba-GeigyChemicalCorp.) manufactures (can step (HuntsmanJapan) (share) from Japanese Hensel to obtain)), EHPD-3150 (trade(brand)name, Daicel (share) manufactures), and annular aliphatic type epoxy resin.
The preferred poly epihydric alcohol amine compound of epoxy compounds, bisphenol A novolac type epoxy compounds, cresol novolak type epoxy compound, and more than one of annular aliphatic type epoxy compounds, more preferably N, N, N', N'-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N', N'-four glycidyl group-4, 4'-diaminodiphenyl-methane, trade(brand)name " TechmoreVG3101L ", 3, 4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl group-p-aminophenol, bisphenol A novolac type epoxy compounds, and more than one of cresol novolak type epoxy compound.
In addition, such as liquid crystal aligning agent of the present invention can contain various additive further.As various additive, include, for example the macromolecular compound beyond polyamic acid and derivative thereof and low molecular compound, can according to each object choice for use.
Such as, as described macromolecular compound, the macromolecular compound dissolving in organic solvent can be enumerated., preferably this kind of macromolecular compound is added in liquid crystal aligning agent of the present invention with regard to the electrical characteristic of liquid crystal orientation film that formed or the viewpoint of orientation with regard to controlling.As this macromolecular compound, include, for example: polymeric amide, polyurethane(s), polyureas, polyester, polyepoxide, polyester polyol, silicone upgrading polyurethane(s) and silicone upgrading polyester.
In addition, as described low molecular compound, such as, 1) when expecting can enumerate the tensio-active agent meeting this object when promoting coating, 2) static inhibitor can be enumerated when needs promote antistatic, 3) when expecting the coupling agent can enumerating silane coupling agent or titanium system when promoting the adhesion with substrate, in addition, 4) imidization catalyst can be enumerated when carrying out imidization at low temperatures.
As silane coupling agent, include, for example: vinyltrimethoxy silane, vinyltriethoxysilane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-amino propyl methyl Trimethoxy silane, p-aminophenyl Trimethoxy silane, p-aminophenyl triethoxyl silane, m-aminophenyl base Trimethoxy silane, m-aminophenyl ethyl triethoxy silicane alkane, 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl dimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi Trimethoxy silane, N-(1, 3-dimethylbutylene)-3-(triethoxysilicane alkyl)-1-propylamine, and N, two [3-(Trimethoxy silane base) propyl group] quadrol of N'-.Preferred silane coupling agent is APTES.
As imidization catalyst, include, for example: the aliphatics amines such as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine; The aromatic amines such as DMA, N, N-Diethyl Aniline, methyl substituted aniline, hydroxyl-substituted amine; The ring type amines such as pyridine, methyl substituted pyridine, hydroxyl substituted pyridines, quinoline, methyl substituted quinoline, hydroxyl substd quinolines, isoquinoline 99.9, methyl substituted isoquinoline 99.9, hydroxyl substituted isoquinoline, imidazoles, methyl substituted imidazoles, hydroxyl substituted imidazole.Described imidization catalyst is preferably selected from DMA, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, a pyridone, one kind or two or more in pyridone and isoquinoline 99.9.
The addition of silane coupling agent is generally the 0wt% ~ 20wt% of the gross weight of polyamic acid or derivatives thereof, preferred 0.1wt% ~ 10wt%.
Relative to the carbonyl of polyamic acid or derivatives thereof, the addition of imidization catalyst is generally 0.01 equivalent ~ 5 equivalent, preferably 0.05 equivalent ~ 3 equivalent.
The addition of other additives is different according to its purposes, but is generally the 0wt% ~ 100wt% of the gross weight of polyamic acid or derivatives thereof, preferred 0.1wt% ~ 50wt%.
Polyamic acid or derivatives thereof of the present invention can manufacture in the same manner as the known polyamic acid or derivatives thereof of the formation of the film for polyimide.The total addition level of tetracarboxylic dianhydride is preferably set to and roughly waits mole (mol ratio is about 0.9 ~ 1.1) with the total mole number of diamines.
The molecular weight of polyamic acid or derivatives thereof of the present invention in the weight average molecular weight of polystyrene conversion (Mw), preferably 7,000 ~ 500,000, more preferably 10,000 ~ 200,000.The molecular weight of described polyamic acid or derivatives thereof can by utilizing the mensuration of gel permeation chromatography (GelPermeationChromatography, GPC) method to obtain.
Polyamic acid or derivatives thereof of the present invention confirms its existence by such as under type: utilize infrared rays (Infrared, IR) solids component that, nucleus magnetic resonance (NuclearMagneticResonance, NMR) obtains making polyamic acid or derivatives thereof of the present invention precipitate in a large amount of poor solvents is analyzed.In addition, by confirm as under type the monomer that uses: utilize vapor-phase chromatography (GasChromatography, GC), high performance liquid chromatography (HighPerformanceLiquidChromatography, or GC-MS (GasChromatography-MassSpectrometry HPLC), GC-MS) to using the aqueous solution of the highly basic such as KOH or NaOH by after described polyamic acid or derivatives thereof decomposition, the extract with an organic solvent extracted from its resolvent is analyzed.
In addition, such as, with regard to the viewpoint of the adjustment of the coating of liquid crystal aligning agent or the concentration of described polyamic acid or derivatives thereof, liquid crystal aligning agent of the present invention can contain solvent further.As long as described solvent has the solvent of the ability of dissolving macromolecule component, then can apply with no particular limitation.Described solvent extensively comprises the solvent of manufacturing step or the purposes aspect being generally used for the macromolecule component such as polyamic acid, soluble polyimide, can be suitable for selecting according to application target.Described solvent can be a kind, also can be mixed solvent of more than two kinds.
As solvent, can enumerate described polyamic acid or derivatives thereof solvophilic or to improve other solvents for the purpose of coating.
As being solvophilic aprotic polar organic solvent relative to polyamic acid or derivatives thereof, can enumerate: METHYLPYRROLIDONE, methylimidazole alkane ketone (dimethylimidazolidinone), N-methyl caprolactam, N-methyl propanamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N, the lactones such as dinethylformamide, N, N-diethylformamide, diethyl acetamide, gamma-butyrolactone.
As the example to improve other solvents for the purpose of coating etc., can enumerate: lactic acid alkyl ester, 3-methyl-3-methoxybutanol, naphthane, isophorone, the ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, the Diethylene Glycol monoalky lethers such as diethylene glycol monoethyl ether, glycol monoalkyl acetic ester or ethylene glycol list phenylacetic acid ester, triethylene glycol monoalky lether, propylene glycol monomethyl ether, the propylene-glycol monoalky lethers such as propylene glycol monobutyl ether, the dialkyl malonates such as diethyl malonate, the dipropylene glycol monoalkylether such as dipropylene glycol monomethyl ether, the ester cpds such as these acetate esters.
Among these solvents, described solvent is METHYLPYRROLIDONE, methylimidazole alkane ketone, gamma-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether particularly preferably.
Preferred 0.1wt% ~ the 40wt% of concentration of the polyamic acid in alignment agent of the present invention.When being coated on substrate by this alignment agent, in order to adjust thickness, sometimes need the operation utilizing solvent to dilute contained polyamic acid in advance.
Solid component concentration in alignment agent of the present invention is not particularly limited, as long as select most suitable value in conjunction with following various coating method.Usually, in order to suppress inequality when being coated with or pin hole etc., relative to varnish weight, preferred 0.1wt% ~ 30wt%, more preferably 1wt% ~ 10wt%.
The viscosity of liquid crystal aligning agent of the present invention is due to the method for coating, the concentration of polyamic acid or derivatives thereof, the kind of polyamic acid or derivatives thereof used, the kind of solvent and ratio and preferably scope is different.Such as, be 5mPas ~ 100mPas (being more preferably 10mPas ~ 80mPas) when being coated with when utilizing printing press.If be less than 5mPas, then become and be difficult to obtain sufficient thickness; If more than 100mPas, then there is the phenomenon that the uneven change of printing is large.When being coated with when utilizing spin coating, what be applicable to is 5mPas ~ 200mPas (being more preferably 10mPas ~ 100mPas).When being coated with when using ink-jet coating apparatus, what be applicable to is 5mPas ~ 50mPas (being more preferably 5mPas ~ 20mPas).The viscosity of liquid crystal aligning agent measures by rotational viscometry, such as, use rotational viscosimeter (the TVE-20L type that eastern machine industry manufactures) and measure (measuring temperature is 25 DEG C).
Liquid crystal orientation film of the present invention is described in detail.Liquid crystal orientation film of the present invention is by heating formed film to the film of described liquid crystal aligning agent of the present invention.Liquid crystal orientation film of the present invention obtains by making the usual method of liquid crystal orientation film from liquid crystal aligning agent.Such as, liquid crystal orientation film of the present invention by through formation liquid crystal aligning agent of the present invention film step, carry out heat drying step and carry out the step of heating and calcining and obtain.For liquid crystal orientation film of the present invention, optionally, friction treatment can be carried out to give anisotropy to the film obtained through heat-drying step, heating and calcining step as described later.Or, optionally, light can be irradiated after film-coating procedures, heat-drying step, or after heating and calcining step, irradiate light to give anisotropy.In addition, vertical orientated (VerticalAlignment, the VA) that also can be used as not carry out friction treatment uses liquid crystal orientation film.
Film in the same manner as the making of common liquid crystal orientation film, can be formed by being coated on by liquid crystal aligning agent of the present invention on substrate in liquid crystal display device.Substrate can be enumerated and can be provided with tin indium oxide (IndiumTinOxide, ITO), indium zinc oxide (In
2o
3-ZnO, IZO), Indium sesquioxide gallium zinc (In-Ga-ZnO
4, IGZO) and the substrate of glass of electrode or the colored filter etc. such as electrode.
As the method be coated on by liquid crystal aligning agent on substrate, oneself knows usually turner method, print process, pickling process, dripping method, ink jet method etc.These methods also can similarly be applied in the present invention.
Usually oneself knows have the method for carrying out heat treated in baking oven or infra-red furnace, the method etc. of carrying out heat treated on hot plate to described heat-drying step.Implement at the temperature of heat-drying step preferably in the transpirable scope of solvent, more preferably implement under being lower temperature relative to the temperature in heating and calcining step.Specifically, the scope that heat drying temperature is preferably 30 DEG C ~ 150 DEG C, the scope of more preferably 50 DEG C ~ 120 DEG C.
Carry out under the condition that described heating and calcining step can present required for dehydration closed-loop reaction at described polyamic acid or derivatives thereof.The calcining of described film there will be a known the method for carrying out heat treated in baking oven or infra-red furnace, the method etc. of carrying out heat treated on hot plate usually.These methods also can similarly be applied in the present invention.Usually preferably at the temperature of 100 DEG C ~ about 300 DEG C, 1 minute ~ 3 hours are carried out, more preferably 120 DEG C ~ 280 DEG C, and then more preferably 150 ~ 250 DEG C.
In the formation method of liquid crystal orientation film of the present invention, in order to make mesomorphic phase carry out orientation in one direction for horizontal direction and/or vertical direction, the known formation such as rubbing manipulation or optical alignment method method can be used aptly to give anisotropic method as to alignment films.
The liquid crystal orientation film of the present invention of rubbing manipulation is used to can be passed through following step and formed: liquid crystal aligning agent of the present invention to be coated on the step on substrate, the substrate being coated with alignment agent to be carried out to the step of heat drying, this film to be carried out to the step of heating and calcining and film carried out to the step of friction treatment.
Friction treatment can be carried out in the same manner as the friction treatment of the common orientation process for liquid crystal orientation film, as long as can obtain the condition postponed fully in liquid crystal orientation film of the present invention.Preferred condition is mao intrusion is 0.2mm ~ 0.8mm, and platform movement speed is 5mm/sec ~ 250mm/sec, and roller speed of rotation is 500rpm ~ 2,000rpm.
Liquid crystal orientation film of the present invention by so that comprise the method for other steps beyond described step and obtain aptly.Such as, although liquid crystal orientation film of the present invention is not using utilizing scavenging solution to the film step of cleaning after calcining or radiation exposure as required step, cleaning step can be set according to the situation of other steps.
As the purging method utilizing scavenging solution, can enumerate: scrub, spray, steam purge or ultrasonic cleaning etc.These methods can be carried out separately, also can be used together.As scavenging solution, can use: pure water, or the various alcohols such as methyl alcohol, ethanol, Virahol, the halogen series solvents such as benzene,toluene,xylene etc. are aromatic hydrocarbon based, methylene dichloride, the ketone such as acetone, methyl ethyl ketone, but be not limited to these scavenging solutions.Certainly, these scavenging solutions can use through the few scavenging solution of fully refining impurity.This kind of purging method also can be applied in described cleaning step when forming liquid crystal orientation film of the present invention.
In order to improve the liquid crystal aligning performance of liquid crystal orientation film of the present invention, can at the front and back of the front and back of heating and calcining step, rubbing process or polarisation or without the front and back applications exploiting heat of the radiation exposure of polarisation or the anneal of light.In this anneal, annealing temperature is 30 DEG C ~ 180 DEG C, preferably 50 DEG C ~ 150 DEG C, preferably 1 minute ~ 2 hours time.In addition, in the annealing light of anneal, UV lamp, luminescent lamp, LED etc. can be enumerated.The preferred 0.3J/cm of irradiation dose of light
2~ 10J/cm
2.
The thickness of liquid crystal orientation film of the present invention is not particularly limited, but preferred 10nm ~ 300nm, more preferably 30nm ~ 150nm.The thickness of liquid crystal orientation film of the present invention measures by known determining film thickness devices such as contourgraph or ellipsometers (ellipsometer).
The feature of liquid crystal orientation film of the present invention is the anisotropy with king-sized orientation.This kind of anisotropic size is evaluated by the method for use polarisation IR described in Japanese Patent Laid-Open 2005-275364 etc.In addition, as shown in following embodiment, also can evaluate by using the method for ellipsometry (ellipsometry).Specifically, light splitting ellipsometer can be used to measure the length of delay of liquid crystal orientation film.The length of delay of film and the orientation degree of main polymer chain increase pro rata.That is, the film with large length of delay has large orientation degree, when alignment films of the present invention is used as liquid crystal orientation film, can think that having larger anisotropic alignment films has large orientation restraint for liquid-crystal composition.
Liquid crystal orientation film of the present invention can be suitably used in the liquid crystal display device of Transverse electric-field type.In for the liquid crystal display device of Transverse electric-field type, Pt angle is less, and liquid crystal aligning ability is higher, then black reveal competence in the dark state more uprises, and contrast gradient more improves.Preferably less than 0.1 °, Pt angle.
Except the orientation purposes of the liquid-crystal composition of liquid-crystal display, liquid crystal orientation film of the present invention can be used for the tropism control of optical compensation material or other all liquid crystal materials.In addition, alignment films of the present invention, therefore can separately for optical compensation material applications owing to having large anisotropy.
Liquid crystal display device of the present invention is described in detail.
The invention provides a kind of liquid crystal display device, it comprise subtend configuration a pair substrate, be formed in described a pair substrate subtend face separately one or two on electrode, the liquid crystal layer that is formed in the liquid crystal orientation film on described a pair substrate subtend face separately and is formed between described a pair substrate, and described liquid crystal orientation film is alignment films of the present invention.
As long as described electrode is formed in the electrode in the one side of substrate, be then not particularly limited.This kind of electrode include, for example the vapor-deposited film etc. of ITO or metal.In addition, electrode can be formed on whole of a face of substrate, also can be formed as such as patterned desired shape.The described desired shape of electrode include, for example combed or broached-tooth design etc.Electrode can be formed on a substrate in a pair substrate, also can be formed on two substrates.The formation form of electrode is different according to the kind of liquid crystal display device, such as when IPS type liquid crystal display device, electrode is configured on one of described a pair substrate, when other liquid crystal display device, electrode is configured on described a pair substrate two.Described substrate or electrode form described liquid crystal orientation film.
Described liquid crystal layer be with by be formed liquid crystal orientation film in the face of to described a pair substrate clamp liquid-crystal composition form formed.In the forming process of liquid crystal layer, optionally can use micropartical or resin sheet etc. between described a pair substrate and form the spacer at suitable interval.
There is no particular restriction for liquid-crystal composition, can use the various liquid-crystal compositions that dielectric constant anisotropy is plus or minus.Dielectric constant anisotropy is that positive preferred liquid-crystal composition can be enumerated: Japanese Patent 3086228, Japanese Patent 2635435, Japanese Patent JP-A 5-501735, Japanese Patent Laid-Open 8-157826, Japanese Patent Laid-Open 8-231960, Japanese Patent Laid-Open 9-241644 (EP885272A1), Japanese Patent Laid-Open 9-302346 (EP806466A1), Japanese Patent Laid-Open 8-199168 (EP722998A1), Japanese Patent Laid-Open 9-235552, Japanese Patent Laid-Open 9-255956, Japanese Patent Laid-Open 9-241643 (EP885271A1), Japanese Patent Laid-Open 10-204016 (EP844229A1), Japanese Patent Laid-Open 10-204436, Japanese Patent Laid-Open 10-231482, Japanese Patent Laid-Open 2000-087040, the liquid-crystal composition disclosed in Japanese Patent Laid-Open 2001-48822 etc.
Even if be add the optically active compound of more than a kind in the liquid-crystal composition of plus or minus to use to dielectric constant anisotropy, also have no effect.
Be that negative liquid-crystal composition is illustrated to described dielectric constant anisotropy.The liquid-crystal composition of negative dielectric constant anisotropy include, for example the composition of at least one liquid crystalline cpd as the 1st composition of the group containing the liquid crystalline cpd be selected from represented by following formula (NL-1).
Herein, R
1aand R
2aindependent for carbon number be 1 ~ 12 alkyl, carbon number be 1 ~ 12 alkoxyl group, carbon number be 2 ~ 12 thiazolinyl or the carbon number that replaced by fluorine of at least one hydrogen be the thiazolinyl of 2 ~ 12, ring A
2and ring B
2independent is Isosorbide-5-Nitrae-cyclohexylidene, tetrahydropyrans (tetrahydropyran)-2,5-bis-base, 1,3-diox-2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-base, Isosorbide-5-Nitrae-phenylene, 2-, 2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-, 2,3-bis-fluoro-1, chloro-Isosorbide-5-Nitrae-the phenylene of the fluoro-3-of 4-phenylene, 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene, 2,6-naphthalene two bases or 7,8-difluoro chroman (chromane)-2,6-bis-base, herein, ring A
2and ring B
2at least one be the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-, the chloro-Isosorbide-5-Nitrae-phenylene of the fluoro-3-of 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene or 7,8-difluoro chroman-2,6-bis-base, Z
1independent is singly-bound ,-(CH
2)
2-,-CH
2o-,-COO-or-CF
2o-, j are 1,2 or 3, j when being 2 or 3, any two ring A
2can be identical, also can be different, any two Z
1can be identical, also can be different.
In order to make dielectric constant anisotropy improve, preferred ring A
2and ring B
2be respectively the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-or tetrahydropyrans-2,5-bis-base, in order to make viscosity reduce, preferred ring A
2and ring B
2be respectively Isosorbide-5-Nitrae-cyclohexylidene.
In order to make dielectric constant anisotropy improve, preferred Z
1for-CH
2o-, in order to make viscosity reduce, preferred Z
1for singly-bound.
In order to make lower limit temperature reduce, preferred j is 1, and in order to make ceiling temperature improve, preferred j is 2.
The concrete example of the liquid crystalline cpd of described formula (NL-1) can enumerate the compound represented by following formula (NL-1-1) ~ formula (NL-1-32).
Herein, R
1aand R
2aindependent for carbon number be 1 ~ 12 alkyl, carbon number be 1 ~ 12 alkoxyl group, carbon number be 2 ~ 12 thiazolinyl or the carbon number that replaced by fluorine of at least one hydrogen be the thiazolinyl of 2 ~ 12, ring A
21, ring A
22, ring A
23, ring B
21, and ring B
22independent is Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, Z
11and Z
12independent is singly-bound ,-(CH
2)
2-,-CH
2o-or-COO-.
In order to make the raising such as stability for ultraviolet or heat, preferred R
1aand R
2ato be carbon number be 1 ~ 12 alkyl, or in order to make the absolute value of dielectric constant anisotropy improve, preferred R
1aand R
2ato be carbon number be 1 ~ 12 alkoxyl group.
Preferred alkyl is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group.In order to make viscosity reduce, and then preferred alkyl is ethyl, propyl group, butyl, amyl group or heptyl.
Preferred alkoxyl group be methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy or heptan oxygen base.In order to make viscosity reduce, and then preferred alkoxyl group is methoxy or ethoxy.
Preferred thiazolinyl is vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 3-butenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl.In order to make viscosity reduce, and then preferred thiazolinyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl.The preferred steric configuration of-CH=CH-in these thiazolinyls (stericconfiguration) depends on the position of double bond.From in order to make the aspects such as viscosity reduction consider, preferably trans in the thiazolinyl as 1-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl.Cis is preferably in the thiazolinyl as crotyl, pentenyl, 2-hexenyl.In these thiazolinyls, be Comparatively speaking preferably the thiazolinyl of straight chain with branch.
The preferred example of the thiazolinyl that at least one hydrogen is replaced by fluorine is 2,2-difluoroethylene base, 3,3-bis-fluoro-2-propenyl, 4,4-bis-fluoro-3-butenyls, 5,5-bis-fluoro-4-pentenyls and the fluoro-5-hexenyl of 6,6-bis-.In order to make viscosity reduce, and then preferred example is the fluoro-3-butenyl of 2,2-difluoroethylene base and 4,4-bis-.
In order to make viscosity reduce, preferred ring A
21, ring A
22, ring A
23, ring B
21, and ring B
22be respectively Isosorbide-5-Nitrae-cyclohexylidene.
In order to make dielectric constant anisotropy improve, preferred Z
11and Z
12-CH
2o-, in order to make viscosity reduce, preferred Z
11and Z
12it is singly-bound.
Described have in the liquid-crystal composition of negative dielectric constant anisotropy, and as the 1st composition, preferred compound (NL-1) is compound (NL-1-1), compound (NL-1-4), compound (NL-1-7) or compound (NL-1-32).
The described preferred example with the liquid-crystal composition of negative dielectric constant anisotropy can be set forth in Japanese Patent Laid-Open No. Sho 57-114532, Japanese Patent Laid-Open 2-4725, Japanese Patent Laid-Open 4-224885, Japanese Patent Laid-Open 8-40953, Japanese Patent Laid-Open 8-104869, Japanese Patent Laid-Open 10-168076, Japanese Patent Laid-Open 10-168453, Japanese Patent Laid-Open 10-236989, Japanese Patent Laid-Open 10-236990, Japanese Patent Laid-Open 10-236992, Japanese Patent Laid-Open 10-236993, Japanese Patent Laid-Open 10-236994, Japanese Patent Laid-Open 10-237000, Japanese Patent Laid-Open 10-237004, Japanese Patent Laid-Open 10-237024, Japanese Patent Laid-Open 10-237035, Japanese Patent Laid-Open 10-237075, Japanese Patent Laid-Open 10-237076, Japanese Patent Laid-Open 10-237448 (EP967261A1), Japanese Patent Laid-Open 10-287874, Japanese Patent Laid-Open 10-287875, Japanese Patent Laid-Open 10-291945, Japanese Patent Laid-Open 11-029581, Japanese Patent Laid-Open 11-080049, Japanese Patent Laid-Open 2000-256307, Japanese Patent Laid-Open 2001-019965, Japanese Patent Laid-Open 2001-072626, Japanese Patent Laid-Open 2001-192657, Japanese Patent Laid-Open 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Japanese Patent spy table 2010-537010, Japanese Patent Laid-Open 2012-077201, the liquid-crystal composition disclosed in Japanese Patent Laid-Open 2009-084362 etc.
Such as, and such as consider from the viewpoint making orientation improve, the liquid-crystal composition used in element of the present invention can also add additive further.This kind of additive is photopolymerization monomer, optically active compound, antioxidant, UV light absorber, pigment, defoamer, polymerization starter, polymerization retarder etc.
In order to improve the orientation of liquid crystal, the most preferred structure of photopolymerization monomer or oligomer can the structure of enumerative (PM-1-1) ~ formula (PM-1-6).
In order to show the effect of the vergence direction of the liquid crystal after determining polymerization, photopolymerization monomer or oligomer it is desirable to more than 0.01 % by weight.And in order to make the orientation effect of the polymkeric substance after polymerization be suitable for, or in order to avoid after uv irradiation, unreacted monomer or oligomer stripping, in liquid crystal, it is desirable to less than 30 % by weight.
In order to cause the spirane structure of liquid crystal to give torsion(al)angle, hybrid optical active compound in the composition.The example of this kind of compound is that compound (PAC-1-1) is to compound (PAC-1-4).
The preferred proportion of optically active compound is less than 5 % by weight.And then preferred ratio is the scope of 0.01 % by weight to 2 % by weight.
Reduce to prevent the ratio resistance (specificresistance) caused owing to heating in an atmosphere, or in order to after long-time use element, not only at room temperature and at high temperature also can maintain large voltage retention, in liquid-crystal composition, mix antioxidant.
The compound (AO-1) etc. of the preferred example of antioxidant to be w the be integer of 1 to 10.In compound (AO-1), preferred w is 1,3,5,7 or 9.And then preferred w is 1 or 7.W is that the volatility of the compound (AO-1) of 1 is large, therefore effective when the ratio resistance preventing from causing owing to heating in an atmosphere reduces.W is that the volatility of the compound (AO-1) of 7 is little, therefore after long-time use element, not only at room temperature and at high temperature also can effectively maintain large voltage retention.In order to obtain its effect, the preferred ratio of antioxidant is more than 50ppm, and in order to not make ceiling temperature reduce or not make lower limit temperature improve, the preferred ratio of antioxidant is below 600ppm.And then preferred ratio is the scope of 100ppm to 300ppm.
The preferred example of UV light absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc.And, as also preferred in the photostabilizer there is the amine of steric hindrance (sterichindrance).In order to obtain its effect, the preferred ratio of these absorption agents or stablizer is more than 50ppm, and in order to not make ceiling temperature reduce or not make lower limit temperature improve, the preferred ratio of these absorption agents or stablizer is below 10000ppm.And then preferred ratio is the scope of 100ppm to 10000ppm.
In order to the element of applicable host and guest (Guesthost, GH) pattern, the dichroism pigment (dichroicdye) of mixing as azo system pigment, anthraquinone system pigment etc. so in the composition.The preferred ratio of pigment is the scope of 0.01 % by weight to 10 % by weight.
In order to prevent bubbling, mix the defoamer such as dimethyl silicone oil, methyl phenyl silicone oil in the composition.In order to obtain its effect, the preferred ratio of defoamer is more than 1ppm, and in order to prevent display bad, the preferred ratio of defoamer is below 1000ppm.And then preferred ratio is the scope of 1ppm to 500ppm.
In order to the element of applicable polymer stabilizing orientation (Polymersustainedalignment, PSA) pattern, polymerisable compound can be mixed in the composition.The compound that the preferred example of polymerisable compound is acrylate, methacrylic ester, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxy compounds (oxirane, trimethylene oxide), vinyl ketone etc. have polymerisable base.Example is particularly preferably the derivative of acrylate or methacrylic ester.The example of this kind of compound is that compound (PM-2-1) is to compound (PM-2-9).In order to obtain its effect, the preferred ratio of polymerisable compound is more than about 0.05 % by weight, and in order to prevent display bad, the preferred ratio of polymerisable compound is less than about 10 % by weight.And then preferred ratio is the scope of about 0.1 % by weight to about 2 % by weight.
Herein, R
3a, R
4a, R
5a, and R
6aindependent is acryl or methacryloyl, R
7aand R
8aindependently for hydrogen, halogen or carbon number are the alkyl of 1 to 10, Z
13, Z
14, Z
15, and Z
16independently for singly-bound or carbon number are the alkylidene group of 1 to 12, at least one-CH
2-also can be replaced by-O-or-CH=CH-, s, t and u are independently 0,1 or 2.
As easily producing free radical or ion, cause the material required for chain polymerization reaction, can mixed polymerization initiator.Such as, as gorgeous good solid (Irgacure) 651 (registered trademark), the Irgacure184 (registered trademark) of Photoepolymerizationinitiater initiater or Da Luoka (Darocure) 1173 (registered trademark) (Japanese Qi Ba limited-liability company (CibaJapanK.K.)) suitable for radical polymerization.Polymerisable compound preferably comprises Photoepolymerizationinitiater initiater in the scope of 0.1 % by weight to 5 % by weight.Particularly preferably be comprise Photoepolymerizationinitiater initiater in the scope of 1 % by weight to 3 % by weight.
In radical polymerization assembly system, following object can be utilized and mixed polymerization inhibitor: promptly react with the free radical produced by polymerization starter or monomer and be changed to stable free radical or the compound of neutrality, its result makes polyreaction stop.Polymerization retarder structurally can be categorized as several.One of them be as three-p-nitrophenyl ylmethyl, two-to himself the stable free radical fluorophenyl amine etc., another kind easily reacts with existing free radical in paradigmatic system and becomes stable free radical, and its representative is nitro, nitroso-group, amino, polyol etc.The representative of the latter can enumerate Resorcinol, dimethoxy benzene etc.In order to obtain its effect, the preferred ratio of polymerization retarder is more than 5ppm, and in order to prevent display bad, the preferred ratio of polymerization retarder is below 1000ppm.And then preferred ratio is the scope of 5ppm to 500ppm.
Use in liquid crystal display device of the present invention and there is the liquid-crystal composition of negative dielectric constant anisotropy, image retention excellent can be provided thus and the good liquid crystal display device of orientation stability.
[embodiment]
Below, by embodiment, the present invention is described.In addition, used in an embodiment evaluation assessment and compound as described below.
< evaluation assessment >
1. weight average molecular weight (Mw)
The weight average molecular weight of polyamic acid is obtained in the following way: use 2695 separation module 2414 differential refractometer (water generation (Waters) manufacture) and utilize GPC method to measure, then carrying out polystyrene conversion.Utilize phosphoric acid-dimethyl formamide (Dimethylformamide, DMF) mixing solutions (phosphoric acid/DMF=0.6/100: weight ratio), the mode becoming about 2wt% with polyamic acid concentration is diluted obtained polyamic acid.Tubing string uses HSPgelRTMB-M (manufacture of water generation), using described mixing solutions as developping agent, tubing string temperature be 50 DEG C, flow velocity measures under being the condition of 0.40mL/min.The TSK polystyrene standard that polystyrene standard uses eastern Cao (Tosoh) (share) to manufacture.
2. tilt angle measures
Measure according to crystal rotation method (Crystalrotationmethod).
3. voltage retention
Utilize method described in people, the 14th liquid crystal discussion collections of thesis the 78th page (1988) such as " " water Shima and carry out.The square wave of wave height (waveheight) ± 5V is applied to unit (cell) and measures.Measure at 60 DEG C.This value represents that applied voltage keeps the index of which kind of degree afterwards in the frame period (frameperiod), if this value 100% represents keep all electric charges.When being more than 99.5% in the unit being equipped with positive type liquid crystal, when being more than 97.5% in the unit being equipped with negative type liquid crystal, become the liquid crystal display device that display quality is good.
4. the ionic weight in liquid crystal measures (ion density)
According to " Applied Physics ", the 65th volume, method described in No. 10,1065 (1996), liquid crystal physical property measurement system 6254 type using Dongyang technology company to manufacture and measuring.Frequency of utilization is the choppy sea of 0.01Hz, carries out measuring that (area of electrode is 1cm under the voltage range, the temperature of 60 DEG C of ± 10V
2).If ion density is large, then easily produce the unfavorable conditions such as the burning trace caused due to ionic impurity.That is, ion density becomes the physics value that the index that trace produces is burnt in prediction.When this value is below 40pC, become the liquid crystal display device that display quality is good.
< tetracarboxylic dianhydride >
(AN-1-1): 1,2,3,4-butane tetracarboxylic acid dianhydride
(AN-1-13): ethylenediamine tetraacetic acid (EDTA) dianhydride
(AN-2-1): 1,2,3,4-tetramethylene tetracarboxylic dianhydride
(AN-3-2): all benzene tertacarbonic acid's dianhydrides
(AN-4-30): N, N'-(Isosorbide-5-Nitrae-phenylene) two (1,3-dioxo octahydro isobenzofuran-5-methane amide)
(AN-7-2): 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
(AN-10-1): octahydro pentalene-1,3,4,6-tetracarboxylic acid-1,3,4,6-dianhydride
< diamines >
(DI-5-1, m=1): 4,4'-diaminodiphenyl-methane
(DI-5-1, m=4): 4,4'-diamino-diphenyl butane
(DI-5-9): 4,4'-diamino-diphenyl ether
Two (4-amino-benzene oxygen) pentane of (DI-5-12, m=3): 1,3-
(DI-5-30, k=2): two (4-aminophenyl)-N, the N'-dimethyl-ethylenediamine of N, N'-
Two (4-((4-aminophenyl) methyl) phenyl) propane of (DI-7-3, m=3, n=1): 1,3-
(DI-13-1): two (4-aminophenyl) piperazine of 4,4'-N, N'-
(DI-34-6, R
41=n-C
5h
11): 4', 4'-(4-(2-(4-aminophenyl) ethyl) phenyl)-4-amyl group bis cyclohexane
(DI-31-44): 3,5-diaminobenzoic acid cholesteryl ester
< solvent >
Tetrahydrofuran (THF): THF
METHYLPYRROLIDONE: NMP
Gamma-butyrolactone: GBL
Ethylene glycol butyl ether (ethylene glycol monobutyl ether): BC
[synthesis example 1]
Compound represented by synthesis type (1-1-1).
The synthesis of < the 1st stage > acid amides body
Taking into account in the there-necked flask of the 300mL of return line to being provided with temperature, adding 4-amino-2,2,6,6-tetramethyl piperidine (15.0g, 96.0mmol) and salt of wormwood (19.9g, 144.0mmol), and add tetrahydrofuran (THF) (THF) 100mL.Solution is remained less than 5 DEG C by one side, and 3,5-dinitrobenzoyl chloride (24.3g, 105.6mmol) is dissolved in the solution in THF100mL by one side wherein slow interpolation.Stop cooling reaction solution, and then at room temperature stir 3 hours.Reaction soln is poured in pure water 500mL, filter and obtain the crystallization of separating out, at 80 DEG C dry 6 hours and obtain following compound.Output is 32.0g, and productive rate is 95%.
The reduction of < the 2nd stage > nitro
In 1L autoclave reactor, add the palladium carbon dust (3.2g) of compound (32.0g, 91.3mmol) and the 5wt% obtained in the 1st stage, and add tetrahydrofuran (THF) 300mL.Under the hydrogen environment of 0.5mPa, carry out stirring with 50 DEG C until the absorption of hydrogen stops.After placing cooling, utilized and filtered palladium carbon dust, and solvent under reduced pressure was heated up in a steamer and obtains coarse crystallization.In ethanol 50mL, recrystallize is carried out to coarse crystallization and the compound obtained represented by formula (1-1-1).Output is 25.0g, and productive rate is 70%.
[synthesis example 2]
Compound represented by synthesis type (1-1-2).
The synthesis of < the 1st stage > acyl chlorides
In the eggplant type flask of 300mL, add the bromo-5-nitrobenzoic acid (25.0g, 101.6mmol) of 2-, and add thionyl chloride 100mL.Carry out 6 hours reflux, after placing cooling, thionyl chloride decompression heated up in a steamer and obtain 2-bromo-5-oil of mirbane acyl chlorides.Output is 23.5g, and productive rate is 87%.
The synthesis of < the 2nd stage > acid amides body
Taking into account in the there-necked flask of the 300mL of return line to being provided with temperature, adding 4-amino-2,2,6,6-tetramethylpiperidine (13.6g, 87.0mmol) and salt of wormwood (14.4g, 104.4mmol), and adding THF100mL.Solution is remained less than 5 DEG C by one side, and the compound (23.0g, 87.0mmol) that the 1st stage obtained is dissolved in the solution in THF100mL by one side wherein slow interpolation.Stop cooling reaction solution, and then at room temperature stir 3 hours.Reaction soln is poured in pure water 500mL, filter and obtain the crystallization of separating out, at 80 DEG C dry 6 hours and obtain following compound.Output is 29.0g, and productive rate is 87%.
< the 3rd stage >
Take into account in the there-necked flask of the 500mL of return line to being provided with temperature, add the compound (29.0g obtained in the 2nd stage, 75.5mmol), benzophenone imine (15.0g, 83.0mmol), [1,3-two (2,6-diisopropyl phenyl) imidazoles-2-subunit] (the chloro-pyridyl of 3-) palladium chloride (II) (2.1g, 3.0mmol) and potassium t-butoxide (12.7g, 113.2mmol), and add toluene 200mL.Reflux 8 hours in a nitrogen environment, utilizes to filter after placing cooling and removes insolubles, then filtrate poured in pure water (500mL), extract with ethyl acetate (500mL).Pure water (500mL) is utilized to carry out 3 cleanings to organic layer.After making organic layer drying with anhydrous magnesium sulfate, solvent under reduced pressure is heated up in a steamer and obtains coarse crystallization.By silicone tube column chromatography (dissolution fluid; Toluene: ethyl acetate=6:4) separation and purification is carried out to coarse crystallization and obtains following compound.Output is 22.4g, and productive rate is 62%.
< the 4th stage > is to the transformation of amino
In the eggplant type flask of 500mL, add the compound (22.0g, 45.3mmol) obtained in the 3rd stage, and add 6N hydrochloric acid 50mL and THF200mL wherein.At room temperature stir after 12 hours, solvent under reduced pressure is heated up in a steamer.In residue, add pure water 100mL, one side stirs one side and adds 20% aqueous sodium hydroxide solution till its fluidity becomes pH > 7, and then at room temperature stirs 2 hours.Filter the crystallization obtaining and separate out, with pure water, crystallization cleaned and obtain following compound.Output is 12.3g, and productive rate is 85%.
The reduction of < the 5th stage > nitro
In 1L autoclave reactor, add the palladium carbon dust (1.2g) of compound (12.0g, 37.5mmol) and the 5wt% obtained in the 4th stage, and add THF100mL.Under the hydrogen environment of 0.5mPa, carry out stirring with 50 DEG C until the absorption of hydrogen stops.After placing cooling, utilized and filtered palladium carbon dust, and solvent under reduced pressure was heated up in a steamer and obtains coarse crystallization.In ethanol 20mL, recrystallize is carried out to coarse crystallization and the compound obtained represented by formula (1-1-2).Output is 9.4g, and productive rate is 86%.
[synthesis example 3]
Compound represented by synthesis type (C1).
The synthesis of < the 1st stage > ester body
Taking into account in the there-necked flask of the 300mL of return line to being provided with temperature, adding 4-amino-2,2,6,6-tetramethylpiperidine (15.0g, 95.4mmol) and salt of wormwood (19.8g, 143.1mmol), and adding THF100mL.Solution is remained less than 5 DEG C by one side, and 3,5-dinitrobenzoyl chloride (24.2g, 105.0mmol) is dissolved in the solution in THF100mL by one side wherein slow interpolation.Stop cooling reaction solution, and then at room temperature stir 3 hours.Reaction soln is poured in pure water 500mL, filter and obtain the crystallization of separating out, at 80 DEG C dry 6 hours and obtain following compound.Output is 30.3g, and productive rate is 90%.
The reduction of < the 2nd stage > nitro
In 1L autoclave reactor, add the palladium carbon dust (3.0g) of compound (30.0g, 85.4mmol) and the 5wt% obtained in the 1st stage, and add THF300mL.Under the hydrogen environment of 0.5mPa, carry out stirring with 50 DEG C until the absorption of hydrogen stops.After placing cooling, utilized and filtered palladium carbon dust, and solvent under reduced pressure was heated up in a steamer and obtains coarse crystallization.In ethanol 40mL, recrystallize is carried out to coarse crystallization and the compound obtained represented by formula (C1).Output is 17.6g, and productive rate is 71%.
[synthesis example 4]
Compound represented by synthesis type (C2).
< the 1st stage > esterification
Take into account in the there-necked flask of the 300mL of return line to being provided with temperature, add 3,5-binitro bromobenzene (20.0g, 81.0mmol), 4-hydroxyl-2,2,6,6-tetramethyl piperidine (14.0g, 89.1mmol), salt of wormwood (13.4g, 97.2mmol) and potassiumiodide (1.3g, 8.1mmol), and add DMF 200mL.In a nitrogen environment, stir 8 hours with 80 DEG C, after placing cooling, reaction soln is poured in pure water 500mL, filter and obtain the crystallization of separating out, at 80 DEG C dry 6 hours and obtain following compound.Output is 18.9g, and productive rate is 72%.
The reduction of < the 2nd stage > nitro
In 1L autoclave reactor, add the palladium carbon dust (1.8g) of compound (18.0g, 55.7mmol) and the 5wt% obtained in the 1st stage, and add THF200mL.Under the hydrogen environment of 0.5mPa, carry out stirring with 50 DEG C until the absorption of hydrogen stops.After placing cooling, utilized and filtered palladium carbon dust, and solvent under reduced pressure was heated up in a steamer and obtains coarse crystallization.In the mixed solvent 30mL of toluene/ethanol=5/1, recrystallize is carried out to coarse crystallization and the compound obtained represented by formula (C2).Output is 11.9g, and productive rate is 81%.
The preparation of [embodiment 1] varnish
To in the eggplant type flask of 200mL being provided with thermometer, purging with nitrogen gas mouth and stirring rod, add Compound D I-7-3 (m=3, n=1) 2.5874g, compound (1-1-1) 0.610g, and add METHYLPYRROLIDONE (NMP) 59.0g and gamma-butyrolactone (GBL) 15.0g.Solution is cooled to less than 5 DEG C, adds compound (AN-3-1) 0.5553g, compound (AN-2-1) 0.9152g and compound (AN-1-13) 0.3261g wherein, and then at room temperature stir 6 hours.Add ethylene glycol butyl ether (BC) 20.0g wherein, at 70 DEG C, carry out the viscosity of heated and stirred until solution for till about 35.0cP, thus obtain the varnish 1 that solids component is 6wt%.The weight average molecular weight (Mw) of this varnish 1 is 68,000.
The varnish that following solids component is 6wt% is obtained according to method described in embodiment 1.The composition of the varnish obtained, weight average molecular weight (Mw) are shown in table 1.Also again embodiment 1 is disclosed.The respective mol ratio in tetracarboxylic compound group, diamine compound group is represented in [].
Table 1
Table 1 (Continued)
[embodiment 35]
The mensuration > of the preparation of < liquid crystal aligning agent, the making method of FFS unit, voltage retention and ion density
In 50mL eggplant type flask, weigh varnish 110g, add METHYLPYRROLIDONE 10g and ethylene glycol butyl ether 10g wherein, vibrate 2 hours and obtain the liquid crystal aligning agent 1 that solids component is 3wt%.
Turner is utilized to be coated on FFS unit glass substrate by obtained coating varnish.Application conditions be 2300rpm, 15 seconds.After carrying out precalcining in about 5 minutes with 80 DEG C after film, carry out 30 minutes calcination processing with 200 DEG C and form the liquid crystal orientation film that thickness is roughly 100nm.The natural pond gauger (IinumaGauge) that makes to have a meal makes the friction treatment device that limited-liability company of institute manufactures, the hair intrusion of friction cloth (staple length is 1.9mm: artificial silk) be 0.40mm, platform movement speed is 60mm/sec, roller speed of rotation is under the condition of 1000rpm, carries out friction treatment to obtained polyimide film.After in ethanol 5 minutes ultrasonic cleaning being carried out to obtained substrate, utilize ultrapure water clean surface then in an oven with 120 DEG C of dryings 30 minutes.Make 2 be formed on substrate the substrate of alignment films be formed alignment films in the face of to, parallel mode is become with the frictional direction of respective alignment films, and then fit behind the space of formation in order to injection liquid crystal composite between the alignment films towards subtend, thus be assembled into the empty FFS unit that element thickness is 4 μm.In made empty FFS unit, vacuum injects following positive type liquid crystal composition A, and with photo-hardening agent sealing inlet.Then, at 110 DEG C, carry out 30 minutes heat treated and make electrical characteristic evaluation FFS liquid crystal display device (FFS unit) 1-1.
< positive type liquid crystal composition A >
Physics value: NI100.1 DEG C; Δ ε 5.1; Δ n0.093; η 25.6mPas.
The voltage retention of the mensuration unit obtained is 99.8% under 5V, 30Hz, and ion density is 10pC.This unit is placed in backlight trier (Fujiphoto (share) manufacture, Fuji color LED viewer (FujiCOLORLEDViewer) ProHR-2 through lighting; Brightness 2,700cd/m
2) on 1,000 hour and carry out reliability test.The voltage retention of the mensuration unit after reliability test is 99.7%, and ion density is 10pC.
[embodiment 36 ~ embodiment 68 and comparative example 5 ~ comparative example 7]
According to method described in embodiment 35, prepared by liquid crystal aligning agent to varnish 2 ~ varnish 34 and varnish C1 ~ varnish C3, makes FFS unit and measure voltage retention, ion density.Show the result in table 2.Also the result of embodiment 35 is again disclosed.
Table 2
About all unit beyond the display element of the alignment films of the alignment agent comprised containing C3, in the early stage, be good result after reliability test.
[embodiment 69 ~ embodiment 102 and comparative example 8 ~ comparative example 10]
When making electrical characteristic evaluation FFS unit, calcining temperature when being formed by liquid crystal orientation film is set to 230 DEG C, in addition, makes electrical characteristic evaluation FFS unit, thus measure voltage retention and ion density according to method described in embodiment 35.Show the result in table 3.
Table 3
About unit 1-2 ~ unit 34-2, in the early stage, all show good result after reliability test, but confirm in unit C1-2 ~ unit C3-2: in the early stage, see that voltage retention and ion density reduce, deterioration further after reliability test.
[embodiment 103 ~ embodiment 136 and comparative example 11 ~ comparative example 13]
The liquid-crystal composition of injection is replaced with negative type liquid crystal composition B from positive type liquid crystal composition A, in addition, makes electrical characteristic evaluation FFS unit according to method described in embodiment 35, thus measure voltage retention and the ion density of these unit.Show the result in table 4.
< negative type liquid crystal composition B >
Physics value: NI75.7 DEG C; Δ ε-4.1; Δ n0.101; η 14.5mPas.
Table 4
About all unit in embodiment, all obtain good result.
[embodiment 137 ~ embodiment 170 and comparative example 14 ~ comparative example 16]
The liquid-crystal composition of injection is replaced with negative type liquid crystal composition B from positive type liquid crystal composition A, and calcining temperature when being formed by liquid crystal orientation film is set to 230 DEG C, in addition, make electrical characteristic evaluation FFS unit according to method described in embodiment 35, thus measure voltage retention and the ion density of these unit.Show the result in table 5.
Table 5
About unit 1-4 ~ unit 34-4, in the early stage, all show good result after reliability test, but confirm in unit C1-4 ~ unit C3-4: in the early stage, see that voltage retention and ion density reduce, deterioration further after reliability test.
Embodiment according to above: the liquid crystal display device comprising the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention have nothing to do in manufacturing process difference and show certain performance, even if also keep good display quality after long-time always.
[embodiment 171 ~ embodiment 177] utilizes the confirmation of the effect of polymer blend system alignment agent
The varnish that following solids component is 6wt% is obtained according to method described in embodiment 1.The composition of obtained varnish, weight average molecular weight (Mw) are shown in table 6.The respective mol ratio in tetracarboxylic compound group, diamine compound group is represented in [].
Table 6
The preparation of [embodiment 178] polymer blend system alignment agent
Weighing varnish 10.2g and varnish 390.8g in sample bottle, adds NMP/BC=1/1 (weight ratio) 1.67g and obtains alignment agent B1.
[embodiment 179 ~ embodiment 207]
The polymer blend system alignment agent similarly prepared is shown in table 7.Also again embodiment 178 is disclosed.Numeral % by weight in table 7 in [].
Table 7
| Embodiment | Liquid crystal aligning agent | Varnish 1 | Varnish 2 |
| 178 | B1 | 1[20] | 39[80] |
| 179 | B2 | 1[50] | 39[50] |
| 180 | B3 | 1[80] | 39[20] |
| 181 | B4 | 1[20] | 40[80] |
| 182 | B5 | 1[50] | 40[50] |
| 183 | B6 | 1[80] | 40[20] |
| 184 | B7 | 35[20] | 39[80] |
| 185 | B8 | 35[50] | 39[50] |
| 186 | B9 | 35[80] | 39[20] |
| 187 | B10 | 35[20] | 40[80] |
| 188 | B11 | 35[50] | 40[50] |
| 189 | B12 | 35[80] | 40[20] |
| 190 | B13 | 36[20] | 39[80] |
| 191 | B14 | 36[50] | 39[50] |
| 192 | B15 | 36[80] | 39[20] |
| 193 | B16 | 36[20] | 40[80] |
| 194 | B17 | 36[50] | 40[50] |
| 195 | B18 | 36[80] | 40[20] |
| 196 | B19 | 37[20] | 39[80] |
| 197 | B20 | 37[50] | 39[50] |
| 198 | B21 | 37[80] | 39[20] |
| 199 | B22 | 37[20] | 40[80] |
| 200 | B23 | 37[50] | 40[50] |
| 201 | B24 | 37[80] | 40[20] |
| 202 | B25 | 41[20] | 37[80] |
| 203 | B26 | 41[50] | 37[50] |
| 204 | B27 | 41[80] | 37[20] |
| 205 | B28 | 41[20] | 38[80] |
| 206 | B29 | 41[50] | 38[50] |
| 207 | B30 | 41[80] | 38[20] |
| Comparative example 17 | C1-B | C1[20] | 39[80] |
| Comparative example 18 | C2-B | C1[50] | 39[50] |
| Comparative example 19 | C3-B | C1[80] | 39[20] |
| Comparative example 20 | C4-B | C1[20] | 40[80] |
| Comparative example 21 | C5-B | C1[50] | 40[50] |
| Comparative example 22 | C6-B | C1[80] | 40[20] |
[embodiment 208] comprises the electrical characteristic evaluation of the alignment films of polymer blend system alignment agent
Use prepared polymer blend system alignment agent B1, the temperature of calcination processing is replaced with 230 DEG C from 200 DEG C, in addition, make electrical characteristic evaluation FFS liquid crystal display device (FFS unit) B1C according to the method described in embodiment 35.
The voltage retention of the mensuration unit B 1C obtained is 99.7% under 5V, 30Hz, and ion density is 10pC.This unit is placed in backlight trier (Fujiphoto (share) manufacture, the FujiCOLORLEDViewerProHR-2 through lighting; Brightness 2,700cd/m
2) on 1,000 hour and carry out reliability test.The voltage retention of the mensuration unit after reliability test is 99.7%, and ion density is 10pC.
[embodiment 209 ~ embodiment 237, comparative example 23 ~ comparative example 28]
According to method described in embodiment 208, also polymer blend system alignment agent B2 ~ polymer blend system alignment agent B30 and polymer blend system alignment agent C1-B to polymer blend system alignment agent C6-B is made to FFS unit, measures voltage retention, ion density and carry out reliability test.Show the result in table 8.Also the result of embodiment 208 is again disclosed.
Table 8
[embodiment 238]
Use prepared polymer blend system alignment agent B1, the temperature of calcination processing is replaced with 230 DEG C from 200 DEG C, and the liquid-crystal composition of injection is replaced with negative type liquid crystal composition B, in addition, electrical characteristic evaluation FFS liquid crystal display device (FFS unit) B1C-N is made according to the method described in embodiment 35.
The voltage retention of the mensuration unit B 1C-N obtained is 98.0% under 5V, 30Hz, and ion density is 15pC.This unit is placed in backlight trier (Fujiphoto (share) manufacture, the FujiCOLORLEDViewerProHR-2 through lighting; Brightness 2,700cd/m
2) on 1,000 hour and carry out reliability test.The voltage retention of the mensuration unit after reliability test is 97.9%, and ion density is 15pC.
[embodiment 239 ~ embodiment 267, comparative example 29 ~ comparative example 34]
According to method described in embodiment 238, also polymer blend system alignment agent B2 ~ polymer blend system alignment agent B30 and polymer blend system alignment agent C1-B ~ polymer blend system alignment agent C6-B is made to FFS unit, measures voltage retention, ion density and carry out reliability test.Show the result in table 9.Also the result of embodiment 238 is again disclosed.
Table 9
Recognize according to above result: the alignment films comprising liquid crystal aligning agent of the present invention also plays the effect of invention in polymer blend system.And the liquid crystal of clamping all plays the effect of invention in eurymeric and minus.
[comparative example 35]
Varnish 411.0g synthesized in weighing embodiment 177, (Ai Dike (ADEKA) limited-liability company manufactures to add amine system antioxidant wherein, Ai Di Coase tower ripple (Adekastab) LA-72) 0.18mg, and add NMP/BC=1/1 (weight ratio) 1.67g, at room temperature vibrate 1 hour and obtain alignment agent R3HA.
Use prepared alignment agent R3HA, the liquid-crystal composition of injection is replaced with negative type liquid crystal composition B, in addition, make electrical characteristic evaluation FFS liquid crystal display device (FFS unit) R3HAC according to method described in embodiment 35.
The voltage retention of the mensuration unit R 3HAC obtained is 97.5% under 5V, 30Hz, and ion density is 20pC.This unit is placed in backlight trier (Fujiphoto (share) manufacture, the FujiCOLORLEDViewerProHR-2 through lighting; Brightness 2,700cd/m
2) on 1,000 hour and carry out reliability test.The voltage retention of the mensuration unit after reliability test is 83.2%, and ion density is 195pC.
[comparative example 36]
The addition of AdekastabLA-72 is replaced with 1.8mg, in addition, prepares alignment agent R3HB by method described in comparative example 35, thus make electrical characteristic FFS liquid crystal display device R3HBC.
The voltage retention of the mensuration unit R 3HBC obtained is 97.8% under 5V, 30Hz, and ion density is 25pC.This unit is placed in backlight trier (Fujiphoto (share) manufacture, the FujiCOLORLEDViewerProHR-2 through lighting; Brightness 2,700cd/m
2) on 1,000 hour and carry out reliability test.The voltage retention of the mensuration unit after reliability test is 91.1%, and ion density is 105pC.But the display confirmed caused by spot from the initial stage in unit R 3HBC is bad.Think this display bad be that the JF-90 segregation added, in most surface, produces spot bad thus when preparing alignment films.
[comparative example 37]
The addition of AdekastabLA-72 is replaced with 18.0mg, in addition, prepares alignment agent R3HC by method described in comparative example 35, thus make electrical characteristic FFS liquid crystal display device R3HCC.
The voltage retention of the mensuration unit R 3HCC obtained is 97.6% under 5V, 30Hz, and ion density is 25pC.This unit is placed in backlight trier (Fujiphoto (share) manufacture, the FujiCOLORLEDViewerProHR-2 through lighting; Brightness 2,700cd/m
2) on 1,000 hour and carry out reliability test.The voltage retention of the mensuration unit after reliability test is 91.9%, and ion density is 95pC.But the display confirmed caused by spot from the initial stage in unit R 3HCC is bad.
[utilizability in industry]
The liquid crystal orientation film formed by liquid crystal aligning agent of the application of the invention, can obtain the liquid crystal display device of the excellence that also can not decline through long-time display quality.This effect is played characteristically in the liquid crystal display device of IPS pattern and FFS mode.
Claims (17)
1. a polyamic acid or derivatives thereof, it makes at least one of the diamines represented by formula (1) and at least one of tetracarboxylic dianhydride react and obtain:
In formula (1), R
1hydrogen or methyl; And
R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
2. polyamic acid or derivatives thereof according to claim 1, at least one of the diamines of the diamines represented by its Chinese style (1) represented by formula (1-1):
In formula (1-1), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
3. polyamic acid or derivatives thereof according to claim 1, at least one of the diamines of the diamines represented by its Chinese style (1) represented by formula (1-2):
In formula (1-2), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
4. polyamic acid or derivatives thereof according to claim 2, the diamines represented by its Chinese style (1) is for being selected from least one in the group of the compound represented by formula (1-1-1) ~ formula (1-1-28):
5. polyamic acid or derivatives thereof according to claim 3, the diamines represented by its Chinese style (1) is for being selected from least one in the group of the compound represented by formula (1-2-1) ~ formula (1-2-28):
6. polyamic acid or derivatives thereof according to any one of claim 1 to 5, it is that at least one of diamines represented by formula (1) and the mixture of at least one of other diamines and at least one of tetracarboxylic dianhydride are carried out reacting and obtained.
7. polyamic acid or derivatives thereof according to any one of claim 1 to 6, wherein tetracarboxylic dianhydride is for being selected from least one in the group of the tetracarboxylic dianhydride represented by following formula (AN-I) ~ formula (AN-VII):
In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently singly-bound or-CH
2-;
In formula (AN-II), G is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-;
In formula (AN-II) ~ formula (AN-IV), Y is independent of being selected from the one in the group of the base of following trivalent,
At least one hydrogen of described base can be replaced by methyl, ethyl or phenyl;
In formula (AN-III) ~ formula (AN-V), ring A
10for the base of carbon number to be the base of the monocyclic hydrocarbon of 3 ~ 10 or carbon number the be condensation polycyclic formula hydrocarbon of 6 ~ 30, at least one hydrogen of described base can be replaced by methyl, ethyl or phenyl, the associative key be connected on ring links with the arbitrary carbon forming ring, and 2 associative keys can link with same carbon;
In formula (AN-VI), X
10for carbon number is the alkylidene group of 2 ~ 6, Me represents methyl, and Ph represents phenyl,
In formula (AN-VII), G
10independent is-O-,-COO-or-OCO-; And r is independently 0 or 1.
8. polyamic acid or derivatives thereof according to claim 7, wherein tetracarboxylic dianhydride is for being selected from following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-11-3), formula (AN-16-3), and at least one in formula (AN-16-4):
In formula (AN-1-2) and formula (AN-4-17), m is the integer of 1 ~ 12.
9. polyamic acid or derivatives thereof according to claim 6, wherein other diamines are for being selected from least one in the group that is made up of following formula (DI-1) ~ formula (DI-16), formula (DIH-1) ~ formula (DIH-3) and formula (DI-31) ~ formula (DI-35):
In formula (DI-1), G
20for-CH
2-, at least one-CH
2-can be replaced by-NH-,-O-, m is the integer of 1 ~ 12, and at least one hydrogen of alkylidene group can be replaced by-OH;
In formula (DI-3) and formula (DI-5) ~ formula (DI-7), G
21independent is singly-bound ,-NH-,-NCH
3-,-O-,-S-,-S-S-,-SO
2-,-CO-,-COO-,-CONH-,-CONCH
3-,-C (CH
3)
2-,-C (CF
3)
2-,-(CH
2)
m'-,-O-(CH
2)
m'-O-,-N (CH
3)-(CH
2)
k-N (CH
3)-,-(O-C
2h
4)
m'-O-,-O-CH
2-C (CF
3)
2-CH
2-O-,-O-CO-(CH
2)
m'-CO-O-,-CO-O-(CH
2)
m'-O-CO-,-(CH
2)
m'-NH-(CH
2)
m'-,-CO-(CH
2)
k-NH-(CH
2)
k-,-(NH-(CH
2)
m')
k-NH-,-CO-C
3h
6-(NH-C
3h
6)
n-CO-or-S-(CH
2)
m'-S-, m' are independently the integer of 1 ~ 12, and k is the integer of 1 ~ 5, and n is 1 or 2;
In formula (DI-4), s is independently the integer of 0 ~ 2;
In formula (DI-6) and formula (DI-7), G
22independent is singly-bound ,-O-,-S-,-CO-,-C (CH
3)
2-,-C (CF
3)
2-or carbon number be the alkylidene group of 1 ~ 10;
In formula (DI-2) ~ formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can be the alkyl ,-OCH of 1 ~ 3 by-F ,-Cl, carbon number
3,-OH ,-CF
3,-CO
2h ,-CONH
2,-NHC
6h
5, phenyl or benzyl replace, in addition, in formula (DI-4), at least one hydrogen of phenyl ring can by a replacement in the group of the base be selected from represented by following formula (DI-4-a) ~ formula (DI-4-e);
In formula (DI-4-a) and (DI-4-b), R
20independent is hydrogen or-CH
3;
The basis representation binding site on which ring that binding site is not fixed on the carbon atom forming ring is any ,-NH
2binding site on cyclohexane ring or phenyl ring is for removing G
21or G
22binding site beyond arbitrary position;
In formula (DI-11), r is 0 or 1;
In formula (DI-8) ~ formula (DI-11) ,-NH of bond on ring
2binding site be arbitrary position;
In formula (DI-12), R
21and R
22independently for carbon number is the alkyl or phenyl of 1 ~ 3, G
23independent for carbon number be 1 ~ 6 alkylidene group, phenylene or the phenylene through alkyl replacement, w is the integer of 1 ~ 10;
In formula (DI-13), R
23independent for carbon number be 1 ~ 5 alkyl, carbon number be 1 ~ 5 alkoxyl group or-Cl, p be independently 0 ~ 3 integer, q is the integer of 0 ~ 4;
In formula (DI-14), ring B is monocyclic heteroaromatic, R
24the thiazolinyl, the carbon number that are 2 ~ 6 for hydrogen ,-F ,-Cl, the carbon number alkyl that is 1 ~ 6, the carbon number alkoxyl group that is 1 ~ 6, carbon number are the alkynyl of 1 ~ 6, and q is independently the integer of 0 ~ 4;
In formula (DI-15), ring C is for containing heteroatomic monocycle;
In formula (DI-16), G
24for alkylidene group or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2 ~ 6, r is 0 or 1;
In formula (DI-13) ~ formula (DI-16), the basis representation binding site on which ring that binding site is not fixed on the carbon atom forming ring is any;
In formula (DIH-1), G
25for singly-bound, carbon number are alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-;
In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl;
In formula (DIH-3), ring E is independently cyclohexane ring or phenyl ring, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl, and Y is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20
2-,-C (CH
3)
2-or-C (CF
3)
2-;
In formula (DIH-2) and formula (DIH-3) ,-CONHNH of bond on ring
2binding site be arbitrary position;
In formula (DI-31), G
26for singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-or-(CH
2)
m'-, m' is the integer of 1 ~ 12, R
25for carbon number be 3 ~ 30 alkyl, phenyl, have the base of steroid skeleton or the base represented by following formula (DI-31-a), in described alkyl, at least one hydrogen can be replaced by-F, at least one-CH
2-can be replaced by-O-,-CH=CH-or-C ≡ C-, the hydrogen of described phenyl can by-F ,-CH
3,-OCH
3,-OCH
2f ,-OCHF
2,-OCF
3, carbon number be 3 ~ 30 alkyl or carbon number be 3 ~ 30 alkoxyl group replace ,-the NH of bond on phenyl ring
2binding site represent for arbitrary position in described ring,
In formula (DI-31-a), G
27, G
28and G
29for bond base, they are independently singly-bound or carbon number is the alkylidene group of 1 ~ 12, the more than one-CH of described alkylidene group
2-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-, ring B
21, ring B
22, ring B
23and ring B
24independent is Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, ring B
21, ring B
22, ring B
23and ring B
24in, at least one hydrogen can by-F or-CH
3replace, s, t and u are independently the integer of 0 ~ 2, they add up to 1 ~ 5, when s, t or u are 2,2 bond bases in each bracket can be identical, also can be different, and 2 rings can be identical, also can be different,
R
26for hydrogen ,-F ,-OH, the carbon number alkyl that is 1 ~ 30, the carbon number fluorine substituted alkyl that is 1 ~ 30, carbon number are alkoxyl group ,-the CN ,-OCH of 1 ~ 30
2f ,-OCHF
2or-OCF
3, described carbon number is at least one-CH of the alkyl of 1 ~ 30
2-can replace by with the base of the divalence represented by following formula (DI-31-b),
In formula (DI-31-b), R
27and R
28independently for carbon number is the alkyl of 1 ~ 3, v is the integer of 1 ~ 6;
In formula (DI-32) and formula (DI-33), G
30independent is singly-bound ,-CO-or-CH
2-, R
29independent is hydrogen or-CH
3, R
30for hydrogen, carbon number be 1 ~ 20 alkyl or carbon number be the thiazolinyl of 2 ~ 20;
The alkyl or phenyl that a hydrogen of the phenyl ring in formula (DI-33) can be 1 ~ 20 by carbon number replaces, and,
In formula (DI-32) and formula (DI-33), the basis representation binding site on which ring that binding site is not fixed on any one carbon atom forming ring is any;
In formula (DI-34) and formula (DI-35), G
31independently for-O-or carbon number are the alkylidene group of 1 ~ 6, G
32for singly-bound or carbon number are the alkylidene group of 1 ~ 3,
R
31for at least one-CH that hydrogen or carbon number are the alkyl of 1 ~ 20, described alkyl
2-can be replaced by-O-,-CH=CH-or-C ≡ C-, R
32for carbon number is the alkyl of 6 ~ 22, R
33for hydrogen or carbon number are the alkyl of 1 ~ 22, ring B
25for Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1, and ,-the NH of bond on phenyl ring
2represent that binding site is on which ring any.
10. polyamic acid or derivatives thereof according to claim 6, wherein other diamines are for being selected from by following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-13-1), formula (DI-16-1), and at least one in the group that forms of formula (DIH-2-1):
In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13) and formula (DI-7-3), m is the integer of 1 ~ 12;
In formula (DI-5-30), k is the integer of 1 ~ 5; And
In formula (DI-7-3), n is 1 or 2.
11. 1 kinds of liquid crystal aligning agent, it contains polyamic acid or derivatives thereof according to any one of claim 1 to 10.
12. 1 kinds of liquid crystal aligning agent, it contains polyamic acid or derivatives thereof according to any one of claim 1 to 10 and the polymkeric substance except them.
13. liquid crystal aligning agent according to claim 11 or 12, it is also containing at least one be selected from the compound group that is made up of alkenyl substituted Na Dike imide compound, the compound with free-radical polymerised unsaturated double-bond, oxazine compounds, oxazoline compound and epoxy compounds.
14. 1 kinds according to claim 11 to the liquid crystal aligning agent according to any one of 13, it is for lateral electric-field type liquid crystal display device.
15. 1 kinds of liquid crystal orientation films, it is formed by according to claim 11 to the liquid crystal aligning agent according to any one of 14.
16. 1 kinds of liquid crystal display device, it comprises liquid crystal orientation film according to claim 15.
17. 1 kinds of diamines, it is represented by formula (1-2):
In formula (1-2), R
2hydrogen ,-OH, carbon number be 1 ~ 6 alkyl or carbon number be the alkoxyl group of 1 ~ 6.
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| JP2014177607A JP6398480B2 (en) | 2014-07-15 | 2014-09-02 | Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| JP2014-177607 | 2014-09-02 |
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| CN106190176A (en) * | 2015-05-26 | 2016-12-07 | 捷恩智株式会社 | Light orientation aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells and lateral electric-field type liquid crystal display cells |
| CN107163952A (en) * | 2017-06-02 | 2017-09-15 | 合肥市惠科精密模具有限公司 | A kind of aligning agent for liquid crystal |
| CN107779207A (en) * | 2016-08-24 | 2018-03-09 | 奇美实业股份有限公司 | Liquid crystal alignment agent and application thereof |
| CN108003614A (en) * | 2016-10-28 | 2018-05-08 | 奇美实业股份有限公司 | Composition for flexible substrate, method for producing same, and flexible substrate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106190176A (en) * | 2015-05-26 | 2016-12-07 | 捷恩智株式会社 | Light orientation aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells and lateral electric-field type liquid crystal display cells |
| CN107779207A (en) * | 2016-08-24 | 2018-03-09 | 奇美实业股份有限公司 | Liquid crystal alignment agent and application thereof |
| CN108003614A (en) * | 2016-10-28 | 2018-05-08 | 奇美实业股份有限公司 | Composition for flexible substrate, method for producing same, and flexible substrate |
| CN108003614B (en) * | 2016-10-28 | 2021-06-29 | 奇美实业股份有限公司 | Composition for flexible substrate, method for producing same, and flexible substrate |
| CN107163952A (en) * | 2017-06-02 | 2017-09-15 | 合肥市惠科精密模具有限公司 | A kind of aligning agent for liquid crystal |
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| CN105315463B (en) | 2019-11-26 |
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