CN100576034C

CN100576034C - Optically anisotropic body, polaroid and liquid crystal indicator

Info

Publication number: CN100576034C
Application number: CN200610151591A
Authority: CN
Inventors: 高桥勇太
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2005-09-16
Filing date: 2006-09-14
Publication date: 2009-12-30
Anticipated expiration: 2026-09-14
Also published as: JP4619249B2; JP2007079337A; CN1932613A; KR101293426B1; KR20070032227A

Abstract

The present invention relates to optically anisotropic body, it is the optically anisotropic body of the stratiform that formed by the composition that contains liquid-crystal compounds, be essentially 0 from the delay of this optically anisotropic body normal to a surface orientation measurement, when the thickness setting with this optically anisotropic body is d, and will make this optically anisotropic body tilt 40 ° and the delay of measuring when being set at Re (40), Re (40)/d is greater than 0.02.

Description

Optically anisotropic body, polaroid and liquid crystal indicator

Technical field

The present invention relates to the technical field of liquid crystal indicator, relate in particular to the liquid crystal indicator of IPS pattern, FFS pattern or VA pattern etc.In addition, the positive contrast that the present invention relates to help to improve liquid crystal indicators such as IPS pattern than and enlarge the optically anisotropic body of field angle etc.

Background technology

As liquid crystal indicator, be widely used in and clip the liquid crystal layer that makes the nematic liquid crystal aligned twisted between the polaroid of two quadratures, apply the mode of electric field, promptly so-called TN pattern along the direction vertical with respect to substrate.In this mode, liquid crystal phase erects for substrate when showing owing to deceive, and produces the birefringence that is caused by liquid crystal compounds when tilted direction is seen, thereby produces the light leakage.At this problem, the following mode that prevents that this light from leaking is put to practical application: use the film of liquid crystal compounds hybrid orientation, liquid crystal cells is carried out optical compensation, thereby prevent that light from leaking.But produced following problem: even use liquid crystal compounds that liquid crystal cells is carried out optical compensation fully no problemly also is very difficult, can not control the gray scale upset of picture below.

In order to address this problem, proposed to use liquid crystal has been applied the so-called IPS pattern of transverse electric field and the liquid crystal indicator of FFS pattern, with dielectric constant anisotropy is carried out the vertical orientated projection that forms for negative liquid crystal and gap electrode is orientated vertical orientated (VA) pattern of cutting apart in panel, and be practical.In recent years, these panels are not limited to the monitor purposes, are carrying out the exploitation as the TV purposes, thereupon the brightness that has improved picture significantly.Therefore, in these operator schemes, generally be not considered to problem in the past, leak to become at little by little light of diagonal position oblique fire Inbound during black the demonstration and cause that the reason that display quality descends becomes obvious.

As one of means of improving this color and the black field angle that shows etc., in IPS pattern and FFS pattern, also study in the method that the optical compensation material with birefringent characteristic is set between liquid crystal layer and the polaroid.For example, the optical axis of having developed the delay increase and decrease effect of liquid crystal layer by will have compensating for tilt the time carries out the birefringent medium that quadrature forms each other and is arranged between substrate and the polaroid, shows or middle tone can be improved painted (referring to Patent Document 1) when showing from the tilted direction direct-view is white.In addition; proposed to use by method and (referred to Patent Document 2 with optical compensating film that negative intrinsic birefringent styrenic polymer and discotic mesogenic compound form; 3; 4) and with birefringence for just and optic axis be positioned at the film of pellicular front and birefringence for just and optic axis be positioned at the film combination of normal direction of film as the method (referring to Patent Document 5) of optical compensating film; use the method (referring to Patent Document 6) of the optical compensating sheet of the biaxiality that postpones a wavelength divided into two parts, use to have the diaphragm of the negative film that postpones as polaroid; and be provided with in its surface and have the mode (referring to Patent Document 7) of the optical compensating layer that is just postponing.

[patent documentation 1] spy opens flat 9-80424 communique

[patent documentation 2] spy opens flat 10-54982 communique

[patent documentation 3] spy opens flat 11-202323 communique

[patent documentation 4] spy opens flat 9-292522 communique

[patent documentation 5] spy opens flat 11-133408 communique

[patent documentation 6] spy opens flat 11-305217 communique

[patent documentation 7] spy opens flat 10-307291 communique

Summary of the invention

But, when the optical compensating sheet that use is made up of stretching birefringent polymer film carries out optical compensation to IPS pattern and FFS mode liquid crystal unit etc., need to use a plurality of films, the thickness of optical compensating sheet has increased as a result, is unfavorable for the slimming of display device.In addition, in order to address these problems, can use liquid crystal material orientation and the optical anisotropic film that obtains, but be difficult in large area with uniform thickness coated with liquid crystal material, and be difficult to make it to be orientated equably, be easy to produce inhomogeneous and concave-convex surface etc., thereby cause qualification rate to descend.In addition, if the orientation deficiency of liquid crystal material, when then being used for liquid crystal indicator, the incident polarized light by polaroid carries out polarized light to be eliminated and is easy to remove in the front, leaks thereby produce light when black the demonstration, produces degradation rough sledding under the contrast.

The present invention proposes in view of above-mentioned variety of issue, its objective is the optically anisotropic body that homogeneity height and filming are provided.In addition, another object of the present invention provide positive contrast than high, field angle enlarges and have the liquid crystal indicator that does not have uneven high-quality display performance under big picture.

Be used to realize that the means of above-mentioned purpose are as follows:

(1) a kind of optically anisotropic body, it is the stratiform optically anisotropic body that is formed by the composition that contains liquid-crystal compounds, wherein, be essentially 0 from the delay of this optically anisotropic body normal to a surface orientation measurement, when the thickness setting with this optically anisotropic body is d, and will makes this optically anisotropic body tilt 40 ° of delays of measuring when being set at Re (40), Re (40)/d is greater than 0.02.

(2) according to (1) described optically anisotropic body, wherein above-mentioned liquid-crystal compounds is the rod shaped liquid crystal compound, and the molecule of this rod shaped liquid crystal compound in fact vertically is orientated with respect to the surface of above-mentioned optically anisotropic body.

(3) according to (1) described optically anisotropic body, wherein above-mentioned liquid-crystal compounds is a disc liquid-crystal compounds, and the molecule of this disc liquid-crystal compounds in fact flatly is orientated the surface of its disc face with respect to above-mentioned optically anisotropic body.

(4) by arbitrary described stratiform optically anisotropic body and the film formed duplexer of polymer thin in above-mentioned (1)-(3).

(5) according to the duplexer of above-mentioned (4), wherein above-mentioned thin polymer film is to show optically anisotropic film by stretching.

(6) according to the duplexer of above-mentioned (4) or (5), wherein above-mentioned thin polymer film is acylated cellulose film or norbornene polymer film.

(7) a kind of polaroid, it comprises in polarizing coating and above-mentioned (1)-(3) arbitrary described duplexer in arbitrary described optically anisotropic body or above-mentioned (4)-(6).

(8) a kind of liquid crystal indicator, it comprises in liquid crystal cells and above-mentioned (1)-(3) polaroid of arbitrary described duplexer in arbitrary described optical anisotropic layer, above-mentioned (4)-(6) or above-mentioned (7).

Description of drawings

Fig. 1 is the synoptic diagram of expression by the pixel region example of the IPS mode liquid crystal unit of embodiment making.

[explanation of symbol]

1 liquid crystal cell pixel region

2 pixel electrodes

3 show electrodes

4 frictional directions

5a, 5b deceive the director of liquid-crystal compounds when showing

The director of liquid-crystal compounds when 6a, 6b show in vain

Embodiment

Embodiment to optical compensating film of the present invention, polaroid and liquid crystal indicator describes successively below.In addition, use the numerical range of "-" expression to be meant in this instructions, be included in the numerical value put down in writing before and after "-" scope as lower limit and higher limit.

In this instructions, so-called " parallel ", " quadrature " be meant, strict angle ± and less than in 10 ° the scope.This scope is preferably less than ± 5 ° with the error of the angle of strictness, more preferably less than ± 2 °.In addition, so-called " vertical in fact " is meant, compares less than in ± 20 ° the scope with the vertical angle of strictness.This scope is preferably less than ± 15 ° with the error of the angle of strictness, more preferably less than ± 10 °.In addition, " slow axis " is meant the direction of refractive index maximum.In addition, unless specifically stated otherwise, the measurement wavelength of refractive index is the value of visible region λ=550nm.

In this instructions, unless specifically stated otherwise, so-called " polaroid " is the polaroid of rectangular to comprise (long size) and with the meaning use of polaroid such as (in this instructions, also comprise as " cutting " " die-cut " and " cutting ") of the big or small cutting that embeds liquid-crystal apparatus.In addition, in this instructions, " polarizing coating " and " polaroid " difference is used, " polaroid " is meant the duplexer of the transparent protective film that has this polarizing coating of protection at least one face of " polarizing coating ".

In this instructions, Re, Rth represent the delay in the face under certain wavelength X nm and the delay of thickness direction respectively.Re injects the film normal direction by the light that makes wavelength nm in KOBRA 21ADH (prince's instrumentation machine (strain) system) to measure.Rth is following to calculate: with the length of delay measured and the assumed value of mean refractive index and the film thickness value of input serves as that the basis is calculated by KOBRA21ADH, and described length of delay is with above-mentioned Re, slow axis in the face (judging by KOBRA21ADH) is injected the length of delay that the light of wavelength X nm is measured as sloping shaft (turning axle) and from+40 ° the direction of tilting with respect to the film normal direction, and the slow axis in the face injected the light of wavelength X nm and the length of delay of three orientation measurements of total of the length of delay measured as sloping shaft (turning axle) and from-40 ° the direction of tilting with respect to the film normal direction.Wherein the assumed value of mean refractive index can be used polymer handbook (JOHN WILEY ﹠amp; SONS, INC), the Directory Value of various optical thin films.Value for mean refractive index is not a known substances, can measure with Abbe refractometer.Following example shows the value of the mean refractive index of main optical thin film: acylated cellulose (1.48), cyclic olefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).When importing the assumed value of these mean refractive indexs and thickness, can calculate nx, ny, nz by KOBRA 21ADH.Calculate Nz=(nx-nz)/(nx-ny) further by this nx that calculates, ny, nz.

[optically anisotropic body]

The present invention relates to the stratiform optically anisotropic body that forms by the composition that contains liquid-crystal compounds.The delay from respect to the normal to a surface orientation measurement of this stratiform optically anisotropic body is essentially 0.Above-mentioned liquid-crystal compounds is preferably rod shaped liquid crystal compound or disc liquid-crystal compounds.When using the rod shaped liquid crystal compound, rodlike molecule carries out vertical orientatedly in the preferred above-mentioned optically anisotropic body, and perhaps when the use disc liquid-crystal compounds, disklike molecule carries out horizontal alignment in the preferred above-mentioned optically anisotropic body.

During horizontal alignment, the delay in the face of optical anisotropic layer is essentially 0 to the molecule of or disc liquid-crystal compounds vertical orientated in fact when the molecule of rod shaped liquid crystal compound in fact.In optically anisotropic body of the present invention will from tilt with respect to the normal to a surface direction 40 ° and the delay of measuring be set at Re (40), when thickness setting is d, Re (40)/d is greater than 0.02, more preferably Re (40)/d is more than 0.202, more preferably more than 0.206.In addition, Nei delay face to face is 0 o'clock, and the axle of its inclination also can be selected arbitrarily.When the birefringence measurement device can detect slow axis or fast axle mutually, any one was as sloping shaft with it, made optically anisotropic body tilt 40 ° and measure and postpone.The direction that tilts can be the dextrorotation direction, also can be left hand direction, but differs 0.2nm when above when both sides' value, gets the mean value of both sides' value.

Kind for liquid crystal compounds has no particular limits.Optically anisotropic body of the present invention also can carry out immobilization by photo-crosslinking and heat cross-linking and make by for example the low molecular weight liquid crystal compound being formed in mesomorphic state after the row orientation.In addition, the high molecule liquid crystal compound is formed in mesomorphic state after the row orientation, by cooling this orientation is carried out immobilization and make.In addition among the present invention, in the making of optically anisotropic body, used liquid crystal compounds, but liquid crystal compounds often is included in the optically anisotropic body with the state that is fixed by polymerization etc. in the process of making, and finally needn't show liquid crystal liquid crystal property.The polymerizable liquid crystal compound can be multi-functional polymerizable liquid crystal, also can be simple function polymerizable liquid crystal compound.In addition, liquid crystal compounds can be the discotic mesogenic compound, also can be the rod shaped liquid crystal compound.

In the optically anisotropic body of the present invention, the molecule of liquid-crystal compounds preferably is fixed to the state of orientation of regulation.Be preferably any state of orientation of vertical orientated or horizontal alignment.In order to form from the delay of frontal is 0 stratiform optically anisotropic body, the major axis of preferred rod shaped liquid crystal compound comes down to vertical with respect to pellicular front (aspect of stratiform optically anisotropic body), perhaps the disc face of discotic mesogenic compound comes down to level with respect to pellicular front (aspect of stratiform optically anisotropic body).So-called rod shaped liquid crystal compound in fact vertically is meant, the formed angle of director of pellicular front (aspect of stratiform optically anisotropic body) and rod shaped liquid crystal compound is in 70 °～90 ° scope, more preferably 80 °～90 °, more preferably 85 °～90 °.So-called discotic mesogenic compound level in fact is meant that the mean value of the formed angle of disc face of pellicular front (aspect of stratiform optically anisotropic body) and discotic mesogenic compound is in 0 °～20 ° scope.More preferably 0 °～10 °, more preferably 0 °～5 °.

Optically anisotropic body of the present invention also can form on supporter.The duplexer of supporter and this optically anisotropic body can be used as optical compensating film and embeds in the liquid crystal indicator etc.Above-mentioned duplexer also can have more than two optically anisotropic body of the present invention as optical anisotropic layer.In addition, optically anisotropic body not only of the present invention and the formed duplexer of supporter can be used as optical compensating film, and optically anisotropic body of the present invention itself also can be used alone as optical compensating film.

Below, at the form that on supporter, has the optical compensating film that optically anisotropic body of the present invention forms as optical anisotropic layer, explain and make used material, method for making etc.

Above-mentioned optical anisotropic layer can be formed by the composition that contains liquid crystal compounds such as rod shaped liquid crystal compound or discotic mesogenic compound and the following polymerization initiators that add as required, orientation controlling agent and other adjuvant etc.

[discotic mesogenic compound]

Among the present invention, preferably use the discotic mesogenic compound to form optical anisotropic layer, more preferably use the luxuriant and rich with fragrance liquid crystal of benzo [9,10].The discotic mesogenic compound various documents (C.Destrade etal., Mol.Crysr.Liq.Cryst., vol.71, page 111 (1981); Japanization association compiles, the quarterly chemistry always is said, No.22, the chemistry of liquid crystal, the 5th chapter, the 10th chapter the 2nd save (1994); B.Kohne et al., Angew.Chem.Soc.Chem.Comm., page 1794 (1985); J.Zhang et al., J.Am.Chem.Soc., vol.116, page 2655 (1994)) on the books.For the polymerization of discotic mesogenic compound, open in the flat 8-27284 communique on the books the spy.

The discotic mesogenic compound preferably has polymerizable group so that can fix by polymerization.For example, can consider on the discoid core of discotic mesogenic compound in conjunction with polymerizable group still,, then in polyreaction, to be difficult to keep state of orientation if polymerizable group directly is connected with discoid core as substituent structure.Therefore, preferably between discoid core and polymerizable group, has the structure that connects base.That is, the discotic mesogenic compound with polymerizable group is preferably the compound of representing with following formula.

D(-L-P) _n

In the formula, D is discoid core, and L is the connection base of divalence, and P is a polymerizable group, and n is 4～12 integer.The preferred object lesson of the discoid core (D) in the above-mentioned formula, the connection base (L) of divalence and polymerizable group (P) is opened the spy respectively and is put down in writing (D1)～(D15), (L1)～(L25), (P1)～(P18) in the 2001-4837 communique, can preferably use the content of putting down in writing in the above-mentioned communique.In addition, the plate-like nematic liquid crystal phase-solid phase inversion temperature of discotic mesogenic compound is preferably 70～300 ℃, more preferably 70～170 ℃.

[rod shaped liquid crystal compound]

Among the present invention, preferably use the rod shaped liquid crystal compound to form optical anisotropic layer.As the rod shaped liquid crystal compound, preferably use azomethine class, azoxy class, cyanobiphenyl class, cyanobenzene ester class, benzoate class, cyclohexane-carboxylic acid phenyl ester class, cyano-phenyl cyclohexanes, cyano group substituted-phenyl miazines, alkoxy substituted phenyl miazines, Ben Ji dioxane, dibenzenyl class and alkenyl cyclohexyl benzonitrile class.Not only can use aforesaid low molecular weight liquid crystal compound, can also use the high molecule liquid crystal compound.More preferably fix orientation by the rod shaped liquid crystal compound polymerization.Has the material that can cause the part-structure of polymerization or cross-linking reaction etc. as suitable use of liquid crystal compounds by active ray and electron ray, heat etc.The number of this part-structure is preferably 1～6, more preferably 1～3.As polymerism rod shaped liquid crystal compound, can use at Makromol.Chem. 190 volumes, 2255 pages (1989), AdvancedMaterials 5 volumes, 107 pages (1993), No. 4683327 instructions of United States Patent (USP), No. 5622648 instructions of United States Patent (USP), No. 5770107 instructions of United States Patent (USP), international open WO95/22586 communique, the international communique that discloses No. 95/24455, the international communique that discloses No. 97/00600, the international communique that discloses No. 98/23580, the international communique that discloses No. 98/52905, Te Kaiping 1-272551 communique, Te Kaiping 6-16616 communique, Te Kaiping 7-110469 communique, Te Kaiping 11-80081 communique, the spy opens the 2001-328973 communique, the spy opens the 2004-240188 communique, the spy opens the 2005-99236 communique, the spy opens the 2005-99237 communique, the spy opens the 2005-121827 communique, the spy opens the middle compounds of putting down in writing such as 2002-30042 communique.

In addition, satisfy the condition of Re (40)/d＞0.02, preferably use the big liquid crystal compounds of intrinsic birefringence in order to make above-mentioned optical anisotropic layer.If use the big liquid crystal compounds of intrinsic birefringence,, can make the optical anisotropic layer that satisfies above-mentioned formula at an easy rate even then the optical anisotropic layer thin layer of Xing Chenging also can show high birefringence.

[vertical orientated promoter]

Vertical orientated for liquid crystal compounds is carried out equably, need vertically be orientated control to liquid crystal compounds in alignment films interface side and air interface side.In order to reach this purpose, also can in alignment films, adopt to have added to produce the compound compositions that makes the vertical orientated effect of liquid crystal compounds by excluded volume effect, electrostatic efficiency or surface energy effect.In addition, about the orientation control of air interface side, also can adopt to have mixed and when the orientation of liquid crystal compounds, be partial to the liquid crystalline composition that is present on the air interface and produces the compound that makes the vertical orientated effect of liquid crystal compounds by its excluded volume effect, electrostatic efficiency or surface energy effect.As the vertical orientated compound (alignment films interface side vertical-tropism agent) of molecule that promotes liquid crystal compounds in this alignment films interface side, the suitable pyridine derivate that uses.As the vertical orientated compound (air interface side vertical-tropism agent) of molecule that promotes liquid crystal compounds in the air interface side, suitable use promotes this compound deflection to be present in the air interface side and contains the fluoro fatty group and be selected from carboxyl (COOH), sulfo group (SO ₃H), phosphine oxygen base { OP (=O) (OH) ₂And their salt among more than one the compound of water wettability base.In addition,, for example, when liquid crystalline composition being modulated to coating liquid, can improve the screening characteristics of this coating liquid, suppress generation inhomogeneous, depression by mixing these compounds.Below vertical-tropism agent is described in detail.

[alignment films interface side vertical-tropism agent]

As being used for alignment films interface side vertical-tropism agent of the present invention, the suitable pyridine derivate (pyridiniujm) that uses by following formula (I) expression.In the above-mentioned liquid crystalline composition of at least a adding, the molecule of discotic mesogenic compound in fact vertically is orientated near alignment films with this pyridine derivate.

[Chemical formula 1]

In the formula (I), L ¹The expression divalent connects base, preferably by alkylidene and-O-,-S-,-CO-,-SO ₂-,-NR ^a-(wherein, R ^aBe that carbon number is 1～5 alkyl or hydrogen atom), the carbon number formed of the combination of alkylene group, alkynylene or arlydene is that 1～20 divalent connects base.Alkylidene can be that straight chain also can be a side chain.

In the formula (I), R ¹Be hydrogen atom, unsubstituted amino or be the substituted-amino that 1～20 substituting group replaces by carbon number.Work as R ¹When being substituted-amino, preferably replaced by fatty group.Fatty group can list for example alkyl, substituted alkyl, alkenyl, substituted alkenyl base, alkynyl and substituted alkynyl.In addition, work as R ¹When being disubstituted amido, two fatty groups also can be bonded to each other and form nitrogen heterocyclic ring.The nitrogen heterocyclic ring that form this moment is preferably 5 yuan of rings or 6 yuan of rings.R ¹Be preferably hydrogen atom, unsubstituted amino or carbon number and be 1～20 substituted-amino, more preferably hydrogen atom, unsubstituted amino or carbon number are 2～12 substituted-amino, and more preferably hydrogen atom, unsubstituted amino or carbon number are 2～8 substituted-amino.Work as R ¹When being amino, preferably 4 at pyridine ring are substituted.

In the formula (I), X is a negative ion.As anionic example, (for example can list halide anion, fluorine ion, chlorion, bromide ion, iodide ion etc.), azochlorosulfonate acid ion (for example, the methane-sulforic acid ion, the trifluoromethanesulfonic acid ion, methyl sulfate ion, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion etc.), sulfate ion, the carbonic acid ion, nitrate ion, the thiocyanic acid ion, the high chloro acid ion, the tetrafluoro boric acid ion, the picric acid ion, acetic acid ion, formate ion, the trifluoracetic acid ion, phosphate ion (for example, hexafluorophosphoric acid ion), hydroxyl etc.X is preferably halide anion, sulfonate ion, hydroxyl.

In the formula (I), Y ¹Be that will to have 5 yuan of rings or 6 yuan of rings be that 1～30 divalent connects base as the carbon number of part-structure.At Y ¹In the annulus structure that contains more preferably cyclohexyl ring, aromatic ring or heterocycle.As aromatic ring, can list phenyl ring, indenes ring, naphthalene nucleus, fluorenes ring, phenanthrene ring, anthracene nucleus, cyclohexyl biphenyl and pyrene ring.More preferably phenyl ring, cyclohexyl biphenyl and naphthalene nucleus.As the heteroatoms that constitutes heterocycle, preferred nitrogen atom, oxygen atom and sulphur atom can list for example furan nucleus, thiphene ring, pyrrole ring, pyrrolin ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazoles ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazan ring, tetrazole ring, pyranoid ring, diox ring, dithiane ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring etc.Heterocycle is preferably 6 yuan of rings.By Y ¹Have 5 yuan of rings or 6 yuan of rings of expression connect base as the divalent of part-structure and also can have substituting group.

In the formula (I), Z is a halogen substituted phenyl, the nitro substituted-phenyl, the cyano group substituted-phenyl, by carbon number is the phenyl that 1～10 alkyl replaces, by carbon number is the phenyl that 2～10 alkoxy replaces, carbon number is 1～12 alkyl, carbon number is 2～20 alkynyl, carbon number is 1～12 alkoxy, carbon number is 2～13 alkoxy carbonyl, carbon number is 7～26 aryloxycarbonyl, carbon number is 7～26 aryl-carbonyl oxygen, is preferably the cyano group substituted-phenyl, halogen substituted phenyl, by carbon number is the phenyl that 1～10 alkyl replaces, by carbon number is the phenyl that 2～10 alkoxy replaces, carbon number is that 7～26 aryloxycarbonyl or carbon number are 7～26 aryl-carbonyl oxygen.

Z can also have substituting group; as substituent example, comprise halogen atom (fluorine atom; the chlorine atom; bromine atoms; the iodine atom); cyano group; nitro; carbon number is 1～16 alkyl; carbon number is 1～16 alkenyl; carbon number is 1～16 alkynyl; carbon number is 1～16 halogen-substituted alkyl; carbon number is 1～16 alkoxy; carbon number is 2～16 acyl group; carbon number is 1～16 alkylthio group; carbon number is 2～16 acyloxy; carbon number is 2～16 alkoxy carbonyl; carbamyl; carbon number is that 2～16 alkyl-substituted amino formoxyl and carbon number are 2～16 amide group.

As the pyridine compounds that uses among the present invention, preferably with the pyridine compounds of following formula (Ia) expression.

[Chemical formula 2]

In the formula (Ia), L ³Be singly-bound ,-O-,-O-CO-,-CO-O-,-C ≡ C-,-CH=CH-,-CH=N-,-N=CH-,-N=N-,-O-AL-O-,-O-AL-O-CO-,-O-AL-CO-O-,-CO-O-AL-O-,-CO-O-AL-O-CO-,-CO-O-AL-CO-O-,-O-CO-AL-O-,-O-CO-AL-O-CO-or O-CO-AL-CO-O-.AL is that carbon number is 1～10 alkylidene.L ³Be preferably singly-bound ,-O-,-O-AL-O-,-O-AL-O-CO-,-O-AL-CO-O-,-CO-O-AL-O-,-CO-O-AL-O-CO-,-CO-O-AL-CO-O-,-O-CO-AL-O-,-O-CO-AL-O-CO-or O-CO-AL-CO-O-, more preferably singly-bound or O-.

In the formula (Ia), L ⁴Be singly-bound ,-O-,-O-CO-,-CO-O-,-C ≡ C-,-CH=CH-,-CH=N-,-N=CH-or N=N-.

In the formula (Ia), R ³Be hydrogen atom, substituted-amino or carbon number are not 2～20 alkyl-substituted amino.Work as R ³When being the dialkyl group substituted-amino, two alkyl also can be bonded to each other and form nitrogen heterocyclic ring.The nitrogen heterocyclic ring that form this moment is preferably 5 yuan of rings or 6 yuan of rings.R ³More preferably hydrogen atom, substituted-amino or carbon number are not 2～12 dialkyl group substituted-amino, most preferably hydrogen atom, substituted-amino or carbon number are not 2～8 dialkyl group substituted-amino.Work as R ³Be not during substituted-amino, 4 of preferred pyridine ring are replaced by amino.

In the formula (Ia), Y ²And Y ³Respectively independently by also having substituent 6 yuan of divalent groups that ring is formed.The example of 6 yuan of rings can list aliphatics ring, aromatic ring (phenyl ring) and heterocycle.The example of 6 yuan of aliphatics rings can list cyclohexane ring, cyclohexene ring and cyclohexadiene ring.The example of 6 yuan of heterocycles can list pyranoid ring, diox ring, dithiane ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring.On 6 yuan of rings, also can condense other 6 yuan of rings or 5 yuan of rings.

It is that 1～12 alkyl and carbon number are 1～12 alkoxy that substituent example can list halogen atom, cyano group, carbon number.Alkyl and alkoxy can be that 2～12 acyl group or carbon number are that 2～12 acyloxy replaces by carbon number also.The definition of acyl group and acyloxy will be described later.

In the formula (Ia), X ¹It is negative ion.X ¹Be preferably the negative ion of monovalence.As anionic example, comprise halide anion (for example, fluorine ion, chlorion, bromide ion, iodide ion) and azochlorosulfonate acid ion (for example, methane-sulforic acid ion, p-toluenesulfonic acid ion, benzene sulfonic acid ion).

In the formula (Ia), Z ¹Be that hydrogen atom, cyano group, carbon number are that 1～12 alkyl or carbon number are 1～12 alkoxy, alkyl and alkoxy also can be respectively is that 2～12 acyl group or carbon number are that 2～12 acyloxy replaces by carbon number.

In the formula (Ia), m is 1 or 2, when m is 2, and two L ⁴And two Y ³Also can be different.

When m is 2, Z ¹Be preferably cyano group, carbon number and be 1～10 alkyl or carbon number and be 1～10 alkoxy.

When m is 1, Z ¹Be preferably carbon number and be 7～12 alkyl, carbon number and be 7～12 alkoxy, carbon number and be 7～12 acyl substituted alkyl, carbon number and be 7～12 acyl substituted alkoxy, carbon number and be 7～12 acyloxy substituted alkyl or carbon number and be 7～12 acyloxy substituted alkoxy.

Acyl group represents with-CO-R, and acyloxy represents that with-O-CO-R R is fatty group (alkyl, substituted alkyl, alkenyl, substituted alkenyl base, alkynyl, substituted alkynyl) or aromatic series base (aryl, substituted aryl).R is preferably fatty group, more preferably alkyl or alkenyl.

In the formula (Ia), p is 1～10 integer.C _pH _2pBe meant the chain alkylidene that also can have branched structure.C _pH _2pBe preferably straight chain shape alkylidene.In addition, p more preferably 1 or 2.

Below, show with the formula (I) and/or (Ia) object lesson of compound of expression.Wherein, Me represents methyl.

[chemical formula 3]

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

Pyridine derivate generally obtains by pyridine ring being carried out alkylation (Men Shute gold reaction).

The content preferable range of the above-mentioned pyridine derivate in the above-mentioned liquid crystalline composition is according to its purposes and difference, be preferably 0.005～8 quality % of liquid crystalline composition (is the liquid crystalline composition of having removed solvent) when as the modulation of coating liquid, more preferably 0.01～5 quality %.

[air interface side vertical-tropism agent]

As operable air interface side vertical-tropism agent among the present invention, suitable use contains the fluoro fatty group and is selected from carboxyl (COOH), sulfo group (SO ₃H), phosphine oxygen base { OP (=O) (OH) ₂And their salt among more than one the polymkeric substance that contains the fluoro fatty group (hereinafter referred to as " fluorine based polymer ") of water wettability base, or with the fluorochemicals of general formula (III) expression.

At first, the fluorine based polymer is described.

Can be used for fluorine based polymer of the present invention is characterised in that and contains the fluoro fatty group and be selected from carboxyl (COOH), sulfo group (SO ₃H), phosphine oxygen base { OP (=O) (OH) ₂And their salt among more than one water wettability base.Kind as polymkeric substance, at " changing the chemistry of Order Polymer Synthesizing " (the grand row work in big Tianjin, distribution: the same people of Co., Ltd.'s chemistry, 1968) on the books in 1～4 page, for example can list polyolefins, polyesters, polyamide-based, polyimide, polyurethanes, polycarbonate-based, polysulfones, polycarbonate-based, polyethers, polyacetals, polyketone class, polyphenyl ethers, polyphenylene sulfide ethers, polyarylate class, polytetrafluoroethylene (PTFE) class, polyvinylidene difluoride, cellulose derivative etc.Above-mentioned fluorine based polymer is preferably polyolefins.

Above-mentioned fluorine based polymer is the polymkeric substance that has the fluoro fatty group at side chain.Above-mentioned fluoro fatty group is preferably carbon number is 1～12, more preferably 6～10.Fatty group can be that chain can be a ring-type also, can be that the straight chain shape also can be a chain when being chain.Wherein, the carbon number of also preferred straight chain shape is 6～10 fluoro fatty group.Have no particular limits for the degree that is replaced by fluorine atom, but the hydrogen atom 50% or more preferably in the fatty group is replaced by fluorine atom, more preferably the hydrogen atom more than 60% in the fatty group is replaced by fluorine atom.The fluoro fatty group is by on the side chain that ester bond, amido link, imide bond, urethane bond, urea key, ehter bond, thioether bond, aromatic ring etc. are included in main polymer chain combines.One of fluoro fatty group makes fluoro-aliphatic compound that usage (being also referred to as the telomer method) or oligomerization method (being also referred to as the oligomer method) make and derives and obtain by telomerizing.Manufacture method about these fluoro-aliphatic compounds, (chief editor: Ishikawa prolongs man, distribution: (Monograph 187 for the シ of Co., Ltd. one エ system シ one, 1987) 117～118 pages and " Chemistryof Organic Fluorine Compounds II " at for example " fluorine compounds synthetic and performances ", Ed byMilos Hudlicky and Attila E.Pavlath, American ChemicalSociety 1995) on the books in 747～752 pages or the like.What is called telomerize as usage be alkyl halide that chain transfer constants such as iodide is big as telogen, fluorine-containing vinyl compound such as tetrafluoroethene carries out free radical polymerization, thus the method (in reaction process 1, example being shown) of synthetic telomer.

[chemical formula 7]

Reaction process 1

The terminally iodized telomer that obtains carries out suitable terminal chemical modification like that according to for example [reaction process 2] usually, and deriving is fluoro-aliphatic compound.These compounds can be transformed to desirable monomer structure as required again, are used for the manufacturing of fluorine based polymer.

[chemical formula 8]

Reaction process 2

Listed the object lesson of the monomer that can be used to make fluorine based polymer of the present invention below, but the present invention is not limited to following object lesson.

[chemical formula 9]

[Chemical formula 1 0]

[Chemical formula 1 1]

[Chemical formula 1 2]

[Chemical formula 1 3]

[Chemical formula 1 4]

[Chemical formula 1 5]

A form that can be used for fluorine based polymer of the present invention is to have by the derive repetitive that obtains and contain multipolymer with the repetitive of the water wettability base of following formula (II) expression of the monomer that contains the fluoro fatty group (below be sometimes referred to as " fluorine is a monomer ").

[Chemical formula 1 6]

In the above-mentioned formula (II), R ¹, R ²And R ³³Represent hydrogen atom or substituting group respectively independently.Q represents that carboxyl (COOH) or its salt, sulfo group (SO ₃H) or its salt or phosphine oxygen base { OP (=O) (OH) ₂Or its salt.L represents that any group or these divalents that is combined to form more than two that are selected from following connection base group connect base.

(connecting the base group)

Singly-bound ,-O-,-CO-,-NR ^b-(R ^bExpression hydrogen atom, alkyl, aryl or aralkyl) ,-S-,-SO ₂-,-P (=O) (OR ^f)-(R ^fExpression alkyl, aryl or aralkyl), alkylidene and arlydene.

In the formula (II), R ¹, R ²And R ³³Represent hydrogen atom respectively independently or be selected from the substituting group of following illustrative substituting group group.

(substituting group group)

Include: alkyl (being preferably carbon number is 1～20, more preferably carbon number is 1～12, more preferably carbon number is 1～8 alkyl, can list for example methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.); Alkenyl (being preferably carbon number is 2～20, more preferably carbon number is 2～12, more preferably carbon number is 2～8 alkenyl, can list for example vinyl, allyl, 2-butenyl group, 3-pentenyl etc.); Alkynyl (being preferably carbon number is 2～20, more preferably carbon number is 2～12, more preferably carbon number is 2～8 alkynyl, can list for example butynyl, 3-pentynyl etc.); Aryl (being preferably carbon number is 6～30, more preferably carbon number is 6～20, more preferably carbon number is 6～12 aryl, can list for example phenyl, p-aminomethyl phenyl, naphthyl etc.); Aralkyl (being preferably carbon number is 7～30, more preferably carbon number is 7～20, more preferably carbon number is 7～12 aralkyl, can list for example benzyl, phenethyl, 3-phenyl propyl etc.); Replace or unsubstituted amino (being preferably carbon number is 0～20, more preferably carbon number is 0～10, more preferably carbon number is 0～6 amino, for example can list not substituted-amino, methylamino, dimethylamino, diethylamino, anilino-etc.); Alkoxy (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～10 alkoxy, can list for example methoxyl, ethoxy, butoxy etc.); Alkoxy carbonyl (being preferably carbon number is 2～20, more preferably carbon number is 2～16, more preferably 2～10 alkoxy carbonyl, can list for example methoxycarbonyl, ethoxy carbonyl etc.); Acyloxy (being preferably carbon number is 2～20, more preferably carbon number is 2～16, more preferably 2～10 acyloxy, can list for example acetoxyl group, benzoyloxy etc.); Amide group (being preferably carbon number is 2～20, more preferably carbon number is 2～16, more preferably carbon number is 2～10 amide group, can list for example acetamido, benzamido etc.); Alkoxycarbonyl amino (being preferably carbon number is 2～20, more preferably carbon number is 2～16, more preferably carbon number is 2～12 alkoxycarbonyl amino, can list for example methoxycarbonyl amino etc.); Aryloxycarbonyl amino (being preferably carbon number is 7～20, more preferably carbon number is 7～16, more preferably carbon number is 7～12 aryloxycarbonyl amino, can list for example phenyloxycarbonyl amino etc.); Sulfoamido (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 sulfoamido, can list for example methylsulfonyl amido, benzene sulfonamido etc.); Sulfamoyl (being preferably carbon number is 0～20, more preferably carbon number is 0～16, more preferably carbon number is 0～12 sulfamoyl, can list for example sulfamoyl, methyl sulfamoyl, dimethylamino sulfonyl, phenyl sulfamoyl base etc.); Carbamyl (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 carbamyl, can list for example unsubstituted carbamyl, methylamino formoxyl, diethylamino formoxyl, phenyl amino formoxyl etc.); Alkylthio group (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 alkylthio group, can list for example methyl mercapto, ethylmercapto group etc.); Arylthio (being preferably carbon number is 6～20, more preferably carbon number is 6～16, more preferably carbon number is 6～12 arylthio, can list for example thiophenyl etc.); Sulfonyl (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 sulfonyl, can list for example mesyl, p-toluenesulfonyl etc.); Sulfinyl (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 sulfinyl, can list for example methylsulfinyl, phenyl sulfinyl etc.); Uride base (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 uride base, can list for example unsubstituted uride base, methyl uride base, phenyl uride base etc.); Phosphoamide base (being preferably carbon number is 1～20, more preferably carbon number is 1～16, more preferably carbon number is 1～12 phosphoamide base, can list for example diethyl phosphoamide base, phosphenylic acid amide group); Hydroxyl; Sulfydryl; Halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom); Cyano group; Sulfo group; Carboxyl; Nitro; The hydroximic acid base; Sulfino; Diazanyl; Imino group; Heterocyclic radical (is preferably carbon number and is 1～30, more preferably 1～12 heterocyclic radical, can list heteroatomic heterocyclic radicals such as for example having nitrogen-atoms, oxygen atom, sulphur atom, for example imidazolinyl, pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazole quinoline base, benzimidazoline base, benzothiazole quinoline base etc.); Silicyl (being preferably carbon number is 3～40, more preferably carbon number is 3～30, more preferably carbon number is 3～24 silicyl, can list for example trimethyl silyl, triphenyl silicyl etc.).These substituting groups also can be replaced by these substituting groups again.In addition, when having two above substituting groups, can be the same or different.In addition, under possible situation, also can be bonded to each other and form ring.

R ¹, R ²And R ³³(for example be preferably hydrogen atom, alkyl, halogen atom independently respectively, fluorine atom, chlorine atom, bromine atoms, iodine atom etc.) or described later with-group that L-Q represents, more preferably hydrogen atom, carbon number be 1～6 alkyl, chlorine atom, with-group that L-Q represents, preferred especially hydrogen atom, carbon number are 1～4 alkyl, and most preferably hydrogen atom, carbon number are 1～2 alkyl.As the object lesson of this alkyl, can list methyl, ethyl, n-pro-pyl, normal-butyl, sec-butyl etc.This alkyl also can have suitable substituting group.As this substituting group, can list halogen atom, aryl, heterocyclic radical, alkoxy, aryloxy group, alkylthio group, arylthio, acyl group, hydroxyl, acyloxy, amino, alkoxy carbonyl, amide group, oxygen base carbonyl, carbamyl, sulfonyl, sulfamoyl, sulfoamido, sulfuryl (ス Le ホリ Le base), carboxyl etc.In addition, the carbon number of alkyl does not comprise substituent carbon atom.Below, even also identical to the carbon number of other group.

L represents that the divalent that is selected from above-mentioned connection base group connects base or these divalents that is combined to form more than two connection base.In the above-mentioned connection base group ,-NR ^b-R ^bExpression hydrogen atom, alkyl, aryl or aralkyl are preferably hydrogen atom or alkyl.In addition ,-PO (OR ^f)-R ^fExpression alkyl, aryl or aralkyl are preferably alkyl.R ^bAnd R ^fIllustrated identical in carbon number when expression alkyl, aryl or aralkyl and " the substituting group group ".As L, preferably comprise singly-bound ,-O-,-CO-,-NR ^b-,-S-,-SO ₂-, alkylidene or arlydene, especially preferably comprise-CO-,-O-,-NR ^b-, alkylidene or arlydene.When L contained alkylidene, the carbon number of alkylidene was preferably 1～10, and more preferably 1～8, more preferably 1～6.As the object lesson of particularly preferred alkylidene, can list methylene, vinyl, trimethylene, four butylidenes, hexa-methylene etc.When L contained arlydene, the carbon number of arlydene was preferably 6～24, more preferably 6～18, more preferably 6～12.As the object lesson of particularly preferred arlydene, can list phenylene, naphthylene etc.When L contained the divalent that the combination of alkylidene and arlydene is obtained and is connected basic (being inferior aralkyl), the carbon number of inferior aralkyl was preferably 7～34, more preferably 7～26, more preferably 7～16.As the object lesson of particularly preferred inferior aralkyl, can list phenylene methylene, phenylene ethylidene, methylene phenylene etc.The group that can list as L also can have suitable substituting group.As this substituting group can list with before as R ¹, R ², R ³³In the identical group of the listed substituting group of enumerating of substituting group.

Listed the concrete structure of L below.

[Chemical formula 1 7]

[Chemical formula 1 8]

In the above-mentioned formula (II), Q represents the salt (that puts down in writing in the cationic example of formation salt and the above-mentioned carboxyl is identical) of salt (for example, lithium salts, sodium salt, sylvite, ammonium salt (for example ammonium, tetramethyl-ammonium, trimethyl-2-hydroxyethyl ammonium, TBuA, tri methyl benzyl ammonium, 3,5-dimethylphenyl ammonium etc.), pyridiniujm etc.), the sulfo group of carboxyl, carboxyl, the salt of sulfo group (that puts down in writing in the cationic example that forms salt and the above-mentioned carboxyl is identical), phosphine oxygen base, phosphine oxygen base.More preferably carboxyl, sulfo group, phosphate particularly preferably are carboxyl or sulfo group.

Above-mentioned fluorine based polymer can contain a kind of repetitive by above-mentioned formula (II) expression, also can contain more than 2 kinds.In addition, above-mentioned fluorine based polymer also can have one or more above-mentioned each repetitives other repetitive in addition.Have no particular limits for above-mentioned other repetitive, can list the repetitive that obtains by the common monomer derived that can carry out Raolical polymerizable as preferred example.Below, having listed derives obtains the object lesson of the monomer of other repetitive.Above-mentioned fluorine based polymer also can contain the repetitive by the monomer derived more than a kind or 2 kinds that is selected from following set of monomers.

Set of monomers

(1) alkenes

Ethene, propylene, 1-butylene, isobutylene, 1-hexene, 1-dodecylene, 1-vaccenic acid, 1-eicosylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, 3,3,3-trifluoro propene, tetrafluoroethene, vinyl chloride, vinylidene chloride etc.;

(2) dienes

1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-pro-pyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl isophthalic acid, 3-pentadiene, 1-phenyl-1,3-butadiene, 1-Alpha-Naphthyl-1,3-butadiene, 1-betanaphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorbutadiene, 2-fluoro-1,3-butadiene, 2,3-two chloro-1,3-butadiene, 1,1,2-three chloro-1,3-butadienes and 2-cyano group-1,3-butadiene, 1,4-divinyl cyclohexane etc.;

(3) α, the derivant of beta-unsaturated carboxylic acid

(3a) alkyl-acrylates

Methyl acrylate, acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, the acrylic acid pentyl ester, the just own ester of acrylic acid, cyclohexyl acrylate, 2-EHA, the acrylic acid n-octyl, acrylic acid uncle monooctyl ester, acrylic acid dodecane ester, phenyl acrylate, benzyl acrylate, acrylic acid 2-chloroethene ester, acrylic acid 2-bromine ethyl ester, acrylic acid 4-neoprene ester, 2 cyanoethyl acrylate, acrylic acid 2-acetoxyl group ethyl ester, the acrylic acid methoxy benzyl ester, acrylic acid 2-chlorine cyclohexyl, acrylic acid chaff ester, tetrahydrofurfuryl acrylate, acrylic acid 2-methoxyl ethyl ester, acrylic acid ω-methoxy poly (ethylene glycol) ester (the addition molal quantity of polyethylene oxide is the material that n=2-100 obtains), acrylic acid 3-methoxyl butyl ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid 2-butoxy ethyl ester, acrylic acid 2-(2-butoxy ethoxy) ethyl ester, acrylic acid 1-bromo-2-methoxyl ethyl ester, acrylic acid 1,1-two chloro-2-ethoxy ethyl esters, glycidyl acrylate etc.);

(3b) alkyl methacrylate

Methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, the secondary butyl ester of methacrylic acid, the metering system tert-butyl acrylate, the methacrylic acid pentyl ester, the just own ester of methacrylic acid, cyclohexyl methacrylate, methacrylic acid 2-Octyl Nitrite, n octyl methacrylate, methacrylic acid stearoyl ester, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, methacrylic acid chaff ester, tetrahydrofurfuryl methacrylate, the methyl methacrylate phenyl ester, methacrylic acid naphthalene ester, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid 3-methoxyl butyl ester, methacrylic acid ω-methoxy poly (ethylene glycol) ester (the addition molal quantity of polyethylene oxide is the material that n=2-100 obtains), methacrylic acid 2-acetoxyl group ethyl ester, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid 2-butoxy ethyl ester, methacrylic acid 2-(2-butoxy ethoxy) ethyl ester, glycidyl methacrylate, methacrylic acid 3-trimethoxysilyl propyl ester, allyl methacrylate, methacrylic acid 2-isocyanate group ethyl ester etc.;

(3c) the diester class of unsaturated polybasic carboxylic acid

Dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl itaconate, butenoic acid dibutyl ester, butenoic acid dihexyl, DEF, dimethyl fumarate etc.;

(3d) amide-type of α, beta-unsaturated carboxylic acid

N, N-DMAA, N, N-diethyl acrylamide, N-n-pro-pyl acrylamide, N tert butyl acrylamide, uncle's N-octyl group Methacrylamide, N-cyclohexyl acrylamide, N phenyl acrylamide, N-(2-acetyl group acetyl oxygen ethyl) acrylamide, N-benzyl acrylamide, N-acryloyl morpholine, diacetone acrylamide, N-methyl maleimide etc.;

(4) unsaturated nitrile

Vinyl cyanide, methacrylonitrile etc.;

(5) styrene and derivant thereof

Styrene, vinyltoluene, ethyl styrene, p-t-butyl styrene, p-vinyl benzoic acid methyl esters, α-Jia Jibenyixi, p-1-chloro-4-methyl-benzene, vinyl naphthalene, p-methoxy styrene, p-methylol styrene, p-acetoxy-styrene etc.;

(6) vinyl ester

Vinyl acetate, propionate, vinyl butyrate, isobutyric acid vinyl acetate, benzoic acid vinyl acetate, vinyl salicylate, chloride vinyl acetate, Methoxy acetic acid vinyl acetate, phenyl vinyl acetate etc.;

(7) vinyl ethers

Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, dodecyl vinyl ether, n-eicosane base vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorine butyl vinyl ether, fluorine butoxyethyl group vinyl ether etc.; And

(8) other polymerizable monomer

N-vinyl pyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, methoxy ethyl vinyl ketone, 2-Yi Xi oxazolin, 2-Yi Bing Xi oxazolin etc.

In the above-mentioned fluorine based polymer, the amount of monomer that contains the fluoro fatty group is preferably more than the 5 quality % of formation monomer total amount of this polymkeric substance, more preferably more than the 10 quality %, more preferably more than the 30 quality %.In the above-mentioned fluorine based polymer, be preferably with the amount of the repetitive of above-mentioned formula (II) expression more than the 0.5 quality % of formation monomer total amount of this fluoropolymer, more preferably 1～20 quality %, more preferably 1～10 quality %.Above-mentioned quality percentage is owing to be easy to change according to the molecular weight of the monomer that uses the numerical value of preferable range, so the mode of representing with functional group's molal quantity of the per unit mass of polymkeric substance can be stipulated the content of the repetitive represented with formula (II) exactly.When using this statement, the preferred amount of the water wettability base that contains in the above-mentioned fluorine based polymer (Q in the formula (II)) is 0.1mmol/g～10mmol/g, and preferred amount is 0.2mmol/g～8mmol/g.

The weight-average molecular weight of the above-mentioned fluorine based polymer that uses among the present invention is preferably 1,000, below 000, more preferably below 500,000, more preferably below 100,000.Weight-average molecular weight can be used gel permeation chromatography (GPC) and the value that converts as polystyrene (PS) and measuring.

The polymerization of above-mentioned fluorine based polymer has no particular limits, and for example can adopt the cationic polymerization and the polymerizations such as free radical polymerization or anionic polymerisation that utilize vinyl, and wherein free radical polymerization is preferred especially because can normally utilize.As the polymerization initiator of free radical polymerization, can use known compounds such as free radical thermal polymerization and radical photopolymerization initiating agent, but especially preferably use the free radical thermal polymerization.Wherein, the free radical thermal polymerization is the compound that produces free radical more than the decomposition temperature by being heated to.As this free radical thermal polymerization, can list for example diacyl peroxide (acetyl peroxide; benzoyl peroxide etc.); ketone peroxide (methyl-ethyl-ketone peroxide; cyclohexanone superoxide etc.); hydroperoxides (hydrogen peroxide; tert butyl hydroperoxide; cumene hydroperoxide etc.); dialkyl peroxide (di-tert-butyl peroxide; dicumyl peroxide; two bay acyl peroxides etc.); peroxyesters (tert-butyl hydroperoxide acetic acid esters; t-butylperoxy pivarate etc.); azo based compound (azoisobutyronitrile; AMBN etc.); persulfuric acid salt (ammonium persulfate; sodium peroxydisulfate; potassium persulfate etc.).This free radical thermal polymerization can use a kind separately, also can be used in combination more than 2 kinds.

Free radical polymerisation process has no particular limits, and can adopt emulsion polymerization, suspension polymerization, mass polymerization, solution polymerization process etc.Below the solution polymerization as typical free radical polymerisation process further is specifically described.Even general introduction is also identical for other polymerization, its detailed content for example is recorded in " polymer science experimental method " macromolecule association and compiles in (the same people of Tokyo chemistry, 1981) etc.

In order to carry out solution polymerization with an organic solvent.These organic solvents can at random be selected in the scope of not damaging purpose of the present invention, effect.These organic solvents normally have the organic compound that boiling point under the atmospheric pressure is the value in 50～200 ℃ the scope, preferably make the organic compound of each constituent uniform dissolution.If the example of expression preferred organic can list alcohols such as isopropyl alcohol, butanols; Ethers such as dibutyl ethers, ethylene glycol dimethyl ether, tetrahydrofuran, diox; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Ester classes such as ethyl acetate, butyl acetate, amyl acetate, gamma-butyrolacton; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based.In addition, these organic solvents can use a kind separately, perhaps are used in combination more than 2 kinds.In addition, can also suitably use above-mentioned organic solvent and used the water mixed organic solvents of water from the viewpoint of dissolubility of the polymkeric substance of monomer and generation etc.

In addition, solution polymerization condition also has no particular limits, but for example, preferably heats 10 minutes～30 hours in 50～200 ℃ temperature range.In addition, in order to make the free radical non-inactivation of generation, preferably in solution polymerization, before beginning, solution polymerization can also carry out inert gas purge certainly.As the suitable usually nitrogen that uses of inert gas.

In order to obtain above-mentioned fluorine based polymer with preferred molecular weight ranges, effectively use the radical polymerization of chain-transferring agent especially.Also (for example can use thio-alcohol as chain-transferring agent, octyl mercaptan, decyl mercaptan, lauryl mercaptan, uncle's lauryl mercaptan, Stearyl mercaptan, thiophenol, to nonyl thiophenol etc.), the multi-haloalkyl class (for example, phenixin, chloroform, 1,1,1-trichloroethanes, 1,1,1-three bromooctanes etc.), low activity monomer class (α-Jia Jibenyixi, α-Jia Jibenyixierjuwu etc.) any, preferred carbon number is 4～16 thio-alcohol.The use amount of these chain-transferring agents is influenced significantly by the combination, polymerizing condition of the activity of chain-transferring agent and monomer etc., need accurate control, but the total mole number with respect to the monomer that uses is preferably about 0.01 mole of %～50 mole %, more preferably 0.05 mole of %～30 mole %, more preferably 0.08 mole of %～25 mole %.These chain-transferring agents exist in the system simultaneously with the target monomer that should control the degree of polymerization in polymerization process and get final product, and its adding method is not particularly limited.Add after can being dissolved in monomer, also can separate adding with monomer.

In addition, in order to make the state of orientation immobilization of discotic mesogenic compound, fluorine based polymer of the present invention preferably has polymerizable group as substituting group.

Show the object lesson that is preferably used as the fluorine based polymer in the present invention below, but the present invention is not limited to these object lessons.Numerical value in its Chinese style (numerical value such as a, b, c, d) is respectively the quality percentage of each monomer ratio of components of expression, and Mw is with gpc measurement and the weight-average molecular weight that converted by PEO.

[Chemical formula 1 9]

[Chemical formula 2 0]

[Chemical formula 2 1]

[Chemical formula 2 2]

[Chemical formula 2 3]

The fluorine based polymer that uses among the present invention can be with known method in common manufacturing.For example can add general radical polymerization initiator, its polymerization is made by being monomer to containing the fluorine of formerly enumerating, having in the organic solvent of monomer etc. of hydrogen bond base.In addition, can add other addition polymerization unsaturated compound sometimes again, with method manufacturing same as described above.According to the polymerism of each monomer, to reaction vessel in drip monomer and initiating agent on one side carry out the dropping polymerization etc. of polymerization because the polymkeric substance that can obtain evenly form on one side, so also be effective.

Above-mentioned liquid crystalline composition is (when as the modulation of coating liquid, be the liquid crystalline composition of having removed solvent) in the preferable range of content of above-mentioned fluorine based polymer different and different according to its purposes, be preferably 0.005～8 quality % of liquid crystalline composition (is the composition of having removed solvent) under the situation of coating liquid, more preferably 0.01～5 quality %, more preferably 0.05～1 quality %.When the addition of above-mentioned fluorine based polymer was lower than 0.005 quality %, effect was insufficient, and if greater than 8 quality %, the drying of then filming can not be carried out fully, bring harmful effect perhaps for performance as optical thin film (for example the homogeneity of Yan Chiing etc.).

Below, to describing as fluorochemicals air interface side vertical-tropism agent, that represent with formula (III) equally.

Formula (III)

(R ⁰) _mo-L ⁰-(W) _no

In the formula, R ⁰Expression alkyl, end have CF ₃The alkyl or the end of base have CF ₂The alkyl of H base, mo are represented the integer more than 1.A plurality of R ⁰Can be the same or different, but at least one expression end has CF ₃Base or CF ₂The alkyl of H base.L ⁰The connection base of expression (mo+no) valency, W represent that carboxyl (COOH) or its salt, sulfo group (SO ₃H) or its salt or phosphine oxygen base { OP (=O) (OH) ₂Or its salt, no represents the integer more than 1.

In the formula (III), R ⁰Play a part the hydrophobicity base of fluorochemicals.With R ⁰The alkyl of expression is to replace or unsubstituted alkyl, can be that the straight chain shape also can be a chain, is preferably carbon number and is 1～20 alkyl, and more preferably carbon number is 4～16 alkyl, is preferably carbon number especially and is 6～16 alkyl.Can suitably use described later illustrative substituent any as substituting group group D as this substituting group.

With R ⁰The end of expression has CF ₃The preferred carbon number of alkyl of base is 1～20, and more preferably carbon number is 4～16, and further preferred carbon number is 4～8.Above-mentioned end has CF ₃The alkyl of base is part or all alkyl that is replaced by fluorine atom of the hydrogen atom that contains in the alkyl.Replaced by fluorine atom more than 50% of hydrogen atom in the preferred alkyl, more preferably be substituted more than 60%, preferably especially be substituted more than 70%.Remaining hydrogen atom can also further be replaced as the illustrative substituting group of substituting group group D by described later.With R ⁰The end of expression has CF ₂The preferred carbon number of the alkyl of H base is 1～20, more preferably 4～16, more preferably 4～8.Above-mentioned end has CF ₂The alkyl of H base is part or all alkyl that is replaced by fluorine atom of the hydrogen atom that contains in the alkyl.Replaced by fluorine atom more than 50% of hydrogen atom in the preferred alkyl, more preferably be substituted more than 60%, further preferably be substituted more than 70%.Remaining hydrogen atom can also further be replaced as the illustrative substituting group of substituting group group D by described later.Below show with R ⁰The end of expression has CF ³The alkyl or the end of base have CF ₂The example of the alkyl of H base.

R1：n-C ₈F ₁₇-

R2：n-C ₆F ₁₇-

R3：n-C ₄F ₉-

R4：n-C ₈F ₁₇-(CH ₂) ₂-

R5：n-C ₆F ₁₃-(CH ₂) ₂-

R6：n-C ₄F ₉-(CH ₂) ₂-

R7：H-(CF ₂) ₈-

R8：H-(CF ₂) ₆-

R9：H-(CF ₂) ₄-

R10：H-(CF ₂) ₈-(CH ₂)-

R11：H-(CF ₂) ₆-(CH ₂)-

R12：H-(CF ₂) ₄-(CH ₂)-

In the formula (III), with L ⁰The connection base of (mo+no) valency of expression be preferably with at least two be selected from alkylidene, alkylene group, aromatic series base, heterocyclic radical ,-CO-,-NR ^d-(R ^dBe 1～5 alkyl or hydrogen atom for carbon number) ,-O-,-S-,-SO-,-SO ₂-in the connection base that forms of moiety combinations.

In the formula (III), W represents that carboxyl (COOH) or its salt, sulfo group (SO ₃H) or its salt or phosphine oxygen base { OP (=O) (OH) ₂Or its salt.The preferable range of W is identical with Q in the formula (II).

In the fluorochemicals with above-mentioned formula (III) expression, preferably with following formula (III)-a or compound that formula (III)-b represents.

[Chemical formula 2 4]

General formula (III)-a

Among formula (III)-a, R ⁴And R ⁵Represent that respectively alkyl, end have CF ₃The alkyl or the end of base have CF ₂The alkyl of H base, but R ⁴And R ⁵Be not alkyl simultaneously.W ¹And W ²Represent that respectively hydrogen atom, carboxyl are (COOH) or its salt, sulfo group (SO ₃H) or its salt, phosphine oxygen base { OP (=O) (OH) ₂Or its salt or have carboxyl, sulfo group or phosphine oxygen base as substituent alkyl, alkoxy or alkyl amino, but W ¹And W ²Be not hydrogen atom simultaneously.

Formula (III)-b

(R ⁶-L ²-) _m2(Ar ¹)-W ³

Among formula (III)-b, R ⁶Expression alkyl, end have CF ₃The alkyl or the end of base have CF ₂The alkyl of H base, m2 are represented the integer more than 1, a plurality of R ⁶Can be the same or different, but at least one expression end has CF ₃Base or CF ₂The alkyl of H base.L ²Expression be selected from alkylidene, aromatic series base ,-CO-,-NR '-(R ' be that carbon number is 1～5 alkyl or hydrogen atom) ,-O-,-S-,-SO-,-SO ₂-and their combination among divalent connect base, a plurality of L ²Can be the same or different.Ar ¹Expression aromatic hydrocarbon ring or heteroaromatic, W ³The expression carboxyl (COOH) or its salt, sulfo group (SO ₃H) or its salt, phosphine oxygen base { OP (=O) (OH) ₂Or its salt or have carboxyl, sulfo group or phosphine oxygen base as substituent alkyl, alkoxy or alkyl amino.

At first, above-mentioned formula (III)-a is described.

R ⁴And R ⁵With the R in the above-mentioned formula (III) ⁰Synonym, its preferred range is also identical.With W ¹And W ²The carboxyl of expression (COOH) or its salt, sulfo group (SO ₃H) or its salt, phosphine oxygen base { OP (=O) (OH) ₂Or its salt and above-mentioned formula (III) in the W synonym, its preferred range is also identical.With W ¹And W ²The have carboxyl, sulfo group, phosphine oxygen base of expression can be that the straight chain shape also can be a chain as substituent alkyl, are preferably carbon number and are 1～20 alkyl, and more preferably 1～8 alkyl is preferably 1～3 alkyl especially.Having carboxyl, sulfo group, phosphine oxygen base has at least one carboxyl, sulfo group or phosphine oxygen base as above-mentioned substituent alkyl and gets final product.As carboxyl, sulfo group, phosphine oxygen base, with carboxyl, sulfo group, phosphine oxygen base synonym that W in the above-mentioned formula (III) represents, its preferred range is also identical.Have carboxyl, sulfo group, phosphine oxygen base and also can be replaced by the substituting group beyond this as above-mentioned substituent alkyl, as this substituting group can use described later as substituting group group D enumerate substituent any.With W ¹And W ²The have carboxyl, sulfo group, phosphine oxygen base of expression can be that the straight chain shape also can be a chain as substituent alkoxy, are preferably carbon number and are 1～20 alkoxy, and more preferably 1～8 alkoxy is preferably 1～4 alkoxy especially.Having carboxyl, sulfo group, phosphine oxygen base has at least one carboxyl, sulfo group or phosphine oxygen base as above-mentioned substituent alkoxy and gets final product.As carboxyl, sulfo group, phosphine oxygen base, with carboxyl, sulfo group, phosphine oxygen base synonym that W in the above-mentioned formula (III) represents, its preferred range is also identical.Alkoxy with above-mentioned carboxyl, sulfo group, phosphine oxygen base also can be replaced by the substituting group beyond this, can use described later illustrative substituent any as substituting group group D as this substituting group.With W ¹And W ²The have carboxyl, sulfo group, phosphine oxygen base of expression can be that the straight chain shape also can be a chain as substituent alkyl amino, are preferably carbon number and are 1～20 alkyl amino, more preferably 1～8 alkyl amino, more preferably 1～4 alkyl amino.Alkyl amino with above-mentioned carboxyl, sulfo group, phosphine oxygen base has at least one carboxyl, sulfo group or phosphine oxygen base and gets final product.As carboxyl, sulfo group, phosphine oxygen base, with carboxyl, sulfo group, phosphine oxygen base synonym that W in the above-mentioned formula (III) represents, its preferred range is also identical.Alkyl amino with above-mentioned carboxyl, sulfo group, phosphine oxygen base also can be replaced by the substituting group beyond this, can use described later illustrative substituent any as substituting group group D as this substituting group.

W ¹And W ²Hydrogen atom or (CH especially preferably respectively do for oneself ₂) _nSO ₃(n represents 0 or 1 to M.)。M represents kation, but when charged when being 0 in the molecule, also can not have M.As the kation of representing with M, preferred suitable use for example hydrogen ion, alkali metal ion (lithium ion, sodion, potassium ion etc.), alkaline-earth metal ion (barium ion, calcium ion etc.), ammonium ion etc.Wherein, be preferably hydrogen ion, lithium ion, sodion, potassium ion, ammonium ion especially.

Below, above-mentioned formula (III)-b is described.

R ⁶With the R among above-mentioned formula (III)-b ⁰Synonym, its preferred range is also identical.L ²Preferred expression by carbon number be 1～12 alkylidene, carbon number be 6～12 aromatic series base ,-CO-,-NR-,-O-,-S-,-SO-,-SO ₂-and the total carbon atom number formed of their combination be 0～40 connection base, more preferably represent by carbon number be 1～8 alkylidene, phenyl ,-CO-,-NR-,-O-,-S-,-SO ₂-and the total carbon atom number formed of their combination be 0～20 connection base.Ar ¹Preferred expression carbon number is 6～12 aromatic hydrocarbon ring, more preferably represents phenyl ring or naphthalene nucleus.With W ³The carboxyl of expression (COOH) or its salt, sulfo group (SO ₃H) or its salt, phosphine oxygen base { OP (=O) (OH) ₂Or its salt, perhaps have carboxyl, sulfo group or phosphine oxygen base as substituent alkyl, alkoxy or alkyl amino, with among above-mentioned formula (III)-a with W ¹And W ²The carboxyl of expression (COOH) or its salt, sulfo group (SO ₃H) or its salt, phosphine oxygen base { OP (=O) (OH) ₂Or its salt, perhaps having carboxyl, sulfo group or phosphine oxygen base as substituent alkyl, alkoxy or alkyl amino synonym, their preferable range is also identical.

W ³Be preferably carboxyl (COOH) or its salt, sulfo group (SO ₃H) or salt, perhaps has carboxyl (COOH) or its salt or sulfo group (SO ₃H) or its salt as substituent alkyl amino, be preferably SO especially ₃M or CO ₂M.M represents kation, but when charged when being 0 in the molecule, also can not have M.As the kation of representing with M, preferred suitable use for example hydrogen ion (プロトニウ system ion), alkali metal ion (lithium ion, sodion, potassium ion etc.), alkaline-earth metal ion (barium ion, calcium ion etc.), ammonium ion etc.Wherein, be preferably hydrogen ion, lithium ion, sodion, potassium ion, ammonium ion especially.

In this instructions, as substituting group group D, comprise that (be preferably carbon number is 1～20 to alkyl, more preferably carbon number is 1～12, be preferably carbon number especially and be 1～8 alkyl, for example can list, methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), (be preferably carbon number is 2～20 to alkenyl, more preferably carbon number is 2～12, more preferably carbon number is 2～8 thiazolinyl, for example can list, vinyl, allyl, the 2-butenyl group, 3-pentenyl etc.), (be preferably carbon number is 2～20 to alkynyl, more preferably carbon number is 2～12, more preferably carbon number is 2～8 alkynyl, for example can list, butynyl, 3-pentynyl etc.), (be preferably carbon number is 6～30 to aryl, more preferably carbon number is 6～20, more preferably carbon number is 6～12 aryl, for example can list, phenyl, the p-aminomethyl phenyl, naphthyl etc.), (being preferably carbon number is 0～20 for replacement or unsubstituted amino, more preferably carbon number is 0～10, more preferably carbon number is 0～6 amino, for example can list, substituted-amino not, methylamino, dimethylamino, diethylamino, dibenzyl amino etc.)

(be preferably carbon number is 1～20 to alkoxy; more preferably carbon number is 1～12; more preferably carbon number is 1～8 alkoxy; for example can list; methoxyl; ethoxy; butoxy etc.); (be preferably carbon number is 6～20 to aryloxy group; more preferably carbon number is 6～16; more preferably carbon number is 6～12 aryloxy group; for example can list; phenoxy group; 2-naphthoxy etc.); (be preferably carbon number is 1～20 to acyl group; more preferably carbon number is 1～16; more preferably carbon number is 1～12 acyl group; for example can list; acetyl group; benzoyl; formoxyl; valeryl etc.); (be preferably carbon number is 2～20 to alkoxy carbonyl; more preferably carbon number is 2～16; more preferably carbon number is 2～12 alkoxy carbonyl; for example can list; methoxycarbonyl; ethoxy carbonyl etc.); (be preferably carbon number is 7～20 to aryloxycarbonyl; more preferably carbon number is 7～16; more preferably carbon number is 7～10 aryloxycarbonyl; for example can list; phenyloxycarbonyl etc.); (be preferably carbon number is 2～20 to acyloxy; more preferably carbon number is 2～16; more preferably carbon number is 2～10 acyloxy; for example can list acetoxyl group; benzoyloxy etc.).

(be preferably carbon number is 2～20 to amide group; more preferably carbon number is 2～16; more preferably carbon number is 2～10 amide group; can list for example acetamido; benzamido etc.); (be preferably carbon number is 2～20 to alkoxycarbonyl amino; more preferably carbon number is 2～16; more preferably carbon number is 2～12 alkoxycarbonyl amino; for example can list; methoxycarbonyl amino etc.); (be preferably carbon number is 7～20 to aryloxycarbonyl amino; more preferably carbon number is 7～16; more preferably carbon number is 7～12 aryloxycarbonyl amino; for example can list; phenyloxycarbonyl amino etc.); (be preferably carbon number is 1～20 to sulfoamido; more preferably carbon number is 1～16; more preferably carbon number is 1～12 sulfoamido; for example can list; the methylsulfonyl amido; benzene sulfonamido etc.); (be preferably carbon number is 0～20 to sulfamoyl; more preferably carbon number is 0～16; more preferably carbon number is 0～12 sulfamoyl; for example can list; sulfamoyl; the methyl sulfamoyl; the dimethylamino sulfonyl; phenyl sulfamoyl base etc.); (be preferably carbon number is 1～20 to carbamyl; more preferably carbon number is 1～16; more preferably carbon number is 1～12 carbamyl; for example can list; unsubstituted carbamyl; the methylamino formoxyl; the diethylamino formoxyl; phenyl amino formoxyl etc.)

(be preferably carbon number is 1～20 to alkylthio group; more preferably carbon number is 1～16; more preferably carbon number is 1～12 alkylthio group; for example can list; methyl mercapto; ethylmercapto group etc.); (be preferably carbon number is 6～20 to arylthio; more preferably carbon number is 6～16; more preferably carbon number is 6～12 arylthio; for example can list; thiophenyl etc.); (be preferably carbon number is 1～20 to sulfonyl; more preferably carbon number is 1～16; more preferably carbon number is 1～12 sulfonyl; for example can list; mesyl; tosyl etc.); (be preferably carbon number is 1～20 to sulfinyl; more preferably carbon number is 1～16; more preferably carbon number is 1～12 sulfinyl; for example can list; methylsulfinyl; phenyl sulfinyl etc.); (be preferably carbon number is 1～20 to the uride base; more preferably carbon number is 1～16; more preferably carbon number is 1～12 uride base; for example can list; unsubstituted uride base; methyl uride base; phenyl uride base etc.); (be preferably carbon number is 1～20 to the phosphoamide base; more preferably carbon number is 1～16; more preferably carbon number is 1～12 phosphoamide base; for example can list; diethyl phosphoamide base; phosphenylic acid amide group etc.); hydroxyl; sulfydryl; halogen atom (fluorine atom for example; the chlorine atom; bromine atoms; the iodine atom); cyano group; sulfo group; carboxyl; nitro; the hydroximic acid base; sulfino; diazanyl; imino group; (be preferably carbon number is 1～30 to heterocyclic radical; 1～12 heterocyclic radical more preferably; can list and for example have nitrogen-atoms; oxygen atom; heteroatomic heterocyclic radical such as sulphur atom; for example; imidazolinyl; pyridine radicals; quinolyl; furyl; piperidyl; morpholinyl benzoxazole quinoline base; the benzimidazoline base; benzothiazole quinoline base etc.); (be preferably carbon number is 3～40 to silicyl; more preferably carbon number is 3～30; more preferably carbon number is 3～24 silicyl; for example, trimethyl silyl; triphenyl silicyl etc.).These substituting groups also can be replaced by these substituting groups again.In addition, when having two above substituting groups, can be the same or different.In addition, under possible situation, also can be bonded to each other and form ring.

In addition, in order to make the state of orientation immobilization of discotic mesogenic compound, fluorochemicals of the present invention also preferably has polymerizable group as substituting group.

Below show the object lesson of operable fluorochemicals with formula (III) expression among the present invention, but the fluorochemicals that the present invention uses is not limited to these.

[Chemical formula 2 5]

[Chemical formula 2 6]

[Chemical formula 2 7]

[Chemical formula 2 8]

[Chemical formula 2 9]

The preferable range of the content of above-mentioned fluorochemicals is according to the difference of its purposes and difference in the above-mentioned liquid crystalline composition, be preferably 0.005～8 quality % of above-mentioned liquid crystalline composition (is the composition of having removed solvent) under the situation of coating liquid, more preferably 0.01～5 quality %, more preferably 0.05～1 quality %.

[polymerism initiating agent]

Preferably the molecule of the liquid crystal compounds that will be orientated according to desirable state of orientation (for example, vertical orientated under the situation of rod shaped liquid crystal compound) keeps its state of orientation and carries out immobilization.This immobilization preferably polyreaction of the polymerizable group (P) by being introduced into liquid crystal compounds is carried out.As polyreaction, comprise heat polymerization that uses thermal polymerization and the photopolymerization reaction that uses Photoepolymerizationinitiater initiater.The preferred light polyreaction.As the example of Photoepolymerizationinitiater initiater, comprise alpha-carbonyl compound (No. 2367661, United States Patent (USP), each instructions record that No. 2367670, United States Patent (USP)), acyloin ether (No. 2448828 instructions records of United States Patent (USP)), α-hydrocarbon substituted aromatic acyloin compound (No. 2722512 instructions records of United States Patent (USP)), multinuclear naphtoquinone compounds (No. 3046127, United States Patent (USP), each instructions record that No. 2951758, United States Patent (USP)), the combination of triarylimidazoles dipolymer and p-aminophenyl ketone (No. 3549367 instructions records of United States Patent (USP)), (spy opens clear 60-105667 communique for acridine and compound phenazine, No. 4239850 instructions record) of United States Patent (USP) are with oxadiazole compound (No. 4212970 instructions records of United States Patent (USP)).

The use amount of Photoepolymerizationinitiater initiater is preferably 0.01～20 quality % of the solid constituent of coating liquid, more preferably 0.5～5 quality %.

[adjuvant of other of optical anisotropic layer]

With above-mentioned liquid crystal compounds and with plastifier, surfactant, polymerizable monomer etc., can improve homogeneity, the film strength of coated film, the orientation of liquid crystal compounds etc.These materials preferably have compatibility with liquid crystal compounds, and do not hinder orientation.

As polymerizable monomer, can list the compound of free-radical polymerised or cationically polymerizable.Preferably multi-functional free radical polymerization monomer is preferably with the above-mentioned material that contains the liquid-crystal compounds copolymerization of polymerizable group.For example, can list the material that the spy opens the middle record in paragraph [0018]～[0020] in the 2002-296423 communique instructions.The addition of above-claimed cpd is generally the scope of 1～50 quality % with respect to discoid liquid crystal liquid crystal property molecule, is preferably the scope of 5～30 quality %.

As surfactant, can list known in the past compound, but preferred especially fluorine based compound.Particularly, can list the compound of record in for example special paragraph [0028]～[0056] of opening in the 2001-330725 communique, the compound of the middle record in paragraph designation [0069]～[0126] in the special Willing 2003-295212 instructions.

Preferably can thickening apply liquid with the polymkeric substance of liquid crystal compounds and usefulness.As the example of polymkeric substance, can list cellulose esters.As the preferred example of cellulose esters, can list the spy and open those that the paragraph [0178] in the 2000-155216 communique instructions put down in writing.In order not hinder the orientation of liquid crystal compounds, the addition of above-mentioned polymkeric substance is preferably the scope of 0.1～10 quality %, the more preferably scope of 0.1～8 quality % with respect to the liquid crystal liquid crystal property molecule.

Can be by with adjuvant dissolving such as for example liquid crystal compounds and the polymerization initiator that adds as required, orientation controlling agent and/or be scattered in and modulate the coating liquid that obtains in the solvent and be coated on the supporter and form as the above-mentioned optical anisotropic layer of optically anisotropic body of the present invention.Preferably by form alignment films on the supporter and on this alignment layer surface the coating above-mentioned coating liquid form.The solvent that uses during as modulation coating liquid, preferably with an organic solvent.As representative examples of organic, comprise acid amides (N for example, dinethylformamide), sulfoxide (for example dimethyl sulfoxide (DMSO)), heterogeneous ring compound (for example pyridine), hydrocarbon (for example benzene, hexane), alkyl halide (for example chloroform, methylene chloride), ester (for example methyl acetate, butyl acetate), ketone (for example acetone, methyl ethyl ketone), ether (for example tetrahydrofuran, 1,2-dimethoxy-ethane).Preferred alkyl halogenide and ketone.Also can be also with the organic solvent more than two kinds.

[coating method]

The coating of coating liquid can be carried out with known method (the excellent coating process that for example winds the line, extrude coating process, direct gravure coating method, reverse gravure coating method, mould be coated with method).Wherein, when forming above-mentioned optical anisotropic layer, the preferred excellent coating process of coiling that utilizes applies, and the rotating speed of coiling rod preferably satisfies following formula.

0.6＜(W×(R+2r)×π)/V＜1.4

[W: rotating speed (rpm), the R of coiling rod: the diameter of excellent core (m), r: the diameter of line (m), V: the transporting velocity of supporter (m/min)]

(scope of W * (R+2r) * π)/V more preferably 0.7～1.3, more preferably 0.8～1.2.

The preferred mould that uses is coated with method in the formation of above-mentioned optical anisotropic layer, especially preferably utilizes the coating method of slip applicator (slide coater) or slit die applicator.For example, can use the spy open 2004-290775 number, spy open 2004-290776 number, spy open 2004-358296 number, spy open 2005-13989 number etc. in the coating method of record.

Then, as mentioned above, by behind coating above-mentioned composition on supporting body surface or the alignment layer surface, the molecule of liquid crystal compounds is orientated (being preferably vertical orientated) for the rod shaped liquid crystal molecule, molecule is fixed according to its state of orientation and formed optical anisotropic layer.The temperature of orientation can consider that the inversion temperature of the liquid crystal compounds that uses, desirable state of orientation etc. determine.If with lower temperature the molecule of liquid crystal compounds is implemented immobilization, then, can easily form the layer that satisfies Re (40)/d＞0.02, so be preferred because the birefringence of the optical anisotropic layer that forms uprises.Immobilized temperature is preferably than low more than 5 ℃ by the temperature that liquid crystal phase is converted into isotropic phase with above-mentioned composition, and is more preferably low more than 8 ℃.Immobilization is preferably undertaken by the polyreaction or the cross-linking reaction of liquid crystal liquid crystal property molecule and the polymerizable monomer that adds as required in composition etc. in addition.The rayed that is used for polymerization is preferably used ultraviolet ray.Irradiation energy is preferably 20mJ/cm ²～50J/cm ², 100～800mJ/cm more preferably ²In order to promote photopolymerization reaction, also can under heating condition, carry out rayed.

The thickness of formed optical anisotropic layer is preferably 0.1～10 μ m, more preferably 0.5～5 μ m, more preferably 1～5 μ m.

[alignment films]

Among the present invention, preferably on the surface of alignment films, apply above-mentioned composition, and the molecule of liquid crystal compounds is orientated.Because alignment films has the performance of the direction of orientation of regulation liquid crystal compounds, so preferably utilize it to realize optimal way of the present invention.But, if fixing its state of orientation, then because alignment films has been brought into play its effect, so may not be necessary as inscape of the present invention with after the liquid crystal compounds orientation.That is, also can on the polarizer, make polaroid of the present invention by the optical anisotropic layer transfer printing on only that state of orientation is the fixing alignment films.

Alignment films can by as oblique side's evaporation of the friction treatment of organic compound (preferred polymers), mineral compound, have fine groove layer formation or utilize the means of organic compound (for example ω-tricosanic acid, octacosyl ammonio methacrylate, methyl stearate) accumulation that Langmuir-Blodgett method (LB film) carries out and so on to be provided with.In addition, also known to applying electric field, apply magnetic field or rayed, thus produce the alignment films of orientation function.

Alignment films preferably forms by the friction treatment of polymkeric substance.

As the example of polymkeric substance, comprise that for example the spy opens methacrylate ester multipolymer, styrene based copolymer, polyolefin, polyvinyl alcohol (PVA) and the modified polyvinylalcohol of putting down in writing in the paragraph [0022] in the flat 8-338913 communique instructions, poly-(N hydroxymethyl acrylamide), polyester, polyimide, vinyl acetate co-polymer, carboxymethyl cellulose, polycarbonate etc.Can use silane coupling agent as polymkeric substance.Preferred water soluble polymer (for example poly-(N hydroxymethyl acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol (PVA), modified polyvinylalcohol), more preferably gelatin, polyvinyl alcohol (PVA) and modified polyvinylalcohol, most preferably polyvinyl alcohol (PVA) and modified polyvinylalcohol.

The saponification degree of polyvinyl alcohol (PVA) is preferably 70～100%, and more preferably 80～100%.The degree of polymerization of polyvinyl alcohol (PVA) is preferably 100～5000.

In the alignment films of the present invention, preferably make and have bridging property functional group the side chain of (for example two key) to combine, perhaps will have the bridging property functional group introducing side chain that makes the performance that the liquid crystal liquid crystal property molecule is orientated with main chain.The polymkeric substance that uses in the alignment films can use polymkeric substance that himself can be crosslinked or carry out any of crosslinked polymkeric substance with crosslinking chemical, a plurality of of these combinations can be used.

If the side chain with bridging property functional group is combined with the main chain of alignment films polymkeric substance, perhaps introduce bridging property functional group having the side chain that makes the liquid crystal liquid crystal property molecule carry out orientation characteristic, then can make the polyfunctional monomer that contains in the polymkeric substance of alignment films and the optical anisotropic layer carry out copolymerization.The result and between alignment films polymkeric substance and alignment films polymkeric substance, and also can carry out combination by covalent bond between polyfunctional monomer and the alignment films polymkeric substance not only between polyfunctional monomer and polyfunctional monomer securely.Therefore, by bridging property functional group is introduced in the alignment films polymkeric substance, can obviously improve the intensity of optical compensating sheet.

The bridging property functional group of alignment films polymkeric substance is identical with polyfunctional monomer, preferably contains polymerizable group.Specifically, for example can listing, the spy opens those that put down in writing in paragraph [0080]～[0100] in the 2000-155216 communique instructions.

The alignment films polymkeric substance also can use crosslinking chemical to make it crosslinked except that above-mentioned bridging property functional group in addition.As crosslinking chemical, comprise aldehyde, N-methylol compound, dioxane derivatives, compound, active vinyl-compound, active halogen compound, isoxazole and dialdehyde starch by the carboxyl activate is worked.Also can be also with the crosslinking chemical more than two kinds.Particularly, can list for example special compound of opening the middle record in paragraph [0023]～[0024] in the 2002-62426 communique instructions etc.The active high aldehyde of preferred reaction, preferred especially glutaraldehyde.

The addition of crosslinking chemical is 0.1～20 quality % with respect to polymkeric substance preferably, more preferably 0.5～15 quality %.Residual unreacted cross-linked dosage is preferably below the 1.0 quality % in the alignment films, more preferably below the 0.5 quality %.By regulating like this,, also can obtain can not produce the sufficient permanance of reticular tissue (reticulation) even alignment films is used for liquid crystal indicator or placement for a long time under hot and humid atmosphere for a long time.

Alignment films can form basically in the following way: the solution of above-mentioned polymkeric substance, crosslinking chemical and adjuvant that will contain as the orientation film formation material is coated on the transparent supporting body, heat drying (make its crosslinked) then, and carry out friction treatment and form.Cross-linking reaction also can be carried out during arbitrarily as mentioned above after applying on the transparent supporting body.In the time will being used as the orientation film formation material as the water-soluble polymers of polyvinyl alcohol (PVA) and so on, preferred coated liquid forms has the organic solvent (for example methyl alcohol) of froth breaking effect and the mixed solvent of water.Its ratio is preferably water by quality ratio: methyl alcohol is 0: 100～99: 1, more preferably 0: 100～91: 9.Thus, suppress the generation of foam, significantly reduced the defective of the laminar surface of alignment films and optical anisotropic layer.

The coating method of alignment films is preferably spin-coating method, dip coating, curtain coating, extrudes coating process, rod is coated with method or rolling method.Preferred especially rod is coated with method.In addition, dried thickness is preferably 0.1～10 μ m.Heat drying can carry out under 20 ℃～110 ℃.Crosslinked fully in order to form, preferably under 60 ℃～100 ℃, carry out, under 80 ℃～100 ℃, carry out.Can be 1 minute～36 hours drying time, is preferably 1 minute～30 minutes.The optimal value of crosslinking chemical that pH also is preferably set to and uses, when using glutaraldehyde, pH is 4.5～5.5, is preferably 5 especially.

Alignment films preferably is arranged on the transparent supporting body.Alignment films can be carried out friction treatment to the surface and obtain by after aforesaid polymeric layer is crosslinked.

Above-mentioned friction treatment can suit to use the disposal route of the liquid crystal aligning treatment process that is widely used as LCD.That is, can make with the following method: on the surface of alignment films, use paper and gauze, felt, rubber or nylon, dacron etc. to carry out wiping in a certain direction, thereby obtain the method for orientation.Usually, length and true fibre are on average carried out cloth that flocking forms etc. carry out friction approximately for several times and carry out by using.

On the friction treatment face of alignment films, apply above-mentioned composition, and the molecule of liquid crystal compounds is orientated.Then, can react by the polyfunctional monomer that makes the alignment films polymkeric substance and be contained in the optical anisotropic layer as required, it is crosslinked perhaps to use crosslinking chemical that the alignment films polymkeric substance is carried out, and forms above-mentioned optical anisotropic layer.

The thickness of alignment films is preferably the scope of 0.1～10 μ m.

[supporter]

As supporter, preferably use the little thin polymer film of wavelength dispersion.The also preferred optical anisotropy of supporter is little.The light transmission of supporter is preferably more than 80%.So-called wavelength dispersion is little, and specifically, the ratio that is preferably Re400/Re700 is lower than 1.2.

Postpone (Re) in the face of supporter and be preferably 0～20nm, more preferably 0～10nm, most preferably 0～5nm.In addition, the delay of the thickness direction of this supporter (Rth) is preferably-1000nm～100nm, more preferably-500nm～60nm, most preferably be-300nm～20nm.

As the example of polymkeric substance, comprise cellulose esters, polycarbonate, polysulfones, polyethersulfone, polyacrylate, polymethacrylate and cyclic polyolefin.Be preferably cellulose esters, more preferably the acetyl group cellulose most preferably is tri acetyl cellulose.As cyclic polyolefin, can use with the ring-opening polymerization polymer of the tetracyclododecane class of the fair 2-9619 communique of spy record or make the tetracyclododecane class and the ring opening copolymer thing of norborene class carry out polymkeric substance that hydrogenation reaction obtains as the polymkeric substance of constituent, can use as the ア one ト Application (JSR system) of trade name and ゼオネ Star Network ス, ゼオノア (Japanese ゼオ Application system) series.Thin polymer film preferably forms with the solvent cast method.

Thin polymer film preferably forms with the solvent cast method.The thickness of transparent supporting body is preferably 20～500 μ m, more preferably 50～200 μ m.Go up the bonding of layer (adhesive linkage, vertical alignment layer or the phase separation layer) that be provided with in order to improve transparent supporting body and its, also can on transparent supporting body, carry out surface treatment (for example, glow discharge processing, Corona discharge Treatment, ultraviolet ray (UV) processing, flame treatment).Adhesive linkage (undercoat) also can be set on transparent supporting body.In addition, as transparent supporting body and rectangular transparent supporting body, the preferred material that uses following formation: in order to give the sliding of carrying operation, or prevent to batch the back back side and surface and carry out bondingly, will mix 5%～40% mean grain size according to solid constituent weight ratio meter and be coated in the one-sided of supporter and carry out the material that common curtain coating forms with supporter for the polymeric layer of the inorganic particulate of about 10～100nm.

[polaroid]

Polaroid of the present invention comprises the duplexer (being sometimes referred to as " optical compensating film ") and the polarizing coating of the stratiform optical anisotropic layer of the present invention that has supporter and form on this supporter.

As polarizing coating, it is that polarizing coating, the dyestuff that uses dichroic dye are that polarizing coating and polyene are polarizing coating that iodine is arranged.Iodine is that polarizing coating and dyestuff are that polarizing coating uses polyvinyl alcohol film manufacturing usually.The absorption axes of polarizing coating is equivalent to the draw direction of film.Therefore, longitudinally the polarizing coating of (throughput direction) stretching is with respect to vertically having parallel absorption axes, and the polarizing coating that edge horizontal (with the throughput direction vertical direction) stretches is with respect to vertically having vertical absorption axes.

The preferred manufacture method of polaroid of the present invention comprises makes polarizing coating and optical compensating film carry out stacked operation continuously with rectangular state respectively.The picture size of the liquid crystal indicator that this rectangular polaroid contrast is used is carried out cutting.

Be ellipsoidal polarizing plate if straight line polarizing coating and optical compensating film constituted, then can easily embed in reflection-type and the transflective liquid crystal display device.In addition, also can be as the antireflection film of organic EL display.In addition, also can be on the ellipsoidal polarizing plate of strip the cholesteric crystal film of the strip of stacked other making etc. again, at this moment, can become the high brightness of throughput rate and improve film.

Polarizing coating generally has diaphragm.Among the present invention, when on transparent supporting body, forming optical anisotropic layer, can make the effect of the diaphragm of this transparent supporting body polarizing film.When except this supporter, also in addition using the diaphragm of polarizing coating, preferably use the high cellulose ester film of the isotropy of optics as diaphragm.

[liquid crystal indicator]

Liquid crystal indicator of the present invention comprises optically anisotropic body of the present invention at least.Above-mentioned optically anisotropic body can be used as independent member and embeds in the liquid crystal indicator, also can be used as the optical anisotropic layer of optical compensating film and a structural sheet of polaroid etc. and embeds in the liquid crystal indicator.Liquid crystal indicator of the present invention can be any of reflection-type, Semitransmissive, transmissive liquid crystal display device etc.Liquid crystal indicator is made of members such as polaroid, liquid crystal cells and polarizer as required, reflection horizon, light diffusion layer, back of the body lamp, headlight, light control film, light guide plate, prismatic lens, color filter usually, but except needs use above-mentioned optically anisotropic body this point, have no particular limits among the present invention.In addition, the use location of above-mentioned optically anisotropic body has no particular limits, and in addition, it also can be a plurality of can being one.Have no particular limits as liquid crystal cells, can use with a pair of transparency carrier and clamp common liquid crystal cells such as the formed liquid crystal cells of liquid crystal layer with electrode.As the above-mentioned transparency carrier that constitutes liquid crystal cells,, have no particular limits so long as the substrate that the material that shows liquid crystal liquid crystal property that will constitute liquid crystal layer is orientated along specific direction of orientation just.Specifically, substrate self has the transparency carrier that makes the character that liquid crystal is orientated, though substrate self lacks alignment capability, the transparency carrier that is provided with alignment films with the character that makes liquid crystal aligning etc. thereon etc. can use.In addition, the electrode of liquid crystal cells can use known.Usually, can be arranged on the surface of transparency carrier of liquid crystal layer contact, when use has the substrate of alignment films, can be arranged between substrate and the alignment films.The material that shows liquid crystal liquid crystal property as forming above-mentioned liquid crystal layer has no particular limits, and can list common various low molecular weight liquid crystal compounds, high molecule liquid crystal compound and their potpourri that can constitute various liquid crystal cells.In addition, can also be to wherein adding pigment, chirality agent, non-liquid crystal compounds etc. in the scope of not damaging liquid crystal liquid crystal property.

Above-mentioned liquid crystal cells can also have the needed various inscapes of liquid crystal cells that form the aftermentioned variety of way except above-mentioned electrode base board and liquid crystal layer.As the mode of above-mentioned liquid crystal cells, can list TN (twisted-nematic) mode, STN (supertwist is to row) mode, ECB (electrically conerolled birefringence) mode, IPS (switching in the plate) mode, VA (vertical orientated) mode, MVA (multizone is vertical orientated) mode, PVA (figure is vertical orientated) mode, OCB (optical compensation birefringence) mode, HAN (mixing) mode vertically to row, ASM (rotational symmetry orientation micro unit) mode, middle tone gray scale (half tone grey scale) mode, Region Segmentation (De メイ Application is cut apart) mode, perhaps utilized strong dielectricity liquid crystal, the variety of ways such as display mode of anti-strong dielectricity liquid crystal.In addition, the type of drive of liquid crystal cells also has no particular limits, and can also be any type of drive such as active matrix mode, plasma address mode that are used for the passive matrix mode of STN-LCD etc. and use active electrodes such as TFT (thin film transistor (TFT)) electrode, TFD (thin film diode) electrode.It also can be the mode of not using the field preface of color filter.

Polaroid of the present invention is preferred for reflection-type, Semitransmissive and transmissive liquid crystal display device.In addition, polaroid of the present invention by with the cholesteric crystal film combinations, also be preferably used as brightness and improve film.Reflection-type liquid-crystal display device has reflecting plate, liquid crystal cells and polaroid is carried out stacked formed structure successively.Polarizer is arranged on (between reflecting plate and the liquid crystal cells or between liquid crystal cells and the polarizing coating) between reflecting plate and the polarizing coating.Reflecting plate also can have liquid crystal cells and substrate.Transflective liquid crystal display device possesses liquid crystal cells at least, be arranged on polaroid than the more close observer's side of this liquid crystal cells, be arranged between above-mentioned polaroid and the above-mentioned liquid crystal cells at least one polarizer and from the observer than the Transflective layer that above-mentioned liquid crystal layer also is provided with by the back, also have at least one polarizer and polaroid after also leaning on than above-mentioned Transflective layer from the observer.In the liquid crystal indicator of the type,, back of the body lamp can use reflective-mode and transmission mode by being set.

The pattern of liquid crystal cells has no particular limits, and is preferably IPS pattern, FFS pattern or VA pattern.

In the liquid crystal cells of VA pattern, the rod shaped liquid crystal molecule is essentially vertical orientated when not applying voltage.Liquid crystal cells as the VA pattern, that the rod shaped liquid crystal molecule is essentially when not applying voltage is vertical orientated except (1), and when applying voltage, be essentially outside the liquid crystal cells (spy open flat 2-176625 communique record) of VA pattern of narrow sense of horizontal alignment, comprise that also (2) are in order to enlarge field angle, with VA pattern multizoneization (the MVA pattern) liquid crystal cells (SID97, Digest of tech.Papers (preliminary draft collection) 28 (1997) 845 records), (3) it is vertical orientated the rod shaped liquid crystal molecule to be essentially when not applying voltage, and when applying voltage with the liquid crystal cells (in LCD International 98, delivering) of the liquid crystal cells that reverses multizone alignment mode (n-ASM pattern) (preliminary draft collection 58～59 (1998) records of Japanese liquid crystal discussion) and (4) SURVAIVAL pattern.

The rod shaped liquid crystal molecule of the liquid crystal cells of IPS pattern is essentially parallel-oriented with respect to substrate, and carries out the plane response by applying the electric field liquid crystal molecule parallel with real estate.The IPS pattern is not applying under the voltage status to deceiving demonstration, the axis of homology quadrature of a pair of up and down polaroid.Use optical compensating sheet, light when oblique black show is leaked reduce, open flat 10-54982 communique, spy and open flat 11-202323 communique, spy and open flat 9-292522 communique, spy and open flat 11-133408 communique, spy and open flat 11-305217 communique, spy and open in the flat 10-307291 communique etc. thereby the method for improving field angle is disclosed in the spy.

Embodiment

Below more specifically describe feature of the present invention by enumerating embodiment and comparative example.Material shown in the following embodiment, use amount, ratio, contents processing, processing sequence etc. only otherwise depart from aim of the present invention just can be carried out appropriate change.Therefore, scope of the present invention should not carried out limited explanation by object lesson shown below.

[embodiment 1]

The making of＜acylated cellulose film (T1) 〉

Following composition is dropped in the mixing channel, heat while stirring, make each composition dissolving, thus modulation cellulose acetate ester solution.

0.1 μ m), 80 mass parts methylene chloride and 20 mass parts methyl alcohol in another mixing channel, drop into the following delay dose B of 16 mass parts above-mentioned delay dose A, 8 mass parts, 0.28 mass parts silicon dioxide microparticle (mean grain size:, heat while stirring, modulation postpones dose solution (also having particle dispersion liquid).In 474 mass parts cellulose acetate ester solutions, mix 45 mass parts and should postpone dose solution, fully stir and be modulated to dope and (be also referred to as dope; Dope).

[chemical formula 30]

Postpone dose (A)

[chemical formula 31]

Postpone dose B

The dope that obtains used to have widely carry out curtain coating as the casting machine of the long travelling belt of 65m as 2m and length.Be that the film of 15 quality % uses stenter to carry out cross directional stretch with 20% stretching ratio under 130 ℃ condition with the residual solvent amount, under the width after the stretching, kept 30 seconds down, take off anchor clamps then, thereby made cellulose acetate film at 50 ℃.Stretching, the residual solvent amount is 5 quality % when finishing, and makes the cellulose acetate film (T1) that the residual solvent amount is lower than 0.1 quality % by drying again.In addition, the Tg of the acylated cellulose of use is 140 ℃.

The wide of the cellulose acetate film T1 that obtains is 1340mm, and thick is 88 μ m.In addition, postponing (Re) in the face is 70nm, and the delay of thickness direction (Rth) is 210nm.

＜contain the formation of the optical anisotropic layer of rod shaped liquid crystal compound 〉

After the surface of the cellulose acetate film T1 of the strip of above-mentioned making carried out saponification, with the oriented film coating liquid of the following composition of coiling rod continuously coating of #14.Under 60 ℃ warm wind dry 60 seconds, under 100 ℃ warm wind dry 120 seconds again, form alignment films.

The composition of oriented film coating liquid

[chemical formula 32]

Modified polyvinylalcohol

The coating liquid that will contain the rod shaped liquid crystal compound of following composition uses the coiling rod continuously coating of #4.6 on the alignment films of above-mentioned making.The transporting velocity of film is 20m/min.From room temperature to the 90 ℃ operation that heats continuously, make solvent seasoning, in 90 ℃ arid region, heating 90 seconds then, making rod shaped liquid crystal compound orientation.Then, the temperature of film is remained 60 ℃, form the optical anisotropic layer B1 that the orientation immobilization with liquid-crystal compounds obtains by the UV irradiation.Then, handle carrying out saponification continuously, thereby made optical compensating film F1 with the cellulose acetate film surface of surface opposite one side that forms optical anisotropic layer B1.

The composition that contains the coating liquid (S1) of rod shaped liquid crystal compound

[chemical formula 33]

Rod shaped liquid crystal compound (I)

[chemical formula 34]

The fluorine based polymer

[chemical formula 35]

Pyridiniujm

The optical anisotropic layer B1 that only will contain the rod shaped liquid crystal compound peels off from the optical compensating film F1 of made, uses automatic birefraction meter (KOBRA-21ADH, prince's instrumentation machine (strain) corporate system) to measure optical characteristics.The Re (0) of the only optical anisotropic layer B1 that measures under wavelength 550nm is 0nm.Re (40) and thickness d that optical anisotropic layer B1 is measured along 40 ° of axle inclinations arbitrarily have been shown in the table 1.In addition, measure R e (40) is equal in fact even change the axle that tilts arbitrarily, is essentially vertical orientated optical anisotropic layer thereby can confirm to form rod shaped liquid crystal molecule with respect to pellicular front.

[embodiment 2]

In the formation of the optical anisotropic layer of the foregoing description 1, the coiling rod replacement of use #4.4 is used the coiling rod of #4.6 will apply liquid S1 and is coated on the alignment films.When the state of orientation of rod shaped liquid crystal compound is carried out immobilization, make the temperature of film remain 40 ℃ and carry out the UV irradiation, thereby form optical anisotropic layer B2.Then, handle carrying out saponification continuously, thereby made optical compensating film F2 with the cellulose acetate film surface of surface opposite one side that forms optical anisotropic layer B2.

The optical anisotropic layer B2 that only will contain the rod shaped liquid crystal compound peels off from the optical compensating film F2 of made, and measures optical characteristics.The Re (0) of the only optical anisotropic layer B2 that measures under wavelength 550nm is 0nm.Re (40) and thickness d that optical anisotropic layer B2 is measured along 40 ° of axle inclinations arbitrarily have been shown in the table 1.In addition, all equal in fact even change the axle measure R e (40) of inclination arbitrarily, be essentially vertical orientated optical anisotropic layer thereby can confirm to form rod shaped liquid crystal molecule with respect to pellicular front.

[embodiment 3]

Make cellulose acetate film T1 according to the step identical, saponification is carried out on its surface handled, then, form alignment films thereon with embodiment 1.

(the S3～S8) use the coiling rod continuously coating of #4.0 on the alignment films of above-mentioned making of coating liquid separately that will contain the rod shaped liquid crystal compound of following composition.The transporting velocity of film is 20m/min.Make solvent seasoning the operation that heats continuously from room temperature, then, heating is 90 seconds in the arid region, makes rod shaped liquid crystal compound orientation.In addition, the temperature of arid region is set at than containing the temperature that the coating composition of liquid-crystal compounds separately becomes low 10 ℃ of the temperature of isotropic phase.Then, according to the mode of the temperature of film in the zone that keeps dry, by the UV irradiation orientation of liquid-crystal compounds is carried out immobilization, thereby form optical anisotropic layer B3-B8 respectively.Then, handle carrying out saponification continuously, thereby made optical compensating film F3～F8 with the cellulose acetate film surface of surface opposite one side that forms optical anisotropic layer B3-B8.

The composition that contains the coating liquid (S3) of rod shaped liquid crystal compound

[chemical formula 36]

Rod shaped liquid crystal compound (II)

The composition that contains the coating liquid (S4) of rod shaped liquid crystal compound

[chemical formula 37]

Rod shaped liquid crystal compound (III)

The composition that contains the coating liquid (S5) of rod shaped liquid crystal compound

[chemical formula 38]

Rod shaped liquid crystal compound (IV)

The composition that contains the coating liquid (S6) of rod shaped liquid crystal compound

[chemical formula 39]

Rod shaped liquid crystal compound (V)

The composition that contains the coating liquid (S7) of rod shaped liquid crystal compound

[chemical formula 40]

Rod shaped liquid crystal compound (VI)

[chemical formula 41]

Rod shaped liquid crystal compound (VII)

[chemical formula 42]

Rod shaped liquid crystal compound (VIII)

The composition that contains the coating liquid (S8) of rod shaped liquid crystal compound

[chemical formula 43]

Rod shaped liquid crystal compound (IX)

Only the optical anisotropic layer B3-B8 that will contain the rod shaped liquid crystal compound peels off from the optical compensating film F3-F8 of made respectively, and measures optical characteristics.The Re (0) of the only optical anisotropic layer B3-B8 that measures under wavelength 550nm is essentially 0nm.Re (40) and thickness d that optical anisotropic layer B3-B8 is measured along 40 ° of axle inclinations arbitrarily respectively have been shown in the table 1.In addition, measure R e (40) is equal in fact even change the axle that tilts arbitrarily, is essentially vertical orientated optical anisotropic layer thereby can confirm to form rod shaped liquid crystal molecule with respect to pellicular front.

[comparative example 1]

In the formation of the optical anisotropic layer of the foregoing description 1, use the coiling rod of #5.0 to replace using the coiling rod of #4.6 will apply liquid S1 and be coated on the alignment films.When the state of orientation of rod shaped liquid crystal compound is carried out immobilization, make the temperature of film remain 90 ℃ and carry out the UV irradiation, thereby form optical anisotropic layer BH1.Then, handle carrying out saponification continuously, thereby made optical compensating film FH1 with the cellulose acetate film surface of surface opposite one side that forms optical anisotropic layer.

The optical anisotropic layer BH1 that will contain the rod shaped liquid crystal compound peels off from the optical compensating film FH1 of made, and measures optical characteristics.The Re (0) of the only optical anisotropic layer BH1 that measures under wavelength 550nm is 0nm.Re and thickness d that this optical anisotropic layer BH1 is measured along 40 ° of axle inclinations arbitrarily have been shown in the table 1.In addition, measure R e (40) is equal in fact even change the axle that tilts arbitrarily, is essentially vertical orientated optical anisotropic layer thereby can confirm to form rod shaped liquid crystal molecule with respect to pellicular front.

[embodiment 4]

The making of＜polaroid 〉

Thickness that will continuous dyeing in iodine aqueous solution is that the roller shaped polyethylene alcohol film of 80 μ m stretches 5 times along throughput direction, dryly obtains rectangular polarizing coating.Use the polyethenol series bonding agent face that does not form the optical anisotropic layer that contains liquid-crystal compounds of the optical compensating film F1 of the above-mentioned making of applying on a face of this polarizing coating continuously, on another face, fit the cellulosic triacetate film (Off ジ Star Network TD80UL, Fujiphoto strain formula meeting corporate system) that saponification is handled is carried out on the surface, thereby made rectangular polaroid P1.

Identical with the making of above-mentioned polaroid P1, use optical compensating film F2～F8 to make polaroid, form P2～P8 respectively.In addition, use the optical compensating film FH1 of comparative example equally, make the polaroid PH1 of comparative example.

＜other the making of polaroid 〉

The making of＜cellulose acetate film (T0) 〉

(modulation of cellulose acetate ester solution)

Following composition is dropped in the mixing channel, stir and make each composition dissolving, thus modulation cellulose ethanoate solution A.

The composition of cellulose ethanoate solution A

(modulation of matting agent solution)

With 20 mass parts mean grain sizes is that silicon dioxide granule (AEROSIL R972, Japanese AEROSIL (strain) system), the 80 mass parts methyl alcohol of 16nm fully mix 30 minutes to form the silicon dioxide granule dispersion liquid.This dispersion liquid is dropped into decollator with following composition, stir again and make each composition dissolving more than 30 minutes, thus modulation matting agent solution.

The matting agent solution composition

(modulation of additive solution)

Additive solution is formed

[chemical formula 44]

The optical anisotropy depressant

[chemical formula 45]

Wavelength dispersion is adjusted agent

(making of cellulose acetate film)

The above-mentioned cellulose ethanoate solution A of 94.6 mass parts, 1.3 mass parts matting agent solution, 4.1 mass parts additive solutions are filtered the back respectively mix, use the travelling belt casting machine to carry out curtain coating.Optically anisotropic compound of reduction and wavelength dispersion adjustment agent is respectively 12% and 1.2% with respect to the mass ratio of cellulose ethanoate in the above-mentioned composition.In the residual solvent amount is 30% time film to be peeled off from travelling belt, 140 ℃ dry 40 minutes down, be the cellulose acetate film T0 of the strip of 80 μ m thereby made thickness.Postponing (Re) in the face of the film that obtains is 1nm (slow axis is the direction vertical with the film length direction), and the delay of thickness direction (Rth) is-1nm.

The making of＜polaroid P0 〉

Thickness that will continuous dyeing in iodine aqueous solution is that the roller shaped polyethylene alcohol film of 80 μ m stretches 5 times along throughput direction, carries out dry to obtain rectangular polarizing coating.Use the polyethenol series bonding agent above-mentioned cellulose acetate film T0 that the applying saponification was handled on a face of this polarizing coating continuously, the commercially available cellulose acetate film that the applying saponification was handled on another face (Off ジ Star Network TD80UL, Fujiphoto strain formula can corporate system), thus the polaroid (P0) that the opposed polaroid as above-mentioned polaroid (P1～P8, PH1) uses made.

[embodiment 5]

The making of＜IPS mode LCD 〉

The liquid crystal cells of structure shown in the construction drawing 1.Among Fig. 1, the 1st, liquid crystal cell pixel region, the 2nd, pixel electrode, the 3rd, show electrode, the 4th, the director of liquid-crystal compounds when frictional direction, 5a, 5b are black demonstration the, and the director of 6a, 6b liquid-crystal compounds when being white the demonstration.Specifically, on a glass substrate, be that the mode of 20 μ m is provided with electrode according to the distance between adjacent electrode, polyimide film is set as alignment films thereon, among Fig. 1, continue to use the directions of 4 expressions and carry out friction treatment.On a surface of a glass substrate of preparing in addition, polyimide film is set, carries out friction treatment, thereby form alignment films.Two glass substrates by making alignment films opposite each other, are set at 3.9 μ m with unit interval (d), and are that parallel mode is carried out overlapping applying according to the frictional direction of two glass substrates.Then, by enclose refractive index anisotropy (Δ n) be 0.0769 and dielectric constant anisotropy (Δ ε) come production technique aligned liquid-crystal unit for positive 4.5 nematic liquid-crystal composition.The value of the Δ nd of liquid crystal layer is 300nm.

On lower glass substrate on the above-mentioned horizontal alignment unit, use bonding agent applying polaroid (P1 and P0).At this moment, on the polaroid of back of the body lamp side, P1 is set, in visual person's side P0 is set, the mode that contacts with the glass substrate of back of the body lamp side according to the optical anisotropic layer that in polaroid (P1), contains, and according to the cellulose acetate film (T0) that contains in the polaroid (P0) is fitted with the mode that the glass substrate of visual person's side contacts.In addition, the absorption axes that carries out quadrature, polaroid (P1) and polaroid (P0) according to the frictional direction of the absorption axes of polaroid (P1) and the liquid crystal cells mode of carrying out quadrature is provided with.Made liquid crystal indicator L1 thus.

In the making of above-mentioned liquid crystal indicator L1, use polaroid P2～P8, PH1 to replace polaroid P1, make liquid crystal indicator, thereby form L2～L8, LH1 respectively.

Apply the square-wave voltage of 55Hz to the display device of making.Form and be shown as 5V, the black standard black mode that is shown as 0V in vain.Use measuring instrument (EZ-Contrast 160D, ELDIM corporate system) to estimate display characteristic.Brightness of having measured from frontal when black show has been shown in the table 2 and the unevenness when observing from tilted direction (absorption axes with respect to polaroid is 45 ° in orientation, becomes 60 ° of polar angles with normal direction).Liquid crystal indicator of the present invention is compared with the liquid crystal indicator of comparative example, and the brightness during black the demonstration is low, thereby has obtained high contrast, in addition when tilted direction is observed inhomogeneous also less.

Table 1

Table 2

Claims

1. optically anisotropic body, it is the stratiform optically anisotropic body that is formed by the composition that contains liquid-crystal compounds, wherein in the face of this optically anisotropic body normal to a surface orientation measurement, postpone to be essentially 0, when the thickness setting with this optically anisotropic body is d, and will make this optically anisotropic body tilt 40 ° and when postponing to be set at Re (40) in the face measured, Re (40)/d is greater than 0.02, and described composition also contains pyridine derivate and contains the fluoro fatty group and be selected from by-carboxyl that COOH represents, by-SO ₃The sulfo group that H represents, by-OP (=O) (OH) ₂The phosphine oxygen base of expression and more than one the compound of water wettability base among their salt, described liquid-crystal compounds is the rod shaped liquid crystal compound, the molecule of this rod shaped liquid crystal compound in fact vertically is orientated with respect to the surface of described optically anisotropic body.

2. optically anisotropic body according to claim 1 wherein under the low temperature more than 5 ℃ of isotropy phase transition temperature than described composition, fixes described composition by polymerization.

3. by claim 1 or 2 described stratiform optically anisotropic bodies and the film formed duplexer of polymer thin.

4. duplexer according to claim 3, wherein said thin polymer film are to show optically anisotropic film by stretching.

5. duplexer according to claim 3, wherein said thin polymer film are acylated cellulose film or norbornene polymer film.

6. polaroid, it comprises polarizing coating and claim 1 or 2 described optically anisotropic bodies.

7. polaroid, it comprises polarizing coating and the described duplexer of claim 3.

8. liquid crystal indicator, it comprises liquid crystal cells and claim 1 or 2 described optically anisotropic bodies.

9. liquid crystal indicator, it comprises liquid crystal cells and the described duplexer of claim 3.

10. liquid crystal indicator, it comprises liquid crystal cells and the described polaroid of claim 6.