The polarizer

 

(57) Abstract:

The invention relates to a light polarizers and can be used in flat panel LCD displays, lighting, optical modulators, matrix systems light modulation, etc., Describes a polarizer, comprising a polymer film or plate, coloured dichroic dye, which it contains organic salt dichroic anionic dye selected from the group of azo, azoxy-, azomethine, stilinovich, polycyclic or metal complex dyes, and/or unbalanced mixed salt specified dichroic anionic dye with raznie cations, and/or associate specified dichroic anionic dye with a surface-active cation and/or amphoteric surface-active substance, and/or organic and/or mixed salt specified dichroic anionic dye polymer structure. The proposed polarizer has a high polarization characteristics, in particular, has a high dichroic ratio. 2 C.p. f-crystals, 1 tab., 1 Il.

The invention relates to optics, in particular for light polarizers, which can be used in prosoy light into polarized, is one of the essential elements of modern display devices liquid crystal control systems and light blocking.

Currently used polarizers are oriented uniaxially stretching a polymer film, coloured throughout the mass compounds of iodine or dichroic dye. As the polymer used mainly polyvinyl alcohol (PVA) or its derivatives.

The polarizers on the basis of iodine compounds have high light fastness and excellent polarization characteristics and are widely used in the production of liquid crystal indicators for screens, clocks, calculators, personal computers.

At the same time iodine polarizers have low thermal stability and low resistance to moisture, which are expressed in a sharp decrease of the polarization characteristics under the influence of these factors [1, L. Bolt, SPIE, 1981, Vol.307, p.22-24].

Higher thermal stability and resistance to moisture have polarizers based on PVA, coloured dichroic dyes.

As well known polarizer [2, US Patent 5007942, 1991], which represents polymer is B>, halogen, R1CONH-, -COOH, CONH2, -CONHR1, -CONR1R2, -COOR1, -OH, -OR, -O-CO-R1, -N=N-Y1or substituted or unsubstituted heterocyclic radical,1, R2represent alkyl, cycloalkyl, aryl or aralkyl, which can be split O and/or S and Y, Y1represent a substituted or unsubstituted aryl or heterocyclic radical. As the polymer polarizer [2] use of Homo - or copolymers of PVA. Polarizer [2] provides a higher thermal stability in comparison with iodine polarizers, however, have a lower polarization characteristics.

The closest in technical essence is a polarizer [3, EP 0530106 B1, 1996], which is a polymeric film, painted metal-containing dye of the formula (II) in the form of free acids or salts of lithium, sodium, potassium, ammonium, ethanolamine, allylamine and the like salts:

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where Me is a metal of transition group (copper, Nickel, zinc and iron);

Z is hydrogen, C1-4the alkyl, C1-4alkoxy, sulfo or amino, which in turn may be unsubstituted or substituted;

Q is a residue of 1 - or 2-naphthol, which may not be amestoy phenylazo or naphthylthiourea and in which the hydroxy-group of the naphthol is adjacent to athropos, associated with the benzene nucleus, Deputy containing Z, and is associated with the transition metal Me, forming a complex;

if Q is the remainder of naphthol, not containing additional athropy, T is unsubstituted or substituted naftilos group

if Q is the remainder of the naphthol containing additional isogroup, T is unsubstituted or substituted phenyl or naftilos group.

Polarizer [3] has polarization characteristics, which are not inferior to the iodine polarizers, but far surpass them in terms of resistance to heat and moisture.

At the same time, it should be noted that used for the manufacture of polarizers dichroic dyes have a tendency to aggregation, which may be the cause of the heterogeneity of the properties of the polarizer [3] area. In addition, the formation within the polymer film of aggregates of dye molecules, resulting from processes of microcrystallization, leads to scattering, which in turn also affects the optical properties of the polarizer.

Another disadvantage of the used dye is uneven setting the dyes using the mixture of cu is the Torah.

The present invention is the creation on the basis of colored dichroic dye polymer films of the polarizers with high settings, in particular, having a high dichroic ratio.

The problem is solved through the use in the manufacture of polarizer at least one dichroic dye in the form of:

- organic salts dichroic anionic dye of General formula (III):

{Chromogen} (HO-Mo+)n(III)

where the Chromogen - hereinafter the chromophore system of the dye;

X=CO, SO2, OSO2, ORO(O-M+); n=1-7;

Mo+- represents an organic cation, for example heteroaromatic cation type N-alkylpyridine, N-alkylidene, N-alkylimidazole, N-alkylthiophene, HE-(CH2-CH2O)m-CH2CH2-NH3+when m=1-9, RR'NH2+; RR'R"NH+, RR'R"R*N+, RR'R"R*P+when R, R', R", R* = alkyl or substituted alkyl type CH3, SS2H4WITH2H5WITH3H7WITH4H9WITH6H5CH2substituted or unsubstituted phenyl or heteroaryl, UNIVERSITY,-(CH2-CH2Y)k-CH2CH2, Y=O and the formula (IV):

(M1+O-X'-)m{Chromogen} (HO-M+)n(IV)

where X, X' here and below, SO2, OSO2, PO(O-M+); n=1-9, m=1-9;

M+M1+M+, M1+= H+, Mabout+or Mn+where Mn+here is a further inorganic cation type NH4+Li+, Na+TO+Cs+, 1/2Mg++, 1/s++, 1/V++, 1/3F+++, 1/2Ni++, 1/2Co++;

and/or associate of a dichroic anionic dye with a surface-active cation and/or amphoteric surface-active substance of General formula (V):

(M+O-X'-)m{Chromogen} (HO-SURFACTANT)n(V)

where n= 1-4, m= 0-9; M+=N+, Mo+, Mn+or surfactant where the surfactant is a here and further surface-active cationic or amphoteric surfactant;

and/or organic and/or mixed salts of a dichroic anionic dye polymer of the structure of General formula (VI):

(M1+ABOUT-X'-)mq[{-Chromogen-L-}q] (HO-M+)nq, (VI)

where L= (CH2)6WITH6H4WITH6H3G6H
for organic salts M+=M1+=Mo: n+m=1-9, q=10-50;

for mixed salt M+M1+M+, Ml+=N+, Mo+, Mn+or surfactants; n=1-9, m=1-9; q=10-50;

The ionic groups of the dye (III-VI) -X OM1+; -XO-M+can be linked directly to the aromatic nucleus or through the bridge-Z-(CH2)p- where Z= SO2NH, SO2, CONH, CO, O, S, NH, CH2; p=1-10.

As a Chromogen can be used chromophore systems azo-, azoxy-, azomethine, stilinovich, polycyclic or metal complex dyes of the formula (VII-XXV):

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where Me is a metal of transition group (copper, Nickel, zinc, iron);

Y=O, NH;

T=O, COO;

J=AG, Soag.

G, G' represents hydrogen, halogen, C1-4alkyl, C1-4alkoxy, sulfo, hydroxy or amino, which in turn may be unsubstituted or substituted;

AG is unsubstituted or substituted phenyl, naphthyl or heteroaryl;

Q is a single bond, O, S, NH, CH2, CONH, SO2, NH-CO-NH, CH=CH, N=N, CH= N;

Q' - -CONRR, -COOR, Ah, where R, R' represent alkyl, cycloalkyl, aryl or aralkyl, which can be split O and/or S; and A', A'-N=N-, where a' represents, as In,', unsubstituted or substituted phenyl, nattily, heterocyclic radical, the remainder acetoacetanilide, the rest of the phenol or aniline, 1 - or 2-naphthol, 1 - or 2-naphtylamine, which may be unsubstituted or substituted and may not contain or may contain additional unsubstituted or substituted, phenylazo or naphthylthiourea.

In the case of metal complex dye In,' represent the balance of 1 - or 2-naphthol, which may be unsubstituted or substituted and may not contain or may contain additional unsubstituted or substituted, phenylazo or naphthylthiourea, in which the hydroxy-group is adjacent to athropos associated with the benzene nucleus containing Deputy G or G', and is associated with the transition metal Me, forming a complex.

These different Chromogens are only illustrative of the present invention and do not limit the possibility of using other chromophore systems (Chromogens) dye for manufacturing the polarizer on the basis of colored and oriented JW moisture has a polarizer, in which at least one dichroic dye forms at least one covalent bond with the macromolecule polymer substrate. The most preferred is the polarizer, in which the active group of the dye, forming a covalent bond with the polymer, is at the end of the dye molecules. As an active group can serve as chlorine or ftoroproizvodnykh triazine or pyrimidine, vinylsulfonate, the remainder of ortho-phosphoric acid (Procion T), etc.

The dyes in the form (III-VI) can be also used for the manufacture of polarizers in combination with inorganic salts dichroic dyes.

For transfer of the dye into one of the following forms (III-VI) can be used several well-known methods.

One of the classic ways is consistent stepwise neutralization of dilute solutions of the corresponding carboxylic, phosphonic or sulfonic acids dichroic anionic dyes with different bases, which can be used metal hydroxide, aliphatic or heterocyclic amines or hydroxides Tetra-substituted ammonium cations:

{Chromogen} (HO-H+H+)n+m+nM+OH--->(H+-OX-)m{ Chromogen} (-XO-M+)n+nH2O; (H+-OH)m{Chromogen} (HO-M+)n+mm1+HE--->(M1+-OH)m{Chromogen} (HO-M+)n+mn2ABOUT

Used acid dyes pre-cleaned of mineral salts, for example, is washed with hydrochloric acid, followed by drying at 100oC.

Another method to obtain is heated solutions of ammonium salts dichroic anionic dye with a calculated amount of the appropriate base at a temperature above 60oWith in which the released ammonia is removed and the corresponding salt is formed:

{Chromogen} (HO-NH4+)n+Nm+HE--->{Chromogen}(-XO-M+)n+nNH3+nH2O

In the case of lack of Foundation is formed corresponding mixed salt, which as one of the cation is ammonium. Can be also used regular exchange reactions of cations using ion exchange resin or membrane technologies.

The third is more universal method suitable for the floor of the personal ions using the methods of membrane technologies (processes dia - and ultrafiltration, reverse osmosis), which allow to carry out simultaneously and cleaning solutions dichroic dyes:

(M1+-OH)m{Chromogen} (HO-Na+)n+nM+X--->(M1+-OH)m{Chromogen} (HO-M+)n+nNa+X-< / BR>
To obtain associates dichroic dyes containing ionogenic groups, or mixtures thereof with at least one mol of surface-active ions or mixtures thereof can also be used similar methods.

One way is to neutralize the diluted solutions of the corresponding acid forms dichroic anionic dyes with aliphatic or heterocyclic amines or hydroxides Tetra-substituted ammonium cations containing as one of the Vice hydrocarbon radical with 8 to 18 carbon atoms. Used acid dyes pre-cleaned of mineral salts, for example, is washed with hydrochloric acid, followed by drying at 100oC.

Another method to obtain is heated solutions of ammonium salts dichroic anionic dye with the appropriate surface-active foundations is at. Can be also used regular exchange reactions of cations using ion exchange resin or membrane technologies.

The third method, suitable for receiving the associates of any of dichroic dyes containing ionogenic groups, or mixtures thereof with at least one mol of surface-active ions or mixtures thereof, consists in the exchange of different ions on the surface-active ions. The exchange can be carried out using methods of membrane technologies, which allow to carry out simultaneously and cleaning solutions associates dichroic dyes containing ionogenic groups, or mixtures thereof with at least one mol of surface-active ions or mixtures thereof from extraneous inorganic and organic impurities. Introduction to the solution during membrane cleaning various types of comicsone, such as trylon B or "crown ethers", allows you to get rid of multivalent cations (CA, Mg, si, Al, and others), which can also be a cause of the formation of particulate matter and sediment.

For the manufacture of the claimed polarizer can be used in aqueous, aqueous-organic or organic solution of the corresponding dye (III-VI), which additionally is obuvki from a number of amides, for example dimethylformamide, alkylamide phosphoric acid, urea and its N-substituted derivatives, N-alkylpyridine, dicyandiamide, and mixtures thereof and mixtures of amides with glycols.

If necessary when dyeing in the composition of the dye bath can be entered inorganic salts, which allow you to adjust the speed and choosing the dye polymer.

One of the ways to obtain polarizers based on asymmetric salts of dyes (IV) is a polymer treatment after dyeing with a solution of chloride of barium, calcium or magnesium. When this is obtained, for example, a polarizer containing a dye in the form (IV), where M+represents a cation of lithium, sodium, potassium, ammonium, ethanolamine, alkylamine, a M1+- barium, calcium or magnesium.

The dye concentration in the dye bath is not critical and, depending on the requirements of the optical density of the polarizers may be in the range of from 0.01 to 15%.

Temperature dyeing also is not critical, and depending on the dye, the dyeing is carried out at 20-80oC.

As the polymer can be used based polymer, providing such polymers can serve as polyvinyl alcohol, polyamide, cellulose acetates, Homo - and copolymers of vinyl alcohol or vinyl acetate, where as co monomer may be ethylene, propylene, acrylic, and/or CROTONALDEHYDE, and/or maleic and/or methacrylic acid and/or their esters, etc.

The above options do not limit the possibility of using other polymer materials for the manufacture of the proposed polarizer.

The polymer can either be previously subjected to tensile and dyed by conventional methods [3], or the polymer dye in the mass, and then subjected to stretching in 6-10 times (see, for example, by the method described in [2]).

To improve the optical properties of the polarizer polymer after dyeing may be subjected to processing, such as in the case of [2] or [3], boric acid. The conditions depend on the type of polymer and dye, and usually spend it in an aqueous solution of boric acid concentration of 1-15% at a temperature of 30-80oC.

The obtained dyed and stretched polymer film or plate, if necessary, protect by laminating the well-known methods (see , for example [3]) using polymer films, which can be used polyamide, polyeste polarizer based on what non-polarized light when passing through the layer is partially absorbed by the chromophore system of the dye. Thus passes only the light waves in which the direction of vibration of the electric component of the electromagnetic field perpendicular to the dipole moment of the optical transition (see drawing).

Should be noted that depending on the Chromogen used dye the claimed polarizer capable of polarization not only in the visible part of the spectrum, but in the UV and near IR region.

The use of fluorescent dye allows you to get a polarizer for enhanced brightness, color saturation and contrast of liquid crystal indicators and displays.

Depending on the nature of the counterion and the location ionogenic group in the molecule of the dye according to the present invention can be obtained polarizers or positive type (dipole moment of the optical transition is located along the long axis of the polymer chain) or negative type, when the dipole optical transition moment perpendicular to the long axis of the polymer chain.

Polarizado Rasa as cation ethoxylated long monoethanolamine, which is associated with one molecule of dye perpendicular to the dipole moment of the optical transition and significantly superior to the long axis of the dye molecules. When dyeing salt molecule of dye (III-IV) will be placed in such a way that the cation is oriented along the polymer chain, whereas a molecule of the dye, and consequently, the dipole moment of the optical transition is perpendicular to the axis of the macroscopic orientation. That is implemented by the polarizer negative type, having compared with positive polarizer improved angular features that allows you to create liquid-crystal displays and displays with wide viewing angles and lack of shadows.

The variation of the hydrophobic-hydrophilic balance in the molecule dichroic dye by means of the form (III-VI) allows you to adjust the dyeing process, in particular, ensures uniformity of dyeing of the polymer, especially when using a mixture of dyes having different affinity for the polymeric material. The uniformity of color in turn leads to improved optical parameters of the polarizer.

The use of different counterions in the proposed forms of (III-VI) krcool dye and which is one of the causes scattering of light in the polarizer, which leads to deterioration of the polarization parameters. The aggregation processes can also serve the cause of poor orientation of the dye molecules with respect to the direction of extrusion of the polymer, which reduces the order parameter and thus dichroic ratio and the polarization efficiency of the polarizer.

The use of dyes in the present form (III-VI) allows you to adjust the aggregation and in some cases almost completely suppress it, which greatly improves the orientation of dye molecules relative to the polymer chains and thus improves the optical parameters.

The table below shows examples that show that the claimed polarizers have higher polarization characteristics, in particular a higher dichroic ratio in comparison with the known polarizers.

In addition, tests showed that the optical parameters of the proposed polarizers are not changed in a long time (over 500 hours) under conditions of 90% humidity at 90oC.

Thus, as can be seen from the table, the use of dichroic dyes in at least one of the above forms (III-VI) can improve the polarization Hara is aristor, comprising a polymer film or plate, coloured dichroic dye, wherein the at least one dichroic dye is an organic salt of a dichroic anionic dye of General formula

{Chromogen} (HO-Mo+)n,

where the Chromogen - chromophore system of a dye selected from the group comprising the chromophore system of azo, azoxy-, azomethine, stilinovich, polycyclic or metal complex dyes:

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where Me is a metal of transition group copper, Nickel, zinc, iron;

Y=O, NH; T=O, COO; J=AG, Saag;

G, G' represents hydrogen, halogen, C1-4alkyl, C1-4alkoxy, sulfo, hydroxy or amino which may be unsubstituted or substituted;

AG is unsubstituted or substituted phenyl, naphthyl or heteroaryl;

Q is a single bond, O, S, NH, CH2, CONH, SO2, NH-CO-NH, CH=CH, N=N, CH= N;

O'-NH, NH-CO-NH;

And represents-CN, -CF3, -NH2, -OTHER, -NRR', -CONH2, -CONHR, -COOH, -halogen, -OH, -OR, OCOR, RCONH-, -CONRR', -COOR, Ar, where R, R' represent alkyl, cycloalkyl, aryl or aralkyl, which is alseny phenyl, nattily, heterocyclic radical, the remainder acetoacetanilide, the rest of the phenol or aniline, 1 - or 2-naphthol, 1 - or 2-naphtylamine, which may be unsubstituted or substituted and may not contain or may contain additional unsubstituted or substituted, phenylazo or naphthylthiourea; in the case of metal complex dye In,' represent the balance of 1 - or 2-naphthol, which may be unsubstituted or substituted and may not contain or may contain additional unsubstituted or substituted, phenylazo or naphthylthiourea, in which the hydroxy-group is adjacent to the azo group, associated with the benzene nucleus containing Deputy G or G', and is associated with perehodnik metal Me, forming a complex;

X=CO, SO2, OSO2, ORO(O-M+);

n=1-7;

Mo+= represents a heteroaromatic cation N-alkylpyridine, N-alkylquinoline, N-alkylimidazole, N-alkylthiophene or organic cation HE-(CH2-CH2O)m-CH2CH2-NH3+when m=1-9, RR-NH2+, RR'R"NH+, RR'R"R*N+, RR'R"R*P+when R, R', R", R* = alkyl or substituted alkyl CH3, l2H4WITH2H5WITH3H7WITH4Y)k-CH2CH2, Y=O or NH, k=0-10;

and/or unbalanced mixed salt dichroic anionic dye with different cations of the General formula:

(M1+O-X'-)m{Chromogen} (HO-M+)n,

where X, X', SO2, OSO2, PO(O-M+);

n=1-9, m=1-9;

M+M1+M+, M1+=H+, Mo+or Mn+where the Chromogen and Mo+have the above values, Mn+is an inorganic cation NH4+Li+, Na+, K+Cs+, 1/MD++, 1/s++, 1/2Ba++, 1/3F+++, 1/2Ni++, 1/2Co++;

and/or associate dichroic anionic dye with a surface-active cation and/or amphoteric surface-active substance of General formula

(M+O-X')m{Chromogen}(HO-SURFACTANT)n,

where n=1-4, m=0-9; M+=N+, Mo+, Mn+or surfactant, where the Chromogen, Mo+and Mn+have the above values, the surfactant is a surface-active cationic or amphoteric surfactant;

and/or organic and/or mixed salt dichroic anionnogo>(HO-M+)nq,

where L= (CH2)6WITH6H4WITH6H3G6H3G6H3G-Q-C6H3G when G=H, Hal, HE, NH2, Alk and Q=O, S, NH, CH2, CONH, SO2, NH-CO-NH, CH=CH, N=N, CH=N;

for organic salts M+=M1+=Mo:n+m=1-9; q=10-50;

for mixed salt M+M1+M+, M1+=N+, Mo+, Mn+or surfactants; n=1-9, m=1-9; q=10-50, where the Chromogen, X, Mo+, Mn+, Surfactants have the above values,

when this ionic groups listed dyes-X OM1+; -XO-M+can be linked directly to the aromatic nucleus or through the bridge-Z-(CH2)p- where Z=SO2NH, SO2, CONH, CO, O, S, NH, CH2; p=1-10.

2. The polarizer under item 1, characterized in that at least one dichroic dye forms at least one covalent bond with the macromolecule polymer.

3. The polarizer under item 2, characterized in that the active group of the dye, forming a covalent bond with the polymer, is at the end of the molecules of the dichroic dye.

 

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