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Optical polarizer
Optical polarizer
IPC classes for russian patent Optical polarizer (RU 2140097):
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(57) Abstract:

The invention relates to optics, and in particular to optical polarizers. The technical result of the present invention is improved polarization characteristics, in particular the increase dichroic relations polarizers in comparison with the known polarizers based dyes capable of forming a stable lyotropic liquid crystal phase, as well as expanding the range of dyes suitable for the manufacture of high-performance optical polarizers. The inventive when manufacturing optical polarizer as at least one polarizing coating is anisotropic absorbing birefringent layer formed from mixed salts dichroic anionic dyes containing various cations. As the dichroic dye of the inventive optical polarizer may contain dyes selected from the class of azo dyes antrahinonovye, polycyclic, indigoids and other , related, in turn, to the category of direct, active, acid, metal complex, etc., 14 C.p. f-crystals, 2 ill., table 1.

The invention relates to optics, and in particular to optical is the number of laminated automotive industry, construction and architecture. In addition, the inventive optical polarizers can also be used in the manufacture of liquid crystal displays and indicators.

Polarizers light, which converts natural light into polarized, are one of the essential elements of modern display devices liquid crystal (LCD), control systems and light blocking.

Currently used polarizers are oriented uniaxially stretching a polymer film dyed with organic dyes or compounds of iodine. As the polymer used mainly polyvinyl alcohol (PVA) [1].

Polarizers based on PVA, stained with iodine, have a high polarization characteristics and are widely used in the production of liquid crystal indicators for screens, clocks, calculators, personal computers, etc.

At the same time, the high cost and low temperature resistance polarizers based on PVA is not used in the production of goods of mass consumption, in particular in the manufacture of laminated glass and film for the automotive industry, polarizator, which is a substrate coated with a molecular oriented layer of dichroic material, capable of forming a nematic phase [2].

To obtain a polarizing light dichroic film material is applied as a true solution of the impervious surface of the substrate, which is pre-attached to the anisotropy due to mechanical rubbing by using different materials (leather, paper, fabric and other). During subsequent partial evaporation of the solvent solution of dichroic material passes through the nematic phase liquid crystal state, during which, under the influence of the anisotropy of the surface occurs orientation of the molecules of the dichroic material. During the evaporation of residual solvent under controlled conditions to prevent misorientation on the surface of the substrate is formed of molecular-based polarizing film consisting of parallel spaced and oriented in the same direction of the molecules of the dichroic substance, which were used dichroic dyes [2].

A similar type optical polarizer [3] represents a polarizing plate, which is made with what uskoi.

Optical polarizers [2] or [3] has a higher thermostability compared to the polarizer on the basis of polyvinyl alcohol, because the molecular oriented film of the dye has a high thermal stability and can be formed on such resistant materials, such as glass.

The disadvantages of optical polarizers [2] or [3] should be attributed primarily to insufficient polarizing ability and low contrast, as well as the need for preliminary orientation of the substrate due to repeated rubbing whose implementation on an industrial scale presents significant complications.

The closest in technical essence is the optical polarizer, which is a substrate with a deposited thin film of ordered molecular layer of the dyes, which are sulfonic acids or inorganic salts of azo - and polycyclic compounds or mixtures thereof of General formula (I): {Chromogen} (SO3M)nwhere:
The Chromogen - chromophore system of the dye;
- M-H+Li+, Na+, K+Cs+, NH4+;
which are capable of forming a stable lyotropic zhidkokristal their basis [4].

For the manufacture of known optical polarizer [4] on the surface of the substrate is applied AGV dye with simultaneous mechanical orientation with subsequent evaporation of the solvent. While on the surface of the substrate is formed a thin film of ordered molecular layer of the dye - polarizing coating (PP), is able to polarize the light.

Optical polarizer [4] has along with the high heat and light resistance higher polarization efficiency compared with optical polarizers [2] or [3], as a way of orientation, based on the mechanical ordering AGV is a more efficient way to create a molecular arrangement of the dye in a nematic liquid-crystalline state, compared with the effect of surface anisotropy.

The main disadvantage of polarizer [4] is still relatively low polarization efficiency (dichroic ratio), which is insufficient for use of polarizers for manufacturing liquid crystal devices " LCD high resolution. One reason for this is the heterogeneity of the properties in the area, caused by thickness variation of PP, and that is acesse removal of the solvent after application AGV-based dyes (1) on the surface of the substrate.

The present invention is to improve polarization characteristics, in particular dichroic relations polarizers in comparison with the known based dyes capable of forming a stable lyotropic liquid crystal phase, as well as expanding the range of dyes suitable for the manufacture of high-performance optical polarizers.

The problem is solved through the use in the manufacture of optical polarizer as at least one polarizing coating anisotropic absorbing birefringent layer formed from mixed salts dichroic anionic dyes containing various cations of General formula (II):
(M1+O-X')m[M1+- O-X'IS-(CH2)p-Z-]g{Chromogen} [-Z-(CH2)p-XO-M+]f- (-XO-M+)n,
where the Chromogen - chromophore system of the dye;
- Z = SO2NH, SO2, CONH, CO, O, S, NH, CH2;
p = 1-10;
f = 0-9; g= 0-9;
n = 0-9, m = 0-9,
n + f = 1-0; m + g = 1-10;
X,X'= CO, SO2, OSO2, PO(O-M+);
M M1, M, M1= H; inorganic cation type NH4, Li, Na, K, Cs, Mg, Ca, Ba, Fe, Ni, keel or substituted alkyl, type CH3, ClC2H4, HOC2H4C2H5C3H7C4H9; C6H5CH2substituted phenyl or heteroaryl, YH-(CH2-CH2Y)k-CH2CH2-, Y = 0 or NH, k = 0-10; heteroaromatic cation type N-alkylpyridine, N-alkylquinoline, N-alkylimidazole, N-alkylthiophene and so on; or mixtures thereof.

As the dye of the inventive optical polarizer may contain dyes selected from the class of azo dyes, antrahinonovye, polycyclic (VAT), indigoids and other, related, in turn, to the category of direct, active, acid, metal complex, etc.

At least one dichroic anionic dye can be selected from a number:
- dyes capable of forming a stable lyotropic liquid crystal phase, for example sulphonic acids derived indanthrene, sulphonic acids derived symmetric definitionid and bibenzimidazole naphthalene-1,4,5,8-, perylene - and antention-3,4,9,10-tetracosanoic acids, direct yellow lightfastness O [4], etc.;
direct dyes, for example, benzopurpurin 4B (C. I. 448), C. I. direct orange 26, C. I. direct red 48 or 51, C. I. direct violet 88, C. I. direct blue 19 and DS.I. active yellow 1, C. I. active blue 4, and others;
acid dyes, such as various derivatives bromamines acid, acid bright red antrahinonovye NS, bright blue antrahinonovye, acid green antrahinonovye NS, acid green antrahinonovye NG, C. I. acid red 138, C. I. acid yellow 135, C. I. acid red 87, C. I. acid black 1, and others;
- from a number of sulfonic acids polycyclic dyes such as asymmetric of phenylimino and benzimidazole naphthalene-1,4,5,8-, perylene - and antention-3,4,9,10-tetracosanoic acids, disulfonate derivatives of Indigo, thioindigo or chinagreen [5] and other sulfonic acids on the basis of VAT dyes and pigments;
- fluorescent dyes.

Thus, the claimed optical polarizer is a substrate coated with at least one polarizing coating (PP) formed from mixed salts dichroic anionic dyes containing different cations, which can provide a polarization not only in the visible part of the spectrum, but in the UV and near IR region. In the case of dichroic dyes with absorption only in the UV region, PP can be used is plausi layer, in which the plane of the chromophore systems of molecules of the dichroic dye and behind them the dipole moments of the optical transition of uniformly oriented relative to the direction which is set or surface anisotropy, or the direction of the mechanical orientation, or under the influence of electrostatic, magnetic or electromagnetic fields.

The essential difference of the present invention is that the optical polarizer contains as at least one polarizing coating anisotropic absorbing birefringent layer formed from mixed salts dichroic anionic dyes containing various cations.

Unlike dyes, used for the manufacture of the known polarizer [4], the use of mixed salts allows you to adjust the hydrophobic-hydrophilic balance in the molecule dichroic anionic dye, which is of great importance for the formation of lyotropic liquid crystal (AGV) phase. Thus, the creation of a specific hydrophobic-hydrophilic balance is one of the conditions of formation of these dye molecules supramolecular aggregates, when reaching a certain concentration which solution the OSC-hydrophobic balance is observed when using as one of the cations of organic ion. Due to this it is possible to obtain a stable lyotropic liquid crystal phase and for solutions of dyes which in the form of a symmetric salts or acid incapable of forming AGV phase.

In addition to the impact on the hydrophilic-hydrophobic balance the nature of the cation has a strong influence on the solubility of the dichroic anionic dye in different solvents, which, in turn, undoubtedly affects the size of the aggregates and the formation of AGV phase.

Thus, the variation of the two factors - hydrophilic-hydrophobic balance and solubility and the solubility of the mixed salts dichroic anionic dyes containing various cations allows you to adjust how the process of education and type AGV phase. This, in turn, depends on the degree of molecular order and, consequently, the polarization characteristics of PP, formed after application AGV composition on the surface of the substrate with the subsequent removal of solvent.

These features allow you to:
first, to significantly expand the number of dyes that can be used for the manufacture of optical polarizers based polarizing coatings,
in which the polarizers in comparison with the known dye-based colours, capable of forming a stable lyotropic liquid crystal phase.

To ensure the necessary physico-mechanical, adhesion, alignment, and other film-forming properties of the at least one polarizing coating optical polarizer may further comprise a modifier, which can be hydrophilic and/or hydrophobic polymers of various types, including liquid crystal, silicone; plasticizers and varnishes, including silicon, and nonionic surfactants. The introduction of the modifier, which can be carried out both at the stage of education AGV. phase, and by processing the obtained PP, can also reduce the scattering of light, which is possible due to the presence of microdefects in polarizing coating.

The principle of the proposed optical polarizer based on the fact that non-polarized light when passing through PP partly absorbed by the chromophore system of the dye. Through PP passes only the light waves in which the direction of vibration of the electric component of the electromagnetic field is perpendicular to the dipole moment of the optical power is alaudio layer formed from mixed salts dichroic anionic dye, containing different cations, allows to obtain an optical polarizer:
in which at least one polarizing coating consists of several fragments of arbitrary shape, which can vary the color and direction of the polarization vector;
- which is multilayered and contains at least two inflicted on each other polarizing coatings, each of which consists of several pieces of arbitrary shape, which can vary the color and direction of the polarization vector, the color and the direction of the polarization vector of the different layers may not be the same;
- which is between the polarizing coating further comprises layers of transparent colorless or colored materials;
- which is between the substrate and the polarizing coating further comprises orienting layer that can be formed from inorganic materials, and on the basis of various polymers;
- which is between the substrate and at least one polarizing coating further comprises a diffuse reflective layer, which can serve simultaneously as a conductive layer;
which the substrate contains birefringent the LCD.

The use of mixed salts dichroic anionic dyes containing various cations to form a polarizing coating in the manufacture of the inventive optical polarizer allow you to use as well as for a known polarizer [4], the standard equipment for applying various coatings, such as installing the paint and coatings industry, and printing various types of equipment, including installation for flexographic printing.

Using cream salt dichroic anionic dyes containing various cations may be made of optical polarizers, which is a substrate coated with PP, consisting of several fragments of arbitrary shape, which can vary the color and direction of the polarization vector. That is, the polarization direction can be changed arbitrarily on the surface of the substrate, which allows you to get so polarized images with different polarization direction of each fragment.

For the manufacture of such optical polarizers can be used the following method: with printing (flexo, screen, high or deep) on the PP with a uniform direction in the varnish unprotected layer PP washed with a suitable solvent (water or a mixture of water with an organic solvent). Then the substrate is again applied PP, which can vary the color and direction of the polarization vector from the fixed layer of lacquer PP. Then again put a layer of varnish, the required form, which leaves unprotected the previous figure. After curing, followed by washing with a solvent receive a polarizing figure in which the parts are different and the color and direction of the polarization vector.

Using different ways Multiroll printing can be multi-color polarizing figures by using the roll-to-roll".

Use instead of varnish, various adhesives allows to produce optical polarizer in the form of a self-adhesive polarizing films, as well as when applying a layer of glue on the PP in the form of a drawing and then migrate to receive optical polarizer on any surface that can be used in the production of LCD indicators with external polarizers, for different types of trademark protection, or to obtain various color effects, for example in advertising. In the manufacture of optical polarizer adhesive technologies is possible and the method of reverse transfer: applying a layer of glue necessary forms noeau surface will be removed layer PP, suitable only form the adhesive layer.

The use of mixed salts dichroic anionic dyes containing different cations, lets implement technology layering PP. Thus, there can be obtained optical polarizers consisting of several inflicted on each other paragraphs, each of which consists of several pieces of arbitrary shape, which can vary the color and direction of the polarization vector.

Subsequent paragraphs of the same dye or another can be applied directly to the preceding paragraphs or intermediate layer of a transparent material, which may be either colorless or colored. When the direction of the polarization vector of the next paragraphs can vary arbitrarily with respect to the direction of the axes of polarization of the preceding paragraphs.

Thus can be obtained an optical polarizer, which between paragraphs may further comprise layers of transparent colorless or colored materials.

When you rotate the plane of polarized light in an optical polarizer may occur enlightenment of some areas and staining other (in the case of monochromatic optical field is the sing of different dyes during the rotation of plane polarized light will be either the disappearance of coloured drawing (in the case when sections of different colors have the same direction of the polarization vector), or the gradual disappearance of areas of different colors, different direction of the polarization vector. In the case of multi-layered PP and especially with an intermediate transparent colored materials the number of options increases.

The above examples of optical polarizers are of interest when creating special color effects (advertising, show business), for the protection of trademarks and securities types of securities, etc.

For the formation of PP using concentrated solutions of mixed salts dichroic anionic dyes containing different cations, can also be used in the methods used to obtain polymer films, for example, cast extrusion, watering etc.

When the formation of the PP as an additional orienting effects can be used magnetic, electromagnetic and electrostatic fields, which can be used in cases where the application time is not limited, or for the manufacture of DPS are dilute solutions of organic salts dichroic anionic dye method [2].

The choice spot or cylindrical, transparent or reflective surface organic or inorganic glass, a silicate glass deposited semiconductor layer, the silicon wafer with a deposited layer of aluminum.

On the surface of the substrate before applying the PP can be formed orientation layer according to the technology used to apply orienting layers in the manufacture of liquid crystal cells [6].

Thus can be manufactured optical polarizer, which is between the substrate and the polarizing coating further comprises orienting layer, formed from inorganic materials, and on the basis of various polymers.

The surface of the substrate during formation of the PP can be also modified using a variety of substrates, including optically active, for example, diffuse reflective, birefringent or passedarray coatings. Thus obtained optical polarizer, characterized in that between the substrate and the polarizing coating additionally contains a diffuse reflecting layer, which can serve simultaneously as a conductive layer.

When using as a substrate of Chetvertaya, and applying the PP at 45oto the main optical axis of the substrate can be made circular polarizer (Fig.2, a and b - direction of ordinary and extraordinary rays, respectively, n is the direction of the polarization vector PP).

During the formation of PP using mixed salts dichroic anionic dyes containing various cations on polymer films (polyethylene terephthalate, polycarbonate, triacetylcellulose, other transparent film materials can be obtained optical polarizers in the form of a flexible polarizing films, including self-adhesive.

In the manufacture of the inventive optical polarizer based on mixed salts dichroic anionic dyes containing different cations, can also be used in various adhesives, including polyvinyl butyral, to obtain various kinds of laminated structures, such as laminated glass or laminated films, which is of interest for the automotive industry and architecture.

For the manufacture of the inventive optical polarizer can be used in aqueous, aqueous-organic or organic solutions of mixed salts dichroic anionic dyes containing rastvorov (for example, using evaporation or membrane ultrafiltration), or by dissolving dry unsymmetrical salts dichroic anionic dye in an appropriate solvent (water, mixtures of water with alcohols, bipolar aprotic solvents of the type DMF or DMSO, cellosolve, ethyl acetate and other miscible with water solvents) to the required concentration.

Depending on the method of formation of PP using dye solutions with a concentration of 1-30%.

When using method [2] on the pre-grated in the desired direction, the surface of the substrate it is advisable to apply more dilute solutions, whereas the formation of PP without pre-polishing substrate using mechanical orientation according to the method of [4] use more concentrated solutions of dyes, including forming a stable lyotropic liquid crystal phase.

As in the case of [4], mechanical ordering stable AGV compositions based on mixed salts dichroic anionic dyes containing different cations, can be carried out under the action of forces which cause deformation of the tension on the meniscus formed by disjoining Otto can be carried out simultaneously with the application of the AGV on the surface of the substrate.

Orientation AGV on the surface of the substrate under the action of shear forces can be applied AGV using a Spinneret or squeegee, the latter may be a knife or cylindrical type.

Solutions of mixed salts dichroic anionic dyes containing different cations, optionally may contain, in addition miscible with water and organic solvents, nonionic surfactants, binders, film forming agents, which can be used polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and its esters, polyacrylamide, polyethylene oxide and polyethylene glycols, polypropylenglycol and their copolymers, ethyl and oxypropylene esters of cellulose, sodium carboxymethyl cellulose, etc.

In addition, to improve the stability of solutions of mixed salts dichroic anionic dyes containing various cations may contain girotropnye supplements 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.

To obtain solutions of the mixed Sol is P CLASS="ptx2">

One way is in a sequential stepwise neutralization of dilute solutions of the corresponding acid forms dichroic anionic dyes with different bases, which can be used metal hydroxide, aliphatic or heterocyclic amines or hydroxides Tetra-substituted ammonium cations. 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 60oC, at which the released ammonia is emitted and formed corresponding mixed salt, which as one of the cation is ammonium. Can be also used regular exchange reactions of cations using ionoobmennyh resin or membrane technologies.

The third is a more General method, suitable for asymmetric salts dichroic dyes containing organic cations, is to exchange ions with the use of dichroic dyes.

As can be seen from the above table, the use of unsymmetrical salts dichroic anionic dye allows you not only to expand the range of dyes which can be used to produce optical polarizers based on polarizing coatings, but also significantly improve the polarization characteristics, in particular to increase the dichroic ratio in comparison with the known polarizers.

Sources of information
1. U.S. patent N 5007942, G 02 B 5/30, 1991.

2. U.S. patent N 2544659, 350-148, 11.03.51.

3. The Japan Patent N 1-183602 (A), G 02 In 5/30, 21.07.89.

4. Application PCT/W0 N 94/28073, C 09 B 31/147, 08.12.94.

5. Patent RF N 95117403, G 02 B 5/30, BI (1997).

6. Cognard J Molecular Crystalls and Liquid Crystalls. - 1, 1982.

1. Optical polarizer comprising a substrate and a deposited one or more polarizing coatings, characterized in that at least one polarizing coating is an anisotropic absorbing birefringent layer formed from mixed salts dichroic anionic dyes containing different cations, the General formula
(M1+O-X')m[M1+O-X'IS-(CH2)p-Z-]g{Chromogen}[-Z-(CH2
Z - SO2NH, SO2, CONH, CO, O, S, NH, CH2;
p = 1 - 10;
f = 0 - 9;
g = 0 - 9;
n = 0 to 9;
m = 0 - 9,
n + f = 1 - 10;
m + g = 1 to 10;
X, X' - CO, SO2, OSO2, PO(O-M+);
M M1, M, M1- H; inorganic cation type NH4, Li, Na, K, Cs, Mg, Ca, Ba, Fe, Ni, Co, etc., organic cation of the type RNH3, PR NH2; RR'R"NH; RR'R"R*N; RR'R"R*P, where R, R', R", R*is alkyl or substituted alkyl of the type CH3, ClC2H4, HOC2H4C2H5C3H7C4H9C6H5CH2substituted phenyl or heteroaryl, YH-(CH2-CH2Y)k-CH2CH2-, Y = 0 or NH, k = 0 - 10; heteroaromatic cation type N-alkylpyridine, N-alkylquinoline, N-alkylimidazole, N-alkylthiophene, etc. or mixtures thereof.

2. Optical polarizer under item 1, characterized in that at least one dichroic anionic dye selected from a number of dyes capable of forming lyotropic liquid crystal phase.

3. Optical polarizer under item 1, characterized in that at least one dichroic anionic dye selected from a number of dyes capable of forming a stable lyotropic liquid crystal phase.

selected from the class of direct dyes.

5. Optical polarizer under item 1, characterized in that at least one dichroic anionic dye selected from the class of active dyes.

6. Optical polarizer under item 1, characterized in that at least one dichroic anionic dye selected from the class of acid dyes.

7. Optical polarizer under item 1, characterized in that at least one dichroic anionic dye selected from a number of sulfonic acids polycyclic dyes.

8. Optical polarizer under item 1, characterized in that at least one dichroic anionic dye is fluorescent.

9. Optical polarizer under item 1, characterized in that at least one polarizing coating further comprises a modifier, which can be hydrophilic and/or hydrophobic polymers of various types, including LCD, silicones, plasticizers and varnishes, including silicon, and nonionic surfactants.

10. Optical polarizer under item 1, characterized in that at least one polarizing coating consists of several fragments of arbitrary shape, which can be different is, that is multilayered and contains at least two inflicted on each other polarizing coatings, each of which consists of several pieces of arbitrary shape, which can vary the color and direction of the polarization vector, the color and the direction of the polarization vector of the different layers may not be the same.

12. The optical polarizer according to p. 11, characterized in that between the polarizing coating further comprises layers of transparent colorless or colored materials.

13. Optical polarizer under item 1, characterized in that between the substrate and the polarizing coating further comprises orienting layer that can be formed from inorganic materials, and on the basis of various polymers.

14. Optical polarizer under item 1, characterized in that between the substrate and at least one polarizing coating further comprises a diffuse reflective layer, which can serve simultaneously as a conductive layer.

15. Optical polarizer under item 1, characterized in that the substrate contains a birefringent plate or film, and polarizing coating formed under the coal is

 

 
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