EP0316980A1 - Composition photochrome et articles à base de cette composition - Google Patents
Composition photochrome et articles à base de cette composition Download PDFInfo
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- EP0316980A1 EP0316980A1 EP88202408A EP88202408A EP0316980A1 EP 0316980 A1 EP0316980 A1 EP 0316980A1 EP 88202408 A EP88202408 A EP 88202408A EP 88202408 A EP88202408 A EP 88202408A EP 0316980 A1 EP0316980 A1 EP 0316980A1
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- EP
- European Patent Office
- Prior art keywords
- photochromatic
- group
- alkyl
- composition according
- spiro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- -1 or (C1-C5)-alkoxy Chemical group 0.000 claims description 16
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000006715 (C1-C5) alkylthio group Chemical group 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 229920005749 polyurethane resin Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940102838 methylmethacrylate Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009747 press moulding Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
Definitions
- the present invention relates to a photochromatic composition which contains at least two organic photochromatic compounds.
- the photochromatic compounds are substances which display the characteristics of reversibly changing in colour and/or degree of light transmission when they are exposed to some types of electromagnetic radiation, and to sun light, turning back into their original colour and transmission status when the initial light source is removed.
- organic photochromatic compounds in particular those belonging to the class of the spiro-indolino-naphtho-oxazines are known, which are capable of conferring photochromatic characteristics on polymerized and transparent organic materials (organic glasses), for their use as sun filters and photochromatic optical articles, such as disclosed, e.g., in the following patents: US 3,562,172; US 3,578,602; US 4,215,010; US 4,342,668; EP 146 135, WO 85/02619; EP 245 020; and in European patent applications publ. Nos. 134,633 and 141,407.
- the known photochromatic compounds belonging to the class of the spiro-indolino-naphtho-oxazines exhibit, as compared to other known organic photochromatic compounds (e.g., those belonging to the class of the spiro-piranes) the advantage of having a much higher fatigue strength, when they are submitted to repeated cycles of colouring and de-colouring; and a much higher ageing resistance when they are exposed to sun light, or to artificial ageing tests. This behaviour is very advantageous for the above set out uses.
- the organic photochromatic compounds known from the prior art are practically colourless in their deactivated status, both in solution in common organic solvents, as well as when they are incorporated in transparent polymeric materials, and turn to a generally blue colour when they are activated.
- This blue colour is a disadvantage for their use as optical photochromatic articles, in particular in the ophthalmic sector, for which more neutral colours please, e.g., the gray colour.
- the photochromatic effect obtained is in many cases of low intensity as regards the change in transmittance in the visible wavelength range. In other cases, such a change, although is satisfactory at low temperatures, is depressed down to unacceptedly low values with increasing temperature, even if within the values as required in practical use.
- the activation of the spiro-indolino-naphtho-oxazines, obtained under controlled laboratory conditions by irradiation with UV light of several wavelengths from about 320 to about 380 nm is often not reproduced with the same satisfactory intensity when the exposure is carried out to the spectrum of frequencies and of relative intensities of sun light, as required for the ophthalmic use, and as sun filter.
- the purpose of the present invention is overcoming the drawbacks which affect the prior art by means of a novel photochromatic composition containing at least two photochromatic compounds belonging to the class of the spiro-indolino-naphtho-oxazines.
- the present invention relates to a photochromatic composition consisting of at least two photochromatic compounds, both of which can be represented by the following general formula (I): wherein: R1 and R2 independently represent a hydrogen atom or a halogen atom (chlorine, bromine or fluorine), or a group selected from: (C1-C5)-alkoxy; nitro; cyano; and a linear or branched (C1-C5)-alkyl either unsubstituted or substituted with one or more halogen (chlorine, bromine and fluorine) atoms, or (C1-C5)-alkoxy, (C1-C5)-alkyl-thio, (C1-C5)-carboxy-alkyl and cyano groups; or R1 and R2, when are not hydrogen, can be linked to any of the 4-, 5-, 6- and 7-positions of the indolinic moiety; R3 and R4 independently represent linear or branched (C1
- the photochromatic compounds of the composition according to the present invention all of which can be defined by means of the general formula (I), and with the proviso that in at least one of them the R7 substituent represents a hydrogen atom and in at least one of them the R7 substituent represents the amino group the R1, R2, R3, R4, R5, R6, R7, and, if present, R8 and R9, substituents, have the following meaning: R1 and R2 independently represent the hydrogen atom, or the methyl, methoxy or halogen groups; R3 and R4 represent each the methyl or ethyl group, or, when considered jointly, represent the cyclohexyl group; R5 represents a (C1-C5)-alkyl group; R6 represents the hydrogen atom or the methoxy group; R8 and R9 jointly represent, together with the nitrogen atom to which they are linked, the piperidino, morpholino, pyrrolidinyl or hexamethylene-imino
- the R1, R2 and R6 groups when they do not represent hydrogen, or, in case of R6 group, a ring structure, are respectively linked to the (4,5)- or (5,6)- and 9′-positions of the molecule.
- photochromatic compounds in which the R7 substituent is different from hydrogen are:
- photochromatic compounds in which the R7 substituent is hydrogen are:
- the simultaneous presence of a photochromatic compound definable by means of formula (I) and having an -NR8 R9 in the 6′-position of the molecule, and of a photochromatic compound definable by means of said formula, but in which the substituent in 6′-position is hydrogen atom, is advantageous.
- both compounds act with a synergistic effect on the regulation of the sun light, generating a more intense colour, and with shorter response times, than the normal photochromatic organic compounds of the prior art, as well as than the individual components of the same mixture.
- the change in transmittance is furthermore maintained at satisfactory values with increasing room temperature, and much higher than as required by the practical application.
- the shades of colour which can be obtained by means of the use of the photochromatic mixture of the present invention are more neutral than the blue colour generally shown by individual components, and can be modulated within a wide range by means of a properly balanced dosage of both basic components, as well as of other components known from the prior art.
- this mutual mol ratio of the two photochromatic components defined by the general formula (I) and respectively bearing the -NR8 R9 group and hydrogen in the 6′-position is a number comprised within the range of from 0.1 and 9 and preferably from 0.2 to 1.5.
- the photochromatic mixture of the present invention can be constituted by more than two compounds as defined by the general formula (I), provided that at least two of them are different from each other as to the 6′-substituent, as above said.
- Said mixtures can furthermore additionally contain other components, such as the U.V. stabilizers known from the prior art, capable of improving the duration of the photochromatic effect, without impairing the intensity of photocolourability of the same mixtures.
- U.V.-stabilizers for the purposes of the present invention are the hindered ammines (HALS).
- the photochromatic mixture according to the present invention is useful in the production of photochromatic articles endowed with particular colour transitions, a high activation by exposure to sun light, a high fatigue and ageing resistance.
- the photochromatic mixture according to the present invention is applied to the surface of, or is incorporated into, the desired articles, generally constituted by transparent polymeric materials, by means of suitable techniques.
- Photochromatic polymeric articles can be obtained by means of moulding techniques (e.g., injection-moulding, press-moulding, and so forth;) by homogeneously dispersing throughout the mass the photochromatic mixture.
- the mixture can be dissolved in a suitable solvent, together with a polymeric material (e.g., poly-methyl-methacrylate, polyvinyl-alcohol, poly-vinyl-butyral, cellulose acetate-butyrate or epoxy resin, polysiloxane resin or urethane resin, and so forth), and deposited on a transparent support in order to form, after the evaporation of the solvent, a photochromatic coating.
- a polymeric material e.g., poly-methyl-methacrylate, polyvinyl-alcohol, poly-vinyl-butyral, cellulose acetate-butyrate or epoxy resin, polysiloxane resin or urethane resin, and so forth
- the photochromatic mixture can be added to a polymerizable monomer, e.g., methyl-methacrylate, so that after a polymerization carried out in the presence of a suitable polymerization initiator, e.g., azo-bis(isobutyronitrile), it results to be evenly incorporated to the formed resin.
- a suitable polymerization initiator e.g., azo-bis(isobutyronitrile
- the photochromatic mixture can be dissolved in a suitable solvent, in the presence of a resin, as above disclosed, and from this solution, by evaporating the solvent, a photochromatic film or sheet can be formed, which contain the uniformly dispersed photochromatic mixture.
- the photochromatic mixture can be applied to a transparent substrate (e.g., a polycarbonate substrate, a polymethyl-methacrylate substrate or a poly-diethylene-glycol-bis(allyl carbonate) substrate) by means of a surface impregnation obtained by placing the substrate into contact, at a suitable temperature, with a solution or dispersion which contains the mixture.
- a transparent substrate e.g., a polycarbonate substrate, a polymethyl-methacrylate substrate or a poly-diethylene-glycol-bis(allyl carbonate) substrate
- photochromatic articles such as photochromatic ophthalmic lenses and photochromatic sun filters, that is to say, which are capable of constituting an at least partial screen towards the sun radiation, in a reversible way.
- Such articles can be advantageously used, e.g., as lenses for sun glasses, prescription-lenses, contact lenses, glasses for cars or transport means in general, and windows in the building sector.
- optical photochromatic articles of polymethyl-methacrylate were obtained by adding the photochromatic compound and the polymerization initiator azo-bis(isobutyro-nitrile) (AIBN) to the monomer and then carrying out the polymerization by casting into moulds of a suitable shape.
- AIBN azo-bis(isobutyro-nitrile)
- Optical articles of poly-diethylene-glycol-bis(allyl-carbonate) were made photochromatic by means of a surface impregnation technique.
- a solution or suspension is prepared of the photochromatic compound in a suitable solvent or dispersant, normally selected from among the usual organic solvents, silicone oils, fluorinated oils, and the like, and the photochromatic compound is transferred on to the polymeric substrate by dipping the polymeric article in said solution or suspension, for suitable times and at suitable temperatures.
- the following characteristics are determined: -The U.V.-visible spectrum in the deactivated status (optical density at ⁇ max ), as determined by the Cary 2300 spectrophotometer. - The change in light transmittance ( ⁇ Y) at 23°C, as determined by the MACBETH spectrophotometer, after a 120-second activation with an UV-A lamp of 9 W/m2 of irradiance. The values of ⁇ Y were also measured after a 4-minute exposure to sun light, by using the Gardner's Hazemeter XL 211.
- - Kinetics of return to the deactivated form (time for recovery of 50% of the initial transmittance, t 1/2 ), by means of a MACBETH spectrophotometer, under the same activation conditions as hereinabove disclosed.
- - Ageing resistance as determined by means of an Atlas Weather-0-Meter equipped with a continous-irradiation xenon lamp of 6,500 W, operating at a temperature of 63°C on the reference black panel, and at a relative humidity of 50%. The ageing resistance is evaluated by measuring, after various times of exposure in the Weather-0-Meter, the values of optical density at ⁇ max of the deactivated form, and the residual value of ⁇ Y after activation with the UV-A lamp.
- Photochromatic lenses of poly-diethylene-glycol-bis(allyl-carbonate) are prepared by means of surface impregnation with mixtures of (A) and (E) photochromatic compounds in the following proportions:
- the lens In order to transfer the photochromatic compound, the lens is dipped into the siliconic dispersion for times ranging from 30 to 90 minutes, and at temperatures comprised within the range of from 170 to 190°C, as a function of the desired value for optical density. At the end of the impregnation, the lens is washed with petroleum ester, and the characteristics as listed hereinabove in the specification are evaluated.
- the photochromatic response to sun light exposure is evaluated of a neutral lens of poly-diethylene-glycol-bis(allyl carbonate) impregnated with the (b) photochromatic mixture of Example 1, as compared to a similar lens impregnated with the spiro-oxazinic photochromatic compound known from the prior art, having the formula: wherein the two methyl groups on the benzene-indolinic ring are in the 4,5- and 5,6-positions.
- the lens obtained with the (b) photochromatic mixture of the present invention shows a more neutral colour of the activated status, a higher photochromatic activity ( ⁇ y), and a twice as high return rate to the deactivated status
- a neutral photochromatic lens of poly-(methyl-methacrylate) is prepared, which has the following composition:
- the polymerization of the lens is carried out by casting, maintaining the mould in a temperature-controlled water bath at 55°C for 80 hours.
- the (b) composition according to the present invention unexpectedly shows photochromatic characteristics as well a stability, which are similar to those of the pure (A) photochromatic compound, even if it is constituted for its major portion by the (E) photochromatic compound, which, in the pure state, displays very bad photochromatic characteristics and ageing resistance.
- a mixture is prepared, which is constituted by a polypropylene powder of MOPLEN FLF 20 type, having a fluidity degree of 11, manufactured by HIMONT, and by the (b) photochromatic mixture of Example 1, in the mutual ratio by weight to each other of respectively 100:0.25.
- Said polymeric mixtures are transformed into films of 50 m of thickness by extrusion at the temperature of 215°C.
- the photochromatic characteristics of the so-obtained films, and the relevant resistances under such conditions as reported in the text, are reported in Table VI.
- a mixture of the (D) and (G) photochromatic compounds in the weight ratio of 60/40 is prepared.
- Said mixture is applied by surface impregnation to neutral lenses of poly-diethylene-glycol-bis(allyl carbonate), and is evaluated as disclosed at Example 1.
- the reported data shows the synergistic effect of the two (A) and (F) products, in that the photochromatic activity of their mixtures is very close to the photochromatic activity displayed by the more active (A) compound alone, and the times of return back to the deactivated form are considerably shorter.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Pyrane Compounds (AREA)
- Inorganic Insulating Materials (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88202408T ATE91033T1 (de) | 1987-11-05 | 1988-10-28 | Photochromische zusammensetzung und diese zusammensetzung enthaltende gegenstaende. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22528/87A IT1223067B (it) | 1987-11-05 | 1987-11-05 | Composto fotocromatico ed articoli fotocromatici che lo contengono |
| IT2252887 | 1987-11-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0316980A1 true EP0316980A1 (fr) | 1989-05-24 |
| EP0316980B1 EP0316980B1 (fr) | 1993-06-23 |
Family
ID=11197462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88202408A Revoked EP0316980B1 (fr) | 1987-11-05 | 1988-10-28 | Composition photochrome et articles à base de cette composition |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0316980B1 (fr) |
| JP (1) | JPH01163184A (fr) |
| AT (1) | ATE91033T1 (fr) |
| AU (1) | AU605929B2 (fr) |
| DE (1) | DE3882015T2 (fr) |
| ES (1) | ES2056906T3 (fr) |
| IT (1) | IT1223067B (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0686685A3 (fr) * | 1994-06-10 | 1995-12-27 | Rodenstock Optik G | |
| WO1996004590A1 (fr) * | 1994-07-29 | 1996-02-15 | Essilor International Compagnie Generale D'optique | Composes photochromiques de structure spiro[indoline-[2,3']-benzoxazine] a groupement cyano ou phenylsulfonyl en 6' et comportant un cycle benzenique condense en 7', 8' du noyau benzoxazine, et leur utilisation dans le domaine de l'optique ophtalmique |
| EP1044978A3 (fr) * | 1999-03-24 | 2001-05-09 | Corning S.A. | 1-N-alkyle-5'-[(N'-(non)substituté)amido]spiroindolinonaphthoxazines, leur préparation, et compositions et matrices de (co)polymères les contenant |
| EP1044979A3 (fr) * | 1999-03-24 | 2001-05-09 | Corning S.A. | 1-[(N-(Non)substitutés)amidoalkyle]spiroindolinonaphthoxazines, leur préparation, compositions et matrices de (co)polymères les contenant |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07233174A (ja) * | 1993-12-28 | 1995-09-05 | Hodogaya Chem Co Ltd | スピロナフトオキサジン化合物および該化合物を使用した感光材料 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4342668A (en) * | 1978-09-08 | 1982-08-03 | American Optical Corporation | Photochromic compounds |
| EP0195898A1 (fr) * | 1985-01-31 | 1986-10-01 | American Optical Corporation | Procédé pour améliorer la résistance d'une composition photochromique à la fatigue à la lumière et composition photochromique |
| EP0245020B1 (fr) * | 1986-05-01 | 1991-10-02 | Pilkington Plc | Articles photochromiques |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440672A (en) * | 1982-03-22 | 1984-04-03 | American Optical Corporation | Photochromic composition resistant to fatigue |
| DE3486132D1 (en) * | 1983-12-16 | 1993-07-01 | Rodenstock Optik G | Photochrome substanzen. |
-
1987
- 1987-11-05 IT IT22528/87A patent/IT1223067B/it active
-
1988
- 1988-10-28 EP EP88202408A patent/EP0316980B1/fr not_active Revoked
- 1988-10-28 AT AT88202408T patent/ATE91033T1/de not_active IP Right Cessation
- 1988-10-28 DE DE88202408T patent/DE3882015T2/de not_active Revoked
- 1988-10-28 ES ES88202408T patent/ES2056906T3/es not_active Expired - Lifetime
- 1988-11-04 AU AU24744/88A patent/AU605929B2/en not_active Ceased
- 1988-11-04 JP JP63277611A patent/JPH01163184A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4342668A (en) * | 1978-09-08 | 1982-08-03 | American Optical Corporation | Photochromic compounds |
| EP0195898A1 (fr) * | 1985-01-31 | 1986-10-01 | American Optical Corporation | Procédé pour améliorer la résistance d'une composition photochromique à la fatigue à la lumière et composition photochromique |
| EP0245020B1 (fr) * | 1986-05-01 | 1991-10-02 | Pilkington Plc | Articles photochromiques |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0686685A3 (fr) * | 1994-06-10 | 1995-12-27 | Rodenstock Optik G | |
| WO1996004590A1 (fr) * | 1994-07-29 | 1996-02-15 | Essilor International Compagnie Generale D'optique | Composes photochromiques de structure spiro[indoline-[2,3']-benzoxazine] a groupement cyano ou phenylsulfonyl en 6' et comportant un cycle benzenique condense en 7', 8' du noyau benzoxazine, et leur utilisation dans le domaine de l'optique ophtalmique |
| US5936016A (en) * | 1994-07-29 | 1999-08-10 | Essilor International Compagnie Generale D'optique | Photochromic compounds and methods for their use |
| EP1044978A3 (fr) * | 1999-03-24 | 2001-05-09 | Corning S.A. | 1-N-alkyle-5'-[(N'-(non)substituté)amido]spiroindolinonaphthoxazines, leur préparation, et compositions et matrices de (co)polymères les contenant |
| EP1044979A3 (fr) * | 1999-03-24 | 2001-05-09 | Corning S.A. | 1-[(N-(Non)substitutés)amidoalkyle]spiroindolinonaphthoxazines, leur préparation, compositions et matrices de (co)polymères les contenant |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0316980B1 (fr) | 1993-06-23 |
| IT8722528A0 (it) | 1987-11-05 |
| AU605929B2 (en) | 1991-01-24 |
| ATE91033T1 (de) | 1993-07-15 |
| DE3882015T2 (de) | 1993-11-04 |
| AU2474488A (en) | 1989-05-11 |
| JPH01163184A (ja) | 1989-06-27 |
| ES2056906T3 (es) | 1994-10-16 |
| DE3882015D1 (de) | 1993-07-29 |
| IT1223067B (it) | 1990-09-12 |
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