EP0316980B1 - Photochromische Zusammensetzung und diese Zusammensetzung enthaltende Gegenstände - Google Patents

Photochromische Zusammensetzung und diese Zusammensetzung enthaltende Gegenstände Download PDF

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EP0316980B1
EP0316980B1 EP88202408A EP88202408A EP0316980B1 EP 0316980 B1 EP0316980 B1 EP 0316980B1 EP 88202408 A EP88202408 A EP 88202408A EP 88202408 A EP88202408 A EP 88202408A EP 0316980 B1 EP0316980 B1 EP 0316980B1
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photochromatic
group
process according
spiro
naphtho
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EP0316980A1 (de
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Nicola Casilli
Luciana Crisci
Fiorenzo Renzi
Franco Rivetti
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Enichem Sintesi SpA
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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
    • G03C1/685—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 sunlight, 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:
  • 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 R 7 substituent represents a hydrogen atom and in at least one of them the R 7 substituent represents the amino group the R 1 , R 2 , R 3 , R 4 , R s , R 6 and, if present, R 8 and Rg, substituents, have the following meaning:
  • photochromatic compounds in which the R 7 substituent is different from hydrogen are:
  • the simultaneous presence of a photochromatic compound definable by means of formula (I) and having an -NR8R9 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 -NR8R9 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 of the photochromatic mixture.
  • the mixture can be dissolved in a suitable solvent, together with a polymeric material (e.g., poly-methyl-methacrylate, polyvinyl-alcohol, polyvinyl pyrrolidone, poly-vinylbutyral, cellulose acetate-butyrate or epoxy resin, polysiloxane resin or urethan 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, polyvinyl pyrrolidone, poly-vinylbutyral, cellulose acetate-butyrate or epoxy resin, polysiloxane resin or urethan 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.
  • 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-diethyleneglycol-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 (A 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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Pyrane Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Inorganic Insulating Materials (AREA)

Claims (15)

1. Photochrome Zusammensetzung aus wenigstens zwei photochromen Verbindungen, wovon beide durch die folgende allgemeine Formel (I) wiedergegeben werden können:
Figure imgb0029
worin:
R1 und R2 unabhängig voneinander für ein Wasserstoffatom oder ein Halogenatom, ausgewählt aus F, CI und Br, oder eine Gruppe, ausgewählt aus (C1-C5)-Alkoxy, Nitro, Cyano und einem linearen oder verzweigten (C1-C5)-Alkyl, entweder unsubstituiert oder substituiert mit einem Halogenatom, ausgewählt aus F, CI und Br, oder (C1-C5)-Alkoxy, (C1-Cs)-Alkylthio, (C1-C5)-Carboxyalkyl, und Cyanogruppen bestehen;
R3 und R4 unabhängig voneinander für eine lineare oder verzweigte (C1-C5)-Alkylgruppe, Phenyl oder Benzyl stehen; oder
R3 und R4 bilden eine (C5-C8)-Cycloalkylgruppe, wenn sie zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, betrachtet werden;
R5 ist eine Phenyl-, Benzyl-, Allylgruppe oder eine lineare oder verzweigte (C1-C5)-Alkylgruppe, entweder unsubstituiert oder substituiert mit wenigstens einem Halogenatom, ausgewählt aus F, CI oder Br, oder (C1-C5)-Alkoxy-, (C1-C5)-Alkylthio-, (C1-C5)-Carboxyalkyl- und Cyanogruppen;
R6 für ein Wasserstoffatom steht, ein Halogen, ausgewählt aus F, CI und Br, oder eine Gruppe, ausgewählt aus (C1-C5)-Alkoxy-, (C1-C5)-Alkylthio-, (C1-C5)-Carboxyalkyl- und Cyanogruppen, und eine lineare oder verzweigte (C1-C5)-Alkylgruppe, entweder unsubstituiert oder substituiert mit wenigstens einem Halogenatom, ausgewählt aus F, CI und Br, oder (C1-Cs)-Alkoxy-, (C1-C5)-Alkylthio-, (C1-C5)-Carboxyalkyl- und Cyanogruppen; oder für einen kondensierten aromatischen oder heterocyclischen
Ring steht;
R6 kann, wenn es nicht für Wasserstoff oder einen kondensierten aromatischen oder heterocyclischen
Ring steht, an irgendeiner der 8'-, 9'-, 10'-Positionen des naphthenischen Teiles stehen;
R7 entweder für ein Wasserstoffatom oder
Figure imgb0030
steht; und
R8 und Rg unabhängig voneinander für ein Wasserstofftom oder eine lineare oder verzweigte (C1-C5)-Alkyl-, Phenyl- oder Benzylgruppe stehen, oder
R8 und Rg bilden, wenn sie zusammen mit dem Stickstoffatom betrachtet werden, an das sie gebunden sind, eine monocyclische oder polycyclische Struktur mit 5 bis 12 Gliedern, möglicherweise enthaltend ein weiteres Heteroatom, ausgewählt aus Sauerstoff und Stickstoff; und
X entweder für eine CH-Gruppe oder N steht, wobei in dieser Zusammensetzung wenigstens eine der photochromen Verbindungen, definiert durch die Formel (I), einen R7-Substituentenhat, der aus Wasserstoff besteht, und wenigstens eine der photochromen Verbindungen, definiert durch die Formel (I), einen R7-Substituenten hat, bestehend aus der Gruppe
Figure imgb0031
worin R8 und Rg die oben angegebenen Bedeutungen haben.
2. Photochrome Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß in wenigstens eine der Verbindungen, definiert nach Formel (I), die Substituenten
R1 und R2 unabhängig voneinander für das Wasserstoffatom oder Methyl oder Methoxygruppe stehen;
R3 und R4 jeweils für die Methyl- oder Ethylgruppe oder, wenn sie zusammen betrachtet werden, für die Cyclohexylgruppe stehen;
R5 für eine (C1-C5)-Alkylgruppe steht;
R6 für das Wasserstoffatom oder die Methoxygruppe steht;
R7 für eine -NR8 R9-Gruppe steht, worin
R8 und Rg zusammen, verknüpft mit dem Stickstoffatom, an das sie gebunden sind, für die Piperidino-, Morpholino, Pyrrolidinyl- oder Hexamethyleniminogruppen stehen; und
X entweder für CH oder N steht.
3. Photochrome Zusammensetzung nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß das Molverhältnis der nach Formel (I) definierten photochromen Verbindungen, worin R7 eine -NR8R9-Gruppe zu den Verbindungen ist, ebenfalls definiert durch die Formel (I), worin R7 Wasserstoff ist, durch eine Zahl innerhalb des Bereichs von 0,1 bis 9 umfaßt wird.
4. Photochrome Zusammensetzung nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das Molverhältnis der photochromen Verbindungen, definiert durch Formel (I), worin R7 eine -NR8R9-Gruppe ist, zu den Verbindungen, ebenfalls definiert durch die Formel (I), worin R7 Wasserstoff ist, durch eine Zahl innerhalb des Bereichs von 0,2 bis 1,5 umfaßt wird.
5. Photochrome Zusammensetzung nach Anspruch 1 oder 2 oder 3 oder 4, enthaltend 1,3,3-Trimethyl-6'-piperidino-spiro-[indolino-2,3'-(3H)-naphtho-(2,1-b)-(1,4)-oxazin].
6. Photochrome Zusammensetzung nach den Ansprüchen 1 bis 4, enthaltend 1,3,3-Trimethyl-6'-morpholino-spiro-[indolino-2,3'-(3H)-naphtho-(2,1-b)-(1,4)-oxazin].
7. Photochrome Zusammensetzung nach den Ansprüchen 1 bis 4, enthaltend 1,3,3,4,5-(oder 1,3,3,5,6- )Pentamethyl-6'-piperidino-spiro-[indolino-2,3'-(3H)-naphtho-(2,1-b)-(1,4)-oxazin].
8. Photochrome Zusammensetzung nach den Ansprüchen 1 bis 4, enthaltend 1,3,3-Trimethyl-6'-piperidino-9'-methoxy-spiro-[indolino-2,3'-(3H)-naphtho-(2,1-b)-(1,4)-oxazin].
9. Photochrome Zusammensetzung nach den Ansprüchen 1 bis 4, enthaltend 1,3,3,4,5-(oder 1,3,3,5,6- )Pentamethyl-spiro-[indolino-2,3'-(3H)-naphtho-(2,1-b)-(1,4)-oxazin].
10. Photochrome Zusammensetzung nach den Ansprüchen 1 bis 4, enthaltend 1,3,3-Trimethyl-spiro-[indolino-2,3'-(3H)-naphtho-(2,1 -b)-(1,4)-oxazin].
11. Photochrome Zusammensetzung nach den Ansprüchen 1 bis 4 enthaltend 1,3,3-Trimethyl-9'-methoxy- spiro-[indolino-2,3'-(3H)-naphtho-(2,1 -b)-(1,4)-oxazin].
12. Photochrome Zusammensetzung nach den vorhergehenden Ansprüchen, weiterhin umfassend einen UV-Stabilisator.
13. Photochrome Zusammensetzung nach Anspruch 12, dadurch gekennzeichnet, daß der UV-Stabilisator ein sterisch gehindertes Amin (HALS) ist.
14. Photochromer Artikel, umfassend ein transparentes organisches Polymer und enthaltend auf seiner Oberfläche oder in der Masse eine photochrome Zusammensetzung nach den Ansprüchen 1 bis 10.
15. Photochromer Artikel nach Anspruch 14, worin das transparente organische Polymer ausgewählt ist aus Polymethylmethacrylat, Polyvinylalkohol, Polyvinylbutyral, Polyvinylpyrrolidon, Celluloseacetat-butyrat, Epoxyharzen, Polysiloxanharzen, Polyurethanharzen, Polycarbonat und Polydiethylenglykol-bis-(allylcarbonat).
EP88202408A 1987-11-05 1988-10-28 Photochromische Zusammensetzung und diese Zusammensetzung enthaltende Gegenstände Revoked EP0316980B1 (de)

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AT88202408T ATE91033T1 (de) 1987-11-05 1988-10-28 Photochromische zusammensetzung und diese zusammensetzung enthaltende gegenstaende.

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IT22528/87A IT1223067B (it) 1987-11-05 1987-11-05 Composto fotocromatico ed articoli fotocromatici che lo contengono
IT2252887 1987-11-05

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EP (1) EP0316980B1 (de)
JP (1) JPH01163184A (de)
AT (1) ATE91033T1 (de)
AU (1) AU605929B2 (de)
DE (1) DE3882015T2 (de)
ES (1) ES2056906T3 (de)
IT (1) IT1223067B (de)

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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
DE4420378C1 (de) * 1994-06-10 1995-11-30 Rodenstock Optik G Photochrome Farbstoffe
FR2723218A1 (fr) * 1994-07-29 1996-02-02 Essilor Internal Cie Gle Optique Composes photochromiques de structure spiro (indoline-(2,3')-benzoxazine) a groupement cyano en 6', et leur utilisation dans le domaine de l'optique ophtalmique
EP1044979A3 (de) * 1999-03-24 2001-05-09 Corning S.A. 1-[(N-(Un)substitutierte)amidoalkyl]spiroindolinonaphthoxazine, deren Herstellung, Zubereitungen und diese enthaltende (Co)polymer-Matrizen
EP1044978A3 (de) * 1999-03-24 2001-05-09 Corning S.A. 1-N-Alkyl-5'-[(N'-(un)substitutierte)amido]spiroindolinonaphthoxazine, deren Herstellung, Zubereitungen und diese enthaltenden (Co)polymer-Matrizen

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US4342668A (en) * 1978-09-08 1982-08-03 American Optical Corporation Photochromic compounds
US4440672A (en) * 1982-03-22 1984-04-03 American Optical Corporation Photochromic composition resistant to fatigue
WO1985002619A1 (en) * 1983-12-16 1985-06-20 Optische Werke G. Rodenstock Photochromic substances
CA1268034A (en) * 1985-01-31 1990-04-24 Nori Y.C. Chu Photochromic composition resistant to fatigue
GB8610709D0 (en) * 1986-05-01 1986-06-04 Plinkington Bros Plc Photochromic lenses

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DE3882015D1 (de) 1993-07-29
IT8722528A0 (it) 1987-11-05
EP0316980A1 (de) 1989-05-24
DE3882015T2 (de) 1993-11-04
AU2474488A (en) 1989-05-11
JPH01163184A (ja) 1989-06-27
AU605929B2 (en) 1991-01-24
IT1223067B (it) 1990-09-12
ATE91033T1 (de) 1993-07-15
ES2056906T3 (es) 1994-10-16

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