CA2056854A1 - Photochromic naphthacenequinones, their preparation and the use thereof - Google Patents
Photochromic naphthacenequinones, their preparation and the use thereofInfo
- Publication number
- CA2056854A1 CA2056854A1 CA002056854A CA2056854A CA2056854A1 CA 2056854 A1 CA2056854 A1 CA 2056854A1 CA 002056854 A CA002056854 A CA 002056854A CA 2056854 A CA2056854 A CA 2056854A CA 2056854 A1 CA2056854 A1 CA 2056854A1
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- Prior art keywords
- formula
- compound
- substituents
- dione
- unsubstituted
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/30—Quinones containing groups having oxygen atoms singly bound to carbon atoms with polycyclic non-condensed quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/36—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/24—Quinones containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
- C09B3/58—Benzanthraquinones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
Abstract
Photochromic naphthacenequinones, their preparation and the use thereof Abstract of the Disclosure Compounds of formula I or V or mixtures thereof
Description
2~S8S~
Photochromic nap}-thacenequinones, process for their preparation and the use thereof The present inven~ion Ielates to naphthacene-6,11- and naphthacene-5,12-diones which are substituted in positions 5,12 and 6,11 by aryloxy groups, and in positions 2, 3, 8 and/or 9 by at least one phenoxy group or at least one fluorine, chlorine or bromine atom, to corresponding 5,12- and 6,11-dichloronaphthacenediones, to a process for their preparation and to the use thereof as photochromic systems for contrast formation, light absorption or for recording information.
In Zhurnal Organicheskoi Khimii, Vol. 7, No. 11, pp. 2413-2415 (1971), Yu. E.
Gerasimenko et al. describe 6-phenoxynaphthacene-5,12-dione as a reversible photochromic compound which, when subjected to irradiation with light, forms the orange 5-phenoxynaphthacene-6,12-dione (anaquinone). In Zhurnal Organicheskoi Khimii, Vol.
16, No. 9, pp. 1938-1945 (1980),Yu. E. Gerasimenko et al. describe 6,11-diphenoxynaphthacene-5,12-dione, whose photoisomerisation is used for synthesising 6-amino derivatives of 12-phenoxynaphthacene-5,1 l-dione.
In one of its aspects, the present inYention relates to compounds of formula I, or mixtures thereof, OR O
;~3 ~ ~ 2 OR o wherein R is unsubstituted C~j-CI4aryl or C6-Cl4aryl which is substituted by Cl-CI2alkyl, Cl-CI2aLIcoxy, Cl-CI2alkylthiol, phenyl, benzyl, -CN, -CF3, halogen or -COORs, and R5 is H, Cl-C18alkyl, cyclohexyl, cyclopentyl, phenyl, C1-Cl2alkylphenyl, benzyl or C1-CI2al-kylbenzyl, and at least one of the substituents Rl to R4 is -F, -Cl or -Br, or is 2C~;~8S4 independently the group RO-, and the other subslituents Rl to R4 are -H, -F, -Cl or -Br.
R in formula I is preferably unsubstituted or substituted C6-C~ yl such as phenyl, or 1-or 2-naphthyl. Preferably R is unsubstitued or substituted phenyl.
The group R may be substituted by one or more, preferably by 1 to 3, substituents. If R is substituted by aL~cyl, alkoxy or alkylthiol, these radicals may be linear or branched and preferably contain 1 to 6, most preferably 1 to 4, carbon atoms. Exemplary of such radicals are methyl, ethyl, the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the corresponding aLkoxy and alkylthio radicals. Preferred radicals are metbyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl, methoxy9 etnoxy, methylthio and ethylthio.
If R is substituted by halogen, preferred halogens are bromo, chloro and fluoro.
Rs as alkyl may be linear or branched. Further examples of the aLkyl radicals mentioned above are the isomers of tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Rs as aLkyl preferably contains 1 to 12, most preferably 1 to 6, carbon atoms.
Rs as aLkylphenyl is preferably Cl-C6aLkylphenyl, most preferably Cl-C4alky]phenyl, for example dodecylphenyl, octylphenyl, hexylphenyl, n-, iso- or tert-butylphenyl, n- or iso-propylphenyl, ethylphenyl or methylphenyl. R5 as alkylbenzyl is preferably Cl-C6alkylbenzyl, most preferably Cl-C4aLkylbenzyl, for example dodecylbenzyl, octylbenzyl, hexylbenzyl, n-, iso- or tert-butylphenyl, n- or isopropylbenzyl, ethylbenzyl or methylbenzyl. Rs is preferably H or Cl-Cl8aLkyl, most preferably Cl-CI2alkyl.
In a preferred embodiment of the invention, R in formula I is unsubstituted or substituted by Cl-C4alkyl, Cl-C4alkoxy, C~-C4alkylthio, -F, -Cl, -Br or -COORs, and Rs is H or Cl-CI8aLI~yl.
In a particularly preferred embodiment of the invention, R in formula I is -COO(CI-C6)alkyl which is unsubstituted or substituted by -Cl or -Br.
Another preferred embodiment of the invention relates to those compounds of formula I, wherein at least one of the substituents Rl to R4 is a group RO- or -F, -Cl or -Br, and the other substituents Rl to R4 are -H.
In yet a further preferred embodiment of the invention, Rl or R4, or Rl and R3 or R4, or R
Photochromic nap}-thacenequinones, process for their preparation and the use thereof The present inven~ion Ielates to naphthacene-6,11- and naphthacene-5,12-diones which are substituted in positions 5,12 and 6,11 by aryloxy groups, and in positions 2, 3, 8 and/or 9 by at least one phenoxy group or at least one fluorine, chlorine or bromine atom, to corresponding 5,12- and 6,11-dichloronaphthacenediones, to a process for their preparation and to the use thereof as photochromic systems for contrast formation, light absorption or for recording information.
In Zhurnal Organicheskoi Khimii, Vol. 7, No. 11, pp. 2413-2415 (1971), Yu. E.
Gerasimenko et al. describe 6-phenoxynaphthacene-5,12-dione as a reversible photochromic compound which, when subjected to irradiation with light, forms the orange 5-phenoxynaphthacene-6,12-dione (anaquinone). In Zhurnal Organicheskoi Khimii, Vol.
16, No. 9, pp. 1938-1945 (1980),Yu. E. Gerasimenko et al. describe 6,11-diphenoxynaphthacene-5,12-dione, whose photoisomerisation is used for synthesising 6-amino derivatives of 12-phenoxynaphthacene-5,1 l-dione.
In one of its aspects, the present inYention relates to compounds of formula I, or mixtures thereof, OR O
;~3 ~ ~ 2 OR o wherein R is unsubstituted C~j-CI4aryl or C6-Cl4aryl which is substituted by Cl-CI2alkyl, Cl-CI2aLIcoxy, Cl-CI2alkylthiol, phenyl, benzyl, -CN, -CF3, halogen or -COORs, and R5 is H, Cl-C18alkyl, cyclohexyl, cyclopentyl, phenyl, C1-Cl2alkylphenyl, benzyl or C1-CI2al-kylbenzyl, and at least one of the substituents Rl to R4 is -F, -Cl or -Br, or is 2C~;~8S4 independently the group RO-, and the other subslituents Rl to R4 are -H, -F, -Cl or -Br.
R in formula I is preferably unsubstituted or substituted C6-C~ yl such as phenyl, or 1-or 2-naphthyl. Preferably R is unsubstitued or substituted phenyl.
The group R may be substituted by one or more, preferably by 1 to 3, substituents. If R is substituted by aL~cyl, alkoxy or alkylthiol, these radicals may be linear or branched and preferably contain 1 to 6, most preferably 1 to 4, carbon atoms. Exemplary of such radicals are methyl, ethyl, the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the corresponding aLkoxy and alkylthio radicals. Preferred radicals are metbyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl, methoxy9 etnoxy, methylthio and ethylthio.
If R is substituted by halogen, preferred halogens are bromo, chloro and fluoro.
Rs as alkyl may be linear or branched. Further examples of the aLkyl radicals mentioned above are the isomers of tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Rs as aLkyl preferably contains 1 to 12, most preferably 1 to 6, carbon atoms.
Rs as aLkylphenyl is preferably Cl-C6aLkylphenyl, most preferably Cl-C4alky]phenyl, for example dodecylphenyl, octylphenyl, hexylphenyl, n-, iso- or tert-butylphenyl, n- or iso-propylphenyl, ethylphenyl or methylphenyl. R5 as alkylbenzyl is preferably Cl-C6alkylbenzyl, most preferably Cl-C4aLkylbenzyl, for example dodecylbenzyl, octylbenzyl, hexylbenzyl, n-, iso- or tert-butylphenyl, n- or isopropylbenzyl, ethylbenzyl or methylbenzyl. Rs is preferably H or Cl-Cl8aLkyl, most preferably Cl-CI2alkyl.
In a preferred embodiment of the invention, R in formula I is unsubstituted or substituted by Cl-C4alkyl, Cl-C4alkoxy, C~-C4alkylthio, -F, -Cl, -Br or -COORs, and Rs is H or Cl-CI8aLI~yl.
In a particularly preferred embodiment of the invention, R in formula I is -COO(CI-C6)alkyl which is unsubstituted or substituted by -Cl or -Br.
Another preferred embodiment of the invention relates to those compounds of formula I, wherein at least one of the substituents Rl to R4 is a group RO- or -F, -Cl or -Br, and the other substituents Rl to R4 are -H.
In yet a further preferred embodiment of the invention, Rl or R4, or Rl and R3 or R4, or R
- 3 2C`~çi85 and R2 or R1 to R4 are a group R~, -F, -Cl or -Br, most preferably a group RO- or Cl.
Preferred compounds of formula I are those wherein R is unsubstituted phenyl.
Particularly preferred compounds of formula I are 6,11-diphenoxy-2-chloronaph-thacene-5,12-dione, 2,6,11-triphenoxynaphthacene-5,12-dione, 6,11-diphenoxy-2,3,8,9-tetrachloronaphthacene-5, 12-dione and 2,3,6,8,9,1 1-hexaphenoxynaphthacene-5,12-dione.
In another of its aspects, the invention relates to a process for the preparation of compounds of formula I, which comprises reacting 1 mol of a compound of formula Il cî o J, ~XX
Cl O
wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or -Br, in the presence of a polar aprotic solvent and at elevated temperature, with at least 2 mol of a compound of formula RoeM~3, wherein R is as previously defined and M is an alkali metal or tertiary ammonium containing 3 to 1~ carbon atoms.
Surprisingly, it has been found that both chlorine atoms can be substituted regioselectively by phenoxy groups even if the naphthacene ring system contains further halogen atoms.
The process of the invention is preferably carried out in the temperature range from 50 to 200C, most preferably from 50 to 150C. The salts of formula ROeM~ may be used as such or produced in 3itU in the reaction mixture by reac~ing a suitable phenol with an alkali metal base or an alkali metal carbonate. The salts can be used in equimolar amounts or in excess, for example in an excess of up to 40 mol%, if it is desired to effect substitution of all halogen atoms.
Typical examples of suitable solvents are N-substituted carboxarnides and lactams tsuch as dimethyl formamide or N-methylpyrrolidone), sulfoxides and sulfones (such as dimethyl sulfoxide, tetramethylene sulfone), or ethers (such as n-dipropyl ether, n-dibutyl ether~ tetrahydrofuran or dioxane).
The compounds of formula I can be isolated and purified by conventional methods, for example by crystallisation and ~crystallisation, or by chromatographic methods.
The compounds of fonnula RoeM~33 are known or obtainable in known manner by reacting suitable phenols with aL~ca}i metal bases, alkali metal carbonates or tertiary amines. They can also be produced in the reaction mixture in situ. Particularly suitable alkali metal cations are Li~, Na~3 and K~. Tertiary ammonium is typically trimethyl-ammonium, triethylammonium, ~i-n-propylammonium and tri-n-butylammonium.
The invention further relates to compounds of formula II
Cl O
~~r~ Xx (~
Cl O
wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or -Br. The preferred meanings of X are the same as those given for Rl to R4 defined as -H, -F, -Cl and -Br in the compounds of formula I.
The compounds of formula II are obtainable by the following process:
The reaction of the known compounds of formula III
~H.
O O
X ) ~ l~X (III), O~ ,0 `H ' 2~85~
wherein X is as defined in formula II7 with a chlorinating agent, typically POCl3, gives the compounds of formula IV which, when unsyrnmetrically substituted, are obtained as a mixture of position isomers of formulae IV and IVa:
cl o ~"_~ (IV), Cl O
x~ 1~ (IVa).
These mixtures can be used direct fior the preparation of compounds of formula II or separated beforehand, for example by chromatographic methods. The compounds of formula III are obtainable in a manner known per se for example, by reacting appropriately halogenated or non-halogenated phthalic anhydrides with appropriately halogenated or non-halogenated 1,4-dihydroxynaphthalene, in the presence of B203, at elevated temperature.
The compounds of forrnula I are crystalline, thermally stable and light-yellow to yellowish-orange in colour. They are soluble in organic solvents. They are effective photoinitiators and photosensitisers for photopolymerisable systems which contain ethylenically unsaturated double bonds. Further, the compounds of formula I are reversibly photochromic compounds which, when irradiated, undergo a marked colour change from yellow to yellowish-orange to orange to red.
When the compounds of formula I are irradiated, alone or incorporated in a substrate, with Z~S85 light having a wavelength of ca. 300 to 450 nm, a pronounced change in colour towards orange to red is observed. In comparison with 6,11-diphenoxynaphthacene-5,12-dione, the light absoIption is displaced to a higher wavelength. The change in colour derives from the photochemical conversion of the paraquinones of this invention into the corresponding anaquinones of formula V. The rate of conversion is surprisingly high and, depending on the amount, thickness of the sample and irradiation intensity, can be less than 3 seconds.
The invention further relates to the anaquinones of formula V
O OR
3 ~ ~ ~ )~ ` Rz OR O
wherein R, Rl, R2, R3 and R4 are as previously defined, including the preferred meanings.
The compounds of formula V can be obtained, after irradiating solutions of the compounds of formula I, by removing the solvent, and, as required, purified by conventional methods.
The change in colour is reversible. Renewed irradiation with light having a wavelength of ca. 450 to 550 nm gives the original colour (reformation of the paraquinone structure). It is especially advantageous that this procedure can be repeated several times. The stability of the photochemical conversion of paraquinones to anaquinones and the reverse reaction to paraquinones is surprisingly high and the fatigue even in air or in substrates is correspondingly low. Thus virtually no changes are observed in more than 200 cycles. It is also advantageous that the light absorption necessary for the photochemical conversion lies in the range of the wavelength of commercially available lasers.
The invention funher relates to the use of compounds of formula I or V, or mixtures thereof, as reversible photochrornic structures for contrast formation or light absorption.
The compounds of formula I can be used as photoinitiators and, preferably, as photosensitisers in photopolymerisible systems, in which case they act simultaneously as 2C`5S85 colour indicators. Thus it is possible to mark irradiated products (for example protective layers, prindng plates, offsct printing plates, printed circuits, solder masks) and to distinguish them from non-irradiated products and, in product control, to sort out imperfectly irradiated products before or after development.
The major advantage in using the compounds of formula I as colour indicators lies in the increase of the sensitiser action. Components normally used as colour change systems generally effect a diminution of the photosensitivity.
The compounds of forrnula I or V can also be used by themselves, in solution or incorporated in polymers, as photochemically modifiable colour indicators or as photochemically modifiable circuit components.
The compounds of formula I can also be used in organic or inorganic glass as photochemically modifiable colour filters, for example in glass for sunglasses, contact lenses, windows and mirrors.
I he invention further relates to a radiation-sensitive composition compAsing a) a radiation-sensitive organic material, and b) at least one compound of formula I or V or a mixture thereof.
The compounds of formulae I and V or mixtures thereof may be present in an amount of 0.001 to 20 % by weight, preferably 0.001 to 10 % by weight and, most preferably, 0.01 to 5 % by weight, based on component a~.
Radiation-sensitive and hence also photostructurable materials are known. They may be positive or negative systems. Such materials are described, for example, by E. Green et al.
in J. Macromol. Sci.; Revs. Macromol. and Chem., C21(2), 187-273 (1981 to 1982) and by G.A. Delzenne in Adv. Photochem., 11, S. 1-103 (1979).
The radiation-sensitive organic material is preferably al) a non-volatile monomeric, oligomeric or polymeric substrate containing photopolymerisable or photodimerisable ethylenically unsaturated groups, a2) a cationically curable system, or a3) photocrosslinkable polyirnides.
Photopolymerisable substances are typically acrylates and, preferably, methacrylates of 2Q~;S85 polyols, for example ethylene glycol, propanediol, butanediol, hexanediol, bis(hydroxy-methyl)cyclohexane, polyoxyaLkylenediols such as di-, tri- or tetraethylene glycol, di- or tri-1,2-propylene glycol, trimethylolmethane, trimethylolethane or trimethylolpropane and pentaerythritol, which may be used by themselves, in mixtures and in admixture with binders.
Exemplary of photodimerisable substances are homo- and copolymers which contain cinnamic acid groups or substituted maleimidyl compounds in side groups or chalcone groups in the polymer chain.
Preferred compositions are those wherein component al) is a homo- or copolymer of acrylates, methacrylates or maleates whose ester groups contain a radical of formula ~C-- \
ll N A
R~ --C
wherein A is linear or branched unsubstituted or hydroxyl-substituted C2-CI2alkylene, cyclohexylene or phenylene, and R7 and R8 are each independently of the other chloro or bromo, phenyl or Cl-C4alkyl, or R7 and Rg, when taken together, are t imethylene, (CH2)2--tetramethylene or ~ .
Such polymers are disclosed, for exarnple, in US patent specification 4 193 927.
The photopolymeAsable or photodimerisable substances can contain further additives customarily used for processing or application, as well as other photoinitiators or photosensitisers .
The cationically curable systems are preferably epoxy compounds containing at least two epoxy groups in the molecule and in which a photoinitiator is incorporated. Suitable photoinitiators are typically cyclopentadienylarene metal salts, cyclopentadienyl metal carbonyl salts and onium salts which are described in the above mentioned publications.
The curable systems may contain additives customarily used for processing and application.
2~ 854 g Photosensitive polyimides are disclosed, for example, in DE-A-1 962 588, EP-A-0 132 221, EP-A- 0 134 752, EP-A-0 162 017, EP-A-0 181 37 and EP-A-0 182 745.
The composition of this invention is applied by known methods as layer to substrates and either a protective layer is produced by iiTadiation over the surface, or a relief image is produced by irradiation through a photomask or by locally defined irradiation with a guided laser beam or by holographic methods and subsequent development.
~n another of its aspects, the invention relates to a composition comprising a) a colourless organic solvent, a polymer or an organic glass or a compound glass, and b) dissolved, incorporated therein or present as layer on at least one surface, a compound of formula I or V or a mixture thereof. Component b) is preferably present in an amount of 0.001 to 20 % by weight, preferably 0.001 to 10 % by weight and. most preferably, 0.01 to 5 % by weight, based on component a). ~rganic solutions can be used for coating other substances, for example solid substrates such as inorganic glasses which can then be used as photochernically modiflable substrates. The compounds of formula I can also be~
sublimed on to substrates. The coated substrates can be provided with a protective layer of, for example, transparent polymers. Solid substrates can also be coated with compositions which contain a polymer and at least one compound of formula I or V.
Suitable solvents are typically hydrocarbons, halogenated hydrocarbons, ketones,carboxylic acid esters and lactones, N~ cylated acid arnides and lactams, alkanols and ethers.
Exemplary of suitable polymers are thermoset plastics, thermoplastics and structurally crosslinked polymers. Ille polymers are preferably transparent. Such polymers and organic glasses are known to those skilled in the art. The incorporation of the compounds of the ;nvention is effected by known methods, for example by dissolving methods and removing the solvent, calendering or extrusion. The compounds of this invention can also be incorporated in the substrates before, during or after their synthesis.
The invention also relates to a process for the preparation of coloured materials under the influence of light, which comprises incorporating a compound of formula I or V in the material and then irradiating said material with light.
The invention further relates to the use of compounds of formula I as photosensitisers and 2~5S85~
colour indicators or photochemically modifiable colour ~llters under the influence of light.
In yet another of its aspects, the invention relates to the use of a compound of formula ~ or V for the reversible optical storage of information, which information is written with light, preferably laser light, into a memory-active layer containing said compound. The written information can be erased, preferably with laser light, thus affording the possibility of cyclic writing-in and erasing.
To produce a memory-active layer, the compound of formula I or V can be dissolved in a transparent matrix by methods desribed above and applied in a thin layer to a flat substrate. The thickness of the memory-active layer is ca. 0.1- 100 ~m, preferably 0.3-3 ~m.
The information can be written by scanned, holographic or photographic irradiation of the memory-active layer with spectral, preferably coherent, laser light in the wavelength range of 440-550 nm, preferably 480-530 nm.
Reading out can be effected with reduced irradiation intensity at the wavelength in which the information is written via the locally altered transmission, reflectance, refraction or fluorescence of the memory-active layer.
Erasure can be made by pin-point or spread irradiation of the memory-active layer containing the compounds of formula I and/or V in the wavelength range of 300-450 nm, preferably 300-420 nrn.
One advantage of the utility of this invention is that the wavelengths necessary for writing in, reading out and erasing are in the range of commercially available lasers (for example argon ion lasers: 488/514 nm and 351/363 nm; neodym-YAG lasers: 532 nm and 355 nm with frequency doubling and trebling; XeF excimer lasers: 351 nm; HeCd lasers: 325 and 442 nm).
A further advantage is the high contrast of absorption obtainable between the written and erased state in the range of 450-550 nm and the wide dynamic range associated therewith of the memory-active layer.
Another advantage is that the quantum yield when writing is fairly low, so that the danger 2C`~ 854 of overwridng when reading out is greatly diminished.
Conversely, it is also advantageous that the quantum yield when erasing is fairly high, thus making possible a rapid erasure over a large area.
Yet a further advantage is that, when reading out, the compound fluoresces and hence makes possible a highly sensitive detection of the memory status via the fluorescence. The fact that the energy pulsed in for reading out dissipates substantially via the fluorescence and not thermally also counteracts an undesirable heating of the memory-active layer.
Another advantage is the high photochemical stability of the compound and the great number of writing/erasing cycles thereby obtainable.
Finally, yet another advantage is the possibility of cyclic data refreshing by admixture of a suitable quantum of light of the erasure wavelength during reading out.
The invention is illustrated by the following Examples.
A) Preparation of the startin~ com~ounds Example A1: 2,3,6,8,9,11-Hexachloronaphthacene-5,12-dione.
30 g (70 mmol) of 2,3,8,9-tetrachloro-6,1 1-dihydroxynaphthacene-5,12-dione, 60 ml of POCl3 and 500 ml of o-dichlorobenzene are stirred for 90 hours under reflux. Excess POCI3 is distilled off, together with the o-chlorobenzene, until the reaction volume is still about 300 ml. The precipitate is isolated by filtration from the cooled reaction mixture, washed repeatedly with water and aqueous sodium carbonate solution and dried. The dry product is stirred in cyclohexane, isolated by filtration and then dried, giving a yield of 28.6 g (88 %), melting point (mp): >260C.
Examp e A2: 2-Fluoro- and 9-fluoro-6,1 1-dichloronaphthacene-5,12-dione (mixture of isomers).
3.0 g (9.73 mmol) of 2- and 9-fluoro-6,1 1-dihydroxynaphthacene-5,12-dione (mixture of position isomers), 4 ml of POCI3 and 30 ml of o-dichlorobenzene are stirred for 10 hours under reflux. The reaction mixture is poured into water and neutralised with 2 N aqueous NaOH. The precipitate is isolated by filtration, washed with water, dried, taken up in 400 ml of toluene. After addition of basic alurnina, the batch is filtered hot. The filtrate is ;~C'5~i~3 concentrated by evaporation, giving 1.57 g (47 %) of the product mixture. Mass spectrum:
344, 346, 348 and 350 (M+: base peak).
B~ Preparation of the inventive compounds Example B 1: 2,3,8,9-Tetrachloro-6,11 -diphenoxynaphthacene-5,12-dione.2.32 g (S mmol) of the compound of Example A 1, 1.41 g ( lS mmol) of phenol, 4.15 g (30 rnmol) of potassium carbonate and 100 ml of tetrahydrofuran are heated for 5 hours under reflux. The mixture is poured into water, with s~rring, and then filtered. The precipitate is washed flrst with water and then with methanoVwater, dried, and then recrystallised from o-dichlorobenzene, affording the title compound in a yield of 2.57 g (89 %) in the form of yellow crystals with a melting point of 326-329C. Mass spectrum 578/580/582 (M+: base peak).
When irradiated, a solution of the compound in toluene undergoes a reversible colour change from yellow to orange.
Example B2: 2,~,6,8,9,11-Hexaphenoxynaphthacene-5,12-dione.
l.S g (3.2 mmol) of compound Al, 2.43 g (25.8 mmol) of phenol, 4.45 g (32.3 g) of potassium carbonate and 120 ml of N-methylpyrrolidone are stirred for 8 hours at 150C.
The mixture is taken up in tetrahydrofuranJtoluene/2 N hydrochloric acid and the organic phase is separated, washed with water, dried over sodium sulfate and then concentrated by evaporation. The crude product is dissolved in toluene and chromatographed over silica gel, affording the title compound in a yield of 0.65 g (25 %) in the form of yellowish-orange crystals.
Mass spectrum: 810 (M+: base peak).
When irradiated, a solution of the compound in toluene undergoes a reversible colour change from yellowish-orange to red.
Example B3: Mixture of 2,6,11- and 6,9,11-triphenoxynaphthacene-5,12-dione.
0.5 g (1.45 mmol) of compound A2, 0.8 g (5.8 mrnol) of potassium carbonate, 0.48 g (5.07 mmol) of phenol and 5 ml of dimethyl sulfoxide are stirred for 4 hours at 100C. The reaction mixture is poured into dilute hydrochloric acid and extracted with tetrahydrofuran/toluene (1:1). The extracts are washed with saturated aqueous NaCl and water, dried over sodium sulfate and concentrated by evaporation. Recrystallisation from toluene gives 0.58 g (75 %) of the title compound of m.p.: 220-23C. Mass spectrum: 534 (M+: base peak).
2C~i85~
When irradiated, a solution of the compound in toluene undergoes a reversible colour change from yellow to orange.
C) Use Examples Example C1: 2.5 g of polystyrene are dissolved in 15 ml of toluene at 60C under argon.
To this solution are added, after 20 minutes, 25 mg of the compound of Example B 1, and the mix~ure is stirred for 20 minutes. The solution is applied with a 200 llm doctor knife at 80C to a glass plate and then dried for 60 minutes at 80C, to give a transparent film having a thickness of about 3011m. The film is mounted on a quartz plate in the testing chamber of a spectrophotometer and irradiated with a 300 W xenon lamp through glass fibres and a W f Iter. The i~Tadiation is discontinued at 60 second intervals and the absorption spectrum is measured. The spectrum of the sample changes from yellow (optical density 1 at about 320 nm, 0.4 at about 400 nm and 0 above 450 nm) to red (absorption band in the range from about 400-450 nm; maximum optical density 0.65 at 480 nm). The time constant of the conversion is 140 seconds.
For the reverse reaction, the UV filter is replaced by a yellow cut-on filter (Schott GG 455). The integral irradiation intensity in the range from 430-540 is 3 mW/ cm2. The irradiation causes the long-wave absorption band to disappear at 400-450 nm to amaximum optical density of 0.2 at 480 nm. The time constant of the reverse react;on is 110 seconds. In further irradiation cycles these critical values of the optical density remain constant.
Example C2: The general procedure of Example C1 is repeated, except that the compound of Example B2 is used. The spectrum changes from yellow (optical density 1 at about 340 nm, 0.35 at about 400 nm and 0 above 450 nm) to red (maximum absorption 0.6 at 480-510 nm) with a time constant of 180 seconds. The time constant of the reverse reaction (irradiation intensity 2.5 mW/cm2) is 160 seconds (maximum optical density 0.15 at 480 nm).
Preferred compounds of formula I are those wherein R is unsubstituted phenyl.
Particularly preferred compounds of formula I are 6,11-diphenoxy-2-chloronaph-thacene-5,12-dione, 2,6,11-triphenoxynaphthacene-5,12-dione, 6,11-diphenoxy-2,3,8,9-tetrachloronaphthacene-5, 12-dione and 2,3,6,8,9,1 1-hexaphenoxynaphthacene-5,12-dione.
In another of its aspects, the invention relates to a process for the preparation of compounds of formula I, which comprises reacting 1 mol of a compound of formula Il cî o J, ~XX
Cl O
wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or -Br, in the presence of a polar aprotic solvent and at elevated temperature, with at least 2 mol of a compound of formula RoeM~3, wherein R is as previously defined and M is an alkali metal or tertiary ammonium containing 3 to 1~ carbon atoms.
Surprisingly, it has been found that both chlorine atoms can be substituted regioselectively by phenoxy groups even if the naphthacene ring system contains further halogen atoms.
The process of the invention is preferably carried out in the temperature range from 50 to 200C, most preferably from 50 to 150C. The salts of formula ROeM~ may be used as such or produced in 3itU in the reaction mixture by reac~ing a suitable phenol with an alkali metal base or an alkali metal carbonate. The salts can be used in equimolar amounts or in excess, for example in an excess of up to 40 mol%, if it is desired to effect substitution of all halogen atoms.
Typical examples of suitable solvents are N-substituted carboxarnides and lactams tsuch as dimethyl formamide or N-methylpyrrolidone), sulfoxides and sulfones (such as dimethyl sulfoxide, tetramethylene sulfone), or ethers (such as n-dipropyl ether, n-dibutyl ether~ tetrahydrofuran or dioxane).
The compounds of formula I can be isolated and purified by conventional methods, for example by crystallisation and ~crystallisation, or by chromatographic methods.
The compounds of fonnula RoeM~33 are known or obtainable in known manner by reacting suitable phenols with aL~ca}i metal bases, alkali metal carbonates or tertiary amines. They can also be produced in the reaction mixture in situ. Particularly suitable alkali metal cations are Li~, Na~3 and K~. Tertiary ammonium is typically trimethyl-ammonium, triethylammonium, ~i-n-propylammonium and tri-n-butylammonium.
The invention further relates to compounds of formula II
Cl O
~~r~ Xx (~
Cl O
wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or -Br. The preferred meanings of X are the same as those given for Rl to R4 defined as -H, -F, -Cl and -Br in the compounds of formula I.
The compounds of formula II are obtainable by the following process:
The reaction of the known compounds of formula III
~H.
O O
X ) ~ l~X (III), O~ ,0 `H ' 2~85~
wherein X is as defined in formula II7 with a chlorinating agent, typically POCl3, gives the compounds of formula IV which, when unsyrnmetrically substituted, are obtained as a mixture of position isomers of formulae IV and IVa:
cl o ~"_~ (IV), Cl O
x~ 1~ (IVa).
These mixtures can be used direct fior the preparation of compounds of formula II or separated beforehand, for example by chromatographic methods. The compounds of formula III are obtainable in a manner known per se for example, by reacting appropriately halogenated or non-halogenated phthalic anhydrides with appropriately halogenated or non-halogenated 1,4-dihydroxynaphthalene, in the presence of B203, at elevated temperature.
The compounds of forrnula I are crystalline, thermally stable and light-yellow to yellowish-orange in colour. They are soluble in organic solvents. They are effective photoinitiators and photosensitisers for photopolymerisable systems which contain ethylenically unsaturated double bonds. Further, the compounds of formula I are reversibly photochromic compounds which, when irradiated, undergo a marked colour change from yellow to yellowish-orange to orange to red.
When the compounds of formula I are irradiated, alone or incorporated in a substrate, with Z~S85 light having a wavelength of ca. 300 to 450 nm, a pronounced change in colour towards orange to red is observed. In comparison with 6,11-diphenoxynaphthacene-5,12-dione, the light absoIption is displaced to a higher wavelength. The change in colour derives from the photochemical conversion of the paraquinones of this invention into the corresponding anaquinones of formula V. The rate of conversion is surprisingly high and, depending on the amount, thickness of the sample and irradiation intensity, can be less than 3 seconds.
The invention further relates to the anaquinones of formula V
O OR
3 ~ ~ ~ )~ ` Rz OR O
wherein R, Rl, R2, R3 and R4 are as previously defined, including the preferred meanings.
The compounds of formula V can be obtained, after irradiating solutions of the compounds of formula I, by removing the solvent, and, as required, purified by conventional methods.
The change in colour is reversible. Renewed irradiation with light having a wavelength of ca. 450 to 550 nm gives the original colour (reformation of the paraquinone structure). It is especially advantageous that this procedure can be repeated several times. The stability of the photochemical conversion of paraquinones to anaquinones and the reverse reaction to paraquinones is surprisingly high and the fatigue even in air or in substrates is correspondingly low. Thus virtually no changes are observed in more than 200 cycles. It is also advantageous that the light absorption necessary for the photochemical conversion lies in the range of the wavelength of commercially available lasers.
The invention funher relates to the use of compounds of formula I or V, or mixtures thereof, as reversible photochrornic structures for contrast formation or light absorption.
The compounds of formula I can be used as photoinitiators and, preferably, as photosensitisers in photopolymerisible systems, in which case they act simultaneously as 2C`5S85 colour indicators. Thus it is possible to mark irradiated products (for example protective layers, prindng plates, offsct printing plates, printed circuits, solder masks) and to distinguish them from non-irradiated products and, in product control, to sort out imperfectly irradiated products before or after development.
The major advantage in using the compounds of formula I as colour indicators lies in the increase of the sensitiser action. Components normally used as colour change systems generally effect a diminution of the photosensitivity.
The compounds of forrnula I or V can also be used by themselves, in solution or incorporated in polymers, as photochemically modifiable colour indicators or as photochemically modifiable circuit components.
The compounds of formula I can also be used in organic or inorganic glass as photochemically modifiable colour filters, for example in glass for sunglasses, contact lenses, windows and mirrors.
I he invention further relates to a radiation-sensitive composition compAsing a) a radiation-sensitive organic material, and b) at least one compound of formula I or V or a mixture thereof.
The compounds of formulae I and V or mixtures thereof may be present in an amount of 0.001 to 20 % by weight, preferably 0.001 to 10 % by weight and, most preferably, 0.01 to 5 % by weight, based on component a~.
Radiation-sensitive and hence also photostructurable materials are known. They may be positive or negative systems. Such materials are described, for example, by E. Green et al.
in J. Macromol. Sci.; Revs. Macromol. and Chem., C21(2), 187-273 (1981 to 1982) and by G.A. Delzenne in Adv. Photochem., 11, S. 1-103 (1979).
The radiation-sensitive organic material is preferably al) a non-volatile monomeric, oligomeric or polymeric substrate containing photopolymerisable or photodimerisable ethylenically unsaturated groups, a2) a cationically curable system, or a3) photocrosslinkable polyirnides.
Photopolymerisable substances are typically acrylates and, preferably, methacrylates of 2Q~;S85 polyols, for example ethylene glycol, propanediol, butanediol, hexanediol, bis(hydroxy-methyl)cyclohexane, polyoxyaLkylenediols such as di-, tri- or tetraethylene glycol, di- or tri-1,2-propylene glycol, trimethylolmethane, trimethylolethane or trimethylolpropane and pentaerythritol, which may be used by themselves, in mixtures and in admixture with binders.
Exemplary of photodimerisable substances are homo- and copolymers which contain cinnamic acid groups or substituted maleimidyl compounds in side groups or chalcone groups in the polymer chain.
Preferred compositions are those wherein component al) is a homo- or copolymer of acrylates, methacrylates or maleates whose ester groups contain a radical of formula ~C-- \
ll N A
R~ --C
wherein A is linear or branched unsubstituted or hydroxyl-substituted C2-CI2alkylene, cyclohexylene or phenylene, and R7 and R8 are each independently of the other chloro or bromo, phenyl or Cl-C4alkyl, or R7 and Rg, when taken together, are t imethylene, (CH2)2--tetramethylene or ~ .
Such polymers are disclosed, for exarnple, in US patent specification 4 193 927.
The photopolymeAsable or photodimerisable substances can contain further additives customarily used for processing or application, as well as other photoinitiators or photosensitisers .
The cationically curable systems are preferably epoxy compounds containing at least two epoxy groups in the molecule and in which a photoinitiator is incorporated. Suitable photoinitiators are typically cyclopentadienylarene metal salts, cyclopentadienyl metal carbonyl salts and onium salts which are described in the above mentioned publications.
The curable systems may contain additives customarily used for processing and application.
2~ 854 g Photosensitive polyimides are disclosed, for example, in DE-A-1 962 588, EP-A-0 132 221, EP-A- 0 134 752, EP-A-0 162 017, EP-A-0 181 37 and EP-A-0 182 745.
The composition of this invention is applied by known methods as layer to substrates and either a protective layer is produced by iiTadiation over the surface, or a relief image is produced by irradiation through a photomask or by locally defined irradiation with a guided laser beam or by holographic methods and subsequent development.
~n another of its aspects, the invention relates to a composition comprising a) a colourless organic solvent, a polymer or an organic glass or a compound glass, and b) dissolved, incorporated therein or present as layer on at least one surface, a compound of formula I or V or a mixture thereof. Component b) is preferably present in an amount of 0.001 to 20 % by weight, preferably 0.001 to 10 % by weight and. most preferably, 0.01 to 5 % by weight, based on component a). ~rganic solutions can be used for coating other substances, for example solid substrates such as inorganic glasses which can then be used as photochernically modiflable substrates. The compounds of formula I can also be~
sublimed on to substrates. The coated substrates can be provided with a protective layer of, for example, transparent polymers. Solid substrates can also be coated with compositions which contain a polymer and at least one compound of formula I or V.
Suitable solvents are typically hydrocarbons, halogenated hydrocarbons, ketones,carboxylic acid esters and lactones, N~ cylated acid arnides and lactams, alkanols and ethers.
Exemplary of suitable polymers are thermoset plastics, thermoplastics and structurally crosslinked polymers. Ille polymers are preferably transparent. Such polymers and organic glasses are known to those skilled in the art. The incorporation of the compounds of the ;nvention is effected by known methods, for example by dissolving methods and removing the solvent, calendering or extrusion. The compounds of this invention can also be incorporated in the substrates before, during or after their synthesis.
The invention also relates to a process for the preparation of coloured materials under the influence of light, which comprises incorporating a compound of formula I or V in the material and then irradiating said material with light.
The invention further relates to the use of compounds of formula I as photosensitisers and 2~5S85~
colour indicators or photochemically modifiable colour ~llters under the influence of light.
In yet another of its aspects, the invention relates to the use of a compound of formula ~ or V for the reversible optical storage of information, which information is written with light, preferably laser light, into a memory-active layer containing said compound. The written information can be erased, preferably with laser light, thus affording the possibility of cyclic writing-in and erasing.
To produce a memory-active layer, the compound of formula I or V can be dissolved in a transparent matrix by methods desribed above and applied in a thin layer to a flat substrate. The thickness of the memory-active layer is ca. 0.1- 100 ~m, preferably 0.3-3 ~m.
The information can be written by scanned, holographic or photographic irradiation of the memory-active layer with spectral, preferably coherent, laser light in the wavelength range of 440-550 nm, preferably 480-530 nm.
Reading out can be effected with reduced irradiation intensity at the wavelength in which the information is written via the locally altered transmission, reflectance, refraction or fluorescence of the memory-active layer.
Erasure can be made by pin-point or spread irradiation of the memory-active layer containing the compounds of formula I and/or V in the wavelength range of 300-450 nm, preferably 300-420 nrn.
One advantage of the utility of this invention is that the wavelengths necessary for writing in, reading out and erasing are in the range of commercially available lasers (for example argon ion lasers: 488/514 nm and 351/363 nm; neodym-YAG lasers: 532 nm and 355 nm with frequency doubling and trebling; XeF excimer lasers: 351 nm; HeCd lasers: 325 and 442 nm).
A further advantage is the high contrast of absorption obtainable between the written and erased state in the range of 450-550 nm and the wide dynamic range associated therewith of the memory-active layer.
Another advantage is that the quantum yield when writing is fairly low, so that the danger 2C`~ 854 of overwridng when reading out is greatly diminished.
Conversely, it is also advantageous that the quantum yield when erasing is fairly high, thus making possible a rapid erasure over a large area.
Yet a further advantage is that, when reading out, the compound fluoresces and hence makes possible a highly sensitive detection of the memory status via the fluorescence. The fact that the energy pulsed in for reading out dissipates substantially via the fluorescence and not thermally also counteracts an undesirable heating of the memory-active layer.
Another advantage is the high photochemical stability of the compound and the great number of writing/erasing cycles thereby obtainable.
Finally, yet another advantage is the possibility of cyclic data refreshing by admixture of a suitable quantum of light of the erasure wavelength during reading out.
The invention is illustrated by the following Examples.
A) Preparation of the startin~ com~ounds Example A1: 2,3,6,8,9,11-Hexachloronaphthacene-5,12-dione.
30 g (70 mmol) of 2,3,8,9-tetrachloro-6,1 1-dihydroxynaphthacene-5,12-dione, 60 ml of POCl3 and 500 ml of o-dichlorobenzene are stirred for 90 hours under reflux. Excess POCI3 is distilled off, together with the o-chlorobenzene, until the reaction volume is still about 300 ml. The precipitate is isolated by filtration from the cooled reaction mixture, washed repeatedly with water and aqueous sodium carbonate solution and dried. The dry product is stirred in cyclohexane, isolated by filtration and then dried, giving a yield of 28.6 g (88 %), melting point (mp): >260C.
Examp e A2: 2-Fluoro- and 9-fluoro-6,1 1-dichloronaphthacene-5,12-dione (mixture of isomers).
3.0 g (9.73 mmol) of 2- and 9-fluoro-6,1 1-dihydroxynaphthacene-5,12-dione (mixture of position isomers), 4 ml of POCI3 and 30 ml of o-dichlorobenzene are stirred for 10 hours under reflux. The reaction mixture is poured into water and neutralised with 2 N aqueous NaOH. The precipitate is isolated by filtration, washed with water, dried, taken up in 400 ml of toluene. After addition of basic alurnina, the batch is filtered hot. The filtrate is ;~C'5~i~3 concentrated by evaporation, giving 1.57 g (47 %) of the product mixture. Mass spectrum:
344, 346, 348 and 350 (M+: base peak).
B~ Preparation of the inventive compounds Example B 1: 2,3,8,9-Tetrachloro-6,11 -diphenoxynaphthacene-5,12-dione.2.32 g (S mmol) of the compound of Example A 1, 1.41 g ( lS mmol) of phenol, 4.15 g (30 rnmol) of potassium carbonate and 100 ml of tetrahydrofuran are heated for 5 hours under reflux. The mixture is poured into water, with s~rring, and then filtered. The precipitate is washed flrst with water and then with methanoVwater, dried, and then recrystallised from o-dichlorobenzene, affording the title compound in a yield of 2.57 g (89 %) in the form of yellow crystals with a melting point of 326-329C. Mass spectrum 578/580/582 (M+: base peak).
When irradiated, a solution of the compound in toluene undergoes a reversible colour change from yellow to orange.
Example B2: 2,~,6,8,9,11-Hexaphenoxynaphthacene-5,12-dione.
l.S g (3.2 mmol) of compound Al, 2.43 g (25.8 mmol) of phenol, 4.45 g (32.3 g) of potassium carbonate and 120 ml of N-methylpyrrolidone are stirred for 8 hours at 150C.
The mixture is taken up in tetrahydrofuranJtoluene/2 N hydrochloric acid and the organic phase is separated, washed with water, dried over sodium sulfate and then concentrated by evaporation. The crude product is dissolved in toluene and chromatographed over silica gel, affording the title compound in a yield of 0.65 g (25 %) in the form of yellowish-orange crystals.
Mass spectrum: 810 (M+: base peak).
When irradiated, a solution of the compound in toluene undergoes a reversible colour change from yellowish-orange to red.
Example B3: Mixture of 2,6,11- and 6,9,11-triphenoxynaphthacene-5,12-dione.
0.5 g (1.45 mmol) of compound A2, 0.8 g (5.8 mrnol) of potassium carbonate, 0.48 g (5.07 mmol) of phenol and 5 ml of dimethyl sulfoxide are stirred for 4 hours at 100C. The reaction mixture is poured into dilute hydrochloric acid and extracted with tetrahydrofuran/toluene (1:1). The extracts are washed with saturated aqueous NaCl and water, dried over sodium sulfate and concentrated by evaporation. Recrystallisation from toluene gives 0.58 g (75 %) of the title compound of m.p.: 220-23C. Mass spectrum: 534 (M+: base peak).
2C~i85~
When irradiated, a solution of the compound in toluene undergoes a reversible colour change from yellow to orange.
C) Use Examples Example C1: 2.5 g of polystyrene are dissolved in 15 ml of toluene at 60C under argon.
To this solution are added, after 20 minutes, 25 mg of the compound of Example B 1, and the mix~ure is stirred for 20 minutes. The solution is applied with a 200 llm doctor knife at 80C to a glass plate and then dried for 60 minutes at 80C, to give a transparent film having a thickness of about 3011m. The film is mounted on a quartz plate in the testing chamber of a spectrophotometer and irradiated with a 300 W xenon lamp through glass fibres and a W f Iter. The i~Tadiation is discontinued at 60 second intervals and the absorption spectrum is measured. The spectrum of the sample changes from yellow (optical density 1 at about 320 nm, 0.4 at about 400 nm and 0 above 450 nm) to red (absorption band in the range from about 400-450 nm; maximum optical density 0.65 at 480 nm). The time constant of the conversion is 140 seconds.
For the reverse reaction, the UV filter is replaced by a yellow cut-on filter (Schott GG 455). The integral irradiation intensity in the range from 430-540 is 3 mW/ cm2. The irradiation causes the long-wave absorption band to disappear at 400-450 nm to amaximum optical density of 0.2 at 480 nm. The time constant of the reverse react;on is 110 seconds. In further irradiation cycles these critical values of the optical density remain constant.
Example C2: The general procedure of Example C1 is repeated, except that the compound of Example B2 is used. The spectrum changes from yellow (optical density 1 at about 340 nm, 0.35 at about 400 nm and 0 above 450 nm) to red (maximum absorption 0.6 at 480-510 nm) with a time constant of 180 seconds. The time constant of the reverse reaction (irradiation intensity 2.5 mW/cm2) is 160 seconds (maximum optical density 0.15 at 480 nm).
Claims (16)
1. A compound of formula I or a mixture thereof (I), wherein R is unsubstituted C6-C14aryl or C6-C14aryl which is substituted by C1-C12alkyl,C1-C12alkoxy, C1-C12alkylthio, phenyl, benzyl, -CN, -CF3, halogen or -COOR5, and R5 is H, C1-C18alkyl, cyclohexyl, cyclopentyl, phenyl, C1-C12alkylphenyl, benzyl or C1-C12alkylbenzyl, and at least one of the substituents R1 to R4 is -F, -Cl or -Br, or is independently the group RO-, and the other substituents R1 to R4 are H, -F, -Cl or -Br.
2. A compound according to claim 1, wherein R in formula I is unsubstituted or substituted C6-C10aryl.
3. A compound according to claim 2, wherein R is unsubstituted or substituted phenyl or 1- or 2-naphthyl.
4. 4. A compound according to claim 1, wherein R in formula I is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, -F, -Cl, -Br or -COORs, wherein R5 is H or C1-C18alkyl.
5. A compound according to claim 1, wherein at least one of the substituents R1 to R4 in formula I is a group RO- or -F, -Cl or -Br, and the other substituents R1 to R4 are H.
6. A compound according to claim 1, wherein R1 or R4, or R1 and R3 or R4, or R1 and R2 or R1 to R4 is a group RO-, -F, -C1 or -Br.
7. A compound according to claim 1, wherein R1 or R4, or R1 and R3 or R4, or R1 and R2 or R1 to R4 is a group RO- or -Cl.
8. A compound according to claim 1, wherein R is unsubstituted phenyl.
9. A compound according to claim 1, wherein the compound of formula I is selected from the group consisting of 6,11-diphenoxy-2-chloronaphthacene-5,12-dione, 2,6,11-tri-phenoxynaphthacene-5,12-dione, 6,11-diphenoxy-2,3,8,9-tetrachloronaphtha-cene-5,12-dione and 2,3,6,8,9,11-hexaphenoxynaphthacene-5,12-dione.
10. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting 1 mol of a compound of formula II
(II) wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or -Br, in the presence of a polar aprotic solvent and at elevated temperature, with at least 2 mol of a compoundof formula RO?M?, wherein R is as defined in claim 1 and M is an alkali metal or tertialy ammonium containing 3 to 18 carbon atoms.
(II) wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or -Br, in the presence of a polar aprotic solvent and at elevated temperature, with at least 2 mol of a compoundof formula RO?M?, wherein R is as defined in claim 1 and M is an alkali metal or tertialy ammonium containing 3 to 18 carbon atoms.
11. A compound of formula II
(II), wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or-Br.
(II), wherein at least one of the substituents X is -F, -Cl or -Br, and the other substituents X are -H, -F, -Cl or-Br.
12. A compound according to claim 11, wherein X in formula II is C1.
13. A compound of formula V
(V), wherein R, R1, R2, R3 and R4 are as defined in claim 1, or a mixture thereof.
(V), wherein R, R1, R2, R3 and R4 are as defined in claim 1, or a mixture thereof.
14. A composition comprising a) a colourless organic solvent, a polymer or an organic glass or a compound glass, and b) dissolved, incorporated therein or present as a layer on at least one surface, a compound of formula I or V according to either claim 1 or claim 13 or a mixture thereof.
15. Use of a compound of formula I or V according to either claim 1 or claim 13, or a mixture thereof, as reversible photochromic system for contrast formation or light absorption.
16. Use of a compound of formula I or V according to either claim 1 or claim 13, or a mixture thereof, for the reversible optical storage of information.
FD 4.6/DA
FD 4.6/DA
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH383790 | 1990-12-05 | ||
| CH3837/90-0 | 1990-12-05 |
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| Country | Link |
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| US (2) | US5208354A (en) |
| EP (1) | EP0489689B1 (en) |
| JP (1) | JPH0558941A (en) |
| KR (1) | KR920011991A (en) |
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| DE59104782D1 (en) * | 1990-12-05 | 1995-04-06 | Ciba Geigy Ag | Photochromic naphthacene quinones, process for their preparation and their use. |
| DE59304881D1 (en) * | 1992-10-15 | 1997-02-06 | Ciba Geigy Ag | Polymerizable photochromic napthacenediones, polymers of these monomers, processes for their preparation and their use |
| JP3027299B2 (en) * | 1994-05-30 | 2000-03-27 | 信越化学工業株式会社 | Rare earth element phosphate particles and method for producing the same |
| US5847141A (en) * | 1995-12-22 | 1998-12-08 | Memory Devices, Inc. | Photochromic material for electro-optic storage memory |
| US5883043A (en) * | 1997-08-27 | 1999-03-16 | Ncr Corporation | Thermal paper with security features |
| US6770687B1 (en) | 1996-11-21 | 2004-08-03 | Ncr Corporation | Water-based dual security ink |
| AU5516598A (en) * | 1996-12-05 | 1998-06-29 | Omd Optical Memory Devices Ltd. | Optical pickup for 3-d data storage reading from the multilayer fluorescent optical disk |
| US6071671A (en) | 1996-12-05 | 2000-06-06 | Omd Devices Llc | Fluorescent optical memory |
| US6027855A (en) * | 1996-12-20 | 2000-02-22 | Omd Devices Llc | Photo-chemical generation of stable fluorescent derivatives of Rhodamine B |
| US5945252A (en) * | 1996-12-20 | 1999-08-31 | Memory Devices, Inc. | Photochemical generation of stable fluorescent amines from peri-phenoxiderivatives of polycyclic P-quinones |
| US5936878A (en) * | 1997-01-06 | 1999-08-10 | Omd Devices Llc | Polymeric photo-chromic composition |
| KR20020047350A (en) * | 2000-12-13 | 2002-06-22 | 이병철 | Method of Confirming Progress in Semi-conductor Assembly Process |
| US6803344B2 (en) * | 2001-12-21 | 2004-10-12 | Ncr Corporation | Thermal paper with preprinted indicia |
| US20050136333A1 (en) * | 2003-12-19 | 2005-06-23 | Lawrence Brian L. | Novel optical storage materials based on narrowband optical properties |
| US7897296B2 (en) * | 2004-09-30 | 2011-03-01 | General Electric Company | Method for holographic storage |
| US20060078802A1 (en) * | 2004-10-13 | 2006-04-13 | Chan Kwok P | Holographic storage medium |
| US7645719B2 (en) * | 2004-10-13 | 2010-01-12 | Ncr Corporation | Thermal paper with security features |
| JP4876455B2 (en) * | 2005-06-30 | 2012-02-15 | 川崎化成工業株式会社 | Novel bis (silyloxy) naphthacenedione, production method thereof, and use thereof |
| US20070054590A1 (en) * | 2005-08-24 | 2007-03-08 | Schmidt Christopher B | Photo-chromic toys |
| US7547109B2 (en) | 2005-09-02 | 2009-06-16 | Shoot The Moon Products Ii, Llc | Photo-chromic material application apparatus |
| US8684784B2 (en) * | 2005-11-23 | 2014-04-01 | Shoot The Moon Products Ii, Llc | Photo-chromic and phosphorescent toys |
| US8951091B2 (en) | 2011-04-06 | 2015-02-10 | Mattel, Inc. | Toy vehicle playset and color changing toy vehicle |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5417877B2 (en) * | 1972-07-28 | 1979-07-03 | ||
| EP0438376B1 (en) * | 1990-01-18 | 1994-01-26 | Ciba-Geigy Ag | Photochromic naphthacenchinones, process for their production and their use |
| DE59104782D1 (en) * | 1990-12-05 | 1995-04-06 | Ciba Geigy Ag | Photochromic naphthacene quinones, process for their preparation and their use. |
-
1991
- 1991-11-27 DE DE59104782T patent/DE59104782D1/en not_active Expired - Fee Related
- 1991-11-27 EP EP91810925A patent/EP0489689B1/en not_active Expired - Lifetime
- 1991-12-02 US US07/801,150 patent/US5208354A/en not_active Expired - Fee Related
- 1991-12-03 CA CA002056854A patent/CA2056854A1/en not_active Abandoned
- 1991-12-04 JP JP3347622A patent/JPH0558941A/en active Pending
- 1991-12-04 KR KR1019910022097A patent/KR920011991A/en not_active Application Discontinuation
-
1993
- 1993-02-01 US US08/012,079 patent/US5407885A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0558941A (en) | 1993-03-09 |
| US5407885A (en) | 1995-04-18 |
| EP0489689A1 (en) | 1992-06-10 |
| KR920011991A (en) | 1992-07-25 |
| DE59104782D1 (en) | 1995-04-06 |
| EP0489689B1 (en) | 1995-03-01 |
| US5208354A (en) | 1993-05-04 |
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