CN101200599B - Dye for anisotropic dye film, dye composition for anisotropic dye film, anisotropic dye film, and polarizing device - Google Patents

Abstract

An anisotropic dye film of high dichroism, a dye composition for anisotropic dye, an anisotropic dye film, a lamination length (L) is 105 or more. Preferably, this anisotropic dye film exhibits a degree of orientation of molecular lamination axis of 85% or greater, having a thickness of 30 m or less and is one produced by a wet film formation method. High dichroism is exhibited by possessing a molecular arrangement suitable for dichroic ratio development. Polarizing devices including this anisotropic dye film excel in heat resistance, light stability and polarization performance.

Description

Anisotropy dye film dyestuff, anisotropy dye film dye composite, anisotropy dye film and polarizer

The application divides an application, the international application no of its original application is PCT/JP2004/015450, the China national application number is 200480029954.X, the applying date is on October 13rd, 2004, and denomination of invention is " anisotropy dye film dyestuff, anisotropy dye film dye composite, anisotropy dye film and a polarizer ".

Technical field

The present invention relates to have high dichromatic anisotropy dye film, this anisotropy dye film for example is used for the used polaroid of display unit of light control device, liquid-crystal apparatus and Organnic electroluminescent device (OLED), the invention still further relates to polarizer that uses described anisotropy dye film and the anisotropy dye film dye composite that is used to obtain this anisotropy dye film.In addition, the present invention relates to be used for the novel azo dyestuff of anisotropy dye film.

Background technology

For LCD (liquid-crystal display), opticity and birefringence when using linear polarizer or circularly polarizing plate to control demonstration.Also use circularly polarizing plate to prevent outside luminous reflectance for OLED.

Up to now, for such polaroid, used the anisotropy dye film obtain in the following manner widely: with iodine or have dichromatic organic dye dissolving or for example be adsorbed in the macromolecular material such as polyvinyl alcohol, with resulting film unilateral stretching film forming, thereby make dichroic dye be orientated (for example spy open flat 3-12606, spy open flat 1-161202, the spy opens flat 1-252904 communique).But the anisotropy dye film of Zhi Bei routine has following problem by this way: according to employed dyestuff or macromolecular material, and thermotolerance or photostabilization deficiency; In the manufacturing of liquid crystal apparatus, the productive rate of bonding anisotropy dye film is relatively poor.And iodine has high sublimability, so when it is used for polaroid, thermotolerance and photostabilization deficiency.And the delustring look becomes darkslateblue, is not the colourless polaroid of ideal that can obtain in whole visible light district.

Therefore, after deliberation the following method for preparing the anisotropy dye film: on base material such as glass or transparent film for example, the wet type that contains the solution of dichroic dye by coating becomes embrane method to form the film that contains dichroic dye, utilize molecular interaction etc. to make dichroic dye be orientated (United States Patent (USP) the 2nd, 400, No. 877 communiques, Te Biaoping 8-511109 communique, special table 2002-528758 communique, the spy opens the 2002-180052 communique, the spy opens the 2002-338838 communique, WO02/099480 communique and Dreyer, J.F., Phys.And Colloid Chem., 1948,52,808, " The Fixing of Molecular Orientation ", Dreyer, J.F., Joumal de Physique, 1969,4,114., " Light Polarization From Films ofLyotropic Nematic Liquid Crystals ", " application of functional dyestuff (Application of Functional Dyes) " ", go into the Jiang Zhenghao chief editor; CMC Publishing Co.; Ltd. publishes, distribution on April 15th, 1996,96-106 page or leaf).

As polarizer the time, in order to obtain higher polarization property, need have high dichromatic anisotropy dye film, still, the dichroism of conventional anisotropy dye film is poor, therefore can not obtain the polarizer of polarization property excellence.

Up to now, various dyestuffs are used for the anisotropy dye film, the selection of dyestuff is one of important factor.For example, the spy opens the application that flat 3-12606 communique discloses the dichroic dye that following structural represents:

In addition, the spy opens the application that flat 1-161202 communique discloses the dichroic dye that following structural represents:

But, above-mentioned spy opens the dichroism deficiency of disclosed compound in flat 3-12606 communique and the flat 1-161202 communique of Te Kai, the particularly special solubleness of disclosed compound in all kinds of SOLVENTS of opening in the flat 3-12606 communique is low, therefore, we can say that they are not enough to be used as the raw material of the anisotropy dye film that is prepared by wet type film forming method.

In addition, special table 2002-528758 communique also discloses the application of the dichroic dye that following structural represents:

But above-claimed cpd all is a tetrazo compound, as raw material, their dichroism and the solubleness deficiency in solvent of the anisotropy dye film that is prepared by wet type film forming method.

No. 02/099480 communique of WO discloses the preparation by the anisotropy dye film of wet type film forming method preparation, and an example as spendable dichroic dye discloses the compound that following structural is represented:

But above-claimed cpd is a tetrazo compound, and bonding has halogen atom on triazine ring, thereby is easy to decompose.

Summary of the invention

An object of the present invention is to provide all excellent polarizer of thermotolerance, photostabilization and polarization property that has high dichromatic anisotropy dye film and use described anisotropy dye film.And, an object of the present invention is to provide novel dichroic dye and anisotropy dye film dye composite, use described dyestuff can obtain a kind of anisotropy dye film, this anisotropy dye film has thermotolerance and photostabilization.

As the result who studies in great detail, the inventor finds, by the crystal parameters of regulation anisotropy dye film, can guarantee to realize having high dichromatic anisotropy dye film, thereby finish the present invention.

That is to say that anisotropy dye film of the present invention is characterised in that, be at the most 3.445 by cycle of the stacked generation of molecule

, stack length is at least 105

And, the inventor finds, as novel dichroic azo dyes, the dichroic azo dyes of being represented by following formula (1) with ad hoc structure has high avidity to base material, and described dichroic azo dyes has triazinyl and have at least three azo bond in a molecule.And the inventor finds that the composition that contains this dyestuff by use is by wet type film forming legal system film forming, and the dichroic dye molecule shows the very high molecular orientation state of degree, that is, can make and have high anisotropic dye film.

That is to say that azoic dyestuff of the present invention is characterised in that and contains the azoic dyestuff of free acid form by following formula (1) expression:

Wherein, A ⁰, B ⁰, C ⁰And D ⁰Expression can have substituent aromatic hydrocarbon ring independently of one another separately,

Ar ⁰Expression hydrogen atom or any substituting group,

X ⁰And Y ⁰Represent any substituting group except that halogen atom separately independently of one another,

K represents 1 or 2, and m represents 1 or 2, when k is 2, is included in a plurality of B in the molecule ⁰Can be identical or different.

The inventor finds that also by using the azoic dyestuff of following formula (2) expression, the anisotropy dye film of being made by wet type film forming method is colourless, has high dichroism, and shows high degree of molecular orientation.

That is to say that azoic dyestuff of the present invention is the anisotropy dye film azoic dyestuff of being made by wet type film forming method, its free acid form is represented by following formula (2):

Wherein, D ¹And E ¹Expression can have substituent phenylene and maybe can have substituent naphthylidene separately,

G ¹Expression carboxyl, sulfo group or phosphonate group,

Q ¹Represent halogen atom, hydroxyl, nitro, can have substituent amino, can have substituent C _1-4Alkyl, can have substituent C _1-3Alkoxyl group, carboxyl or sulfo group,

Q ²And Q ³Represent hydrogen atom separately independently of one another, can have substituent C _1-4Alkyl maybe can have substituent phenyl,

P represents 0 or 1, and t represents 1 or 2.

Anisotropy dye film of the present invention is characterised in that with dye composite and contains above-mentioned azoic dyestuff of the present invention.

The feature of anisotropy dye film of the present invention also is to contain above-mentioned azoic dyestuff of the present invention.

The feature of anisotropy dye film of the present invention is that also it uses above-mentioned anisotropy dye film of the present invention to make with dye composite.

Polarizer of the present invention is characterised in that and uses above-mentioned anisotropy dye film of the present invention.

Description of drawings

Fig. 1 is the synoptic diagram of anisotropy dye film, and molecular arrangement wherein is the stacked axle of dye molecule plane and molecule non-vertical.

Fig. 2 is the synoptic diagram of anisotropy dye film, and molecular arrangement wherein is that the dye molecule plane is vertical with the stacked axle of molecule.

Fig. 3 (a) is the synoptic diagram that is in the anisotropy dye film of the low state of the stacked axle of molecule degree of orientation, and Fig. 3 (b) is the synoptic diagram that is in the anisotropy dye film of the high state of the stacked axle of molecule degree of orientation.

Fig. 4 is the X-ray diffraction graphic representation of the anisotropy dye film made by embodiment 1.

Fig. 5 is the in plane vibration graphic representation of the anisotropy dye film made by embodiment 1.

Fig. 6 is the figure of the transmittance of anisotropy dye film on absorption axes direction and polarization axis direction that obtained by embodiment 7.

Fig. 7 is the figure of the transmittance of anisotropy dye film on absorption axes direction and polarization axis direction that obtained by embodiment 10.

Fig. 8 is the figure of the transmittance of anisotropy dye film on absorption axes direction and polarization axis direction that obtained by Comparative Examples 2.

Embodiment

At length explain embodiment of the present invention below.

Explanation about composed component is an example (typical example) of embodiment of the present invention below, and in the scope that does not exceed main idea of the present invention, the present invention is not limited to this embodiment.

Anisotropy dye film of the present invention is following dye film: in the three-dimensional system of coordinate that rectangular any both direction is formed in by the thickness direction of dye film and plane, amounting on any both direction of selecting three directions from this, the electro permanent magnetic of described dye film is anisotropic.Electro permanent magnetic is for for example absorbing and optical property and for example electrical property such as resistance and electric capacity such as refraction, or the like.Have optically anisotropic films such as absorption and refraction and be for example linear polarization membrane, circular polarizer, tidal epock film or resistivity anisotropy film.That is, anisotropy dye film of the present invention can be used for polarizing coating, tidal epock film or resistivity anisotropy film.Especially, because anisotropy dye film of the present invention has absorptivity in the visible region, so it can be used for polarizing coating.

In anisotropy dye film of the present invention, be at the most 3.445 by cycle (after this being sometimes referred to as the stacked cycle of molecule) of the stacked generation of molecule

, the molecule stack length is at least 105

The stacked cycle of molecule is at the most 3.445

Be at least 105 with the molecule stack length

Anisotropy dye film of the present invention have high dichromatic reason and be presumed as follows.

Know that dye molecule has the planar molecule structure that is formed by aromatic nucleus usually,, form the crystal of the overlapped stepped construction of planes of molecules owing to for example π-strong molecular interactions such as π interaction.In the situation of anisotropy dye film, for example in following document 1 and 2 disclosed X-ray diffractions mensuration, except that observing other diffraction peak, also observe diffraction peak by the stacked cycle generation of dye molecule stepped construction.

Document 1:M.Ofuji etc., Jpn.J.Appl.Phys. (Japanese applicating physical magazine), 2002,41,5467, " Grazing Incidence In-Plane X-Ray Diffraction Study on OrientedCopper Phthalocyanine Thin Films ".

Document 2:M.Ofuji etc., Jpn.J.Appl.Phys. (Japanese applicating physical magazine), 2003,42,7520, " Growth Process of Vacuum Deposited Copper PhthalocyanineThin Films on Rubbing-treated Substrates ".

The stacked periodictable of the molecule that the analysis of X-ray diffraction peak obtains shows the value that is reflected in the stacked and ordered state of dye molecule in the crystal.Especially, by inference, for the stacked cycle of molecule, the dye molecule plane is important with respect to the obliquity of stacked axle.

Now, explain the stacked cycle of molecule of anisotropy dye film and the dichroism of stack length and anisotropy dye film with reference to Fig. 1～3.

Fig. 1, Fig. 2 and Fig. 3 (a) and 3 (b) are the synoptic diagram of arrangement of the dichroic dye molecule of the anisotropy dye film seen from the top of anisotropy dye film.In Fig. 1～3, dotted line is represented the stacked axle of molecule, and thick black line is represented the dye molecule of planar molecule structure.In Fig. 1 and 2, d represents the stacked cycle of molecule, and dm represents the minor increment between the stacked molecule, and L represents stack length.In addition, get when making x axle and y axle k respectively when the absorption direction in the anisotropy dye film plane and polarization direction ₀Be the optical extinction coefficient that is projected in the dyestuff on the xy plane, k _xAnd k _yBe respectively the component of optical extinction coefficient on x axle and y direction of principal axis.

Fig. 1 represents to arrange with dye molecule plane and the stacked axle of molecule off plumb state the anisotropy dye film of molecule, and Fig. 2 represents to arrange perpendicular to the state of the stacked axle of molecule with the dye molecule plane anisotropy dye film of molecule.Here, because for example π-π interaction equimolecular interphase interaction, the planes of molecules minor increment dm substantially constant that may have according to estimates.As shown in Figure 1, when the stacked axle of planes of molecules and molecule obviously during non-vertical, the stacked cycle d of molecule is greater than dm, thereby the value of the stacked cycle d of molecule becomes bigger.In addition, as shown in Figure 2, when planes of molecules perpendicular to molecule stacked when axle, d equals dm, can expect that the value of the stacked cycle d of molecule is little.

On the other hand, determine the dichroic ratio of anisotropy dye film with the ratio that absorbs the optical extinction coefficient on direction and the polarization direction.So, when the absorption direction in the anisotropy dye film plane and polarization direction during respectively as x axle and y axle: arrange many molecules, make the x axle component k of optical extinction coefficient of employed dichroic dye in order to increase dichroic ratio, preferred following molecular arrangement _xBig as much as possible.

Usually, the absorption axes of dichroic dye consistent with the stacked direction of principal axis of molecule basically (" Application of functional Dyes ", go into the Jiang Zhenghao chief editor, CMC Publishing Co., Ltd. publish distribution on April 15th, 1996, the 96th page), so it is present in the planes of molecules.When getting the optical extinction coefficient that is projected in the dichroic dye on the xy plane is k ₀The time, in the situation (Fig. 2) of planes of molecules stacked axle perpendicular to molecule, k _x=k ₀, k _xThe k of (Fig. 1) when tilting than molecule plane _x(＜k ₀) height.So from increasing dichromatic angle, preferred planes of molecules is more approaching vertical with respect to the obliquity of stacked axle, i.e. the less anisotropy dye film of the stacked cycle d of molecule, this is owing to can make optical extinction coefficient k like this _xValue higher.

And, to analyze by the X-ray diffraction peak, the stacked distance between the molecule of cycle estimator arrangement simultaneously is stack length (L among Fig. 1 and 2).The number that is included in the dye molecule of arranging with equidirectional in the stack length is L/d.As above-mentioned, in order to obtain high dichroic ratio, need a large amount of molecules to arrange with optimum arrangementing mode, therefore, it is believed that to want preferred stacked molecule number L/d big, promptly have the anisotropy dye film of long stack length L.

Based on above-mentioned consideration, the inventor finds, uses the part with following parameter, and promptly the stacked cycle of molecule is at the most 3.445 Be at least 105 with stack length

Part, can obtain a kind of anisotropy dye film, this anisotropy dye film has the molecular arrangement that can produce high dichroic ratio.

On the other hand, as conventional anisotropy dye film, use the extraneous anisotropy dye film of above-mentioned parameter usually.That is, according to estimates, in conventional anisotropy dye film, many dichroic dye molecules are not arranged on the direction of the most suitable performance dichroic ratio, therefore can not obtain high dichroic ratio.

For the anisotropy dye film of the present invention by the above-mentioned parameter regulation, as shown in Figure 3, the degree of orientation of the stacked axle of molecule also is important to showing high dichroism.That is, in order to arrange more substantial molecule in the same direction, it also is high needing the degree of orientation of the stacked axle of molecule.Therefore, measure estimation with the X-ray diffraction of describing later, anisotropy dye film of the present invention preferably has at least 85% degree of orientation.

The stacked cycle of the molecule of anisotropy dye film of the present invention is preferably at least 3.300

, more preferably at least 3.380

, most preferably at least 3.400 , and at the most 3.445

, preferably at the most 3.440

, more preferably at the most 3.435 If the stacked cycle of the molecule of anisotropy dye film surpasses this upper limit, the inclination of molecule will become significantly in molecule is stacked, and dichroic ratio can reduce.And if it is lower than lower limit, molecule is too approaching mutually, can damage the stacked of molecule.

In addition, the molecule stack length of anisotropy dye film of the present invention is at least 105

, preferably at least 115

, more preferably at least 140

, and preferred 1 μ m at the most, more preferably 500nm at the most, most preferably 100nm at the most.If the molecule stack length of anisotropy dye film surpasses this upper limit, crystalline structure may twist, and the degree of orientation of the stacked axle of molecule reduces.And if it is lower than lower limit, the molecule number of Pai Lieing is little in the same direction, can not obtain high dichroic ratio like this.

With film evaluation X-ray diffraction equipment (diffraction system in " RINT2000 PC " face, produce by motor of science (strain)) or the X-ray diffraction curve measured of similar devices obtain the above-mentioned parameter of anisotropy dye film, the i.e. value (for example above-mentioned document 1,2) of stacked cycle of molecule and its stack length.

For example obtain the above-mentioned parameter of anisotropy dye film of the present invention according to follow procedure (1)～(3).

(1) at first,, carry out measuring in the face, wherein to observing perpendicular to the diffraction surfaces of absorption axes with perpendicular to the diffraction surfaces of polarization axle from both direction for the anisotropy dye film.For anisotropy dye film of the present invention, in the mensuration of a direction in only in from the face of both direction, measuring usually, at diffraction angle (2 θ with respect to CuK α _x) be between about 24.7 °～about 27 °, measure the high strength diffraction peak that produces by the stacked cycle of molecule.

(2) at 20 °～30 ° 2 θ _xIn the scope, according to following mathematical expression f (2 θ _x), the X-ray diffraction curve on the direction of observing the stacked peak of molecule is optimized:

f(2θ _x)＝B(2θ _x)+C ₁exp[-((2θ _x-2θ ₁)/2σ ₁) ²]+C ₂exp[-((2θ _x-2θ ₂)/2σ ₂) ²]

That is, suppose that crystal block section and any stacked noncrystal part of molecule that molecule is stacked periodically are present in the anisotropy dye film of the present invention simultaneously, then use the above-mentioned formula of being described by two Gaussian functions.

Here, C ₁And C ₂The expression coefficient, 2 θ ₁With 2 θ ₂The expression peak position, σ ₁And σ ₂The expression standard deviation.

And, B (2 θ _x) the expression baseline, in this case, the X-ray diffraction curve of getting the direction that does not observe the stacked diffraction peak of molecule is as baseline.But, when the diffraction peak that exists from another diffraction surfaces, the peak removed goes forward side by side row interpolation and obtain baseline.

(3) because the parameter that the present invention obtains is the structural parameter of the stacked periodically crystal block section of molecule, so work as σ ₁＜σ ₂The time, the peak position of diffraction peak is 2 θ ₁, the half breadth β at peak ₁For ${\mathrm{\β}}_1=2{\mathrm{\σ}}_1\sqrt{2\ln 2}.$ 2 θ from the peak position ₁Rise, can estimate the stacked cycle d of molecule by following Prague (Bragg) condition:

d＝λ/(2sinθ ₁)

Wherein, λ is an X ray wavelength (=1.54

).

In addition, according to following Scherrer (Scherrer) equation, by half breadth β (=β ₁* π/180 rad (radian)) estimation stack length L:

L＝Kλ/(βcosθ ₁)

Wherein, K is the Scherrer constant, uses the value of K=1 here.

By the measurement result of aforesaid device, for example by the following method, also can obtain the degree of orientation (for example above-mentioned document 1 and 2) of the stacked axle of molecule of anisotropy dye film.That is, when the observed above-mentioned diffraction peak of mensuration is carried out 360 ° in plane vibration sweep measuring in the opposite, in the situation of anisotropy dye film of the present invention, observe pairing two peaks of degree of orientation of the stacked axle of molecule usually.According to following mathematical expression g (Φ), optimize vibration curve:

g(Φ)＝C ₀+C ₁exp[-((Φ-Φ ₁)/2σ ₁) ²]+C ₂exp[-((Φ-Φ ₂)/2σ ₂) ²]

Here, C ₀, C ₁And C ₂The expression coefficient, Φ represents rotation angle, Φ ₁And Φ ₂The expression peak position, σ ₁And σ ₂The expression standard deviation.

According to following formula determine the stacked axle of molecule of the present invention degree of orientation P (unit: %):

P＝(360-2σ ₁-2σ ₂)/360×100

The degree of orientation of the stacked axle of the molecule of the above-mentioned definition of anisotropy dye film of the present invention is preferably at least 85%.Degree of orientation more preferably at least 88%, most preferably at least 90%, especially preferably at least 94%.If degree of orientation is lower than above-mentioned lower limit, the molecule number of arranging on the equidirectional is little, can not obtain high dichroic ratio like this.

The anisotropy dye film of the present invention that satisfies above-mentioned parameter has high dichroic ratio, and dichroic ratio is preferably at least 11, and more preferably at least 13, most preferably at least 15.

The film thickness of anisotropy dye film of the present invention typically refers to dried film thickness, is preferably 10nm at least, more preferably 50nm at least, and preferred 30 μ m at the most, more preferably 1 μ m at the most.If the film thickness of anisotropy dye film surpasses 30 μ m, be difficult to obtain the even orientation of dye molecule in film, if it is thinner than 10nm, be difficult to obtain uniform film thickness.

By selecting to be included in the dyestuff in the anisotropy dye film and the combination of additive, can obtain being at the most 3.445 by cycle of the stacked generation of molecule

Be at least 105 with stack length

The anisotropy dye film.Much less, the method for preparing the anisotropy dye film also is one of important factor that obtains such anisotropy dye film, in order to obtain such anisotropy dye film, preferably uses wet type to become embrane method.

The dyestuff that is used for anisotropy dye film of the present invention is for example azoic dye, stilbene type dye, cyanine-type dyestuff, phthalocyanine type dye or fused polycycle type dye (perylene Xing Huo oxazine type).In these dyestuffs, as the most suitable dyestuff that obtains anisotropy dye film of the present invention, preferred especially azoic dye, the degree of alignment height of their molecule in the anisotropy dye film.Preferred especially dyestuff by the formula of describing later (1) and (2) expression.

Azoic dye is the dyestuff with at least one azo group.From colourity and productive angle, the number of the azo group in molecule is preferably at least 1, and more preferably at least 2, and preferably at the most 6, more preferably at the most 4.

This dyestuff is preferably water miscible, so that the wet type of carrying out describing later becomes embrane method.Therefore, dyestuff preferably has following groups as water miscible substituting group is provided: acidic-groups such as sulfo group, carboxyl or phosphonate group for example; Basic group such as amino acid group for example; Or solubility group such as hydroxyl for example, from the angle of highly water-soluble, especially preferably have sulfo group or carboxyl.

From the productive angle of color harmony, the molecular weight of this dyestuff unbound state rather than salt form is preferably at least 200 usually, and particularly at least 350, and usually at the most 5000, particularly at the most 3500.

Object lesson as this dyestuff, can mention those disclosed dyestuff in the following document: above-mentioned United States Patent (USP) the 2nd, 400, No. 877, Dreyer, J.F., Phys.And Colloid Chem.1948,52,808, " The Fixing of Molecular Orientation ", Dreyer, J.F., Journal de Physique, 1969,4,114., " Light Polarization From Films of Lyotropic Nematic LiquidCrystals " and J.Lyndon, " Chromonics " in " Handbook of Liquid Crystals Vol.2B:LowMolecular Weight Liquid Crystals II ", D.Demus, J.Goodby, G.W.Gray, H.W.Spiessm, V.Villed., Willey-VCH, 981-1007 page or leaf (1998).

And especially, anisotropy dye film of the present invention preferably contains the novel azo dyestuff, and its free acid form is represented by following formula (1):

Wherein, A ⁰, B ⁰, C ⁰And D ⁰Expression can have substituent aromatic hydrocarbon ring independently of one another separately,

Ar ⁰Expression hydrogen atom or any substituting group,

X ⁰And Y ⁰Any substituting group of representing non-halogen atom separately independently of one another,

K represents 1 or 2, and m represents 1 or 2, when k is 2, is included in a plurality of B in the molecule ⁰Can be identical or different.

This azoic dyestuff has dichroism, has excellent colourity, has excellent solvability in solvent, has high stability in solution.Therefore, it can be used for various uses, still, when being used for the anisotropy dye film, can obtain good especially effect.That is, use the anisotropy dye film of the present invention of this dyestuff to have high dichroism, simultaneously, compare with conventional iodine class polarizing coating, it has high thermotolerance and photostabilization.

Especially,,, in solution, have high stability, have high stability in storage with dye composite so contain the anisotropy dye film of this dyestuff because this dyestuff has high solubleness in solvent as above-mentioned.Therefore, azoic dyestuff of the present invention preferably becomes embrane method to form the anisotropy dye film by the wet type of describing later.Become embrane method with wet type, can on the contour heat-resistant material of for example glass, form the anisotropy dye film, thereby can obtain the high heat resistance polarizer, these high heat resistance polarizers needing can be used for the purposes of high heat resistance, for example liquid crystal projection apparatus and vehicle-mounted display panel.

In following formula (1), as A ⁰～D ⁰The aromatic hydrocarbon ring can be aromatic hydrocarbon ring with about 6～about 20 carbon atoms, preferably they are phenyl ring or naphthalene nucleus independently.In them, work as D ⁰During for phenyl ring, D ⁰More preferably 1, the 4-phenylene when it is naphthalene nucleus, is preferably 2, the 6-naphthylidene.And, be preferably 1-naphthols ring or beta naphthal ring deutero-divalent group, owing to can obtain dimmed dyestuff, therefore especially preferably by 1-naphthols ring deutero-group.

A ⁰～D ⁰The substituting group that the aromatic hydrocarbon ring can have for example is: be selected from the group in electron-withdrawing group or the electron-donating group rightly, introduce this group and can control tone; Or hydrophilic radical, introduce this group and can be increased in solubleness in the solvent.Particularly, for example can mention as A in the formula of describing later (1-a) ¹～C ¹The substituting group that is had and the group mentioned.

As Ar ⁰Any substituting group for for example being selected from the group in electron-accepting group or the electron-donating group rightly, introduce this group and can control tone, perhaps be hydrophilic radical, introduce this group and can be increased in solubleness in the solvent.Particularly, for example can mention in the formula of describing later (1-a) as Ar ¹The group of being given an example.

As X ⁰And Y ⁰Any substituting group of every kind of substituent non-halogen atom can be for example hydrophilic radical or hydrophobic group, introduces these groups and can be controlled at solubleness in the solvent.Particularly, for example can mention and be the X in the formula of describing later (1-a) ¹And Y ¹Every kind of group that substituting group is cited.

The azoic dyestuff of the present invention of following formula (1) expression is preferably the dyestuff of its free acid form by following formula (1-a) expression:

Wherein, A ¹Expression can have substituent phenyl maybe can have substituent naphthyl,

B ¹And C ¹Expression can have substituent phenylene and maybe can have substituent naphthylidene independently of one another separately,

Ar ¹The expression hydrogen atom maybe can have substituent C _1-5Alkyl,

X ¹And Y ¹Expression-NR independently of one another separately ¹R ²Group ,-OR ³Group or-SR ⁴Group,

Its condition is: R ¹, R ², R ³And R ⁴Represent hydrogen atom separately independently of one another, can have substituent C _1-18Alkyl, can have substituent C _2-18Thiazolinyl, can have substituent C _3-15Cyclic hydrocarbon radical, can have the substituent heterocyclic group of forming by 5 or 6 yuan of monocycles or monocyclic condensed ring that two or three are such, perhaps R ¹And R ²Bonding forms 5 or 6 yuan of rings that contain nitrogen-atoms mutually, by R ¹And R ²The ring that bonding forms can have substituting group,

K represents 1 or 2, and m represents 1 or 2, when k is 2, is included in a plurality of B in the molecule ¹Can be identical or different.

In following formula (1-a), A ¹Expression can have substituent phenyl maybe can have substituent naphthyl.

At A ¹Be in the situation of phenyl, the substituting group of phenyl for for example sulfo group, carboxyl, hydroxyl, nitro, halogen atom, can have substituent amino, can have substituent alkyl and maybe can have substituent alkoxyl group.

As halogen atom, amino, alkyl and alkoxyl group, can mention following groups particularly.

Halogen atom: fluorine atom, chlorine atom, bromine atoms or iodine atom;

Amino;

C _1-18(preferred C _1-8) alkylamino, for example N-methylamino, N, N-dimethylamino or N, N-diethylamino;

C _6-18(preferred C _6-10) virtue amino, for example N-phenyl amino or N-naphthyl amino;

C _2-18(preferred C _2-11) amido, for example kharophen or benzamido;

C _1-18(preferred C _1-12) alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or dodecyl;

C _1-18(preferred C _1-12) alkoxyl group, for example methoxyl group, oxyethyl group, isopropoxy, n-butoxy or n-dodecane oxygen base;

Above-mentioned amino, alkyl and alkoxyl group can have substituting group, and these substituting groups can be for example hydroxyl or alkoxyl group.

At A ¹Be to have in the situation of substituent phenyl, consider solubleness and tone in solvent, the substituting group that phenyl has more preferably sulfo group, carboxyl, halogen atom, can have substituent amino, can have substituent alkyl and maybe can have substituent alkoxyl group.Preferred especially sulfo group, carboxyl, amido or alkyl.At A ¹Be in the situation of phenyl, phenyl preferably has 1～3 substituting group that is selected from these substituting groups.

At A ¹Be in the situation of naphthyl, the preferred substituents of naphthyl is for example sulfo group, carboxyl or hydroxyl, and naphthyl preferably has 1～3 substituting group that is selected from these substituting groups.Particularly preferred substituting group is a sulfo group.

B ¹And C ¹Expression can have substituent phenylene and maybe can have substituent naphthylidene independently of one another separately, and phenylene is preferably 1, the 4-phenylene, and naphthylidene is preferably 1, the 4-naphthylidene.

At B ¹And C ¹All be in the situation of phenylene, the substituting group that phenylene can have is preferably sulfo group, carboxyl, can have substituent alkyl, can have substituent alkoxyl group maybe can have substituent amino.

As alkyl, alkoxyl group and amino object lesson, for example can mention following groups:

C _1-4Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl or normal-butyl;

C _1-4Alkoxyl group, for example methoxyl group, oxyethyl group, hydroxyl-oxethyl, positive propoxy, isopropoxy or n-butoxy;

Amino;

C _1-8Alkylamino, for example N-methylamino, N, N-dimethylamino or N, N-diethylamino etc.;

Virtue is amino, for example the N-phenyl amino;

C _2-8Amido, for example kharophen or benzamido.

Abovementioned alkyl, alkoxyl group and amino can have substituting group, and substituting group can be for example hydroxyl, alkoxyl group or halogen atom.

At B ¹And C ¹All be can have in the situation of substituent phenylene, in above-mentioned group, the substituting group of phenylene is preferably sulfo group, carboxyl, can have substituent alkyl, can have substituent alkoxyl group maybe can have substituent amido.Particularly consider hydrophobic associativity (intermolecular interaction) and tone, preferred alkyl, alkoxyl group or amido.

At B ¹And C ¹All be in the situation of phenylene, preferably have 1～3 substituting group representing by above-mentioned substituting group, more preferably 1～2 substituting group.

At B ¹And C ¹All be in the situation of naphthylidene, the substituting group of naphthylidene can maybe can have substituent alkoxyl group for for example hydroxyl, sulfo group.

As alkoxyl group, particularly, for example can mention for example C such as methoxy or ethoxy _1-4Alkoxyl group.The substituting group that alkoxyl group can have is preferably hydroxyl, hydroxyalkyl or alkoxyl group.

As B ¹And C ¹Naphthylidene preferably have 1～6 that is selected from these substituting groups, more preferably 1～3 substituting group.As B ¹And C ¹The naphthylidene substituting group that can have, be preferably sulfo group especially and maybe can have substituent alkoxyl group.

Ar ¹For hydrogen atom maybe can have substituent C _1-5Alkyl is preferably hydrogen atom and maybe can has substituent C _1-4Alkyl (for example methyl, ethyl or further substituted this class group).Be preferably hydrogen atom especially.The substituting group that this alkyl can have is for example hydroxyl, sulfo group or carboxyl.

X ¹And Y ¹Expression-NR independently of one another separately ¹R ²Group ,-OR ³Group or-SR ⁴Group, its condition is: R ¹, R ², R ³And R ⁴Represent hydrogen atom separately independently of one another, can have substituent alkyl, can have substituent thiazolinyl, (aryl or alicyclic radical) maybe can have substituent heterocyclic group can to have substituent cyclic hydrocarbon radical.

It is for example represented particularly:

Hydrogen atom;

C _1-18(preferred C _1-12) alkyl, for example methyl, ethyl, sec.-propyl, normal-butyl, n-octyl or dodecyl;

C _2-18(preferred C _2-8) thiazolinyl, for example vinyl or allyl group;

C _6-18(preferred C _6-12) aryl, for example phenyl or naphthyl;

C _6-18(preferred C _6-10) alicyclic radical, for example cyclohexyl or cyclohexenyl; Or

Fragrance or the nonaromatic heterocycles group formed by 5 or 6 yuan of monocycles or monocyclic condensed ring that two or three are such, for example pyridyl, thiadiazolyl group, benzothiazolyl, morpholinyl, piperidyl or piperazinyl.

The substituting group that abovementioned alkyl, thiazolinyl, aryl, alicyclic radical or heterocyclic radical can have is for example hydroxyl, carboxyl, sulfo group or aryl, more preferably hydroxyl, carboxyl or sulfo group.

R ¹And R ²All more preferably hydrogen atom, can have substituent alkyl and maybe can have substituent aryl, be preferably especially and can have substituent aryl.

And, preferred R ¹And R ²In one be hydrogen atom, the situation of another non-hydrogen atom.

R ³And R ⁴Be preferably hydrogen atom separately and maybe can have substituent alkyl.

About X ¹And Y ¹, more preferably the two all is-NR ¹R ²(its condition is R to the situation of group ¹And R ²Can be identical or different) or one be-NR ¹R ²Group, another is-OR ³The situation of group.

X ¹And Y ¹Bonding mutually, formation can have the substituent azo-cycle that contains, at R ¹And R ²In the situation of 5 or 6 yuan of rings of bonding formation nitrogen atom, this ring is preferably morpholine ring, piperazine ring or piperidine ring mutually.

K represents 1 or 2, and m represents 1 or 2, when k is 2, is included in a plurality of B in the molecule ¹Can be identical or different.

The azoic dyestuff of the present invention of following formula (1) expression more preferably its free acid form by the dyestuff of following formula (1-b) expression:

Wherein, A ²Expression can have substituent phenyl maybe can have substituent naphthyl,

B ²And C ²Expression can have substituent phenylene and maybe can have substituent naphthylidene independently of one another separately,

Ar ²The expression hydrogen atom maybe can have substituent C _1-4Alkyl,

X ²And Y ²Expression-NR independently of one another separately ⁵R ⁶Group ,-OR ⁷Group or-SR ⁸Group,

Its condition is: R ⁵, R ⁶, R ⁷And R ⁸Represent hydrogen atom separately independently of one another, can have substituent C _1-18Alkyl, can have substituent C _2-18Thiazolinyl, can have substituent C _3-15Cyclic hydrocarbon radical, can have the substituent heterocyclic group of forming by 5 or 6 yuan of monocycles or monocyclic condensed ring that two or three are such, perhaps R ⁵And R ⁶Bonding forms 5 or 6 yuan of rings that contain nitrogen-atoms mutually, by R ⁵And R ⁶The ring that bonding forms can have substituting group,

K represents 1 or 2, and n represents 0 or 1, when k is 2, is included in a plurality of B in the molecule ²Can be identical or different.

In following formula (1-b), A ², B ², C ², Ar ², X ²And Y ²The example of preferred substituents to be similar to respectively be A in the following formula (1-a) ¹, B ¹, C ¹, Ar ¹, X ¹And Y ¹Preferred substituents those groups of giving an example.

For example at following formula (1), (1-a) with (1-b), when k=1, the azoic dyestuff of the present invention of following formula (1) expression is a trisazo dye, and when k=2, it is a Tetrakisazo dyes.From the angle of industrial synthetic easiness and being easy to get property of raw material, preferred k=1, i.e. trisazo dye.Obtain the angle of stronger molecular interaction during from the anisotropy dye film that is used for mentioning later when dyestuff, preferred k=2, i.e. Tetrakisazo dyes.

Azoic dyestuff by following formula (1) expression of the present invention, no matter be by following formula (1), (1-a) or (1-b) which kind of free acid form of expression, the molecular weight of its free acid form all is at least 500 usually, preferably at least 550, usually at the most 5,000, preferably at the most 4,000, more preferably at the most 3,500.If molecular weight surpasses the above-mentioned upper limit, then color developing reduces, if it is lower than above-mentioned lower limit, short wavelength side (tone will shoal) will be shifted in the absorption spectrum peak.

As the object lesson of the azoic dyestuff by following formula (1) expression of the present invention, for example can mention the dyestuff of its free acid form by following formula (I-1)～(I-31) expression, still, azoic dyestuff of the present invention is not limited to them:

Azoic dyestuff itself by following formula (1) expression can prepare according to currently known methods.For example, the dyestuff by (I-1) expression can prepare according to the following step (A)～(E).

(A) according to conventional methods (for example, " reactive monoazo dyestuffs chemistry (New Dye Chemical) ", thin Tian Fengzhu (on December 21st, 1973 was published by skill newspaper hall), the 396-409 page or leaf), utilize diazotization and linked reaction to prepare Monoazo compound by 4-aniline sulfonic acid (Sulphanilic Acid) and 2-methoxyl group-5-monomethylaniline.

(B) make resulting Monoazo compound and 2-methoxyl group-5-monomethylaniline carry out diazotization and linked reaction according to conventional methods in the same way, the preparation tetrazo compound.

(C) 6-amino-1-naphthols-3-sulfonic acid (J acid) is dissolved in and makes pH become 6 in the water, solution is cooled to 0～5 ℃.To wherein adding cyanuryl chloride, with temperature maintenance under 0～5 ℃, react 2 hours to finish reaction.Then, at room temperature,, under 6～7 pH, carry out condensation reaction a few hours to its aqueous solution that adds 3-aniline sulfonic acid (m-sulfanilic acid).

(D) according to conventional methods, for example by adding the tetrazo compound that the dissolving of entry and N-N-methyl-2-2-pyrrolidone N-is obtained by step (B), using the caustic soda aqueous solution of 25 weight % to make pH is 9, then is cooled to 0～5 ℃, carries out diazotization thus.Make the product that obtains carry out linked reaction and prepare tris-azo compound with the condensation reaction products that obtains by step (C).After reaction is finished, make temperature rise to 60 ℃, add the aqueous solution of the sodium hydroxide of 25 weight %, making mixture is strong basicity, is hydrolyzed to finish reaction.

(E) after the cooling, saltout with sodium-chlor, to obtain target dyestuff (I-1).

And especially, anisotropy dye film of the present invention preferably contains and is useful on the azoic dyestuff that is become the anisotropy dye film that embrane method forms by wet type, and its free acid form is represented by following formula (2):

Wherein, D ¹And E ¹Expression can have substituent phenylene and maybe can have substituent naphthylidene independently of one another separately,

G ¹Expression carboxyl, sulfo group or phosphonate group,

Q ¹Represent halogen atom, hydroxyl, nitro, can have substituent amino, can have substituent C _1-4Alkyl, can have substituent C _1-3Alkoxyl group, carboxyl or sulfo group,

Q ²And Q ³Represent hydrogen atom separately independently of one another, can have substituent C _1-4Alkyl maybe can have substituent phenyl,

P represents 0 or 1, and t represents 1 or 2.

Explain the trisazo dye of following formula (2) expression now.

Described trisazo dye is the water-soluble black dichroic dye.The molecular structure of this trisazo dye makes can arrange the strong substituting group that attracts other molecule on the specific position at molecular long axis two ends, and at D ¹And E ¹On have hydrophobicity.Therefore, each is intermolecular because of hydrophobicity has interaction (hydrophobic interaction), and each is intermolecular to be easy to be in the association state.

That is, (i) it is believed that,,, be easy to be in the association state so they attract each other because each dye molecule has the substituting group of strong other molecule of attraction at the two ends of molecular long axis.And, (ii) it is believed that, because each molecule is at D ¹And E ¹On have hydrophobicity, attract each other in the aqueous solution so have hydrophobic part, be easy to be in the association state.In addition, (iii) it is believed that, because the substituting group of strong other molecule of attraction at molecular long axis two ends on certain location (have substituent phenyl in the 3-position and have in the 7-position amino naphthyl), so when forming salt, the substituting group of aforementioned 3-position and the amino of 7-position can be close mutually because its position concerns, so their strong mutually attractions are easy to be in stable association state.

Can think that owing to be easy to obtain above-mentioned three factors (i)～(iii) of the state of associating, the azoic dyestuff of following formula (2) expression forms high lytropic liquid crystals state.

In addition, not only the azoic dyestuff of following formula (2) expression is a black, and uses wet type to become the peculiar process of embrane method, the lamination process that promptly for example on substrate surface, is coated with, and this dyestuff or the composition that contains this dyestuff can provide the molecular orientation state of height.This means and to form the high leuco dye film of anisotropy.

Up to now, when attempting to use a kind of dichroic dye to obtain colourless anisotropy dye film, molecular orientation may be subjected to being incorporated into the interference of the substituent steric exclusion in the dye molecule, is difficult to obtain high dichroism.Therefore, become in the embrane method, make up multiple dyestuff in many cases and obtain colourless anisotropy dye film in the wet type of routine.But the azoic dyestuff of following formula (2) expression has above-mentioned specific dye structure, thereby forms high lytropic liquid crystals state, produces the molecular orientation state of height, and can only use a kind of dyestuff that black just is provided.Therefore, the composition that contains the azoic dyestuff of following formula (2) expression can provide dichroism high anisotropy dye film.

In following formula (2), D ¹And E ¹Expression can have substituent phenylene and maybe can have substituent naphthylidene separately.In order to obtain hydrophobic interaction, phenylene is preferably 1, the 4-phenylene, and naphthylidene is preferably 1, the 4-naphthylidene.From the formation of lytropic liquid crystals, by the angle of hydrophobic interaction improvement association performance, the substituting group of phenylene is preferably low polar group, for example can have substituent C _1-4Alkyl (for example methyl, ethyl, n-propyl or normal-butyl), can have substituent C _1-4Alkoxyl group (for example methoxyl group, oxyethyl group, positive propoxy or n-butoxy) maybe can have substituent C _2-7Amido (for example kharophen or benzamido).

From the formation of lytropic liquid crystals, by the angle of hydrophobic interaction improvement association performance, the substituting group of naphthylidene is preferably low polar group, for example can have substituent C _1-4Alkoxyl group (for example methoxy or ethoxy).The substituting group that abovementioned alkyl, alkoxyl group and amido can have can be for example hydroxyl, alkyl or alkoxyl group.

G ¹Expression sulfo group, carboxyl or phosphonate group are the above-mentioned substituting groups of giving strong magnetism, in order to give magnetism in wide pH scope, are preferably sulfo group especially.

Q ¹Expression halogen atom, hydroxyl, nitro, can have substituent amino (preferred amido, for example kharophen or benzamido), can have substituent C _1-4Alkyl (for example methyl or ethyl), can have substituent C _1-3Alkoxyl group, carboxyl or sulfo group.Preferred especially hydrogen atom, hydroxyl, carboxyl or sulfo group.The substituting group that abovementioned alkyl or alkoxyl group can have can be for example hydroxyl, alkyl or alkoxyl group.

Q ²And Q ³Represent hydrogen atom separately independently of one another, can have substituent C _1-4Alkyl (for example methyl or ethyl) maybe can have substituent phenyl, preferred especially Q ²Or Q ³It is hydrogen atom.The substituting group that abovementioned alkyl or alkoxyl group can have can be for example hydroxyl, carboxyl or sulfo group.

P represents 0 or 1, and t represents 1 or 2.

About the azoic dyestuff of following formula (2) expression, in its dye structure, specify a substituting group (the 3-position has substituent phenyl and the 7-position has amino naphthyl) by two ends and replacement position at molecular backbone chain, and the D that has hydrophobic interaction by appointment ¹And E ¹, as top detailed explanation, the association performance is improved, and can form high lytropic liquid crystals state.Therefore, the azoic dyestuff of following formula (2) expression is suitable as by wet type and becomes embrane method to form the dyestuff of anisotropy dye film, and has high dichroic ratio.Therefore, be used for the anisotropy dye film, can obtain having high dichromatic anisotropy dye film by the dye composite that will use this dyestuff.

The azoic dyestuff of following formula (2) expression provides black, and especially preferably its excitation purity is 0%～12%.That is, be 0%～12% dyestuff by using excitation purity, mixes different molecules also not disturbing molecule be orientated, can obtain high dichroism.

Here, obtain excitation purity as follows: in chromaticity diagram, with straight line the tristimulus coordinates N of standard light source and the tristimulus coordinates C of resulting dyestuff are coupled together, the pairing wavelength of intersection point of getting this collinear extended line and spectrum locus is a predominant wavelength, calculates excitation purity by the ratio of each point.Obtain tristimulus coordinates C as follows: dyestuff is added to the aqueous solution that obtains dyestuff in the water, with the visible light transmittance rate of the spectrophotometric determination aqueous solution, can calculate the D that CIE 1964 replenishes in the standard colorimetric system (supplementary standard colorimetric system) ₆₅Colourity x under the standard light source and y.

The excitation purity of dyestuff of the present invention is meant this dyestuff is added to the excitation purity that resulting aqueous dye solutions is measured and calculated in the water.

And, disclosed currently known methods in the following document of method of calculation foundation: for example, " (newly organized color science handbook) New Color Science Handbook ", can compile by Japanese chromatology, (the consortium as a juridical person Tokyo University publishes meeting, published (second edition) on November 25th, 1989), the 104-105 page or leaf.

The excitation purity of the azoic dyestuff of following formula (2) expression is preferably at least 0% and at the most 12%, but excitation purity is at least 0%, and more preferably at the most 9%, most preferably at the most 6%.

And the molecular weight of the dyestuff of the following formula of free acid form (2) expression is generally at least 595 and usually at the most 1,500, preferably at the most 1,200.

As the object lesson of the dyestuff of following formula (2) expression, can mention the dyestuff of structure with (II-1)～(II-15) expression, still, described dyestuff is not limited to these.

The azoic dyestuff of following formula (2) expression itself can prepare according to currently known methods.For example the dyestuff by (II-1) expression can prepare according to the following step (a)～(c).

(a) according to conventional methods (for example, " reactive monoazo dyestuffs chemistry (New Dye Chemical) ", thin Tian Fengzhu (on December 21st, 1973 was published by skill newspaper hall), the 396-409 page or leaf), prepare Monoazo compound by 3-aniline sulfonic acid (m-sulfanilic acid) and 2-anisidine (ORTHO ANISIDINE) diazotization and coupling.

(b) make resulting Monoazo compound and 3-monomethylaniline (meta-aminotoluene) carry out diazotization and linked reaction according to conventional methods in the same way, with the preparation tetrazo compound.

(c) make resulting tetrazo compound and 7-amino-1-naphthols-3 according to conventional methods in the same way, 6-disulfonic acid (RR acid) carries out diazotization and linked reaction, saltouts with sodium-chlor, to obtain required dyestuff (II-1).

Especially, the dyestuff of being represented by said structure formula (II-1) forms lytropic liquid crystals in the aqueous solution, therefore, can have high dichromatic anisotropy dye film with its preparation, and it is to be particularly suitable for the useful dyestuff that wet type becomes embrane method.

In the dyestuff of giving an example in the above, the dyestuff that anisotropy dye film of the present invention preferably contains (I-1), (I-31), (II-3) or (II-15) represents.

In the dyestuff that the present invention uses, the dyestuff with acidic-group can use with free acid form, or the part acidic-group can be a salt form.In addition, the dyestuff of the dyestuff of salt form and free acid form can exist simultaneously.And, when when preparation obtains dyestuff with the form of salt, can use on former state ground, perhaps change the salt form that needs into.As the method that changes salt form into, can use known method arbitrarily, for example can mention following method.

Method 1): in the aqueous solution of the dyestuff that obtains with salt form, add for example strong acid such as hydrochloric acid, be settled out dyestuff with free acid form, apparatus has in the basic solution (for example lithium hydroxide or sodium hydroxide) of required counterion and the acidic-group of dyestuff then, carries out the salt exchange.

Method 2): in the aqueous solution of the dyestuff that obtains with salt form, add a large amount of excessive required balance ionic neutral salt (for example lithium chloride or sodium-chlor) that have, carry out the salt exchange with the form of the cake of saltouing.

Method 3): the aqueous solution of handling the dyestuff that obtains with salt form with strong acid ion exchange resin, be settled out dyestuff with free acid form, apparatus has in the basic solution (for example lithium hydroxide or sodium hydroxide) of required counterion and the acidic-group of dyestuff, thereby carries out the salt exchange.

Method 4): apparatus has the basic solution (for example lithium hydroxide or sodium hydroxide) of required counterion to anticipate strong-acid ion exchange resin, with the reactant aqueous solution of this strong-acid ion exchange resin with the dyestuff that obtains with salt form, thereby carries out the salt exchange.

Acidic-group is that free acid form or salt form depend on the pKa of dyestuff and the pH of aqueous dye solutions.

As the example of above-mentioned salt form, for example can mention alkali-metal salt such as Na, Li or K, can be substituted with C _1-16Alkyl or C _1-12The ammonia salt of hydroxyalkyl and the salt of organic amine.As the example of organic amine, for example can mention C _1-6Low-grade alkylamine, be substituted with the C of hydroxyl _1-6Low-grade alkylamine and the C that is substituted with carboxyl _1-6Low-grade alkylamine.In the situation of salt form, its type is not limited to a kind of, can have broad variety.

In the present invention, can use above-mentioned dyestuff individually, or use at least two kinds in combination, the dyestuff except that the dyestuff that exemplifies above can mix use with the degree that does not reduce orientation, thereby can prepare the anisotropy dye film with various form and aspect.Especially, when being used for polarizing coating, preferred shade film, in the visible wavelength region of 380～780nm, form and aspect are that (neutral black is for example at L for muted color ^*a ^*In the b colour system, satisfy $\sqrt{\{\left(a^{*}\right)2+\left(b^{*}\right)2\}}\≤5$ Color) the polarizer used as display unit of formula optimization, especially for the polarizer of colour display device.

When mixing another kind of dyestuff, as the example that mixes with dyestuff, for example can mention directly Huang 12 of C.I., C.I. direct yellow 34, C.I. direct yellow 86, C.I. direct yellow 142, C.I. direct yellow 132, C.I. turmeric yellow 25, C.I. direct orange 39, C.I. direct orange 72, C.I. direct orange 79, C.I. von Muller's indicator 28, C.I. directly red 39, C.I. directly red 79, C.I. directly red 81, C.I. directly red 83, C.I. directly red 89, C.I. Xylene Red 37, C.I. direct purple 9, C.I. direct purple 35, C.I. direct purple 48, C.I. direct purple 57, C.I. sun blue 1, C.I. sun blue 67, C.I. sun blue 83, C.I. sun blue 90, C.I. sun green 42, C.I. sun green 51 and C.I. sun green 59.

The preferred dry type of mentioning later of using becomes embrane method to become embrane method with wet type, uses the anisotropy dye film dye composite that contains at least a dyestuff, prepares anisotropy dye film of the present invention.For anisotropy dye film dye composite of the present invention, can use above-mentioned dyestuff individually, or use above-mentioned multiple dyestuff, or the mixture of use and another kind of dyestuff, the usage quantity of described another kind of dyestuff is not for to reduce the degree of orientation, thereby can prepare the anisotropy dye film with various form and aspect.

Anisotropy dye film of the present invention contains solvent usually with dye composite, and described dyestuff dissolves usually or is dispersed in the solvent.For example from the angle of the solubleness solvent, the anisotropy dye film is preferably the dyestuff of following formula (1) or (2) expression with the dyestuff that dye composite contained.And, in described composition, can mix for example additive such as tensio-active agent or pH regulator agent.Such additive also is dissolved in the solvent usually and uses.

As solvent, water, the organic solvent or their mixture that dissolve each other with water are suitable.As the object lesson of organic solvent, for example can use individually: alcohols, for example methyl alcohol, ethanol, Virahol or glycerol; Dibasic alcohol, for example ethylene glycol or Diethylene Glycol; Or cellosolve, for example methylcyclohexane or ethyl cellosolve perhaps use in them at least two kinds mixed solvent.

At anisotropy dye film dye composite is to contain in the situation of solution of this solvent, although dyestuff depends on the formation concentration of supramolecular structures such as the solubleness of film, dyestuff and for example lytropic liquid crystals state at the anisotropy dye film with the concentration in the dye composite, but, this concentration is generally at least 0.01 weight %, preferred at least 0.1 weight %, more preferably at least 0.5 weight %, and 50 weight % at the most usually, preferred 30 weight % at the most, more preferably 25 weight % at the most, especially preferred 20 weight % at the most, most preferably 15 weight % at the most.If dye strength is too low, the anisotropy dye film of gained can not obtain sufficient dichroism, if concentration is too high, dyestuff comes out segregation.

In order to improve wettability and the coating on base material, according to circumstances need, can add for example additive such as tensio-active agent in dye composite to the anisotropy dye film.As tensio-active agent, can use any tensio-active agent in negatively charged ion, positively charged ion and the nonionogenic tenside.As at the anisotropy dye film with the concentration in the dye composite, it adds concentration and is preferably at least 0.05 weight % and 5 weight % at the most usually, more preferably 0.5 weight % at the most, the orientation that this tittle is enough to obtain target effect and does not damage dye molecule.

And, dyestuff forms unstable such as salt and gathering in anisotropy dye film usefulness dye composite in order for example to suppress, can mix the anisotropy dye film with before the moiety of dye composite, afterwards or during, add for example known pH regulator agent such as acid or alkali to regulate pH.From the stability of solution with the angle of the operation efficiency producing, preferably the pH regulator with dye composite be at least 3, more preferably at least 4 and preferably at the most 13, more preferably at the most 12.

And, as the additive beyond the above-mentioned additive, can use disclosed additives known in " Additive for Coating " (Willey-VCH (2000)) that J.Bieleman edits.

Preferably become embrane method or wet type to become embrane method, use the anisotropy dye film dye composite that contains at least a dyestuff, prepare anisotropy dye film of the present invention with the dry type of mentioning later.But, anisotropy dye film of the present invention is preferably the anisotropy dye film with the preparation of wet type film forming method, rather than with for example with the anisotropy dye film of dry type film forming methods such as film stretching preparations, this is because wet type becomes embrane method can improve molecular arrangement performance in the anisotropy dye film, and utilizes the molecular interaction between the dye molecule and obtain high dichroism.

Can use the azoic dyestuff of following formula (1) expression, particularly in the aqueous solution, form the dyestuff of lytropic liquid crystals, dyestuff as above-mentioned structural formula (I-1) expression becomes embrane method to prepare with wet type and has high dichromatic polarizing coating (anisotropy dye film), and this azoic dyestuff is useful.Free acid form has high dichroism by of the present invention many azoic dyestuffs of following formula (1) expression, forms lytropic liquid crystals in the aqueous solution, and various substrate surfaces are had high avidity, and therefore, they are suitable for such film.

And the trisazo dye of being represented by following formula (2) has specific dye structure, therefore forms the lytropic liquid crystals state of height, the molecular arrangement state of height can be provided, and only just can provide black with a kind of dyestuff, so high dichroism can be provided.

Become embrane method from the also preferred wet type of following angle: can form the anisotropy dye film at the contour heat-resistant material of for example glass, and can obtain the high heat resistance polarizer, this polarizer need can be used to the purposes of high heat resistance, for example liquid crystal projection apparatus or vehicle-mounted display panel.

In the film of anisotropy dye film, dry type becomes embrane method can enumerate following method: for example, after high molecular polymer being formed film, use the anisotropy dye film painted method of dye composite, perhaps by being added to the anisotropy dye film in the solution of high molecular polymer with dye composite, carry out film forming method of shape etc. behind the solution-dyed, obtain not tensile film, then with this tensile film tensile method not; Or heating evaporation anisotropy dye film dye composite in a vacuum, make it be deposited on method on the base material such as glass for example in a vacuum.As with the constituent material of anisotropy dye film, can mention the macromolecular material that has high affinity with dyestuff, for example polyvinyl alcohol with the painted film of dye composite.

Wet type becomes embrane method can use known method, for example following method: above-mentioned anisotropy dye film is made coating fluid with dye composite, for example be coated on the base material such as sheet glass, and drying, thus make described dyestuff orientation and stacked.

For example, can mention that for example (Co., Ltd. is towards storehouse bookstore at " the Coating Engineering " of former rugged brave work, on March 20th, 1971 published) the 253-277 page or leaf, perhaps at the grand chief editor of city village state " Creation and Applications of Harmonized Molecular Materials " (CMCPublishing Co., Ltd., published on March 3rd, 1998) disclosed method in the 118-149 page or leaf, use perhaps that for example spin coating, spraying, rod are coated with, roller coat or scraper plate coating method etc. are in the method for carrying out in advance being coated with on the base material of orientation process.

Temperature when coating anisotropy dye film is with dye composite on base material is generally at least 0 ℃ and 80 ℃ at the most, preferably at the most 40 ℃.And humidity is generally 10%RH (relative humidity) at least, preferred 30%RH at least, and be generally 80%RH at the most.

Become in the embrane method in wet type, use coating anisotropy dye film on base material is made dye film with the step and the drying step of dye composite.Preferred operational condition of regulating in these steps keeping the molecular orientation state based on the formed height of high lyotropic liquid crystalline of dyestuff self-assembly, thereby is met the anisotropy dye film of the present invention of stacked cycle of above-mentioned molecule and molecule stack length.

Therefore, particularly at drying step, the quick increase of temperature is disadvantageous, usually preferred seasoning.As optimum condition, the temperature when dry is generally at least 0 ℃, and preferably at least 10 ℃, and be generally 120 ℃ at the most, preferably at the most 110 ℃.And humidity is generally 10%RH at least, preferred 30%RH at least, and be generally 80%RH at the most.

As base material, for example can mention glass or triacetate, esters of acrylic acid (acryl), polyester, tri acetyl cellulose or polyurethane-type resin molding.And, on substrate surface, can (ball be apt to Co., Ltd. with for example " liquid crystal brief guide (Liquid Crystal Handbook) ", publication on October 30th, 2000) disclosed currently known methods in the 226-239 page or leaf, form orientation process layer, fluororesin layer etc., with the orientation of control dichroic dye.And, can be used in combination rayed, corona treatment or plasma treatment etc. and carry out for example modification of surface energy state etc.

Preferred configuration protection layer on the surface of anisotropy dye film of the present invention.Form above-mentioned protective layer by transparent polymer films such as stacked for example triacetate, esters of acrylic acid, polyester, polyimide, tri acetyl cellulose or polyurethane-type films, in fact also use protective layer.

Anisotropy dye film of the present invention has high dichroic ratio, and dichroic ratio is preferably at least 9, and more preferably at least 12, especially preferably at least 15.

And the film thickness for particularly become the anisotropy dye film that embrane method forms on base material with wet type is preferably 50nm at least at dried film thickness usually, more preferably 100nm at least, and be preferably 50 μ m at the most, more preferably 10 μ m at the most, especially preferably 1 μ m at the most.

And, use anisotropy dye film of the present invention for example as situation as the polarizing filter of various display unit such as LCD and OLED in, can on the electrode base material that for example constitutes this display unit, directly form this anisotropy dye film, maybe can use the base material that is formed with this anisotropy dye film on it composed component as this display unit.

Utilize the photoabsorption anisotropy, anisotropy dye film of the present invention serves as polarizing coating, thereby obtain for example linearly polarized photon, circular polarized light or oval polarized light, and, by being chosen to membrane method and base material or containing the composition of this dyestuff, it can serve as and for example has refraction ansiotropy or conduct anisotropic various anisotropic membrane, and can obtain being used for the various polarizers of various uses.

Polarizer of the present invention uses anisotropy dye film of the present invention, still, when obtaining polarizer of the present invention when form anisotropy dye film of the present invention on base material, can use formed anisotropy dye film itself.In addition, except that above-mentioned protective layer, can also stacked layer with various functions, for example bonding coat and anti-reflecting layer use thereby can be used as duplexer.In this case, according to the purpose of using, can suitably select lamination order.

Embodiment

Explain the present invention in further detail with reference to embodiment below.But in the scope that does not exceed main idea, the present invention is in no way limited to the following example.

In the following example, use film evaluation X-ray diffraction equipment (diffraction system in " RINT2000PC " face, produce by motor of science (strain)) carry out measuring in the face, obtain diffraction curve, and by the in plane vibration sweep measuring, obtain vibration curve, analyze diffraction curve and vibration curve, thereby obtain the degree of orientation of stacked axle of stacked cycle of molecule and stack length and molecule with preceding method.These two kinds of mensuration all are to carry out at 1 ° input angle place with CuK α.

In addition, employing is furnished with the transmittance of spectrophotometer (production of " Spectro Multichannel Photodetector MCPD2000 " You Da mound electronics society) the mensuration anisotropy dye film of iodine class polarizer in incident optical system, calculate according to following formula, thereby obtain dichroic ratio (D):

Dichroic ratio (D)=Az/Ay

Az＝-log(Tz)

Ay＝-log(Ty)

Tz: the polarized light transmittance on the absorption axes direction of dye film

Ty: the polarized light transmittance on the polarization axis direction of dye film

In addition, above-mentioned Tz and Ty are incorporated in the disclosed method of JIS-Z-8701:1995, (CIE 1964 replenishes standard colorimetric systems, at D for the colourity x of calculating anisotropy dye film and y ₆₅Under the standard light source).

In addition, behind the transmittance with the spectrophotometric determination dye film,, obtain tristimulus values X, Y and the Z of non-luminous object color in CIE 1931 standard colorimetric systems, calculate according to following calculating formula, thereby obtain degree of polarization according to JIS-Z-8701:1995.Use the spectral distribution of D65 light source as the standard light source that is used to calculate tristimulus values X, Y and Z.

Degree of polarization (ρ)={ (Y2-Y1)/(Y2+Y1) } ^1/2* 100

Y2: the tristimulus values Y when two polarization axles of dye film are parallel to each other placement

Y1: the tristimulus values Y when two polarization axles of dye film are vertically placed mutually

In the following description, " part " is meant " weight part ".

(1) stacked cycle and stack length (embodiment 1～6 and Comparative Examples 1)

Embodiment 1

Under agitation, illustrative dyestuff (I-31) below 10 parts and 0.2 part of nonionogenic tenside EMULGEN 109P (being produced by Hua Wangshe) are dissolved in 89.8 parts of water, obtain anisotropy dye film dye composite:

On the other hand, prepare a base material, this base material comprises glass baseplate (75mm * 25mm, thickness 1mm) and organizine prints alignment film of polyimide (the polyimide thickness: about 800 that forms thereon

), and carry out friction treatment with cloth in advance.Be coated with device (by Tester Sangyo Co., " No.3 " that Ltd. produces) aforementioned anisotropy dye film dye composite of coating on the base material that makes like this with rod, then seasoning obtains the anisotropy dye film that film thickness is about 0.4 μ m.

The X-ray diffraction curve and the in plane vibration curve of resulting anisotropy dye film are illustrated respectively among Fig. 4 and Fig. 5.Fig. 4 represents to carry out the result that measures in the face from both direction, has wherein observed perpendicular to the diffraction surfaces of the polarization axle of this anisotropy dye film with perpendicular to the diffraction surfaces of absorption axes.Solid line and dotted line are represented the X-ray diffraction curve that obtains from observing perpendicular to the diffraction surfaces direction of polarization axle and absorption axes respectively.Fig. 5 represents the measurement result of in plane vibration curve of diffraction peak of the stacked generation of molecule of this anisotropy dye film.

In addition, the orientation degree and the dichroic ratio of stacked cycle of resulting molecule, stack length, the stacked axle of molecule are presented in the table 1.

These results confirm that the anisotropy dye film of present embodiment has the molecular arrangement that is fit to the performance dichroic ratio, and has high dichroic ratio.

Embodiment 2

Under agitation, illustrative dyestuff (II-15) below 10 parts is dissolved in 90 parts of water, obtains anisotropy dye film dye composite:

Remove and use rod to be coated with device (by Tester Sangyo Co., Ltd. " No.2 " of Sheng Chaning), in the mode identical with embodiment 1, be formed with this anisotropy dye film dye composite of coating on the glass baseplate of alignment film of polyimide thereon, then seasoning, thus the anisotropy dye film obtained.

Test the orientation degree and the dichroic ratio of the stacked axle of stacked cycle of molecule, stack length, molecule of resulting anisotropy dye film, the result is illustrated in the table 1.

Table 1 confirms that the anisotropy dye film of present embodiment has the molecular arrangement that is fit to the performance dichroic ratio, and has high dichroic ratio.

Embodiment 3

Under agitation, illustrative dyestuff (I-1) below 8 parts is dissolved in 92 parts of water, obtains anisotropy dye film dye composite:

Except that using the gap is the spreader (making society of institute by well unit produces) of 10 μ m, same way as with embodiment 1, be formed with this anisotropy dye film dye composite of coating on the glass baseplate of alignment film of polyimide thereon, follow seasoning, thereby obtain the anisotropy dye film.

Test the orientation degree and the dichroic ratio of the stacked axle of stacked cycle of molecule, stack length, molecule of resulting anisotropy dye film, the result is illustrated in the table 1.

Table 1 confirms that the anisotropy dye film of present embodiment has the molecular arrangement that is fit to the performance dichroic ratio, and has high dichroic ratio.

Embodiment 4

Under agitation, illustrative dyestuff (I-31) above 12 parts is dissolved in 80 parts of water, adds 8 parts of glycerine, obtain anisotropy dye film dye composite to it.

Except that using the gap is the spreader (making society of institute by well unit produces) of 10 μ m, same way as with embodiment 1, be formed with this anisotropy dye film dye composite of coating on the glass baseplate of alignment film of polyimide thereon, follow seasoning, thereby obtain the anisotropy dye film.

Test the orientation degree and the dichroic ratio of the stacked axle of stacked cycle of molecule, stack length, molecule of resulting anisotropy dye film, the result is illustrated in the table 1.

Table 1 confirms that the anisotropy dye film of present embodiment has the molecular arrangement that is fit to the performance dichroic ratio, and has high dichroic ratio.

Embodiment 5

Under agitation, illustrative dyestuff (II-3) below 15 parts is dissolved in 76 parts of water, adds 9 parts of glycerine, obtain anisotropy dye film dye composite to it:

Remove and use rod to be coated with device (by Tester Sangyo Co., Ltd. " No.2 " of Sheng Chaning), same way as with embodiment 1, be formed with this anisotropy dye film dye composite of coating on the glass baseplate of alignment film of polyimide thereon, then seasoning obtains the anisotropy dye film.

Test the orientation degree and the dichroic ratio of the stacked axle of stacked cycle of molecule, stack length, molecule of resulting anisotropy dye film, the result is illustrated in the table 1.

Table 1 confirms that the anisotropy dye film of present embodiment has the molecular arrangement that is fit to the performance dichroic ratio, and has high dichroic ratio.

Embodiment 6

Under agitation, 15 parts of dyestuffs of giving an example above (II-3) are dissolved in 85 parts of water, obtain anisotropy dye film dye composite.

Remove and use rod to be coated with device (by Tester Sangyo Co., Ltd. " No.2 " of Sheng Chaning), same way as with embodiment 1, be formed with this anisotropy dye film dye composite of coating on the glass baseplate of alignment film of polyimide thereon, then seasoning obtains the anisotropy dye film.

Test the orientation degree and the dichroic ratio of the stacked axle of stacked cycle of molecule, stack length, molecule of resulting anisotropy dye film, the result is illustrated in the table 1.

Table 1 confirms that the anisotropy dye film of present embodiment has the molecular arrangement that is fit to the performance dichroic ratio, and has high dichroic ratio.

Comparative Examples 1

6 parts of dyestuffs with following structural are added in 94 parts of water, and dissolving is under agitation then filtered, and obtains anisotropy dye film dye composite:

Use rod to be coated with device (by " No.2 " of Coating Tester Kogyo K.K. production), go up this anisotropy dye film dye composite of coating at slide glass (loose unrestrained nitre industrial " Colorless edge polish frosted slide glass No.1 "), then seasoning obtains the anisotropy dye film.

Test the orientation degree and the dichroic ratio of the stacked axle of stacked cycle of molecule, stack length, molecule of resulting anisotropy dye film, the result is illustrated in the table 1.

Estimate that from table 1 in the anisotropy dye film of this Comparative Examples, stack length is lower than 105

, the number deficiency of the orientation molecule of suitable performance dichroic ratio, therefore, this anisotropy dye film has low dichroic ratio.

Table 1

(2) preparation (preparation example 1) of the azoic dyestuff of formula (2) expression

Preparation example 1

Prepare following dyestuff (I-31) according to the following step (A)～(E):

(A) according to conventional methods (for example, thin Tian Fengzhu " reactive monoazo dyestuffs chemistry (New DyeChemical) ", (on December 21st, 1973, skill newspaper hall is published), 396-409 page or leaf disclosed method), prepare Monoazo compound by 4-aniline sulfonic acid (Sulphanilic Acid) and 2-methoxyl group-5-monomethylaniline through diazotization and coupling.

(B) Monoazo compound and the 2-methoxyl group-5-monomethylaniline that step (A) is obtained carries out diazotization and linked reaction, thus the preparation tetrazo compound.

(C) in addition, 6-amino-1-naphthols-3-sulfonic acid (J acid) is dissolved in and makes pH become 6 in the water, solution is cooled to 0～5 ℃.To wherein adding cyanuryl chloride, with temperature maintenance under 0～5 ℃, reacted 2 hours, to finish reaction.Then, at room temperature,, under 6～7 pH, carry out condensation reaction a few hours to its aqueous solution that adds 3-aniline sulfonic acid (m-sulfanilic acid).

(D) compound that tetrazo compound that step (B) obtains and step (C) are obtained carries out diazotization and linked reaction, thus the preparation tris-azo compound.After reaction is finished, add 3-amino-1, the 2-propylene glycol rises to 60 ℃ with temperature, and it is 9～9.5 that the aqueous sodium hydroxide solution that adds 25 weight % makes pH, finishes reaction.

(E) after the cooling, saltout with sodium-chlor, thereby obtain target dyestuff (I-31).

(3) preparation of anisotropy dye film (embodiment 7～17 and Comparative Examples 2～7)

Embodiment 7

10 parts of dyestuffs (I-1) and 0.2 part of nonionogenic tenside EMULGEN 109P (being produced by Hua Wangshe) are added in 100 parts of water, then the lithium hydroxide aqueous solution with 5 weight % neutralizes, making pH is 8.0, dissolving under agitation, filter, obtain the aqueous solution (being used to form the composition of anisotropy dye film) of dyestuff.The aqueous solution of this dyestuff is dropped on the slide glass,, confirm that thus this solution is isotropic aqueous solution in the starting stage, but drying concentrates formation lytropic liquid crystals state with the dry spissated process of polarized light microscope observing.

On the other hand, preparation comprises glass baseplate and organizine and is imprinted on and is formed with alignment film of polyimide (polyimide thickness: about 800 on this glass baseplate

) base material, carry out friction treatment with cloth in advance.Be coated with device (by Tester Sangyo Co., " No.3 " that Ltd. produces) aqueous solution of coating dye film on the base material that makes like this with rod, then at room temperature dry, obtain the anisotropy dye film.

The light transmission features of dye film on absorption axes and polarization axle is illustrated among Fig. 6.The maximum absorption wavelength of resulting anisotropy dye film (λ max) is 555nm, and dichroic ratio is 12.

Embodiment 8

5 parts of above-mentioned dyestuffs (I-1) are added in 100 parts of water, and then with the lithium hydroxide aqueous solution neutralization of 5 weight %, making pH is 8.0, and dissolving is under agitation filtered, to obtain the aqueous solution of dyestuff.Then, 4 parts of boric acid are added in this aqueous dye solutions of 96 parts, to obtain dyeing solution.

In addition, be that 10 parts of polyvinyl alcohol of 1,750 are added in 90 parts of water with mean polymerisation degree, then dissolving under agitation in water-bath expands into 1mm thickness, drying, thus obtain polyvinyl alcohol (PVA) film.

This PVA film is immersed in the dyeing solution, stretches three times, to obtain the anisotropy dye film.The tristimulus values of this dye film is illustrated in the table 2, and degree of polarization is 79.9%.

Embodiment 9

5 parts of above-mentioned dyestuffs (I-1) and 0.2 part of nonionogenic tenside EMULGEN 109P (being produced by Hua Wangshe) are added in 100 parts of water, then with the lithium hydroxide aqueous solution neutralization of 5 weight %, making pH is 8.0, under agitation dissolving, filter, obtain the aqueous solution of dyestuff.

Use spin coater, on the glass baseplate that the same procedure with embodiment 7 prepares, be coated with the aqueous solution of this dyestuff, then at room temperature dry, obtain the anisotropy dye film.The dichroic ratio of resulting dye film is 20.

Embodiment 10

25 parts of following dyestuffs (I-25) and 0.2 part of nonionogenic tenside EMULGEN 109P (being produced by Hua Wangshe) are added in 100 parts of water, then with the lithium hydroxide aqueous solution neutralization of 5 weight %, making pH is 8.0, under agitation dissolving, filter, to obtain the aqueous solution of dyestuff.

With the same procedure of embodiment 7,, confirm that it is in the lytropic liquid crystals state with the aqueous solution of this dyestuff of polarized light microscope observing.

And, use the scraper coating method, on the glass baseplate that the same procedure with embodiment 7 prepares, be coated with the aqueous solution of this dyestuff, then at room temperature dry, obtain the anisotropy dye film.

The light transmission features of this dye film on absorption axes and polarization axle is illustrated among Fig. 7.The maximum absorption wavelength of resulting anisotropy dye film (λ max) is 570nm, and dichroic ratio is 15.

Embodiment 11

Except that dyestuff being changed into above-mentioned dyestuff (I-25), prepare the aqueous solution of dyestuff with the same way as of embodiment 8, make the dyeing of PVA film, thereby obtain dye film.

The tristimulus values of resulting dye film is illustrated in the table 2, and degree of polarization is 64%.

Table 2

Embodiment 12

Sodium salt and 0.2 part of nonionogenic tenside EMULGEN109P (being produced by Hua Wangshe) of 5 parts of following dyestuffs (II-1) are added in 95 parts of water, and then dissolving is under agitation filtered, and obtains the aqueous solution (anisotropy dye film dye composite) of dyestuff.

On the other hand, as base material, preparation comprises glass baseplate and is formed with the glass baseplate of the alignment films of polyimide with spin-coating method on this glass baseplate that (alignment film of polyimide thickness is about 800 for 75mm * 25mm, thick 1.1mm

, carry out friction treatment with cloth in advance).With spin coater (SC-200, by giving as security Zhong She production) aqueous solution of this dyestuff of coating (was coated with 5 seconds down at 1000 rev/mins on the base material that makes like this, be coated with 15 seconds down at 2500 rev/mins then), then seasoning obtains the anisotropy dye film of dye molecule along the frictional direction orientation.

For resulting anisotropy dye film, (CIE 1964 compensation standard colorimeter systems are at D for the colourity x of the transmitted light (Tz) of the polarized light on the absorption axes direction of vibration plane in the dye film plane and y ₆₅Under the standard light source) and the polarization axis direction of vibration plane in the dye film plane on the colourity x of transmitted light (Ty) of polarized light and y (CIE 1964 compensation standard colorimeter systems are at D ₆₅Under the standard light source), maximum absorption wavelength (λ max) and dichroic ratio (D) be illustrated in the table 3.

Resulting anisotropy dye film has high dichroic ratio (photoabsorption anisotropy), can serve as polarizing coating fully.

Embodiment 13

Except that the dyestuff that uses is changed into the sodium salt of following dyestuff (II-9), prepare anisotropy dye film dye composite with the same way as of embodiment 12, under similar condition, be coated on the similar base material, obtain the anisotropy dye film.

The colourity x of resulting anisotropy dye film and y (CIE 1964 compensation standard colorimeter systems), maximum absorption wavelength (λ max) and dichroic ratio (D) are illustrated in the table 3.Resulting anisotropy dye film has high dichroic ratio, can serve as polarizing coating fully.

Embodiment 14

The sodium salt of 10 parts of following dyestuffs (II-2) is added in 90 parts of water, and then dissolving is under agitation filtered, and obtains anisotropy dye film dye composite.Be coated with device No.3 (by TesterSangyo Co., Ltd. produces) with rod and be coated with this dye composite on the employed base material in embodiment 12, then seasoning obtains the anisotropy dye film.

The colourity x of resulting anisotropy dye film and y (CIE 1964 compensation standard colorimeter systems), maximum absorption wavelength (λ max) and dichroic ratio (D) are illustrated in the table 3.Resulting anisotropy dye film has high dichroic ratio, can serve as polarizing coating fully.

Embodiment 15

The sodium salt of 10 parts of following dyestuffs (II-3) is added in 90 parts of water, and then dissolving is under agitation filtered, and obtains anisotropy dye film dye composite.With the gap is the spreader (making society of institute by well unit produces) of 10 μ m this dye composite of coating on the employed base material in embodiment 12, and then seasoning obtains the anisotropy dye film.

The colourity x of resulting anisotropy dye film and y (CIE 1964 compensation standard colorimeter systems), maximum absorption wavelength (λ max) and dichroic ratio (D) are illustrated in the table 3.Resulting anisotropy dye film has high dichroic ratio, can serve as polarizing coating fully.

Embodiment 16

The sodium salt of 9 parts of following dyestuffs (II-4) is added in 91 parts of water, and then dissolving is under agitation filtered, and obtains anisotropy dye film dye composite.Under the condition identical, be coated with, obtain the anisotropy dye film with embodiment 15.

The colourity x of resulting anisotropy dye film and y (CIE 1964 compensation standard colorimeter systems), maximum absorption wavelength (λ max) and dichroic ratio (D) are illustrated in the table 3.Resulting anisotropy dye film has high dichroic ratio, can serve as polarizing coating fully.

Embodiment 17

The sodium salt of 7 parts of following dyestuffs (II-6) is added in 93 parts of water, and then dissolving is under agitation filtered, and obtains anisotropy dye film dye composite.Under the condition identical, be coated with, obtain the anisotropy dye film with embodiment 15.

The colourity x of resulting anisotropy dye film and y (CIE 1964 compensation standard colorimeter systems), maximum absorption wavelength (λ max) and dichroic ratio (D) are illustrated in the table 3.Resulting anisotropy dye film has high dichroic ratio, can serve as polarizing coating fully.

Table 3

Comparative Examples 2

Except that the dyestuff that uses following structural replaces the above-mentioned dyestuff (I-1), prepare aqueous dye solutions and dye film with the same way as of embodiment 8:

In the transmissison characteristic presentation graphs 8 of dye film on absorption axes and polarization axis direction.The maximum absorption wavelength of resulting dye film (λ max) is 585nm, and dichroic ratio is 3.

Comparative Examples 3

Use the sodium salt of dyestuff (III-1) to replace above-mentioned dyestuff (II-1), described dyestuff (III-1) has the substituting group G of dyestuff (II-1) in the contraposition of azo group ¹, in addition, prepare the dye film dye composite with the same way as of embodiment 12, under similar condition,, obtain dye film similarly being coated with on the base material.

For resulting dye film, carry out various tests in the mode identical with embodiment 12.The result is illustrated in the table 4.The dichroic ratio of resulting dye film (absorption anisotropy) is at most 2, and enough anisotropy can not be provided.

Comparative Examples 4

Use following dyestuff (III-2) to replace above-mentioned dyestuff (II-1), described dyestuff (III-2) has the substituting group G of dyestuff (II-1) on the ortho position ¹, in addition, prepare the dye film dye composite in the mode identical with embodiment 12, under similar condition,, obtain dye film similarly being coated with on the base material.

For resulting dye film, carry out various tests in the mode identical with embodiment 12.The result is illustrated in the table 4.The dichroic ratio of resulting dye film (absorption anisotropy) is at most 2, and enough anisotropy can not be provided.

Comparative Examples 5

5 parts of following dyestuffs (III-3) are added in 95 parts of water, and then dissolving is under agitation filtered, and obtains anisotropy dye film dye composite.Be coated with device No.3 (by Tester Sangyo Co., Ltd. produces) with rod and be coated with this dye composite on the employed base material in embodiment 12, then seasoning obtains the anisotropy dye film.

For resulting dye film, carry out various tests in the mode identical with embodiment 12.The result is illustrated in the table 4.The dichroic ratio of resulting dye film (absorption anisotropy) is at most 2, and enough anisotropy can not be provided.

Comparative Examples 6

Except that using following dyestuff (III-4) to replace the above-mentioned dyestuff (II-1), prepare the dye film dye composite in the mode identical with embodiment 12, under similar condition, on similar base material, be coated with, obtain dye film.

For resulting dye film, carry out various tests in the mode identical with embodiment 12.The result is illustrated in the table 4.The dichroic ratio of resulting dye film (absorption anisotropy) is at most 2, and enough anisotropy can not be provided.

Comparative Examples 7

Except that the sodium salt that uses following dyestuff (III-5) replaces the above-mentioned dyestuff (II-1), prepare the dye film dye composite in the mode identical with embodiment 12, under similar condition, on similar base material, be coated with, obtain dye film.

For resulting dye film, carry out various tests in the mode identical with embodiment 12.The result is illustrated in the table 4.The dichroic ratio of resulting dye film (absorption anisotropy) is at most 2, and enough anisotropy can not be provided.

Table 4

(4) excitation purity (embodiment 18 and 19)

Embodiment 18

The sodium salt of 0.1 part of above-mentioned dyestuff (II-1) is added in 99.9 parts of water, and then dissolving is under agitation filtered, and obtains the aqueous solution of dyestuff.This aqueous solution is expelled in the quartz cell (cuvette) of optical path length 0.1mm.Measure the visible light transmittance rate of the anisotropy dye film that the aqueous dye solutions that is injected in the cuvette and embodiment 12 obtain separately with spectrophotometer, calculate CIE 1964 and replenish standard colorimetric systems, D ₆₅Colourity x under the standard light source and y.

In addition, in chromaticity diagram, with straight line with D ₆₅The tristimulus coordinates N of standard light source couples together with the tristimulus coordinates C1 of resulting aqueous dye solutions and the tristimulus coordinates C2 of anisotropy dye film respectively, the pairing wavelength of intersection point of getting each collinear extended line and spectrum locus is a predominant wavelength, calculates the excitation purity (pe1) of aqueous dye solutions and the excitation purity (pe2) of anisotropy dye film by the ratio of each point.The excitation purity of the excitation purity of aqueous dye solutions and anisotropy dye film is illustrated in the table 5.

The excitation purity of the dyestuff of present embodiment (aqueous dye solutions) is at the most 12%.And, use the excitation purity of the anisotropy dye film of this dyestuff preparation also to be at most 12%, this anisotropy dye film can be as the colourless anisotropy dye film of low colourity.

Embodiment 19

Measure and calculate the excitation purity of the anisotropy dye film that obtains among the dyestuff that uses among the embodiment 13～17 and the embodiment 13～17 in the mode identical with embodiment 18.The excitation purity of the excitation purity of the aqueous solution of each dyestuff and anisotropy dye film is illustrated in the table 5.

The excitation purity of the dyestuff of present embodiment (aqueous dye solutions) is at the most 12%.And, use the excitation purity of the anisotropy dye film of this dyestuff preparation also to be at most 12%, this anisotropy dye film can be as the colourless anisotropy dye film of low colourity.

Table 5

Industrial applicibility

According to the present invention, can provide to have high dichromatic anisotropy dye film. And, use the dichromatic anisotropy dye film of described height, the polarizer of the polarization property with excellent heat resistance and light resistance and excellence can be provided.

The present invention introduces its full content here by reference based on Japanese patent application 2003-353832 number (submission on October 14th, 2003), Japanese patent application 2003-378399 number (submission on November 7th, 2003) and Japanese patent application 2004-234415 number (submission on August 11st, 2004).

Claims (6)

1. anisotropy dye film azoic dyestuff, described anisotropy dye film is made by wet type film forming method, and the free acid form of described azoic dyestuff is represented by following formula (2):

Wherein, D ¹And E ¹Expression has or does not have C independently of one another separately _1-4Alkyl, C _1-4Alkoxyl group or C _2-7Amido is as substituent phenylene or have or do not have C _1-4Alkoxyl group is as substituent naphthylidene, and wherein, described alkyl, alkoxyl group or amido have or do not have hydroxyl independently of one another as substituting group,

G ¹Expression carboxyl, sulfo group or phosphonate group,

Q ¹The expression halogen atom, hydroxyl, nitro, have or do not have acyl group as substituent amino, have or do not have hydroxyl as substituent C _1-4Alkyl, has or do not have hydroxyl as substituent C _1-3Alkoxyl group, carboxyl or sulfo group,

Q ²And Q ³Represent hydrogen atom, C independently of one another _1-4Alkyl or phenyl, described alkyl and phenyl have or do not have hydroxyl, carboxyl or sulfo group as substituting group,

P represents 0 or 1, and t represents 1 or 2.

2. azoic dyestuff as claimed in claim 1, described azoic dyestuff are that excitation purity is 0%～12% dyestuff.

3. anisotropy dye film dye composite, described dye composite contains claim 1 or 2 described azoic dyestuffs.

4. anisotropy dye film, described anisotropy dye film contains claim 1 or 2 described azoic dyestuffs.

5. anisotropy dye film, described anisotropy dye film use the described anisotropy dye film of claim 3 to form with dye composite.

6. polarizer, described polarizer has used claim 4 or 5 described anisotropy dye films.

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