IMPROVED CHEMICAL COMPOUNDS THAT UNDERGO REVERSIBLE CHANGES IN PROPERTIES AND USES THEREOF

Abstract

Free radical scavengers, especially those that require the presence of oxygen, are useful in extending the life of photochromic, thermochromic, electrochromic, radiochromic, magnetochromic, photo-electrochromic and similar dyes. Particularly, preferred scavengers are the quinones be it O, M or p- and, most preferably, either the ortho, meta or para-hydroquinone. The so-enhanced dye can be used as a coating or cast as a film.

Claims

1. An extended useful life reversible dye comprising: (a) a dye selected from the group consisting of: photochromic, thermochromic, electrochromic, radiochromic, magnetochromic and photo-electrochromic dyes; and (b) an effective amount of a free radical scavenger.

2. The dye of claim 1 wherein the free radical scavenger is a quinone.

3. The dye of claim 2 wherein the quinone is selected from the group consisting of: ##STR00017##

4. The dye of claim 3 wherein, the quinone is hydroquinone.

5. The dye of claim 1 wherein the free radical scavenger is a quinone selected from the group consisting of: ##STR00018##

6. The dye of claim 1 wherein the scavenger is a hydroquinone.

7. The dye of claim 1 wherein, the quinone is present in an amount ranging from about 0.001 percent to about 200 percent based on the total weight of the mixture of dye and quinone.

8. The dye of claim 1 further comprising: (a) a solvent, the solvent being present in an amount ranging from about five percent to about fifty percent, by weight, based on the total weight of the composition.

9. A cast film comprising: the extended useful life dye of claim 1.

10. The dye of claim 1 wherein, the dye is an ink.

11. A method for extending the useful life of a reversible dye, comprising: admixing with a reversible dye an effective amount of a free radical scavenger.

12. The method of claim 11 wherein, the free radical scavenger is a quinone.

13. The method of claim 12 wherein, the quinone is selected from the group consisting of: ##STR00019##

14. The method of claim 13 wherein, the dye is selected from the group consisting of: photochromic, thermochromic, electrochromic, radiochromic, magnetochromic, and photo-electrochromic.

15. The method of claim 14 which further comprises: admixing the dye and quinone with a solvent and a polymer resin.

16. The method of claim 15 wherein the resin is polystyrene.

17. The method of claim 16 which further comprises: casting the admixture into a surface to form a film thereon.

Description

DESCRIPTION OF INVENTION

[0034] At the outset, it should be noted that as used herein, terms such as thermochromic, photochromic, electrochromic, radiochromic, magnetochromic photo-electrochromic and the like may be used interchangeably and refers to chemicals and, in particular, dyes which change physical properties in reaction to the environmental conditions to which they are exposed.

[0035] As noted above, the prior art teaches incorporation of UV blockers and absorbers increases photochromic dye life to extend the useful service life of the dyes up to a few months. By incorporating free radical scavenger(s), alone, or with other protective moieties, the useful service life of photochromic dyes, and other such chemical species as described above, can be significantly extended over the teachings of the prior art.

[0036] Further, and as noted above, the present invention is based on the discovery that that free radical scavengers, especially those that require the presence of oxygen, are useful in extending the life of photochromic, thermochromic, electrochromic, radiochromic, magnetochromic, photo-electrochromic and similar dyes. Particularly, free radical scavenging quinones have been found to be particularly effective because they not only scavenge free radicals, they, also, require the presence of oxygen to accomplish this. These moieties thus perform two functions that protect the dyes, to wit: [0037] (c) scavenge free radicals, and; [0038] (d) scavenge singlet oxygen, oxygen and OH groups that are suspected of damaging the dyes.

[0039] The quinones that can be used herein correspond to the formula:

##STR00002##

[0040] The quinone may be used either as a liquid or as a powder and is admixed with the dye at ambient conditions.

[0041] Among the useful quinones, the preferred quinone is a hydroquinone be it the ortho-, meta- or para-isomer. Each isomer exhibits utility in the practice of the present invention.

[0042] The quinones of the present invention may be used in connection with the following compounds which undergo dynamic reversible changes in structure and/or other properties, including, for example:

(a) triarylmethanes; (b) stilbenes; (c) bisimidazols; (d) spirodihydroindolizines; (e) azastilbenes; (f) nitrones; (g) benzos; (h) fulgides; (i) fulgimides; (j) spiropyrans, such as thiospyropyrans; (k) spiroxazines; (l) naphthopyrans; (m) quinones, such as phenoxynaphthacene quinone; (n) quinines; (o) indenopyrans; (p) perimidinespirocyclohexadienones; (q) viologens; (r) ideno-fused napthopyrans; (s) inorganic metal halides, such as, for example, silver chloride, zinc halides and the like; (t) coordination compounds such as, for example, sodium nitroprusside, ruthenium sulfoxide compounds, including ruthenium polypyridine; (u) diarylethenes; (v) hydrazines; (w) anils; (x) aryl thiosulfonates; (y) spiroperimindines and the like.

[0043] For example, among the dyes which may be used in conjunction with the free radical scavenger(s) hereof, are: benzyl viologen dichloride with molecular formula of (C.sub.20H.sub.22C.sub.12N.sub.2) and molecular structure of:

##STR00003##

[0044] 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3-[3H]naphth[2,1-b][1,4]oxazine] with molecular formula of (C.sub.22H.sub.20N2O) and molecular structure of:

##STR00004##

[0045] 1,3-dihydro-1,3,3-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2-(2H)-indole] with molecular formula of (C.sub.18H.sub.18N.sub.2O.sub.3) and molecular structure of:

##STR00005##

[0046] 1,1-diheptyl-4,4-bipyridinium dibromide with molecular formula of (C.sub.26H.sub.38Br.sub.2N.sub.2O.sub.2) and molecular structure of:

##STR00006##

[0047] 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3-[3H]naphth[2,1-b][1,4]oxazine] with molecular formula of (C.sub.21H.sub.38Br.sub.2NO.sub.2) and molecular structure of:

##STR00007##

[0048] 4,4-dipyridyl with molecular formula of (C.sub.10H.sub.18N.sub.2) and molecular structure of:

##STR00008##

[0049] Indoine blue dye with molecular formula of (C.sub.29H.sub.24ClN.sub.5O) and molecular structure of:

##STR00009##

[0050] Methyl viologen dichloride hydrate with molecular formula of (C.sub.12H.sub.14C.sub.12N.sub.2.xH.sub.2O) and molecular structure of:

##STR00010##

[0051] 2,3,3-trimethyl-1-propyl-3H-indolium iodide with molecular formula of (C.sub.14H.sub.20IN) and molecular structure of:

##STR00011##

[0052] The present invention may also be used with leuco dye(s). A leuco dye is a thermochrome coloring agent or ink which can acquire two different forms: a colorless form and a colored form. At warm temperatures, the thermochromic ink is colorless. At cold temperatures, the thermochromic ink takes on a different color, e.g., blue. The thermodynamically reversible interconversion is pushed to the blue form of the excited state when the ink cools below the color changing temperature.

[0053] Again, although not wishing to be bound by any theory, it is believed that the following mechanism is how the subject chemicals develop coloring: Typically, a molecule will absorb one wavelength of light better than other wavelengths, and this wavelength of maximum absorption is designated .sub.max. For example, lycopene is red because its .sub.max is in the blue region. It absorbs light in the blue region and reflects light in the red region and thus appears red. If the extended conjugated -electron system in the middle of the -bond system is disrupted, the extended -system would be severely shortened, and the molecule would, shift color or become colorless. For this reason the most widely used thermochromic inks contain an extended conjugated -system that is easily interrupted.

[0054] This is represented as follows:

##STR00012##

##STR00013##

##STR00014##

[0055] The present invention is also applicable to spiropyrans and spiroxazines. One of the oldest and, perhaps, the most studied families of photochromes are the spiropyrans. Very closely related to these are the spiroxazines. For example, the spiro form of an oxazine is a colorless leuco dye; the conjugated system of the oxazine and another aromatic part of the molecule is separated by a sp3-hybridized spiro carbon. After exposure to UV light, the bond between the spiro-carbon and the oxazine breaks, the ring opens, the spiro-carbon achieves sp2 hybridization, becomes planar, the aromatic group rotates, aligns its -orbitals with the rest of the molecule, and a conjugated system forms with ability to absorb wavelengths of visible light, and therefore appears colorful. When the UV source is removed, the molecules gradually return to their ground state, the carbon-oxygen bond reforms, the spiro-carbon becomes sp3 hybridized again, and the molecule returns to its colorless state.

[0056] This class of photochromes, in particular, are thermodynamically unstable in one form and revert to the stable form in the dark unless cooled to low temperatures. Their lifetime can also be affected by exposure to UV light. Like most organic dyes they are susceptible to degradation by oxygen and free radicals. Incorporation of the dyes into a polymer matrix or providing a barrier to oxygen and chemicals by other means prolongs their lifetime.

[0057] Still another class of useful dyes which are enhanced by the present invention are the diarylethenes. The diarylethenes, such as dithienylethenes, have gained widespread interest, largely on account of their high thermodynamic stability. They operate by means of a 6- electrocyclic reaction, the thermal analog of which is impossible due to steric hindrance.

[0058] Pure photochromic dyes usually have the appearance of a crystalline powder, and in order to achieve the color change, they usually have to be dissolved in a solvent or dispersed in a suitable matrix. However, some diarylethenes have so little shape change upon isomerization that they can be converted while remaining in crystalline form.

##STR00015##

[0059] Azobenzenes may also be used in the practice hereof. The trans-cis isomerization of azobenzenes has been used extensively in molecular switches, often taking advantage of its shape change upon isomerization to produce a supramolecular result. In particular, azobenzenes incorporated into crown ethers give switchable receptors and azobenzenes in monolayers can provide light-controlled changes in surface properties.

##STR00016##

[0060] The forces responsible for the spatial organization may vary from weak (intermolecular forces, electrostatic or hydrogen bonding) to strong (covalent bonding), provided that the degree of electronic coupling between the molecular component remains small with respect to relevant energy parameters of the component. While traditional chemistry focuses on the covalent bond, supramolecular chemistry examines the weaker and reversible, non-covalent interactions between molecules. These forces include hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, - interactions and electrostatic effects. Important concepts that have been demonstrated by supramolecular chemistry include molecular self-assembly, folding, molecular recognition, host-guest chemistry, mechanically-interlocked molecular architectures, and dynamic covalent chemistry.

[0061] As noted above, quinones are capable of being enhanced by the practice of the present invention. Some quinones, and phenoxynaphthacene quinone in particular, have photochromacity resulting from the ability of the phenyl group to migrate from one oxygen atom to another. Quinones with good thermal stability also have the additional feature of redox activity, leading to the construction of many-state molecular switches that operate by a mixture of photonic and electronic stimuli.

[0062] The scavengers, and in particular the quinones hereof, can be used alone or in combination with other adjuvants, such as desiccants, oxygen scavengers, and the like including, for example: hydrazine; ascorbic acid; tocopherol; naringenin; n-aminomorpholine; 1-amino-4-methylpiperazinen-aminohexamethylleneimine; 1-aminopyrrolodine; 1-aminopiperidine and the like as well as mixtures thereof. Similarly, mixtures of quinones may be used.

[0063] In cases of highly complex mixtures of chemical species that are detrimental to the dyes, equally complex mixtures of scavengers/stabilizers, desiccants and other adjuvants may be needed to overcome those detrimental species that limit the dye service life.

[0064] Generally, the quinone is used in amounts ranging from about 0.0001 percent to about 200 percent or greater of the total weight of the dye itself; and preferably from about 0.0025 percent to about 100 percent, by weight, based on the total weight of the dye. The concentration, complexion and complexity of scavengers/stabilizers, desiccants and such other adjuvants is dependent upon the type of aggression in processing the dyes, i.e., solvent drawdown versus thermal extrusion. This is due to the fact that different processing methods present conditions that damage certain stabilizers and compensations must me made to overcome components that are rendered inert from processing.

[0065] Where used with other adjuvants, the scavengers are present in a weight ratio of scavenger to adjuvant of from about 1:10 to about 10:1.

[0066] The improved dyes hereof can be deployed as either a liquid, pellets or as a powder for use as a coating or cast as a film. Typically, however, a dye formulation is prepared by admixing the dye, per se, with the scavenger(s), at room temperature.

[0067] In use, the dye(s) are solubilized in a suitable organic solvent such as, for example, toluene, methyl ethyl ketone, ethyl acetate, hexane, heptane, xylenes, tetrahydrofuran, acetone or the like with stirring until a homogeneous liquid mixture or liquid composition is obtained. It should be noted that dependent upon the selected dye and its solubility it may be necessary to solubilize the scavenger and any adjuvants in a second solvent batch and then mix the two together. Regardless of which way the dye and scavenger mixture is obtained, i.e., a single or double batch, the resulting mixture can then be cast as a film or incorporated into a coating composition or the like.

[0068] Ordinarily, the solvent will comprise about 1 percent to about 75 by weight, of the liquid composition, and preferably from about 5 percent to about 50 percent, by weight of the total liquid composition.

[0069] The dye composition may be admixed, at room temperature, with a polymer resin. When used with a polymer resin, the amount of the dye composition, i.e., dye, scavenger(s), solvent and resin, will vary depending on the desired density of the dye, i.e., the degree of desired darkness as well as the thickness of any film or extrusion which incorporates the dye composition.

[0070] Although many polymer resins may be used, among those useful polymer resins is, for example, polystyrene, polycarbonate, polypropylene, polyurethane, polyuria, polyethylene and the like. Mixtures of resins may be used.

[0071] Preferred resins are polystyrene and polycarbonate.

[0072] Ordinarily, the polymer resin will comprise from about one percent to about sixty-five percent, by weight, of the entire dye composition and usually from about five percent to about fifty percent, by weight, of the dye composition.

[0073] The improved photochromic, thermochromic and electrochromic dye compositions hereof have many commercial uses, including, as noted above, sunglasses, glass/window tint such as automotive grade window tinting films, and other films, coatings, extrusions, co-extrusions, blow molding slugs as well as specified performance grades of materials, e.g., military, optical, automotive, medical, etc.; for bottles and other plastic packaging and containers; as well as in printing and textile inks; paints and other coatings; bulk plastics, such as plastic toys and other structural, laminating and decorative plastics. These improved dye systems can be cast as thin films for use as window tints, as well. When cast as a film, the plastic resin may be directly admixed or coated with the dye(s), scavenger(s) and solvent(s).

[0074] As is known, molecular switches can be used to impart functionality, e.g., turning on and off molecules, such as activating enzymes (and other molecular species) and deactivating them on command. The present invention may be used to increase the switch life of molecular switches, which ordinarily exhibit a short useful service life, to make them commercially viable.

[0075] Other uses for the extended life photochromic dyes hereof include, for example, in positionally-controlled diamond mechanosynthesis and in conjunction with diamondoid medical nanorobots. Other uses include for example, nanofactory, suparmolecular chemistry, data storage, molecular robotics, biochips, DNA machines and the like.

[0076] For a more complete understanding of the present invention, reference is made to the following illustrative example. In the example all parts are by weight absent indications to the contrary.

Example

[0077] This example illustrates the preparation of a cast film in accordance with the present invention: At room temperature and into a suitable container is added 7.0 parts of polystyrene along with 6.0 parts of xylene. Contemporaneously, 0.04 parts of parabenzophenone and 0.06 parts of 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3-[3H]naphth[2,1-b][1,4]oxazine] is added thereto. The mixture is stirred until a homogeneous liquid is obtained. Thereafter the mixture is cast on to a glass substrate and drawn to a thin film and let to stand until the solvent evaporates. The so-obtained film easily separates from the glass and may then be used as desired.

[0078] From the above it is to be readily appreciated that the present invention provides both means and methods for extending the useful service life of the reversible property dyes described herein.