CN101633780A - Light alignment agent, alignment firm and liquid crystal display element using alignment film - Google Patents
Light alignment agent, alignment firm and liquid crystal display element using alignment film Download PDFInfo
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- CN101633780A CN101633780A CN200910129305A CN200910129305A CN101633780A CN 101633780 A CN101633780 A CN 101633780A CN 200910129305 A CN200910129305 A CN 200910129305A CN 200910129305 A CN200910129305 A CN 200910129305A CN 101633780 A CN101633780 A CN 101633780A
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- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an alignment film with good alignment performance and less color. The light alignment agent is composed of a polymer component A with the light alignment ability, a polymer component B having the liquid crystal temperature range during 100 DEG C to 300 DEG C and a solvent; wherein component A is 10wt.% to 90wt.% of the total weight of A and B components; additionally, the solvent is 70wt.% to 99.9wt.% of the total weight of the composition; component A is preferably polyamide acid or polyimide whose main chain has at least one component from the photosensitive groups shown in formula (I) to formula (V) and formula (X); component B is preferably liquid crystal polyamide acid or polyimide whose main chain has straight chain alkylidene structure with 6-20 carbon atoms; and R1, R2 and R3 are aromatic divalent groups.
Description
Technical field
The liquid crystal display device that the present invention relates to the manufacture method of a kind of alignment film, this alignment film and have this alignment film.
Background technology
It is in the view finder (view finder), the projected display various liquid crystal indicators such as (projection display) of representative, pick up camera (video camera) that liquid crystal display device is used in the screen (monitor) of notebook computer (notebook computer) or desktop computer (desktop computer), also begins to be used for TV (television) recently.In addition, liquid crystal display device also can be used as optical print head (optical printer head), optical Fourier transform element, light valve photoelectronics (optoelectronics) related elements such as (light valve).The main flow of existing liquid crystal display device is to use the display element of nematic liquid crystal (nematic liquid crystal), and the liquid crystal display device of following pattern is put to practicality: twisted-nematic (TwistedNematic, TN) pattern, the alignment direction that is positioned near the liquid crystal the substrate is turned round the angle that turn 90 degrees to each other with the alignment direction that is positioned near the liquid crystal another substrate; Supertwist to row (SuperTwisted Nematic, STN) pattern, described alignment direction reverse usually more than or equal to 180 the degree angle; And so-called thin film transistor (Thin-film-transistor, TFT) pattern of using thin film transistor.
But, these liquid crystal display device can watch the visual angle of image narrow suitably, when vergence direction is watched, the situation that exists brightness or contrast gradient to descend, and exist the situation that brightness is reversed takes place shadow tone (halftone) under.In recent years, utilize to use the TN type liquid crystal display device of optical compensation films, use multiregional vertical align (the Multi-domain Vertical Alignment of the technology of vertical orientation and raised structures thing simultaneously, MVA) switch (In-Plane Switching in the face of pattern (for example with reference to No. 2947350 communique of Japanese Patent) or transverse electric field mode, IPS) pattern (for example with reference to No. 2940354 communique of Japanese Patent) etc. is improved described visual angle problem.
The development of liquid crystal display device technology not only can be reached by the improvement of these type of drive or component structure, also can reach by employed member of formation in the display element is improved.In the employed member of formation of display element, particularly liquid crystal orienting film is an important key element that is related to the display quality of liquid crystal display device, is accompanied by high-qualityization of display element, and the effect of liquid crystal orienting film becomes more and more important.
For this liquid crystal orienting film, in order to make liquid crystal display device obtain uniform display characteristic, must control the molecular arrangement of liquid crystal evenly, therefore, require described liquid crystal orienting film to make the liquid crystal molecule on the substrate form certain pitch angle (tilt angle) towards an even orientation of direction and with substrate surface.So, the liquid crystal orienting film that the direction of the liquid crystal molecule on the substrate is arranged in same direction becomes important in the manufacturing step of liquid crystal display device and must obligato technology.
Liquid crystal orienting film is to use the LCD alignment agent to prepare.The main at present LCD alignment agent of using is the solution that the polyimide (polyimide) of polyamic acid (polyamic acid) or solubility is dissolved in gained in the organic solvent.After this solution coat is on substrate, form film by methods such as heating, be liquid crystal orienting film thereby form polyimide.Also the various LCD alignment agent beyond the polyamic acid are studied, but nearly all can not be put to practicality from aspects such as thermotolerance, chemical resistant properties (anti-liquid crystal liquid crystal property), coating, LCD alignment, electrical characteristic, optical characteristics, display characteristics.
Industrial, extensively adopt rubbing manipulation (rubbing) easy and that can carry out large-area high speed processing to be used as the orientation facture.Rubbing manipulation is to use the processing of the cloth of fibers such as being implanted with nylon (nylon), artificial silk (rayon), polyester along the surface of a direction friction liquid crystal orienting film, can make liquid crystal molecule obtain same orientation thus.But the someone points out that rubbing manipulation can cause producing problems such as dust, static.
Up to now, the LCD alignment mechanism of having implemented on the liquid crystal orienting film that orientation handles by friction treatment has proposed following two kinds:
(1) the surface shape effect of the liquid crystal orienting film that brought of the microgroove groove (microgroove) that produces by friction treatment
(2) by the liquid crystal orienting film of friction treatment and single shaft orientation and the molecular interaction of the liquid crystal unimolecular layer that contacts with this liquid crystal orienting film
In recent years, confirm that the effect of (1) surface shape effect is less relatively, in the highest flight be the effect that (2) molecular interaction is brought into play.
On the other hand, implement the light orientation method that orientation is handled about irradiates light, proposed multiple orientation mechanism such as photolysis method, photoisomerization method, photodimerization method, optical cross-linking method (for example opening 2005-275364 communique and Japanese patent laid-open 11-15001 communique) with reference to " liquid crystal " the 3rd volume No. 4 the 262nd page of (1999), Japanese Patent spy.Particularly light orientation method is different with rubbing manipulation, is a kind of non-contacting alignment method, plays a role as the orientation mechanism of liquid crystal so it is generally acknowledged (2) molecular interaction only.In addition, because light orientation facture does not contact, so dust that is produced on principle or static lack than friction treatment.
Therefore, particularly utilize light orientation method to implement the good liquid crystal orienting film of regiospecific that orientation is handled by use, can expect the molecule orientation state of the liquid crystal unimolecular layer that contacts with liquid crystal orienting film is controlled, thereby improve the performance of liquid crystal display device.
Summary of the invention
The objective of the invention is to, provide a kind of regiospecific good especially and painted less, alignment film that photostabilization is high, technical problem to be solved is the polymkeric substance that makes it have liquid crystal liquid crystal property by fusion in light orientation agent, can improve the light regiospecific, orientation stability is high, and can reduce painted when making film, thereby be suitable for practicality more.
The object of the invention to solve the technical problems realizes by the following technical solutions.For achieving the above object, will be shown in following [1] item according to smooth orientation agent of the present invention.
[1] a kind of smooth orientation agent, it is to contain as at least a A composition with polymkeric substance of light orientation ability, as the B composition of at least a polymkeric substance that has liquid crystal temperature range in 100 ℃～300 ℃ scope and the constituent of solvent, it is characterized in that: with the total weight of A composition and B composition as benchmark, the A components in proportions is 10 weight %～90 weight %, in addition, as benchmark, the ratio of solvent is 70 weight %～99.9 weight % with the total amount of this constituent.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, light orientation agent of the present invention, alignment film and use the liquid crystal display device of this alignment film to have following advantage and beneficial effect at least: if use smooth orientation agent of the present invention as for example LCD alignment agent, it is identical with the orientation that utilizes the rubbing manipulation gained or than higher film then can to obtain LCD alignment by the rayed of short period of time.And the painted of film also can obviously reduce.In addition, can obtain the light alignment film that can not change owing to this light in irradiation light time orientations such as (backlight) backlight.
In sum, the object of the present invention is to provide the good especially and painted few alignment film of a kind of regiospecific.Light orientation agent is to contain as at least a A composition with polymkeric substance of light orientation ability, as the B composition of at least a polymkeric substance that has liquid crystal temperature range in 100 ℃～300 ℃ scope and the constituent of solvent, and, with the total weight of A composition and B composition as benchmark, the A components in proportions is 10 weight %～90 weight %, in addition, as benchmark, the ratio of solvent is 70 weight %～99.9 weight % with the total amount of this constituent.The preference of A composition is at least a polyamic acid or the polyimide that has on the main chain with in the represented photosensitive group of formula (I)～formula V and formula (X), and the preference of B composition is to have polyamic acid or the polyimide that carbon number is the liquid crystal liquid crystal property of 6～20 straight-chain alkyl-sub-structure on the main chain.R1, R2 and R3 are the aromatic series divalent group.
-R
1-C≡C-R
2-???????????????????????????(I)
-R
1-C≡C-C≡C-R
2-??????????????????????(II)
-R
1-C≡C-CH＝CH-R
2-????????????????????(III)
-R
1-C≡C-R
2-C≡C-R
3-???????????????????(IV)
-R
1-C≡C-R
2-CH＝CH-R
3-?????????????????(V)
-N＝N-?????????????????????????????????(X)
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is the alignment film B that measured among the embodiment 15 and the UV-Vis spectrum of alignment film O.
Fig. 2 is the photo of the liquid crystal cells S behind the light fastness test that is carried out among the embodiment 18.
Fig. 3 is the photo of the liquid crystal cells Y behind the light fastness test that is carried out in the comparative example 4.
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, light orientation agent, alignment film that foundation the present invention is proposed and its embodiment of liquid crystal display device, structure, feature and the effect thereof of using this alignment film, describe in detail as after.
Relevant aforementioned and other technology contents, characteristics and effect of the present invention can be known to present in the detailed description of graphic preferred embodiment is consulted in following cooperation.By the explanation of embodiment, when can being to reach technique means that predetermined purpose takes and effect to obtain one more deeply and concrete understanding to the present invention, yet appended graphic only provide with reference to the usefulness of explanation, be not to be used for the present invention is limited.
Employed term among the present invention is described.Sometimes will be designated as compound (I-1) with the represented compound of formula (I-1).The compound sometimes similarly abbreviation represented to other formulas.During the definition chemical structural formula employed " arbitrarily ", represent that not only the position is any, and number is also any.In the chemical structural formula, use the hexagon frame to live the group of the group representative ring structure of letter (for example B) (ring B), group Me represents methyl.
The present invention is made of described [1] item and following [2] item～[11] item.
[2] according to [1] described smooth orientation agent, it is characterized in that: the A composition is at least a polymkeric substance that is selected from the group that polyamic acid, part imidization polyamic acid and polyimide form.
[3] according to [1] described smooth orientation agent, it is characterized in that: the A composition is at least a polymkeric substance that is selected from the group that polyamic acid, part imidization polyamic acid and polyimide form, and has photosensitive group on the main chain of this polymkeric substance.
[4] according to [a 1] described smooth orientation agent, it is characterized in that: the A composition is to be selected from polyamic acid, at least a polymkeric substance in the group that part imidization polyamic acid and polyimide are formed, and have at least a with in the represented photosensitive group of formula (I)～formula V and formula (X) on the main chain of this polymkeric substance, in addition, the B composition is to be selected from polyamic acid, at least a liquid-crystalline polymer in the group that part imidization polyamic acid and polyimide are formed, and has carbon number on the main chain of this polymkeric substance and is 6～20 straight-chain alkyl-sub-structure, one or non-conterminous two-CH in this straight-chain alkyl-sub-structure
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-replace;
-R
1C≡C-R
2-?????????????????????(I)
-R
1C≡C-C≡C-R
2-????????????????(II)
-R
1C≡C-CH＝CH-R
2-??????????????(III)
-R
1C≡C-R
2-C≡C-R
3-?????????????(IV)
-R
1-C≡C-R
2-CH＝CH-R
3-??????????(V)
-N＝N-??????????????????????????(X)
Wherein, R
1, R
2And R
3Be the aromatic series divalent group independently.
[5] according to [a 4] described smooth orientation agent, it is characterized in that: the A composition is to use at least a polymkeric substance that obtains as raw material in the represented compound of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (X-1)～formula (X-8);
[6] according to [a 4] described smooth orientation agent, it is characterized in that: the B composition is polyimide or its precursor polyamic acid that has with the represented structural unit of formula (VI);
Wherein, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-the carbon number that replaces is 2～20 alkylidene group, with the represented divalent group of formula (VIII) or with the represented divalent group of formula (IX), the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2The carbon number of-replacement is 6～20 alkylidene group;
In the formula (VIII), X
1And X
2For singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G
1And G
2Be singly-bound, comprise perhaps that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the alicyclic ring; R
5For hydrogen, fluorine ,-CN ,-OH or carbon number are 1～30 alkyl, perfluoroalkyl or alkoxyl group; In addition, work as X
1, G
1, X
2And G
2When being singly-bound, R
5For alkyl, perfluoroalkyl or the alkoxyl group of carbon number 3～30, work as G
2Be singly-bound and X
2Neither when singly-bound neither alkylidene group, R
5For hydrogen or carbon number are 3～30 alkyl, work as G
1And G
2When being singly-bound, X
1, X
2And R
5The total carbon number more than or equal to 3;
In the formula (IX), R
6It for hydrogen or carbon number 1～12 alkyl; Ring B for hydrogen arbitrarily can by carbon number be 1～4 alkyl replace 1, the 4-phenylene or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the 4-cyclohexylidene; X
0It for singly-bound or carbon number 1～5 alkylidene group; S is 0～3 integer; When s was 2, two ring B both can be the same or different two X
0Also be both to can be the same or different; When s is 3, three or any two the ring B both can be the same or different three or any two X
0Also be both to can be the same or different; Z
1And Z
2Be independently singly-bound ,-CH
2-,-CH
2CH
2-or-O-; T1 and t2 are 0～3 integer independently; When t1 is 2, two Z
1Both can be the same or different; When t1 is 3, three or any two Z
1Both can be the same or different; When t2 is 2, two Z
2Both can be the same or different; When t2 is 3, three or any two Z
2Both can be the same or different.
[7] according to [a 4] described smooth orientation agent, it is characterized in that: the A composition is to use at least a polymkeric substance that obtains as raw material in the represented compound of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (X-1)～formula (X-8), and the B composition is polyimide or its precursor polyamic acid that has with the represented structural unit of formula (VI);
Wherein, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-the carbon number that replaces is 2～20 alkylidene group, with the represented divalent group of formula (VIII) or with the represented divalent group of formula (IX), the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2The carbon number of-replacement is 6～20 alkylidene group;
In the formula (VIII), X
1And X
2Independently for singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G
1And G
2Be singly-bound independently, comprise perhaps that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the alicyclic ring; R
5For hydrogen, fluorine ,-CN ,-OH or carbon number are 1～30 alkyl, perfluoroalkyl or alkoxyl group; In addition, work as X
1, G
1, X
2And G
2When being singly-bound, R
5For alkyl, perfluoroalkyl or the alkoxyl group of carbon number 3～30, work as G
2Be singly-bound and X
2Neither when singly-bound neither alkylidene group, R
5For hydrogen or carbon number are 3～30 alkyl, work as G
1And G
2When being singly-bound, X
1, X
2And R
5The total carbon number more than or equal to 3;
In the formula (IX), R
6It for hydrogen or carbon number 1～12 alkyl; Ring B for hydrogen arbitrarily can by carbon number be 1～4 alkyl replace 1, the 4-phenylene or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the 4-cyclohexylidene; X
0It for singly-bound or carbon number 1～5 alkylidene group; S is 0～3 integer; When s was 2, two ring B both can be the same or different two X
0Also be both to can be the same or different; When s is 3, three or any two the ring B both can be the same or different three or any two X
0Also be both to can be the same or different; Z
1And Z
2Be independently singly-bound ,-CH
2-,-CH
2CH
2-or-O-; T1 and t2 are 0～3 integer independently; When t1 is 2, two Z
1Both can be the same or different; When t1 is 3, three or any two Z
1Both can be the same or different; When t2 is 2, two Z
2Both can be the same or different; When t2 is 3, three or any two Z
2Both can be the same or different.
[8] according to [a 7] described smooth orientation agent, it is characterized in that: the R in the formula (VI)
4For the alkylidene group of carbon number 2～20 or with the represented divalent group of formula (VIII-1), and the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Alkylidene group for carbon number 6～20;
Wherein, ring B
1And ring B
2Be singly-bound or 1 independently, 4-cyclohexylidene, G
3For singly-bound or-CH
2CH
2-, in addition, R
7It for hydrogen or carbon number 1～20 alkyl.
[9] a kind of liquid crystal orienting film is characterized in that: it is to use basis [1] item to each described smooth orientation agent in [8] item to make.
[10] a kind of liquid crystal display device is characterized in that: it is to use basis [9] described liquid crystal orienting film to make.
[11] a kind of manufacture method of liquid crystal orienting film, it is characterized in that: will contain have light orientation ability polymkeric substance as the A composition and contain the polymkeric substance that in 100 ℃～300 ℃ scope, has liquid crystal temperature range and be coated on the substrate as the light orientation agent of B composition and form film, irradiates light and after making this film orientation is warmed up to the heat treated till the liquid crystal temperature of B composition.
It is important that the A composition of smooth orientation agent of the present invention not only utilizes this film of photoinduction to produce aspect anisotropic when film is made in smooth orientation agent of the present invention, and also important aspect anisotropic maintenance.For example, when improving the aftermentioned alignment film formation method of light regiospecific etc. when adopt using polyamic acid to carry out roasting after being used as A composition, irradiates light, preferably, the temperature range that is chosen in the roasting of carrying out usually promptly be the composition of non-liquid crystal liquid crystal property in 100 ℃～300 ℃, so that can be owing to heating causes anisotropy decline.According to identical therewith reason, more preferably, further be chosen in and be less than or equal to 300 ℃ and do not have glass transition point (glass transition point, composition Tg).Particularly, the A composition preferably have light orientation ability polyamic acid, make the polymkeric substance of this polyamic acid part imidization gained or make this polyamic acid polyimide of cyclodehydration gained fully, more preferably have these polymkeric substance of photosensitive group on the main chain.
Polymkeric substance with light orientation ability, promptly there is no particular restriction for the photosensitive group that polymkeric substance had of light regiospecific, can select well-known all photosensitive groups.The example of known photosensitive group has: nitrogen benzide (azobenzene) derivative, maleimide (maleimide) derivative, cinnamophenone (chalcone) derivative, styracin (cinnamic acid) derivative, 1,2-vinylidene derivative, 1, contained photosensitive group in 2-acetylene-derivative, spiro-pyrans (spiropyran) derivative, spirobenzopyran (spirobenzopyran) derivative and fulgide (fulgide) derivative.
Smooth orientation agent of the present invention preferably contains at least a as the A composition of at least a polymkeric substance that is selected from the group that following polymkeric substance forms: have polyamic acid with at least a non-liquid crystal liquid crystal property in the represented photosensitive group of formula (I)～formula V and formula (X) on the main chain, make the polymkeric substance of this polyamic acid part imidization gained and make this polyamic acid polyimide of cyclodehydration gained fully.
-R
1-C≡C-R
2-???????????????????(I)
-R
1-C≡C-C≡C-R
2-??????????????(II)
-R
1-C≡C-CH＝CH-R
2-????????????(III)
-R
1-C≡C-R
2-C≡C-R
3-???????????(IV)
-R
1-C≡C-R
2-CH＝CH-R
3-?????????(V)
-N＝N-?????????????????????????(X)
R in formula (I)～formula V
1, R
2And R
3Be the aromatic series divalent group independently.The preference of aromatic series divalent group has 1,4-phenylene, 1,3-phenylene, 2-methyl isophthalic acid, 4-phenylene, 2-methyl isophthalic acid, 3-phenylene, 4,4 '-biphenylene and ditan-4,4 '-two bases, the hydrogen arbitrarily of these rings can be replaced by fluorine or chlorine.In addition, in these groups, more preferably 1,4-phenylene and 1,3-phenylene, most preferably 1,4-phenylene.
By selecting with formula (I)～formula V and the represented photosensitive group of formula (X), can the light regiospecific is big and characteristic painted few of the present invention smooth orientation agent perform to greatest extent.Two keys of the photosensitive group of formula (III) and formula V exist cis (cis-) or trans (trans-) two kinds of isomers, but smooth orientation agent of the present invention uses in these isomers any all can.
In order to obtain to have on the main chain, use diamines or/and carboxylic acid dianhydride to be used as raw material and to get final product with this photosensitive group with at least a polyamic acid in the represented photosensitive group of formula (I)～formula V and formula (X).Particularly, preferably use diamines to be used as raw material with photosensitive group in order to obtain high light regiospecific.
Have in the diamines with the represented photosensitive group of formula (I)～formula V, specially suitable example can be enumerated with formula (I-1)～represented diamines of formula (V-1).
Have and be shown in following with the diamines of the represented photosensitive group of formula (X) or tetracarboxylic dianhydride's suitable example.
According to the desired characteristic of alignment film, when the polymkeric substance of making as A composition of the present invention, can use the described well-known diamines that has the diamines of photosensitive group and do not have photosensitive group simultaneously.For example, when alignment film is used as the alignment film that the nematic liquid crystal constituent uses in the liquid-crystal display purposes, can use show voltage retention (Voltage Holding Ratio, VHR) high and be difficult for producing image persistance (image persistance) etc. characteristic, be the well-known diamines of so-called electrical characteristic excellence.
Suitable diamines in the described well-known diamines can be enumerated with the represented diamines of formula (2).
In the formula (2), A
1, A
2, A
3And A
4Be cyclohexylidene or phenylene independently; X
3And X
4Independently for singly-bound, carbon number be 1～5 alkylidene group or-O-; X
5And X
6Be independently singly-bound ,-CH
2-,-CH
2CH
2-,-O-or-S-; Y
1For-CH
2-,-C (R
11) (R
12)-,-CO-or-SO
2-, R
11And R
12Be that 1～12 alkyl or carbon number are 1～12 perfluoroalkyl for hydrogen, carbon number independently; M1, m2, m3, m4 and n are 0 or 1 independently.In addition, in described cyclohexylidene and the phenylene, hydrogen can be 1～4 alkyl or benzyl replacement by carbon number arbitrarily, and these substituent bonding positions are any.The position of the free radical of cyclohexylidene and phenylene is also any, and is preferred 1,3-or 1,4-, most preferably 1,4-.
Preference with the represented diamines of formula (2) is shown in following.
In these diamines, just liquid crystal orienting film is given high VHR with regard to the viewpoint that suppresses the image persistance phenomenon, more preferably formula (2-6)～formula (2-23), formula (2-38), formula (2-39), formula (2-44), formula (2-45), formula (2-49) or formula (2-50)～represented diamines of formula (2-54), more preferably formula (2-6), formula (2-7), formula (2-11), formula (2-12)～formula (2-16), formula (2-19)～formula (2-24) or the represented diamines of formula (2-51).
Described among the present invention do not have the usage ratio of the diamines of photosensitive group can be according to target regiospecific, electrical characteristic and selected arbitrarily.But, regiospecific can descend when the usage ratio of these diamines is big, so the usage ratio of these diamines preferably, with respect to synthetic as the A composition polyimide or during polyamic acid employed diamines total amount be the scope of 0 mole of %～50 mole %, the more preferably scope of 0 mole of %～30 mole %.
Other examples that can suitably be used to make the diamines that does not have photosensitive group of described A composition polymkeric substance have: with formula (3) or the represented diamines with side chain radical of formula (4).
In the formula (3), X
1And X
2Independently for singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G
1And G
2Be singly-bound independently, comprise perhaps that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the alicyclic ring; R
5For hydrogen, fluorine ,-CN ,-OH or carbon number are 1～30 alkyl, perfluoroalkyl or alkoxyl group.Wherein, work as X
1, G
1, X
2And G
2When being singly-bound, R
5Alkyl, perfluoroalkyl or alkoxyl group for carbon number 3～30; Work as G
2Be singly-bound and X
2Neither when singly-bound neither alkylidene group, R
5Be hydrogen or alkyl; In addition, work as G
1And G
2When being singly-bound, X
1, X
2And R
5The total carbon number more than or equal to 3.
In the described formula (3), two amino bondeds on the carbon of phenyl ring, position (meta-) or contraposition (para-) between the bonding position of two amino relation is preferred.And, when with X
1Bonding position when being made as 1, two amino preferably are bonded in respectively on 3 and 5 or 2 and 5, especially preferably are bonded on 3 and 5.
In the formula (4), R
6It for hydrogen or carbon number 1～12 alkyl; Ring B for hydrogen arbitrarily can by carbon number be 1～4 alkyl replace 1, the 4-phenylene or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the 4-cyclohexylidene; X
0It for singly-bound or carbon number 1～5 alkylidene group; S is 0～3 integer; When s was 2, two ring B both can be the same or different two X
0Also be both to can be the same or different; When s is 3, three or any two the ring B both can be the same or different three or any two X
0Also be both to can be the same or different; Z
1And Z
2Be independently singly-bound ,-CH
2-,-CH
2CH
2-or-O-; T1 and t2 are 0～3 integer independently; When t1 is 2, two Z
1Both can be the same or different; When t1 is 3, three or any two Z
1Both can be the same or different; When t2 is 2, two Z
2Both can be the same or different; When t2 is 3, three or any two Z
2Both can be the same or different.
Preference with the represented diamines of formula (3) is shown in following.
In formula (3-1)～formula (3-25), R
20Be the alkyl or the alkoxyl group of carbon number 1～20, preferred carbon number is 5～16 alkyl.R
21Be the alkyl or the alkoxyl group of carbon number 1～20, preferred carbon number is 3～10 alkyl.R
22Be the alkyl of carbon number 4～20, preferred carbon number is 6～16 alkyl.R
23Be the alkyl of carbon number 6～20, preferred carbon number is 8～20 alkyl.R
24Be the alkyl or the alkoxyl group of carbon number 3～20, preferred carbon number is 5～12 alkyl.R
25Be the alkyl or the alkoxyl group of carbon number 1～20, preferred carbon number is 3～10 alkyl.
In these diamines, preferred example is formula (3-1), formula (3-2), formula (3-4), formula (3-5) and the represented separately diamines of formula (3-6), and preferred example is formula (3-1) and the represented separately diamines of formula (3-2).
Preference with the represented diamines of formula (4) is shown in following.
In formula (4-1)～formula (4-16), R
26For hydrogen or carbon number are 1～12 alkyl or alkoxyl group, preferred carbon number is 4～7 alkyl.
Described usage ratio with diamines of side chain radical among the present invention can be selected arbitrarily according to target regiospecific, electrical characteristic or tilt angle.Particularly in order to show the tilt angle more than or equal to 2 degree, this usage ratio preferably is made as 5 moles of %～70 mole % in the employed diamines total amount when making A composition polymkeric substance, more preferably is made as 10 moles of %～50 mole %.
When making A composition polymkeric substance, can use at least a siloxane-based diamines simultaneously.The preference of this siloxane-based diamines can the represented diamines of enumerative (15).
In the formula (15), R
30And R
31Be the alkyl or phenyl of carbon number 1～3 independently respectively, R
32Be alkylidene group, the phenylene of carbon number 1～6 or the phenylene that is replaced by alkyl, y is 1～10 integer.
The concrete example of the diamines that formula (15) is represented can be enumerated following compound or polymkeric substance.
The molecular weight of the polymkeric substance of formula (15-2) is 850～3000.
When using these siloxane-based diamines, in order to have given play to described effect and to have prevented other characteristic variation, be used as the total amount of the diamines of raw material during with respect to manufacturing A composition and B composition, that the addition of these siloxane-based diamines is suitable is 0.5 mole of %～30 mole %, more suitably is 1 mole of %～10 mole %.
In these diamines, with regard to the viewpoint of liquid crystal being given good regiospecific, fragrant family (the comprise aromatic heterocycle system) diamines of preferred especially amino Direct Bonding on aromatic nucleus.More preferably do not contain the oxygen of ester that the electrical characteristic that cause liquid crystal display device easily descend or ehter bond etc. or the diamines of sulphur in the structure.Even if but diamines has this structure, as long as the amount of this structure can not produce electrical characteristic in the dysgenic scope with regard to there not being any problem.
Tetracarboxylic dianhydride as the raw material of making A composition polymkeric substance can unrestrictedly select from well-known compound.This tetracarboxylic dianhydride can belong to following arbitrary group: two 2-oxa-propane-1; 3-diacyl (2-oxapropane-1; 3-dioyl) aromatic dicarboxylic acid acid anhydride and the heterocycle of (dicarboxylic anhydride base) Direct Bonding on aromatic nucleus is the aromatic nucleus dicarboxylic anhydride, and the dicarboxylic anhydride base not aliphatic dicarboxylic acid acid anhydride and the heterocycle of Direct Bonding on aromatic nucleus be the aliphatic dicarboxylic acid acid anhydride.The oxygen or the sulphur that do not conform to ester that the electrical characteristic that cause liquid crystal display device easily descend or ehter bond etc. in polyimide or the polyamic acid preferred structure.So the tetracarboxylic dianhydride does not contain aerobic or sulphur in the preferred structure yet.But, even if the tetracarboxylic dianhydride has this structure, as long as the amount of this structure can not produce electrical characteristic in the dysgenic scope with regard to there not being any problem.
The tetracarboxylic dianhydride can use formula (20) expression.
R in the formula (20)
40Preference have with formula (21)～represented quaternary groups of formula (29).
(G
3For singly-bound, carbon number are 1～12 alkylidene group, 1,4-phenylene or 1,4-cyclohexylidene, X
7Be independently singly-bound or-CH
2-.)
(R
41, R
42, R
43And R
44Be hydrogen, methyl, ethyl or phenyl independently.)
(ring D
1Be cyclohexane ring or phenyl ring.)
(G
4For singly-bound ,-CH
2-,-CH
2CH
2-,-O-,-CO-,-S-,-C (CH
3)
2-or-C (CF
3)
2-, ring D
2Be cyclohexane ring or phenyl ring independently.)
(R
45Be hydrogen or methyl.)
(X
8Be independently singly-bound or-CH
2-, v is 1 or 2.)
(X
6For singly-bound or-CH
2-.)
(R
46Be hydrogen, methyl, ethyl or phenyl, ring D
3Be cyclohexane ring or phenyl ring.)
(w1 and w2 are 0 or 1 independently.)
Described tetracarboxylic dianhydride's concrete example can be enumerated the compound of following formula (A-1)～formula (A-43).
Among these tetracarboxylic dianhydrides, with regard to the viewpoint of the light orientation ability that improves liquid crystal orienting film, the compound of preferred use formula (A-1), formula (A-2), formula (A-12), formula (A-14), formula (A-18), formula (A-20), formula (A-21), formula (A-28), formula (A-30), formula (A-37) or formula (A-40) especially preferably uses the compound of formula (A-1), formula (A-12), formula (A-14) or formula (A-18).In addition, with regard to the VHR that improves liquid crystal orienting film or alleviate with regard to the painted viewpoint, the compound of preferred use formula (A-14), formula (A-18), formula (A-19), formula (A-20), formula (A-21), formula (A-28), formula (A-29), formula (A-30), formula (A-32), formula (A-39), formula (A-40), formula (A-41) or formula (A-43) especially preferably uses the compound of formula (A-14), formula (A-18) or formula (A-21).The tetracarboxylic dianhydride is not limited to above-claimed cpd, also can use other well-known compounds in the scope that can reach purpose of the present invention.And these tetracarboxylic dianhydrides can use separately, perhaps also can be used in combination of two or more.
Constitute raw material as employed another in the smooth orientation agent of the present invention, importantly select as showing the polymkeric substance of liquid crystal liquid crystal property or the B composition of its precursor.The application target of the B composition among the present invention is to make being increased by photo-induced anisotropy of alignment film of the present invention.At this moment, in order to obtain bigger regiospecific, preferably use the liquid-crystalline polymer that under lower temperature, has mesomorphic phase.But,, preferably use the liquid-crystalline polymer that under higher relatively temperature, has mesomorphic phase in order to improve the stability of orientation.With regard to above viewpoint, use the B composition that in 100 ℃～300 ℃, preferred 150 ℃～300 ℃ scope, has liquid crystal temperature range.When making alignment film of the present invention, given play to the effect that increases orientation, must be heated to the heat treated till the liquid crystal temperature range simultaneously in order to make the B composition.In addition, when as described hereinafter, utilize when using polyamic acid to form alignment film, preferably in the liquid crystal temperature range of B composition, make A composition imidization as A composition and the method for after implementing the light orientation, carrying out imidization.
The kind of the B composition polymkeric substance among the present invention is not particularly limited, and can use well-known all liquid-crystalline polymers.But with regard to the stable aspect of orientation, only liquid-crystalline polymer can be enumerated: become the polyamic acid of polyimide when forming film, with the poly amic acid ester or the soluble polyimide of the carboxyl esterification gained of polyamic acid.Certainly, consider, also can use the polyamic acid of part imidization from practical aspect.The object lesson of this liquid crystalline polyimide for example can be enumerated: Macromol.Chem.Phys., that is put down in writing in 198,519 (1997) etc. has a polyimide with the represented structural unit of formula (VI).
Wherein, R
4For the alkylidene group of carbon number 2～20, with the represented divalent group of formula (VIII) or with the represented divalent group of formula (IX), the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Alkylidene group for carbon number 6～20.Work as R
4During for alkylidene group, one or non-conterminous two-CH in this alkylidene group
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-replace.
In order to show the liquid crystal liquid crystal property of B composition, for example importantly, the R in the formula (VI)
4For the structural unit of the alkylidene group of carbon number 6～20, promptly the structural unit with flexible spacer (flexible spacer) exists more than or equal to 60% with respect to structural unit is whole.But, as long as can show liquid crystal liquid crystal property, even if then the amount of this structural unit also can be selected as B composition smaller or equal to 60% polymkeric substance.
In order to show the liquid crystal liquid crystal property of B composition, for example preferably use the skeleton that has the aromatic nucleus shown in the formula (VI) and be formed by connecting, promptly long (core, acid anhydrides core) or diamines are as raw material to the plane of extending.Have the ratio of raw material of this core suitable be, be to select between 50 weight %～100 weight % with respect to the raw material total amount, more suitably be to be to select between 70 weight %～100 weight % with respect to the raw material total amount.But, as long as can make the polymkeric substance that is obtained show liquid crystal liquid crystal property, even if the ratio of raw material that then has this core also can be selected as B composition for smaller or equal to the polymkeric substance of 50 weight %.
As long as the liquid crystal liquid crystal property that does not hinder the B composition then can use other well-known acid anhydrides or diamines to be used as the raw material of B composition.At this moment, with regard to keeping the liquid crystal liquid crystal property aspect, other well-known raw materials particularly preferably are, and select following formula (VIII) or the represented diamines of formula (IX) to be used as R
4Constituent.
Wherein, X
1And X
2Independently for singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G
1And G
2Be singly-bound independently, comprise perhaps that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the alicyclic ring; R
5For hydrogen, fluorine ,-CN ,-OH or carbon number are 1～30 alkyl, perfluoroalkyl or alkoxyl group; In addition, work as X
1, G
1, X
2And G
2When being singly-bound, R
5For alkyl, perfluoroalkyl or the alkoxyl group of carbon number 3～30, work as G
2Be singly-bound and X
2Neither when singly-bound neither alkylidene group, R
5For hydrogen or carbon number are 3～30 alkyl, work as G
1And G
2When being singly-bound, X
1, X
2And R
5The total carbon number more than or equal to 3.
Wherein, R
6It for hydrogen or carbon number 1～12 alkyl; Ring B for hydrogen arbitrarily can by carbon number be 1～4 alkyl replace 1, the 4-phenylene or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the 4-cyclohexylidene; X
0It for singly-bound or carbon number 1～5 alkylidene group; S is 0～3 integer; When s was 2, two ring B both can be the same or different two X
0Also be both to can be the same or different; When s is 3, three or any two the ring B both can be the same or different three or any two X
0Also be both to can be the same or different; Z
1And Z
2Be independently singly-bound ,-CH
2-,-CH
2CH
2-or-O-; T1 and t2 are 0～3 integer independently; When t1 is 2, two Z
1Both can be the same or different; When t1 is 3, three or any two Z
1Both can be the same or different; When t2 is 2, two Z
2Both can be the same or different; When t2 is 3, three or any two Z
2Both can be the same or different.
When the structural unit of the structure of selecting to have formula (VIII) or formula (IX), in order to give sufficient liquid crystal liquid crystal property to the B composition, the existence of these structural units is smaller or equal to 50% than preferably with respect to all structural units.
When being used in liquid crystal orienting film of the present invention in the IPS purposes,, preferably, select described R for the tilt angle (Pretilt Angle, Pt angle) that reduces liquid crystal, the regiospecific on the raising azimuth direction
4It only is the structural unit of the alkylidene group of carbon number 2～20.On the other hand, when liquid crystal orienting film of the present invention is used in TN or vertical orientation (Vertical Alignment, in the time of VA) in the purposes, in order to control the Pt angle of liquid crystal, preferably, comprise have described formula (VIII) or formula (IX) structure as R
4Structural unit.At this moment, in order to keep the liquid crystal liquid crystal property of B composition, more preferably the structure of selecting type (VIII-1) is used as R
4
Wherein, ring B
1And ring B
2Be singly-bound or 1 independently, 4-cyclohexylidene, G
3For singly-bound or-CH
2CH
2-, in addition, R
7It for hydrogen or carbon number 1～20 alkyl.
Blended ratio about A composition of the present invention and B composition, painted etc. the desirable value that can cooperate the stability of light regiospecific, orientation of film and film, is to select arbitrarily between 5 weight %～95 weight % at the B composition with respect to the ratio of the total amount of A composition and B composition, and suitable is to select between 10 weight %～90 weight %.At this moment, in order to improve the light regiospecific, to reduce the painted of film, suitable is this ratio of selecting between 50 weight %～90 weight %.In addition, in order to improve the stability of orientation, suitable is this ratio of selecting between 30 weight %～80 weight %.
Just regulate alignment film to regard to the viewpoint of the adherence of glass substrate, orientation agent of the present invention can more contain silicoorganic compound.The example of silicoorganic compound has: TSL 8330, aminopropyltriethoxywerene werene, vinyltrimethoxy silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, vinyltriethoxysilane, the 3-methacryloxypropyl trimethoxy silane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) silane coupling agent (silane coupling agent) such as ethyl trimethoxy silane, and dimethyl polysiloxane (dimethyl polysiloxane), polydimethylsiloxane (polydimethylsiloxane), silicone oils (silicone oil) such as poly-diphenyl siloxane.
As for the adding proportion of these silicoorganic compound in the orientation agent, so long as in the scope that can obtain effect of the present invention, then there is not special restriction.But if described silicoorganic compound add manyly, the orientation that liquid crystal then takes place when making alignment film sometimes is bad.So when being added with organic silicon compound, with respect to the weight of polymkeric substance contained in the orientation agent, the scope of the preferred 0.01 weight % of the concentration of these silicoorganic compound～5 weight %, the scope of preferred especially 0.1 weight %～3 weight %.
With regard to the characteristic that prevents orientation agent of the present invention deterioration or because for the viewpoint of environment and deterioration in time, orientation agent of the present invention can more contain the compound that has more than or equal to the functional group of carboxylic acid residues reaction two and the polyamic acid or derivatives thereof, promptly so-called linking agent.The example of this linking agent can be enumerated: Japanese Patent No. 3049699 communique, Japanese Patent spy open multi-functional epoxy's material of being put down in writing in 2005-275360 communique, the Japanese patent laid-open 10-212484 communique etc., isocyanic ester (isocyanate) material etc.
In addition, for above identical purpose, thereby also can use the linking agent id reaction and form the linking agent that cancellated polymkeric substance improves the film toughness of polyamic acid or polyimide.This linking agent can be enumerated: Japanese patent laid-open 10-310608 communique, Japanese Patent spy open multifunctional Vinyl Ether, maleimide or diallyl Na Dike imide (bisallyl nadiimide) derivative of being put down in writing in 2004-341030 communique etc. etc.When using these linking agents, the preferred proportion of these linking agents be that total amount with respect to component of polymer is 5 weight %～100 weight %, more preferably the total amount with respect to component of polymer is 10 weight %～50 weight %.
Orientation agent of the present invention contains the solvent that has polyamic acid or derivatives thereof dissolved ability.Common used solvent when this solvent comprises manufacturing widely or uses the polyamic acid or derivatives thereof can suitably be selected according to application target.The illustration of these solvents is as follows.
For polyamic acid is that the example of the non-proton property polar organic solvent of good solvent can be enumerated: N-N-methyl-2-2-pyrrolidone N-(N-methyl-2-pyrrolidone, NMP), dimethyl-imidazolinone (dimethyl imidazolidinone), N-methyl caprolactam (N-methylcaprolactam), N-methyl propanamide (N-methylpropionamide), N, the N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) (dimethyl sulfoxide), N, dinethylformamide (N, N-dimethylformamide, DMF), N, the N-diethylformamide, N, N-N,N-DIMETHYLACETAMIDE (N, N-dimethylacetamide, DMAc), and gamma-butyrolactone (gamma-butyrolactone, GBL) lactone such as grade.
Solvent beyond the described solvent and can enumerate: lactic acid alkyl ester in order to the example of other solvents of improving coating etc., 3-methyl-3-methoxybutanol, naphthane (tetralin), isophorone (isophorone), (Butyl cellosolve BCS) waits ethylene glycol monoalkyl ether to ethylene glycol monobutyl ether, Diethylene Glycol monoalky lethers such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetic ester and ethylene glycol phenyl ether acetate, the triethylene glycol monoalky lether, propylene-glycol monoalky lethers such as propylene glycol monobutyl ether, dialkyl malonates such as diethyl malonate, dipropylene glycol monoalky lethers such as dipropylene glycol monomethyl ether, and the ester cpds of these glycol monoethers etc.In these solvents, especially preferably use NMP, dimethyl-imidazolinone, GBL, BCS, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether etc. to be used as described solvent.
Orientation agent of the present invention can contain various additives as required and more.For example, when expectation further improved coating, orientation agent of the present invention can contain an amount of tensio-active agent that adapts to this purpose, and when needs improved static resistance, orientation agent of the present invention can contain an amount of static inhibitor.
The concentration of the polyamic acid or derivatives thereof in the orientation agent of the present invention is not particularly limited, preferred 0.1 weight %～30 weight %.When this orientation agent of coating on substrate,, need sometimes to implement in advance with the operation of solvent with polyamic acid dilution contained in this orientation agent in order to adjust thickness.
In order to show better characteristic as alignment film, orientation agent of the present invention can be selected from other all polymkeric substance of more knowing in more than one mix.At this moment, in order to have given play to effect of the present invention, the summation of A composition and B composition shared ratio in all polymkeric substance is preferably greater than and equals 50 weight %, more preferably greater than equaling 80 weight %.
The concentration of the solids component in the orientation agent of the present invention is not particularly limited, and can cooperate following various coating method to select only value.Usually, the inequality in order to suppress to be coated with or pin hole (pinhole) etc., with respect to varnish (varnish) weight, the preferred 0.1 weight % of the concentration of solids component～30 weight %, more preferably 1 weight %～10 weight %.
As mentioned above, alignment film of the present invention can contain described A composition, B composition, described other compositions that add as required and the orientation agent (varnish) of these composition dissolved solvents is obtained by use.Utilize following method that this orientation agent is coated on the substrate, and under relatively low temperature, solvent added heat extraction (preparation roasting) as required explanation.Then,, make alignment film show the inherent characteristic for further promotion imidization of polyimide, polyamic acid or polyamic acid derivative or removing of solvent, and heating under higher relatively temperature (formal roasting).To like this and the film irradiates light that obtains and make the polymkeric substance orientation can obtain alignment film of the present invention thus.
At this moment, with regard to the viewpoint that shows sufficient regiospecific, alignment film of the present invention preferably uses polyamic acid also to make in the following sequence as the A composition.
(1) utilize hairbrush coating method, pickling process, method of spin coating (spinner method), spray method (spray method), print process etc. that described varnish is coated on the substrate.
(2) under 50 ℃～120 ℃, preferred 80 ℃～100 ℃ to substrate on formed film heat, make solvent evaporation.
(3), make the polyamic acid orientation in the described film to described film irradiates light.
(4) the described film to polyamic acid orientation heats under 150 ℃～300 ℃, preferred 180 ℃～250 ℃, to carry out imidization.
In addition, when desiring to make the liquid crystal display device that utilizes alignment film to show predetermined tilt angle, can adopt following method to realize: during irradiates light, to the method for substrate from arbitrarily angled irradiation rectilinearly polarized light; Perhaps will be to the rectilinearly polarized light irradiation and the method that is made up from non-polarized light irradiation at any angle from vertical direction of substrate.
When making alignment film of the present invention, use rectilinearly polarized light to make described polyamic acid orientation.By the irradiation rectilinearly polarized light, the orientation of polyamic acid main chain in the vertical direction in the polarization direction of rectilinearly polarized light on.Described rectilinearly polarized light is so long as can make the light of the polyamic acid orientation in the described film then be not particularly limited.Alignment film of the present invention can make the film orientation by the low-energy light of irradiation.So, in the light orientation of described polyamic acid is handled, the preferred 0.5J/cm of the irradiation dose of rectilinearly polarized light
2～10J/cm
2And, the preferred 300nm～400nm of the wavelength of rectilinearly polarized light.Rectilinearly polarized light is not particularly limited with respect to the irradiating angle on film surface, and when desire revealed strong orientation restraint to liquid crystal watch, with regard to the viewpoint that shortens the orientation treatment time, preferably rectilinearly polarized light was tried one's best and the film Surface Vertical.
In addition, in the manufacturing processed of alignment film of the present invention, the light to described film irradiation when desiring to make liquid crystal display device show tilt angle can be that polarized light also can be a non-polarized light.The preferred 0.5J/cm of irradiation dose of the light that when desiring to make liquid crystal display device show tilt angle described film is shone
2～10J/cm
2, the preferred 300nm～400nm of the light wavelength of being shone.The light that when desiring to make liquid crystal display device show tilt angle described film is shone is not particularly limited with respect to the irradiating angle on described film surface, with regard to the viewpoint that shortens the orientation treatment time, and preferred 30 degree of this irradiating angle～60 degree.
Alignment film of the present invention is characterised in that to have king-sized orientation anisotropy.The method that this anisotropic size can utilize the Japanese Patent spy to open the use polarized ir line of being put down in writing among 2005-275364 etc. (Polarized Infrared Ray, Polarized IR) is estimated.In addition, use the method for ellipsometer (ellipsometry) to estimate this anisotropic size also can be utilized shown in following examples.It is generally acknowledged that when using alignment film of the present invention to be used as liquid-crystal composition when using alignment film, the anisotropic material that possesses big more film has big more orientation restraint to liquid-crystal composition.
The orientation purposes of the liquid-crystal composition of using except liquid-crystal display, alignment film of the present invention also can be used for the orientation control of optical compensation material and other all liquid crystal materials.And, because alignment film of the present invention has big anisotropy, so can be used for the optical compensation material applications individually.
The invention provides a kind of liquid crystal display device, this liquid crystal display device possesses: a pair of substrate that is disposing in opposite directions, be formed on electrode on one or two face in the described a pair of substrate face in opposite directions separately, be formed on the liquid crystal orienting film on the described a pair of substrate face in opposite directions separately and be formed on liquid crystal layer between the described a pair of substrate, this liquid crystal display device is characterised in that described liquid crystal orienting film is an alignment film of the present invention.
As long as described electrode is formed on the face of substrate and then is not particularly limited.Kind electrode for example can enumerate tin indium oxide (Indium Tin Oxide, ITO) or the vapor-deposited film of metal etc.In addition, electrode can be formed on whole an of face of substrate, also can form for example desired shape of patterning.The described desired shape of electrode for example can be enumerated comb teeth shape or zigzag structure (zigzagstructure) etc.Electrode can be formed on the substrate in a pair of substrate, also can form on two substrates.The formation form of electrode is according to the kind of liquid crystal display device and difference, for example under the situation of IPS type liquid crystal display device, electrode is configured on the substrate in the described a pair of substrate, under the situation of other liquid crystal display device, electrode is configured on two substrates of described a pair of substrate.On described substrate or electrode, form described liquid crystal orienting film.
To form described liquid crystal layer in opposite directions and by the form of described a pair of substrate holding liquid crystal constituent with the face that has formed liquid crystal orienting film.When forming liquid crystal layer, can use micropartical or resin sheet etc. to be inserted between the described a pair of substrate as required to form the spacer (spacer) of appropriate intervals.Described liquid-crystal composition is not particularly limited, and can use well-known liquid-crystal composition.
When alignment film of the present invention is formed liquid crystal display device as liquid crystal orienting film, alignment film of the present invention can be improved the characteristic of well-known all liquid-crystal compositions, and the alignment film of the present invention that utilizes described method manufacturing particularly has big effect in the orientation defective of the big view display that is difficult to carry out friction treatment aspect improving.This big view display drives control by TFT.In addition, employed liquid-crystal composition is recorded in No. 3086228 communique of Japanese Patent, No. 2635435 communiques of Japanese Patent, the special flat 5-501735 communique of table of Japanese Patent and the Japanese patent laid-open 9-255956 communique in this TFT type liquid crystal display device.So, alignment film of the present invention preferably with these communiques in the liquid-crystal composition put down in writing be used in combination.
The tilt angle of liquid crystal display device of the present invention can use for example central smart machine manufacturing OMS-CA3 type liquid crystal characteristic evaluating apparatus, utilize Journal of Applied Physics, Vol.48, No.5, the crystal rotation method of p.1783-1792 being put down in writing in (1977) (crystal rotationmethod) is measured.
The electrical characteristic excellence of liquid crystal display device of the present invention, these electrical characteristic are relevant with the reliability of liquid crystal display device.This electrical characteristic can be enumerated voltage retention and ion density (ion density).
Voltage retention (VHR) is that the voltage that imposes on liquid crystal display device between the frame period (frame period) remains on the ratio on the liquid crystal display device, the display characteristic of expression liquid crystal display device.With regard to preventing to show bad viewpoint, liquid crystal display device of the present invention preferably, use voltage retention that 5V and frequency measure under 60 ℃ temperature condition as the square wave of 30Hz more than or equal to 90.0%, use voltage retention that 5V and frequency measure under the condition of 60 ℃ temperature as the square wave of 0.3Hz more than or equal to 85.0%.
Ion density is the transient current beyond the caused electric current of the driving by liquid crystal that produces when liquid crystal display device is applied voltage, the concentration of contained ionic impurity in the liquid crystal in the expression liquid crystal display device.
With regard to the viewpoint of the image persistance that prevents liquid crystal display device, the ion density of liquid crystal display device of the present invention is preferably smaller or equal to 500pC.
Embodiment
Below, by embodiment and comparative example the present invention is described, but the present invention is not limited to these embodiment.Pyromellitic dianhydride (PMDA, compound (A-1)), 1,2,3,4-tetramethylene tetracarboxylic acid (CBTA, compound (A-14)), compound (2-13) and DATP are to be used for experiment after with commercially available compound purifying by recrystallize.1,8-diamino octane, 1,9-diamino nonane and 1,12-diamino dodecane are that commercially available product distillation back is used.Compound (I-1), compound (II-1), compound (A-21) are respectively according to Tetrahedron, Vol.60,9977 (2004), the special fair 5-65530 communique of Japanese Patent and Japanese Patent spy open clear 58-109479 communique and synthesize.Following compound TPDA and compound (30) are according to Macromolecules, Vol.28,6368 (1995) and the Japanese Patent spy open the 2004-341030 communique and synthesize.Compound (X-1) is to make commercially available product be used for experiment behind the recrystallize from ethanol.Compound (3-5-1) is to use to be opened the identical method of the method put down in writing in the 2002-162630 communique with the Japanese Patent spy and synthesizes.The preparation of polymkeric substance is to carry out in nitrogen gas stream.
Rayed is to use the high pressure mercury vapour lamp of the 250W that contains flourish hall manufacturing in the well, and illumination wavelength is near the ultraviolet ray 310nm～380nm.Irradiation is to carry out in room temperature, air.
The evaluation method of employed liquid crystal display device among the embodiment below is described.
The mensuration of the phase differential of＜alignment film (retardation), thickness and tilt angle 〉
Use spectroscopic ellipsometer (spectroscopic ellipsometer) M-2000U (J.A.Woollam Co.Inc. manufacturing) to measure.In the present embodiment, the orientation degree of the phase difference value of film and main polymer chain increases in direct ratioly.That is, having greatly, the alignment film of phase difference value has bigger orientation degree.
＜UV-Vis spectrographic is measured 〉
Use uv-vis spectra (Ultraviolet-Visible spectroscopy, UV-Visspectroscopy) determinator (Japanese beam split V-660), with the glass substrate that is not formed with alignment film as a reference (reference) measure.
＜voltage retention 〉
Utilize the method for being put down in writing in " water Shima he, the 14th the pre-original text collection of liquid crystal discussion p78 (1988) " to measure voltage retention.During mensuration, liquid crystal cells is applied the square wave of wave height ± 5V.Under 60 ℃, measure.The value of voltage retention is the index that the voltage that applied of expression with which kind of degree kept after the frame period, if the value of voltage retention is 100%, represents that then all electric charges all are being held.
Ionic weight in the＜liquid crystal is measured (ion density) 〉
Roll up the method for being put down in writing in No. 10 1065 (1996) according to " Applied Physics " the 65th, the 6254 type liquid crystal physical property measurement systems that use Japan company (TOYO Corporation) to make measure.Frequency of utilization is the choppy sea (triangle-wave) of 0.01Hz, measures under 60 ℃ temperature with the voltage range of ± 10V.If ion density is big, then be easy to generate the undesirable conditions such as image persistance that cause by ionic impurity.That is to say that ion density is the physics value that becomes the prediction index of image persistance generation.
＜weight average molecular weight (Mw) 〉
Use gel permeation chromatograph (GPC, Shodex company makes, GF 7MHQ), use contains the dimethyl formamide (dimethylformamide of the phosphoric acid of 0.6 weight %, DMF) as elutriant, 50 ℃ of tubing string temperature, and use polystyrene as standardized solution, measure the weight average molecular weight (Mw) of the polyamic acid in the LCD alignment agent.
The transformation temperature of＜high molecule liquid crystal 〉
Under 230 ℃ to substrate on formed film (thickness is about 70nm) roasting after 10 minutes, use polarizing microscope to observe and obtain the transformation temperature of high molecule liquid crystal.In addition, use the differential scanning calorimetric analysis device that the high molecule liquid crystal that obtains by redeposition is measured, but because filminess is different with transformation temperature, so adopt last method to measure.
＜viscosity 〉
(eastern machine industry company makes, and TV-22), measures viscosity down at 25 ℃ to use viscometer.
＜second-order transition temperature 〉
(DSC, Perkin Elmer company makes, and DiamondDSC) measures second-order transition temperature to use differential scanning calorimetry device.
[synthesis example 1]
The preparation of＜polyamide acid varnish A 〉
With 4,4 '-diamino tolane (compound number I-1; 1.2534g, 6.018mmol) be dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP, 22.5g) in, remain on the one hand smaller or equal to room temperature, add pyromellitic dianhydride (PMDA on the one hand, 0.5901g, 3.009mmol) and 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBTA, 0.6564g, 3.009mmol).Stir after 2 hours, and the adding ethylene glycol monobutyl ether (BC, 22.5g).The viscosity of gained solution is 350mPas.With about 4 hours of this solution stirring, obtaining viscosity was the varnish A of 33mPas under 60 ℃.The weight average molecular weight of the polyamic acid of this varnish is 45,000, and in addition, second-order transition temperature (Tg) has surpassed 300 ℃.
[synthesis example 2～synthesis example 7]
The preparation of＜polyamide acid varnish B～polyamide acid varnish G 〉
Form with the raw material shown in the table 1, utilize the method identical to prepare polyamide acid varnish B～polyamide acid varnish G, and similarly measure rerum natura with synthesis example 1 with synthesis example 1.In addition, the numeral mole % in the bracket.
Table 1
| Synthesis example No. | The varnish title | Diamines | Acid anhydrides | Viscosity (mPas) | Weight average molecular weight | ??Tg ??(℃) |
| ??1 | ??A | ??I-1 | ??A-1(50) ??A-14(50) | ??33 | ??45,000 | ??＞300 |
| ??2 | ??B | ??II-1 | ??A-1(50) ??A-14(50) | ??28 | ??37,000 | ??＞300 |
| ??3 | ??C | ??II-1(80) ??2-13(20) | ??A-1(50) ??A-14(50) | ??33 | ??52,000 | ??＞300 |
| ??4 | ??D | ??II-1 | ??A-21 | ??30 | ??38,000 | ??＞300 |
| ??5 | ??E | ??2-13 | ??A-1(50) ??A-14(50) | ??34 | ??48,000 | ??＞300 |
| ??6 | ??F | ??X-1 | ??A-1 | ??41 | ??34,000 | ??＞300 |
| ??6′ | ??F′ | ??X-1 | ??A-14 | ??33 | ??47,000 | ??＞300 |
| ??7 | ??G | ??X-1(80) ??3-5-1(20) | ??A-14 | ??29 | ??35,000 | ??＞300 |
[synthesis example 8]
The preparation of＜polyamide acid varnish I 〉
With 1,8-diamino octane (DAO) (0.7009g 4.858mmol) is dissolved among the NMP (22.5g), at room temperature add TPDA (1.7991g, 4.858mmol).Stirring is after 2 hours down at 60 ℃, and cool to room temperature adds BC (22.5g) and acquisition varnish H.The viscosity of this varnish is 18.7mPas.(weight average molecular weight: 18,000).In addition, transformation temperature (nematic phase-each to homophase) is 235 ℃.
[synthesis example 9]
The preparation of＜polyamide acid varnish J 〉
Use DAO and 1, the mixture of 9-diamino nonane (mol ratio is 1: 1) replaces DAO, obtains varnish I with the method identical with synthesis example 6.The viscosity of this varnish is 28.6mPas.(weight average molecular weight: 24,000).In addition, transformation temperature (nematic phase-each to homophase) is 212 ℃.
[synthesis example 10]
The preparation of＜soluble polyimide varnish K 〉
With DAO (0.7009g 4.858mmol) is dissolved among the NMP (22.5g), at room temperature add TPDA (1.7991g, 4.858mmol).60 ℃ down stir 2 hours after, cool to room temperature, add diacetyl oxide (0.58g, 5.7mmol) and pyridine (0.45g 5.7mmol), at room temperature stirred 3 hours.This reaction solution is added in the pure water (500ml), filter out the precipitation that is generated.After with pure water 100ml gained precipitation being cleaned twice, 100 ℃ of following vacuum-dryings 8 hours.This polymkeric substance (1.0g) is dissolved among the NMP (10g), adds BC (10g) and acquisition varnish J.The viscosity of this varnish is 9.8mPas.(weight average molecular weight: 16,000).In addition, transformation temperature (nematic phase-each to homophase) is 231 ℃.
[synthesis example 11～synthesis example 16]
The preparation of＜polyamide acid varnish K～polyamide acid varnish P 〉
Form with the raw material shown in the table 2, and utilization and synthesis example 8 identical methods prepare polyamide acid varnish K～polyamide acid varnish P.In addition, the numeral mole % in the bracket.
Table 2
| Synthesis example No. | The varnish title | Diamines | Acid anhydrides | Viscosity (mPas) | Weight average molecular weight | Transformation temperature (℃) |
| ??11 | ??K | ??DAO(80) ??3-5-1(20) | ??TPDA | ??14.6 | ??28,000 | ??221 |
| ??12 | ??L | ??DAO(70) ??3-5-1(30) | TPDA | ??20.3 | 34,000 | ??228 |
| ??13 | ??M | ??DAO(70) ??3-5-1(30) | ??TPDA(90) ??A-14(10) | ??12.6 | ??32,000 | ??233 |
| ??14 | ??N | ??DAO(50) ??3-5-1(30) ??DATP(20) | ??TPDA(80) ??A-14(20) | ??13.9 | ??26,000 | ??23.7 |
| ??15 | ??O | ??DAD(70) ??3-5-1(30) | ??TPDA | ??13.2 | ??24,000 | ??21.2 |
| ??16 | ??P | ??DAD(70) ??3-5-1(30) | ??TPDA(40) ??A-14(60) | ??14.1 | ??31,000 | ??- |
In the table 2, DAD represents 1,12-diamino dodecane.
[embodiment 1]
In sample bottle, take by weighing varnish A and each 0.50g of varnish H respectively, add NMP/BC=1/1 (weight %) and reach 1.67g.The polyamic acid solution of these about 3 weight % is added drop-wise on the transparent glass substrate, utilizes method of spin coating to be coated with (2,000rpm, 15 seconds).After the coating, under 80 ℃ to substrate heating 3 minutes and after making solvent evaporation, (365nm and energy are about 4J/cm across Polarizer substrate to be shone rectilinearly polarized light
2).To in baking oven (oven), under 230 ℃, carry out 10 minutes heat treated through the substrate after the rayed, obtain the alignment film A that thickness is about 70nm.Measure the phase differential of this alignment film A, the result is 2.0nm.
[embodiment 2～embodiment 14]
Use the varnish shown in the table 3, obtain alignment film B～alignment film N similarly to Example 1.Measure phase differential, the result of measurement result and embodiment 1 is shown in Table 3 together.
Table 3
| Embodiment No. | The alignment film title | The varnish of A composition (weight %) | The varnish of B composition (weight %) | Phase differential (nm) |
| ??1 | ??A | Varnish A (50) | Varnish H (50) | ??2.0 |
| ??2 | ??B | Varnish B (70) | Varnish H (30) | ??3.2 |
| ??3 | ??C | Varnish B (50) | Varnish H (50) | ??4.8 |
| ??4 | ??D | Varnish B (30) | Varnish H (70) | ??8.6 |
| ??5 | ??E | Varnish B (20) | Varnish H (80) | ??9.1 |
| ??6 | ??F 1) | Varnish B (20) | Varnish H (80) | ??8.7 |
| ??7 | ??G | Varnish B (10) | Varnish H (90) | ??3.7 |
| ??8 | ??H | Varnish B (30) | Varnish H (70) | ??4.0 |
| ??9 | ??I | Varnish C (30) | Varnish H (70) | ??4.3 |
| ??10 | ??J 2) | Varnish D (30) | Varnish I (70) | ??5.7 |
| ??11 | ??K | Varnish B (50) | Varnish J (50) | ??3.7 |
| ??12 | ??L | Varnish F (50) | Varnish H (50) | ??3.2 |
| ??13 | ??M | Varnish F (30) | Varnish H (70) | ??3.5 |
| ??14 | ??N | Varnish F (20) | Varnish H (80) | ??2.4 |
F
1): it is 0.20 compound (30) that the component of polymer identical with the component of polymer that is used to obtain alignment film E more added weight ratio.
J
2): under the polymkeric substance condition identical, change roasting condition into 200 ℃, 10 minutes with alignment film I.
[comparative example 1]
Replace the mixture of varnish B and varnish H and use varnish B separately, obtain alignment film O similarly to Example 1, measure the phase differential of this alignment film O.The result is 0.6nm.
[comparative example 2]
Use varnish E to replace the mixture of varnish B and varnish H, obtain alignment film P similarly to Example 1, measure the phase differential of this alignment film P.The result is 0.1nm.
[comparative example 3]
Use varnish F to replace the mixture of varnish F and varnish H, obtain alignment film Q similarly to Example 1, measure the phase differential of this alignment film Q.The result is 1.3nm.
[embodiment 15]
Measure the UV-Vis spectrum of the alignment film B of made among the embodiment 2.The results are shown in Fig. 1.
[comparative example 4]
Measure the UV-Vis spectrum of the alignment film O of made in the comparative example 1.The data of measurement result and alignment film B are shown in Fig. 1 together.
With embodiment and comparative example 1～comparative example 3 more as can be known, being used in combination the alignment film of the present invention that the A composition obtains with the B composition compares with the alignment film that only uses A to become branch to obtain, has bigger phase difference value, that is to say, in order to increase phase difference value, annex solution crystallinity polymer in light orientation agent importantly.And as shown in Figure 1, O compares with alignment film, and the transmissivity of alignment film B under 380nm～500nm is higher, and painted less.
[embodiment 16]
Glass substrate is replaced to the transparent glass substrate that the ITO electrode is being set on the single face, and the combination that makes varnish is identical when making alignment film B, E and F respectively, in addition, obtains alignment film B ', E ' and F ' that thickness is about 60nm similarly to Example 1.With two baseplate-laminatings that on the ITO electrode, are formed with these alignment films, so that to the polarization direction of the rectilinearly polarized light of each alignment film irradiation parallel and make be formed with alignment film face in opposite directions and between alignment film in opposite directions, form and be used for the gap of dispenser method constituent, thereby be assembled into liquid crystal cells B, E and the F (liquid crystal display device) that element thickness is 7 μ m.Then, in these liquid crystal cells, show liquid-crystal composition A under the instillation.
＜liquid-crystal composition A 〉
These liquid crystal cells of visual observations B, E and F, result all do not observe the mobile orientation of what is called that liquid crystal is arranged along its flow direction fully.Under 110 ℃, these liquid crystal cells B, E and F are carried out isotropy processing in 30 minutes, till the cool to room temperature.Then, with these liquid crystal cells of microscopic examination B, E and F, the result does not all observe the orientation defective of liquid crystal.With polarizing microscope furnishing cross-polarized light (crossnicol) state, rotation liquid crystal cells B, E and F then observe tangible bright state and dark state.With the tilt angle of these liquid crystal cells B, E and F, VHR (voltage retention) and ion density are shown in the following table 4.
Table 4
So as can be known, when alignment film of the present invention should be used as the alignment film of used for liquid crystal display element, this alignment film had the sufficient characteristic that can withstand practical application.
[embodiment 17]
In sample bottle, take by weighing varnish G and each 1.60g of varnish K respectively, add NMP/BC=1/1 (weight %) and reach 4.00g.The described mixing varnish that the concentration of polyamic acid is about 4 weight % is added drop-wise on the transparent glass substrate that the ITO electrode is being set on the single face, and utilizes method of spin coating to be coated with (1,600rpm, 15 seconds).After the coating, after making solvent evaporation, make base plan with respect to light source incline 45 degree to substrate heating 3 minutes under 80 ℃, (365nm and energy are about 5J/cm to the irradiation non-polarized light
2).Under 230 ℃, the substrate after rayed is carried out 30 minutes heat treated, obtain the alignment film R that thickness is about 60nm.
With two baseplate-laminatings that on the ITO electrode, are formed with described alignment film,, thereby be assembled into the liquid crystal cells R that element thickness is 4 μ m between alignment film in opposite directions so that the face that is formed with alignment film in opposite directions and form and be used for the gap of dispenser method constituent.As for the applying direction of substrate, about vergence direction is made as, when being made as up and down with the vertical direction of vergence direction, the identical applying up and down on the contrary mutually about making.Then, in these liquid crystal cells, show liquid-crystal composition B under the instillation.
Under 110 ℃ this liquid crystal cells R carried out that 30 minutes isotropy are handled and cool to room temperature till.Use polarizing microscope to observe this liquid crystal cells R, even if rotate liquid crystal cells R under the cross-polarized light state, dark state does not change yet, and does not observe the caused light leak of orientation defective by liquid crystal.Measure the tilt angle of this liquid crystal cells R with described method, the result is 89.1 degree.The vergence direction of liquid crystal is the rayed direction of non-polarized light.And, this liquid crystal cells R being applied voltage (5V) back observe with polarizing microscope, the result has obtained not observe the striation that caused by the orientation defective and orientation attractive in appearance in the whole zone of liquid crystal cells.In addition, when rotation liquid crystal cells R under this state, observe tangible light and shade state.The VHR (voltage retention) of this liquid crystal cells R is 97.9% under 30Hz, is 91.7% under 0.3Hz, and ion density is 460pC.
＜liquid-crystal composition B 〉
[embodiment 18]
The weight ratio of the mixture of varnish G and varnish K is become varnish G/ varnish K=1/9 by varnish G/ varnish K=1/1, in addition, make liquid crystal cells S similarly to Example 17.Use polarizing microscope to observe this liquid crystal cells S, even if the result rotates liquid crystal cells S under the cross-polarized light state, dark state does not change yet, and does not observe the caused light leak of orientation defective by liquid crystal.Measure the tilt angle of this liquid crystal cells S with described method, the result is 89.1 degree.In addition, this liquid crystal cells S is applied voltage (5V) back observe with polarizing microscope, the result has obtained not observe the striation that caused by the orientation defective and orientation attractive in appearance in the whole zone of liquid crystal cells.The VHR (voltage retention) of this liquid crystal cells S is 95.6% under 30Hz, is 88.7% under 0.3Hz, and ion density is 820pC.
Liquid crystal cells S is shone the light 72 hours of the luminescent lamp (8W) of 10cm at interval with the illumination angles of 45 degree, carry out light fastness test.The tilt angle of this liquid crystal cells S of mensuration after rayed, the result is 89.1 degree.
Then, with aluminium foil (aluminium foil) half covering, with the light fastness test that similarly carries out mentioned above with liquid crystal cells S.After applying voltage (3.2V) through the liquid crystal cells S after the rayed, under cross-polarized light, observe display part, the result does not observe variation (Fig. 2) at illumination part and light between irradiation portion.
[embodiment 19～embodiment 23]
Use the varnish shown in the table 5, obtain liquid crystal cells T～liquid crystal cells X similarly to Example 18.With the vertical orientation of liquid crystal cells T～liquid crystal cells X, tilt angle, when applying voltage demonstration, VHR, ion density, light fastness test the results are shown in table 5.
Table 5
Tilt angle behind (notes) Pt angle-2 expression light fastness test.
[comparative example 5]
Except the mixture with varnish G and varnish K changes to varnish G, make liquid crystal cells Y similarly to Example 17.Use polarizing microscope to observe this liquid crystal cells Y, even if the result rotates liquid crystal cells Y under the cross-polarized light state, dark state does not change yet, and does not observe the caused light leak of orientation defective by liquid crystal.Measure the tilt angle of this liquid crystal cells Y with described method, the result is 89.1 degree.In addition, this liquid crystal cells Y is applied voltage (5V) back observe with polarizing microscope, the result has obtained not observe the striation that caused by the orientation defective and orientation attractive in appearance in the whole zone of liquid crystal cells.Measure the tilt angle of this liquid crystal cells Y, the result is 89.0 degree.
Similarly to Example 18 this liquid crystal cells Y is carried out light fastness test.The tilt angle of this liquid crystal cells Y of mensuration after rayed, the result is 89.6 degree.In addition, to illumination part and not irradiation portion observe, the result does not observe evident difference (Fig. 3) at illumination part and light between irradiation portion.
[comparative example 6]
The mixture (varnish G/ varnish P=1/9, weight ratio) that changes to varnish G and varnish P except the mixture with varnish G and varnish K in addition, is made liquid crystal cells Z similarly to Example 17.Use this liquid crystal cells of polarized light microscope observing Z, even if the result rotates liquid crystal cells Z under the cross-polarized light state, dark state does not change yet, and does not observe the caused light leak of orientation defective by liquid crystal.Measure the tilt angle of this liquid crystal cells Z, the result is 89.9 degree.In addition, this liquid crystal cells Z is applied voltage (5V) back observe with polarizing microscope, the result observes the orientation of several places in the whole zone of liquid crystal cells bad.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (11)
1, a kind of smooth orientation agent, it is to contain as at least a A composition with polymkeric substance of light orientation ability, as the B composition of at least a polymkeric substance that has liquid crystal temperature range in 100 ℃～300 ℃ scope and the constituent of solvent, it is characterized in that: with the total weight of A composition and B composition as benchmark, the A components in proportions is 10 weight %～90 weight %, and, as benchmark, the ratio of solvent is 70 weight %～99.9 weight % with the total amount of this constituent.
2, smooth orientation agent according to claim 1 is characterized in that: the A composition is at least a polymkeric substance that is selected from the group that polyamic acid, part imidization polyamic acid and polyimide form.
3, smooth orientation agent according to claim 1, it is characterized in that: the A composition is at least a polymkeric substance that is selected from the group that polyamic acid, part imidization polyamic acid and polyimide form, and has photosensitive group on the main chain of this polymkeric substance.
4, smooth orientation agent according to claim 1, it is characterized in that: the A composition is to be selected from polyamic acid, at least a polymkeric substance in the group that part imidization polyamic acid and polyimide are formed, and have at least a with in the represented photosensitive group of formula (I)～formula V and formula (X) on the main chain of this polymkeric substance, and, the B composition is to be selected from polyamic acid, at least a liquid-crystalline polymer in the group that part imidization polyamic acid and polyimide are formed, has carbon number on the main chain of this polymkeric substance and is 6～20 straight-chain alkyl-sub-structure, one or non-conterminous two-CH in this straight-chain alkyl-sub-structure
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-replace;
—R
1—C≡C—R
2—???????????????????????(I)
—R
1—C≡C—C≡C—R
2—?????????????????(II)
—R
1—C≡C—CH＝CH—R
2—???????????????(III)
—R
1—C≡C—R
2—C≡C—R
3—?????????????(IV)
—R
1—C≡C—R
2—CH＝CH—R
3—???????????(V)
—N＝N—???????????????????????????????(X)
Wherein, R
1, R
2And R
3Be the aromatic series divalent group independently.
5, smooth orientation agent according to claim 4 is characterized in that: the A composition is to use at least a polymkeric substance that obtains as raw material in the represented compound of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (X-1)～formula (X-8);
6, smooth orientation agent according to claim 4 is characterized in that: the B composition is polyimide or its precursor polyamic acid that has with the represented structural unit of formula (VI);
Wherein, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-the carbon number that replaces is 2～20 alkylidene group, with the represented divalent group of formula (VIII) or with the represented divalent group of formula (IX), the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2The carbon number of-replacement is 6～20 alkylidene group;
In the formula (VIII), X
1And X
2For singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G
1And G
2Be singly-bound, comprise perhaps that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the alicyclic ring; R
5For hydrogen, fluorine ,-CN ,-OH or carbon number are 1～30 alkyl, perfluoroalkyl or alkoxyl group; And, work as X
1, G
1, X
2And G
2When being singly-bound, R
5For alkyl, perfluoroalkyl or the alkoxyl group of carbon number 3～30, work as G
2Be singly-bound and X
2Neither when singly-bound neither alkylidene group, R
5For hydrogen or carbon number are 3～30 alkyl, work as G
1And G
2When being singly-bound, X
1, X
2And R
5The total carbon number more than or equal to 3;
In the formula (IX), R
6It for hydrogen or carbon number 1～12 alkyl; Ring B for hydrogen arbitrarily can by carbon number be 1～4 alkyl replace 1, the 4-phenylene or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the 4-cyclohexylidene; X
0It for singly-bound or carbon number 1～5 alkylidene group; S is 0～3 integer; When s was 2, two ring B both can be the same or different two X
0Also be both to can be the same or different; When s is 3, three or any two the ring B both can be the same or different three or any two X
0Also be both to can be the same or different; Z
1And Z
2Be independently singly-bound ,-CH
2-,-CH
2CH
2-or-O-, t1 and t2 are 0～3 integer independently; When t1 is 2, two Z
1Both can be the same or different; When t1 is 3, three or any two Z
1Both can be the same or different; When t2 is 2, two Z
2Both can be the same or different; When t2 is 3, three or any two Z
2Both can be the same or different.
7, smooth orientation agent according to claim 4, it is characterized in that: the A composition is to use at least a polymkeric substance that obtains as raw material in the represented compound of formula (I-1)～formula (I-3), formula (II-1)～formula (II-3), formula (III-1), formula (IV-1)～formula (IV-3), formula (V-1) and formula (X-1)～formula (X-8), and the B composition is polyimide or its precursor polyamic acid that has with the represented structural unit of formula (VI);
Wherein, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2-the carbon number that replaces is 2～20 alkylidene group, with the represented divalent group of formula (VIII) or with the represented divalent group of formula (IX), the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Be one or non-conterminous two-CH
2-can by-O-,-NH-,-N (CH
3)-or-Si (CH
3)
2OSi (CH
3)
2The carbon number of-replacement is 6～20 alkylidene group;
In the formula (VIII), X
1And X
2Independently for singly-bound ,-O-,-COO-,-OCO-,-NH-,-CONH-or carbon number are 1～12 alkylidene group; G
1And G
2Be singly-bound independently, comprise perhaps that to be selected from carbon number be that 6～12 aromatic ring and carbon number are the divalent group of 1～3 rings in 3～12 the alicyclic ring; R
5For hydrogen, fluorine ,-CN ,-OH or carbon number are 1～30 alkyl, perfluoroalkyl or alkoxyl group; And, work as X
1, G
1, X
2And G
2When being singly-bound, R
5For alkyl, perfluoroalkyl or the alkoxyl group of carbon number 3～30, work as G
2Be singly-bound and X
2Neither when singly-bound neither alkylidene group, R
5For hydrogen or carbon number are 3～30 alkyl, work as G
1And G
2When being singly-bound, X
1, X
2And R
5The total carbon number more than or equal to 3;
In the formula (IX), R
6It for hydrogen or carbon number 1～12 alkyl; Ring B for hydrogen arbitrarily can by carbon number be 1～4 alkyl replace 1, the 4-phenylene or arbitrarily hydrogen can by carbon number be 1～4 alkyl replace 1, the 4-cyclohexylidene; X
0It for singly-bound or carbon number 1～5 alkylidene group; S is 0～3 integer; When s was 2, two ring B both can be the same or different two X
0Also be both to can be the same or different; When s is 3, three or any two the ring B both can be the same or different three or any two X
0Also be both to can be the same or different; Z
1And Z
2Be independently singly-bound ,-CH
2-,-CH
2CH
2-or-O-; T1 and t2 are 0～3 integer independently; When t1 is 2, two Z
1Both can be the same or different; When t1 is 3, three or any two Z
1Both can be the same or different; When t2 is 2, two Z
2Both can be the same or different; When t2 is 3, three or any two Z
2Both can be the same or different.
8, smooth orientation agent according to claim 7 is characterized in that: the R in the formula (VI)
4For the alkylidene group of carbon number 2～20 or with the represented divalent group of formula (VIII-1), and the R of each structural unit
4Can be different; And, the structural unit sum more than or equal in 60% the structural unit, R
4Alkylidene group for carbon number 6～20;
Wherein, ring B
1And ring B
2Be singly-bound or 1 independently, 4-cyclohexylidene, G
3For singly-bound or-CH
2CH
2-, and, R
7It for hydrogen or carbon number 1～20 alkyl.
9, a kind of liquid crystal orienting film is characterized in that: it is to use makes according to each described smooth orientation agent in the claim 1 to 8.
10, a kind of liquid crystal display device is characterized in that: it is to use liquid crystal orienting film according to claim 9 to make.
11, a kind of manufacture method of liquid crystal orienting film, it is characterized in that: will contain have light orientation ability polymkeric substance as the A composition and contain the polymkeric substance that in 100 ℃～300 ℃ scope, has liquid crystal temperature range and be coated on the substrate as the light orientation agent of B composition and form film, irradiates light and after making this film orientation is warmed up to the heat treated till the liquid crystal temperature of B composition.
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| JP2008073166 | 2008-03-21 | ||
| JP2008073166 | 2008-03-21 | ||
| JP2008-073166 | 2008-03-21 | ||
| JP2008189846 | 2008-07-23 | ||
| JP2008-189846 | 2008-07-23 | ||
| JP2008189846 | 2008-07-23 | ||
| JP2009028036A JP5407394B2 (en) | 2008-03-21 | 2009-02-10 | Photo-alignment agent, alignment film, and liquid crystal display device using the same |
| JP2009028036 | 2009-02-10 | ||
| JP2009-028036 | 2009-02-10 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5407394B2 (en) | 2014-02-05 |
| TW200940690A (en) | 2009-10-01 |
| JP2010049230A (en) | 2010-03-04 |
| TWI385241B (en) | 2013-02-11 |
| CN101633780B (en) | 2012-06-20 |
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