KR100255249B1 - Light-polarizing material based on ethylenediamine polyacetic acid derivatives - Google Patents

Abstract

It relates to the use of such materials in polarizers and liquid suspensions, coagulation suspensions and light valves.

Description

Polarizer based on ethylenediamine polyacetic acid derivative

The present invention relates to polarizers, coagulation suspensions and fluid suspensions thereof, and light valves containing such fluid suspensions. In particular, the present invention relates to an organic polarizer derived from an organic compound having no nitrogen heteroatom, which is a characteristic of a known organic polarizer.

Polarizers, such as colloidal suspensions of hepatite and hepatite polarized crystals, have been published (U.S. Patents 1,951,644 (Land), 2,178,996 (Land)). US Pat. No. 2,237,567 (Land) discloses the production of plate-shaped polarizers by applying iodine and iodide solutions to polyvinyl alcohol plates pre-stretched to orient molecules. There are several patents relating to polarizers and coagulation suspensions thereof, and laminated products and uses derived therefrom (US Patent Nos. 2,041,138 (Land), 2,078,254 (Land), 2,168,220 (Land), 2,168,221 (Land), 2,185,018 (Sauer) ), 2,230,262 (Pollack), 2,246,087 (Bailey et al), 2,256,108 (Blake), 2,263,249 (Rogers), 2,306,108 (Land et al), 2,328,219 (Land), 2,375,963 (Thomas)), British Patent No. 433,455 We report the use of leo cobalt-chloridesulphateperi odide particles for polarizer formation. See other prior art and patents.

Significant applications of the entangled solidification suspension of polarizers, now referred to as "plate polarizers", are lenses for polarized sunglass, components of twisted nematic liquid crystal displays, and various filters, including contrast enhancing filters used in light emitting displays. However, it is known that the plate-shaped polarizers used are easily decomposed due to high heat, ultraviolet radiation or moisture.

Polarized fluid suspensions have been used in light valves comprising batteries containing microfluidic fluid suspensions that can be oriented by electric or magnetic fields to change the light transmission through the suspension. (US Patent Nos. 3,708,219 (Forlini et al), 3,743,382 (Rosenberg), 4,078,856 (Thompson et al), 4,113,362 (Saxe et al), 4,164,365 (Saxe), 4,407,565 (Saxe), 4,422,963 (Thompson et al)).

U.S. Patent 4,131,334 (Witte et al) discloses a process for preparing polarized particles by hydrogenating a nitrogen-containing organic compound and then reacting with an appropriate acid to form a salt. The salt is then reacted with iodine and inorganic iodide to produce stable polyiodide particles.

It is an object of the present invention to provide a polarizing material having high stability against ultraviolet radiation, elevated temperature and high humidity.

Polyhalogenates, including polyiodide, have been introduced for some time. Polyiodes are complexes of iodine atoms with inorganic or organic matrices. Godina et al. Studied polyiodide and other polyhalides in detail (J. Gen, Chem. USSR, 20, (1950), pages 1005-1016). Among the known polyiodes are herapatite, which is a polarizing crystalline substance produced by the reaction of quinine bisulfate, iodine and HI. The quinine alkaloid family of salts also reacts with iodine and HI to form polarizable polyiodes such as cyanide bisulfate. In these materials there is elemental iodine is combined with the acid addition salt of the alkaloid in the form of polyiodide anion, the anion is I ₃ by Godina ^- was presented in (JACS, 100 (1978) pages 3215-3217) - I 5 by, Teitelbaum . Godina et al. Demonstrated that polyyorod anions can be produced by the reaction between iodine and HI.

Similarly, the I5 _- polyiodine anion is formed next.

Godina et al. Explain that polarizable polyiodide is a cation such as an acid addition salt of polyiode anion and quinine. However, polyiodes can be formed without cations such as starch-iodine complexes and elongated or oriented polyvinyl alcohol-iodine complexes. Teitelbaum et starch-iodine complex, and this includes an iodine adsorption with iodine in the form of SARS-amylase component of starch, the chain I is mainly ^_5-announced consists of polyiodide anions. Godina et al. Theorized that the hepatite, starch-iodine and oriented PVA-iodine complexes are ″ adsorbed polyiodide ″ in the form of molecular iodine adsorbed in layers in the polyiodide chain.

The polarizer of the present invention is a complex having no nitrogen hetero atom, which is a characteristic of the organic polarizer of the prior art. This complex is obtained by reacting (i) elemental iodine, (ii) halide or ammonium or alkali or alkaline earth metal halides and (iii) ethylenediamine derivatives of the following formula (I). This complex contains adsorbed molecular iodine. When the HI or iodide is used, such as Godina as Teitelbaum is the complex also I _X as a poly iodide published formed by reaction between (i) original compact iodine and (ii) ^{iodide-polyiodide} anion (x 3 Or 5). Moreover, Godina et al. Showed that crystals containing adsorbed molecular polyiode anions are polarizable.

In the following examples, polarizers can be prepared by reacting compound (I) with iodine and iodide, bromide or chloride. In this case, each anion can be represented as follows by modeling the structure described by Teitelbaum et al.

Gdoina et al. Reported that polarizable complexes containing adsorbed molecular iodine cannot be defined stoichiometrically by structural formula. Therefore, the polarizing material of the present invention is defined in the form of a process-specific creature.

Compound (I) useful for preparing the polarizing paper of the present invention is a compound represented by the following general formula:

Where R ¹ and R ² are hydrogen or lower alkyl, R ³ is hydrogen or —CH ₂ COOR ⁴ , R ⁴ is hydrogen or M / n, where M is an alkali or alkaline earth metal and n is the valence of M .

When R ¹ or R ² is lower alkyl, it is a straight or branched chain alkyl such as methyl, ethyl, propyl, isopropyl, butyl isobutyl, t-butyl. Lower alkyl usually has 1 to 6 carbon atoms, in particular I to 4 carbon atoms.

The compound (I) itself is known and may be an isomer, analog or homolog of the known compound, and is preferably similar to the known compound.

Free acid form of compound (I), ie ethylenediamine tetraacetic acid, ethylenediamine diacetic acid, 1,2-diaminopropyl tetraacetic acid (ie R ¹ is methyl R ² is hydrogen, each R ³ is -CH ₂ COOH) Etc., since the solubility in water is limited, the compound (I) may be used in the form of a water-soluble alkali metal or alkaline earth metal salt, or a water-soluble salt may be formed in situ during the formation of the polarizing material. Useful compounds (I) include ethylenediamine tetraacid or its disodium, dipotassium, tetrasodium, tetrapotassium or disodium magnesium salt, ethylenediamine diacetic acid or its 1,2 sodium or 1,2 potassium salt, 1, 2-diaminopropyl tetraacetic acid and its disodium, dipotassium, tetrasodium, and tetrapotassium salts.

The polarizing material of the present invention is prepared by compounding the compound of formula (I) in half with an iodine element and a hydrofluoric acid or ammonium, alkali metal or alkaline earth metal halide in a suitable solvent such as water. (US Patent nos. 1,951,661; 2,176,516 and 2,289,712). Halides are usually iodides, but can also be foams or chlorides. The reaction to form the polyhalide is carried out in the presence of protective colloids such as nitrocellulose or copolymers disclosed in US Pat. No. 4,164,365. It is preferable to provide compound (I) in the first solution and a mixture of iodine and ammonium or an alkali or alkaline earth metal halide in the second solution, but the halide may be added to both solutions or one if necessary. The solution is then mixed to form polyhalide easily even at room temperature. Thereafter, the polarizing polyhalide crystal is recovered by a suitable technique, particularly by filtration.

Until now, organic polarizers have been described as organic precursors having nitrogen heteroatom-containing heterocycles such as quinine bisulfate, bisulfate dihydrocinconidine, quinalic anhydride, and Western compounds disclosed in US Pat. No. 4,877,313. Prepared by reaction with Surprisingly, the present invention provides organic polarizers obtained from precursor compound (I) which do not contain nitrogen heteroatoms.

The polyhalide particles are suspended in a liquid suspending medium for use in a light valve. As is known, the liquid suspending medium can be any electrically resistive liquid as long as the particles are suspended and the polymeric stabilizer is dissolved. Liquid suspension media having a relatively high electrical resistance and low vapor pressure and which do not decompose or attack suspension particles or other components are preferred (see US Pat. No. 4,270,841, 4,407,565).

For use in coagulation suspensions, polyhalide particles are dispersed or distributed in plates formed of suitable film-forming materials such as cellulose acetate or polyvinyl alcohol (see US Pat. No. 2,178,996, 2,041,138).

Example 1-3

2 g of sodium ethylenediamine tetraacetic acid is dissolved in 5 g of water and the solution is again mixed with 5 g of an aqueous solution of 0.8 g of iodine and 1 g of calcium iodide. Blue polarizable crystals are easily formed. Similar results may be obtained using ethylenediamine tetraacetic acid dipotassium and disodium magnesium using the same method instead of ethenediamine tetraacetic acid disodium.

Example 4-5

0.5 g of ethylenediamine diacetic acid is dissolved in 5 g of 2% aqueous sodium hydroxide solution and the solution is mixed again with 5 g of aqueous solution of 0.8 g of iodine and 1 g of calcium iodide. Similar results can be obtained by using the same method for 1,2-diaminopropyl tetraacetic acid instead of ethylenediamine diacetic acid.

Comparative Example 6-12

In Comparative Example 6-12, the following compound 6-12 was used.

6-1,6-hexanediaminetetraacetic acid

7-nitrilotriacetic acid

8-ethylene (oxyethylenenitrilo) tetraacetic acid (EGTA)

9-methyliminothiacetic acid

10-imino diacetic acid

11-10- (2-hydroxyethyl) ethylenediamine triacetic acid

12-N- (2-hydroxyethyl) ethylenediamine triacetic acid

0.5 g of compound (6) is dissolved in 5 g of 2% aqueous sodium hydroxide solution, and the solution is again mixed with 5 g of aqueous solution in which iodide and calcium iodide are dissolved in the same amount, and the procedure is carried out according to the method in Example 4-5. No polarizing crystals are formed. It can be seen that polarizing crystals do not occur even when using compounds 7-12 according to the same method instead of compound (6).

The failure to form polarizing crystals in Comparative Example 6 (using 1,6-hexanediamine tetraacetic acid) is in stark contrast to the previous results achieved using EDTA under similar reaction conditions. The large distance between nitrogen atoms is the only difference that can cause failure in Examples 6 and 8.

The failure to make polarized crystals in Comparative Examples 7,9, 10 and 12 is because this compound contains only one nitrogen atom. In the case of having two nitrogen atoms separated by two or less carbon atoms, it is essential to form polarizable crystals.

All of the compounds (I) used in the present invention form metal salts or metal-chelated compounds as shown below. R ⁴ is calcium.

Therefore, when explaining the formation of the polarizing material of the present invention, when the compound (I) reacts with iodine and halide, halogen ions and iodine participate in the reaction in the form of ions. For example, if the halide of calcium iodide (CaI2) iodine is Ca ²⁺ (I _{X) 2} ^{- anion-participate} in the reaction and as a calcium ion is positively charged chelated and by the compound (I) (I _X) It binds to the calcium cations to form foriodide crystals. This description is reasonable but the present application is not bound to this theory.

The liquid suspension of the polyhalogenide particles of the present invention is similar to the process for preparing the liquid suspension of dihydrocinconidine sulfate polyiodide as described in Example 2 of US Pat. No. 4,131,334 and Example 1 of US Pat. No. 4,407,565, Compound (I) of the present invention may be used instead of hydrocinconidine sulphate and the amount of reactants may be readily prepared by adjusting the values given in the previous examples.

Example 13

A. Preparation of Ethylenediamine Tetraacetic Acid Polypotassium Dipotassium-Nitro Cellulose Complex.

Solution A is made by dissolving 3 g of ethanol diamine tetraacetic acid dipotassium in a mixed solvent of 15 g of 5 g of water and 100 g of 2-ethoxyethanol.

Solution B is a 33-1 / 3% nitrocellulose solution dissolved in 2-ethoxyethanol. Nitrocellulose is mixed viscosity (18-25 cps and 15-20 seconds).

Solution C is made by mixing solution A with 22 g of solution B.

Solution D is prepared by dissolving 48 g of calcium iodide hexahydrate in 10 g of 2 ethoxyethanol, adding 1.4 g of I ₂ and 20 g of tricresylphosphate (TCP) and shaking for 10 minutes.

Solution C is mixed with Solution D vigorously in a Waring mixer and stirred with a polyethylene spatula. After stirring for 2 minutes, the wet paste is spread over an 8 mm thick glass plate and dried overnight. The polarizing crystal is formed when the paste is dried.

B. Preparation of Liquid Suspensions

The dry paste is scraped off, dispersed in 150 g of isopentyl acetate (IPA) and shaken well to allow the paste to form a liquid suspension. The suspension is ultrasonically stirred for 10 hours and again centrifuged at 11,000 PPM for 1 hour. The precipitate is resuspended in IPA and an effective amount of a suitable polymer solution is added to a 10-15 g solution of 15.75% / 3.25% neopentyl acrylate / methylol acrylamide copolymer dissolved in neopentyl neopentano. do. This new suspension is placed in a vacuum for 5 hours to evaporate almost all IPA. Other solvents that do not have very high boiling points are also evaporated. The suspension is then diluted to the desired degree with other solvents such as halocarbon oil type 0.8 / 100 (Halocarbon Products, Hackensack, New Jersey) and neopentyl neopentanoate to achieve the desired off-state light density and response time. Additional polymers may be added.

The above-mentioned liquid suspensions can be used in light valves utilizing AC electric fields to orient particles in the suspension to change or control the permeability of light passing through the suspension. Such light valves can be used, for example, in various submission windows, filters, mirrors or glasses and also in electronic alphanumeric and graphic image display devices.

However, changing the composition of the suspension can produce what is known as a coagulant suspension rather than a fluid suspension or liquid suspension that can be used in the light valve. The coagulation suspension of the particles of the invention is a polarizing polarizing plate or film in which these particles are included in combination with other materials.

There are many known techniques for producing polarizing plates and films. For example, U. S. Patent No. 2,178, 996 discloses a needle axis of polarized crystals dispersed by forming polarizing particles and mixing the particles into a dispersion medium containing cellulose acetate or by flowing, extruding, stretching or rolling the particle dispersion. The thin plate-shaped polarizers are oriented in parallel directions and are formed. In US Pat. No. 2,041,138, a polarizer is prepared in the form of a plate or film comprising a suspending medium and sprayed microparticles. If necessary, the polarizer itself may be permanently or detachably fixed to a glass tube or a transparent support such as a celluloid plate or a glass plate. This support is necessary if the polarizer itself requires protection. It also discloses the use of asymmetric particles, the flow of the medium comprising the particles, and the solidification or curing of the medium to keep the particles in the oriented position.

U. S. Patent No. 2,168, 220 also discloses information relating to commercially available polarizing materials under the trademark ″ Polaroid ″. Laminate formation methods and the use of plasticizers and adhesives also disclose various laminates.

Various types of polarizing films and urethros as polarizers are disclosed in US Pat. No. 2,246,087, which can be used in windshields, windows, glasses, goggles, sunglasses, camera lenses, microscopes, mirrors and stereoscopic cinemas.

A process for transferring a polarizing film from one support to another and the materials used are disclosed in US Pat. No. 2,256,108. Information obtained from the aforementioned patents and other patents can be used to produce polarizing coagulated suspensions, films and plates containing parallel oriented particles, polarizers and various products.

However, many commercially available polarizers do not include films or plates in which solid particles are oriented in parallel but rather have an optical axis in the plane of the plate and transmit only polyvinyl alcohol polyiodide which does not absorb light oscillating perpendicularly to the optical axis. Using plates (see US Patents 2,237,567 and 2,375,963). It is known that the polarizer which is commonly used for a long time in bad environmental conditions such as high temperature, high humidity and ultraviolet radiation tends to be degraded.

In terms of environmental degradation, despite the problems of commercially available plate-shaped polarizers, a number of individual mentions have been made of reacting polymer-stretched polymer plates with dyes or colorants or with iodine and iodide to form polarizing complexes. It is better than using a polarization crystal. Useful embodiments of the invention also include compounds in which each molecule is attached to a polymerizable unsaturated group as a compound of the invention.

However, polarizers made from the particle coagulation suspension of the present invention and other materials are stable to high heat and ultraviolet radiation and have excellent water resistance. Accordingly, the present invention can greatly improve the quality of polarizers and products in which such materials are mixed.

While specific embodiments of the invention have been described, many modifications are possible without departing from the spirit and scope of the invention.

Claims (12)

Adsorption iodine-containing polarizing materials, including complexes obtained by reacting iodine with hydrogen halide or ammonium or alkali or alkaline earth metal halides and also with compounds of the general formula (I): Where R ¹ and R ² are hydrogen or lower alkyl, R ³ is hydrogen or —CH ₂ COOR ⁴ , and each R ⁴ is hydrogen or M / n, where M is an alkali or alkaline earth metal and n is the valence of M to be. The polarizing material of claim 1, wherein the halogen ions or the halogen ions of ammonium, an alkali metal or an alkaline earth metal halide are chlorine ions, bromine ions or iodine ions. The compound of formula (I) is ethylenediamine tetraacetic acid or disodium, tetrasodium, tetrapotassium or disodium magnesium salt, ethylenediamine diacetic acid or its 1,2 sodium or 1,2 potassium salt. Or 1,2-diaminopropyl tetraacetic acid disodium, dipotassium, tetrasodium or tetrapotassium salt thereof. Electrically resistive liquid suspension, adsorption iodine-containing non-axial polarized light containing a complex obtained by reacting the iodine element of claim 1 with a hydrogen halide or an ammonium or alkali metal or alkaline earth metal halide and a compound of formula (I) A liquid suspension for a light valve composed of particles and a dispersant dispersing the particles: 5. A liquid suspension according to claim 4, wherein the halogen halide or halogen ions of ammonium, alkali metal or alkaline earth metal halides are chlorine, bromine or iodine ions. The compound according to claim 4, wherein the compound of general formula (I) is ethylenediamine tetraacetic acid or disodium, dipotassium, tetrasodium, tetracarium, or disodium magnesium salt, ethylenediamine diacetic acid or its 1, disodium or 1 And dicarium salts or 1,2-diaminopropyl tetraacetic acid or disodium, dipotassium, tetrasodium or tetrapotassium salts thereof. A polarizer comprising the polarizing material particles according to claim 1 dispersed in a carrier, wherein the polarization axes of the particles are oriented in equilibrium and are kept immovably parallel by the carrier. 8. The polarizer according to claim 7, wherein the halogen ions or the halogen ions of the ammonium, alkali metal or alkaline earth metal halide are chlorine ions, bromine ions or iodine ions. 8. A compound according to claim 7, wherein the compound of formula (I) is ethylenediamine tetraacetic acid or disodium, dipotassium, tetrasodium, tetrapotassium, or disodium magnesium salt, ethylenediamine diacetic acid or 1,2 sodium thereof, or A 1,2 potassium salt or 1,2-diaminopropyl tetraacetic acid or its sodium, dipotassium, tetrasodium, or tetrapotassium salt, The polarizing body characterized by the above-mentioned. An optical valve comprising a cell containing a suspension of polarizing particles in a liquid suspending medium, wherein the polarizing factor is the polarizing material particle of claim 1. 11. The light valve according to claim 10, wherein the halogen ions or the halogen ions of the ammonium or the alkali or alkaline earth metal halides are chlorine, bromine or iodine ions. The compound according to claim 10, wherein the compound of general formula (I) is ethylenediamine tetraacetic acid or disodium, dipotassium, tetrasodium, tetrapotassium or disodium magnesium salt, ethylenediamine diacetic acid or its 1,2sodium or 1, A light valve comprising a dipotassium salt or 1,2-diaminopropyl tetraacetic acid or a disodium, dipotassium, tetrasodium or tetrapotassium salt thereof.