EP1119572A1 - Photochromatic compounds, preparation, use in polymeric materials - Google Patents

Photochromatic compounds, preparation, use in polymeric materials

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Publication number
EP1119572A1
EP1119572A1 EP99950636A EP99950636A EP1119572A1 EP 1119572 A1 EP1119572 A1 EP 1119572A1 EP 99950636 A EP99950636 A EP 99950636A EP 99950636 A EP99950636 A EP 99950636A EP 1119572 A1 EP1119572 A1 EP 1119572A1
Authority
EP
European Patent Office
Prior art keywords
group
groups
branched
linear
general formula
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.)
Withdrawn
Application number
EP99950636A
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German (de)
English (en)
French (fr)
Inventor
Vincenzo Malatesta
Christiane Salemi-Delvaux
Marie-Hélène DENIEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Switzerland GmbH
Original Assignee
Great Lakes Chemical Europe GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Great Lakes Chemical Europe GmbH filed Critical Great Lakes Chemical Europe GmbH
Publication of EP1119572A1 publication Critical patent/EP1119572A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring

Definitions

  • the present invention relates to photochromatic compounds .
  • the present invention relates to silylated photochromatic compounds, a process for their preparation and their use in polymeric materials.
  • a further object of the present invention relates to polymeric compositions containing said photochromatic compounds and the photochromatic articles obtained from their processing.
  • Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or degree of light transmission when exposed to solar or artificial light in the band ranging from UV to visible, or to some types of electromagnetic radiation, returning to their original state of colour and transmission when the initial light source is removed.
  • photochromatic characteristics which belong to various groups of both organic and inorganic compounds such as, for example, those described in the texts "Photochromism”, by G.H. Brown (Ed.), Vol. Ill of the Weissberger series “Techniques of Organic Chemistry", Wiley Interscience, New York (1971) and in "Photochromism: Molecules and Systems", by H. D ⁇ rr and H. Bouas- Laurent (Ed.), Vol.
  • organic photochromatic compounds those belonging to the groups of spiro-indolino-oxazines, spiro-pyrans and chromenes, are particularly known and used.
  • the above compounds are capable of giving photochromatic characteristics to polymerized organic materials used, for example, in the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
  • the Applicant has now found new silylated photochromatic compounds which have good photochromatic characteris- tics , good fatigue resistance and good colourability char- acteristics .
  • the present invention therefore relates to photochromatic compounds having general formula ( I ) :
  • X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NR a group wherein R a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1- 5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci-C ⁇ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group;
  • R' ⁇ represents a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups, wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C ⁇ -C 3 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; a (meth) allyl group; a (meth) acrylic group; a C 3 -C 8 1-alkenyloxyl group; a linear or branched C 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C ⁇
  • R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C 2 -C ⁇ 0 acyl group; a linear or branched C 2 -C ⁇ o heteroalkyl group in which the heteroa- tom is selected from nitrogen, oxygen, sulfur and selenium; a vinyl group; a (meth) ally1 group; a (meth) acrylic group; a C 3 -C 8 1-alkenyloxyl group; R 1 ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-C ⁇ alkyl group; a linear or branched Ci-C ⁇ alkoxyl group; a phenyl group; a phenoxyl group; P' represents one of the following groups having general formula (III), (IV) or (V):
  • R and R 7 represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-C ⁇ alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2, 6, 6-tetramethylpiperidine group; a vinyl group; a (meth)allyl group; a linear or branched C 2 -C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched Ci-C ⁇ alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Ci-C ⁇ ) amine groups; a COOR' a ester group wherein R' is selected from fluorine,
  • Ri and R 2 represent a linear or branched Cj-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluo-
  • R 2 considered jointly with the carbon atom to which they are bound, represent a C 4 -C ⁇ 0 cycloalkyl group, said cy- cloalkyl group optionally substituted with halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched Ci-C ⁇ alkoxyl groups, carboxyl groups, cyano groups, amine groups, N- alkyl (C ⁇ -C 3 ) amine groups, N,N-dialkyl (C ⁇ -C 6 ) amine groups; an N,N-dialkyl (C ⁇ -C 6 ) amide group; an aryl group selected from phenyl and biphenyl; a cyano group; R 3 , R, R5 and Re, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched C 1 -C 6 alkyl group, said alkyl
  • I boxyamide group a cyano group; a nitro group; a sul- fonic group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N-dialkyl (C ⁇ -C 6 ) amine groups, linear or branched Ci-C ⁇ alkoxyl groups, hydroxyl groups, linear or branched Ci-C ⁇ alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; a (meth)allyl group; a (meth) acrylic group; a C3-C8 1-alkenyloxyl group; a linear or branched C 2 -C 6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-dialkyl- (d- C ⁇ ) -4-aniline groups; an N-2, 3-dihydroindoline group;
  • P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: ben- zenic represented by general formula (VI); naphthalenic represented by general formula (VII); quinolinic represented by general formula (VIII); isoquinolinic represented by general formula (IX); cumarinic represented by general formula (X) ; quinazolinic represented by general formula (XI); phenanthrenic represented by gen- eral formula (XII); anthracenic represented by general
  • Ri3, Ri4 and R 2i , R 22 and R 28 , R29 and R 35 , R 3 e and R i , R 2 and R 4 , R 48 and R 5 , R58 and R 67 , Res and R 75 represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R 3 , R, R5 and Re;
  • Xi represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; an NR a group wherein R a represents a linear or branched C1-C 10 alkyl group;
  • Y represents CH or a nitrogen atom; or R' 2 represents a compound having general formula
  • R , ,! 7 , R''' 8 , R'''9 and R' ' ' ⁇ o represent a hydrogen atom; a linear or branched C1-C10 alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-C ⁇ alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a vinyl group; a (meth)allyl group; a (meth) acrylic group; a C 3 -C 8 1- alkenyloxyl group; a linear or branched C 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally
  • Preferred photochromatic compounds having general for- mula (I) for the purposes of the present invention are those wherein:
  • X represents an oxygen atom
  • R' ⁇ represents a methyl
  • R' 2 represents an OH group; a photochromatic compound having general formula (II) ; a compound having general formula (XV) ;
  • R' represents a linear or branched C 1 -C 4 alkyl group; a linear or branched C 2 -C 4 acyl group; a linear or branched C 2 -C 4 heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium; a (meth)allyl group; a (meth) acrylic group; a C 3 - C 8 1-alkenyloxyl group;
  • R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group
  • - Y represents a nitrogen atom; or CH;
  • P 1 represents one of the groups having general formula (III), (IV) or (V) wherein:
  • R and R 7 represent one of the following groups: methyl, ethyl, isopropyl, 2- allyl, 2-methallyl, 2-hydroxyethyl, 2-carbo- xymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4- methoxybenzene, 4-cyanobenzene;
  • Ri and R 2 represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group;
  • R 3 , R , R5 and R5 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-di- methylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, phenylketone, phenyl;
  • P represents one of the groups having general formula from (VI) to (XIV), wherein:
  • Xi represents an oxygen atom; a sulfur atom; a selenium atom; an NH group;
  • R' ' ' represents a hydrogen atom; a methyl
  • R* " ⁇ , R' "2/ R'''3 and R''' 4 represent a methyl
  • R"'s, R'" 6 , R' " 7 , R'''9 and R''' ⁇ o represent a hydrogen atom
  • R''' 8 represents a C 3 -C 8 1-alkenyloxyl group.
  • a further object of the present invention relates to a process for the preparation of photochromatic compounds having general formula (I) .
  • the photochromatic compounds having general formula (I) can be prepared by the condensation of photochromatic compounds having general formula (II):
  • R''' 7 , R''' 8 , R'''9 and R''' ⁇ o have the same meanings described above, with silylated tetramers having general formula (I 'a) :
  • substituents R' ⁇ and X have the same meanings described above, in the presence of an inert organic solvent such as, for example, acetone, acetonitrile, ethyl alcohol, isopropanol, toluene, dioxane, xylene, or a mixture of these solvents, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 80°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 5 hours.
  • an inert organic solvent such as, for example, acetone, acetonitrile, ethyl alcohol, isopropanol, toluene, dioxane, xylene, or a mixture of these solvents
  • the reaction product thus obtained is generally purified on a silica column, with subsequent crystallization from a solvent such as, for example, acetone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene.
  • the photochromatic compounds having general formula (II) are obtained by the condensation of isoindoline compounds having general formula (XVI), or of indoline compounds having general formula (XVII), or of compounds deriving from propargyl alcohol having general formula (XVIII), or of compounds deriving from ⁇ , ⁇ -unsaturated aldehydes hav-
  • Said condensation reaction is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, acetonitrile, or a mixture of said solvents, and in the presence of an amine such as, for example, triethylamine, morpholine, piperidine, or of an acid such as, for example, paratoluenesulfonic acid, sulfu- ric acid, acid alumina, or of a metal complex such as, for example, titaniu (IV) tetra-ethoxide, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 75°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 3 hours.
  • an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, acetonitrile, or a mixture of said solvents
  • the reaction product thus obtained is generally purified by elution on a silica column and subsequent crystallization from a solvent such as, for example, acetone, toluene, hexane, heptane, pentane, diethyl ether, di- chloromethane .
  • a solvent such as, for example, acetone, toluene, hexane, heptane, pentane, diethyl ether, di- chloromethane .
  • the isoindoline compounds having general formula (XVI) can be prepared according to processes known in the art and described, for example, in: “Tetrahedron” (1966), Vol. 22, page 2481; “Journal of Organic Chemistry” (1979), Vol. 44, page 1519; “Angewandte Chemie International (1968), Vol. 7, page 373.
  • the indoline compounds having general formula (XVII) can be prepared by the reaction of 2, 3, 3-trimethylindolenine compounds with an alkyl or (meth)allyl halide as described, for example, in Japanese patent application JP 03/176467.
  • the isoindoline compounds having general formula (XVI) and the indoline compounds having general formula (XVII) are usually kept in the form of salts such as, for example, iodides, bromides, chlorides, as the free base is very oxidable in air.
  • the compounds deriving from propargyl alcohol having general formula (XVIII) can be prepared by the reaction of ketone compounds with sodium acetylide in xylene or with a lithium acetylide/ethylenediamine complex as described, for example, in USA patents 5,585,042 and 5,238,981.
  • the nitroso compounds having general formula (XX) can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent IT 1,176,858.
  • the aldehyde compounds having general formula (XX) can be prepared by the reaction of phenol compounds with para- formaldehyde, hexamethylenetetramine, or acetic acid, followed by the addition of an aqueous solution of sulfuric acid at 60%-70%, as described, for example, in German patent DE 2,425,430.
  • hydroxy-aryl compounds having general formula (XXI) are normally products which are commercially available such as, for example, ⁇ -naphthol or phenol.
  • isoindoline compounds having gen- eral formula (XVI), or indoline compounds having general formula (XVII), are the following:
  • nitroso compounds having general formula (XX) are the following:
  • the photochromatic compounds having general formula (I) of the present invention are colourless or yellow/brown col- oured, oily or crystalline products.
  • the photochromatic compounds having general formula (I) can be applied to the surface or incorporated in mass into the desired articles, using techniques already known in the art and described hereunder.
  • polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which one or more of the photochromatic compounds having formula (I) are homogeneously dispersed in mass.
  • the photochromatic compounds having general formula (I) can be dissolved in a solvent, together with the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellu- lose acetate butyrate or epoxy, polysiloxane, urethane resin.
  • the mixture thus obtained is deposited on a transparent support to form, after evaporation of the solvent, a photochromatic coating.
  • the photochromatic compounds having general formula (I) can also be added to a polymerizable monomer such as, for example, a meth (acrylic) or allyl carbonate monomer, so that, after polymerization carried out in the presence of a suitable initiator such as, for example, azo-bis (isobutyro- nitrile) in the case of the met (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
  • a suitable initiator such as, for example, azo-bis (isobutyro- nitrile) in the case of the met (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
  • photochromatic compounds having general formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate), by surface im-
  • the photochromatic compounds having general formula (I) of the present invention have the characteristic of being able to be incorporated in mass or using one of the techniques described above, into various organic polymers such as, for example, high density polyethylene (HDPE) , low density polyethylene (LDPE) , ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate bu- tyrate, epoxy, polysiloxane or urethane resins, polycarbon- ate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, polystyrene, polyvinylchloride, polyethy- lacrylate, siliconic polymers.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • ethylene-vinylacetate copolymer polyether amides
  • polypropylene polymethyl methacrylate
  • polyvinyl alcohol polyvinyl
  • a further object of the present invention therefore relates to polymeric compositions comprising the above poly- meric materials and the above photochromatic compounds having general formula (I) and the photochromatic articles obtained from their processing.
  • the photochromatic compounds having general formula (I) of the present invention are added to the above polymeric compositions in a quantity ranging from 0.01% to 5% by
  • the photochromatic compounds having general formula (I) of the present invention can also be added to coating compo- sitions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials.
  • a further object of the present invention consequently relates to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, comprising said photochromatic compounds .
  • the photochromatic compounds having general formula (I) of the present invention are added to the above coating com- positions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said coating compositions.
  • Paints or lacquers based on hybrid polysiloxanes and/or silica gel are obtained by means of the "sol-gel" process described, for example, by M. Noga i, Y. Abe in: “Journal of Materials Science” (1995), Vol. 30, pages 5789-5792.
  • the above coating compositions can be applied to the substrate (metal, plastic, wood, etc.) using the conventional methods such as, for example, brushing, spraying, pouring, dipping or electrophoresis.
  • the photochromatic compounds having general formula (I) of the present invention can optionally be used in the presence of usual additives for organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophenones, phosphites or phosphonites.
  • organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophenones, phosphites or phosphonites.
  • photochromatic compounds having general formula (I) of the present invention which, as already mentioned above, are colourless or yellow/brown coloured, can be used as such, mixed with each other, or combined with other suitable organic photochromatic compounds, in order to obtain, after activation, the formation of other colourings such as brown and grey.
  • photochromatic compounds belonging to the group of spiro-indolino-oxazines or spiro-pyrans described in the art such as, for example, in USA patent 5,066,818, are particularly useful for the purpose.
  • the above mixture is heated to 90°C for 8 hours. At the end, the raw product obtained is washed with water, with toluene and with hydrochloric acid until pH 7.
  • the aqueous phase is further washed with toluene, treated with aqueous sodium hydroxide (solution at 30%) until pH 14 is reached and with toluene.
  • the organic phases obtained are concentrated and dried.
  • the above mixture is heated to 90°C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 6 hours.
  • the raw reaction product obtained is dried and repeatedly extracted with boiling heptane to which 1 g of activated carbon has been added.
  • the heptane extracts are concentrated and boiled with an additional 0.6 g of activated carbon.
  • the reaction raw product obtained is filtered and subsequently purified by passage on a silica column eluating with a mixture of toluene/hexane in a ratio of 1/1.
  • the above mixture is heated to 80°C, under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane.
  • the aqueous phase obtained is treated with aqueous sodium hydroxide (solution at 30%) until pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane.
  • a quantity equal to 31.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 23.8 g of methyl-iodide.
  • the autoclave is heated to 85°C and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
  • the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
  • the above mixture is heated to 70°C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 1 hour.
  • the reaction raw product obtained is filtered and subsequently purified by passage on a silica gel column, eluating with a mixture of heptane/ethyl acetate in a ratio of 1/1.
  • the reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
  • Example 4 dissolved in 40 ml of anhydrous toluene are then added: the mixture obtained is maintained at 80°C for 5 hours. At the end the solvent is eliminated by evaporation under vacuum.
  • the reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
  • the reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
  • Solutions are prepared at a concentration equal to 10 ⁇ 4 M of the various Compounds (Ia)-(Ic) in ethanol and subsequently 2 ml of each solution is placed in a 1 cm quartz cell.
  • the quartz cell containing the solution is introduced into a temperature control system, equipped with a magnetic stirrer (the solution is maintained under stirring during the measurement) .
  • the spectrum of the activated and deactivated forms and the decolouring kinetics are registered with a UV/visible spectrophotometer with a diode battery (HP 8453) equipped with perpendicular optical fibres which give a continuous monochromatic irradiation.
  • the light source is a high pressure Hg lamp and the irradiation wave length is determined by monochromatic filters.
  • This system allows the absorbance to be contemporaneously monitored at all wavelengths.
  • the following parameters are determined using the measurements obtained as described above and with a calculation effected with the GRAFit program of Erithaeus Software Ltd. for the mathematical treatment of the graphs: t ⁇ /2 (s) : time in which the absorbance of the merocya- nine open form is equal to half of the initial absorb- ance value;
  • ⁇ PMC (nm) wave-length of the maximum absorbance of the merocyanine open form
  • colourability difference between the final absorbance and initial absorbance of the merocyanine open form.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Paints Or Removers (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP99950636A 1998-10-09 1999-10-07 Photochromatic compounds, preparation, use in polymeric materials Withdrawn EP1119572A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITMI982175 IT1302637B1 (it) 1998-10-09 1998-10-09 Composti fotocromatici, procedimento per la loro preparazione e loroutilizzo in materiali polimerici.
ITMI982175 1998-10-09
PCT/EP1999/007446 WO2000021968A1 (en) 1998-10-09 1999-10-07 Photochromatic compounds, preparation, use in polymeric materials

Publications (1)

Publication Number Publication Date
EP1119572A1 true EP1119572A1 (en) 2001-08-01

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EP99950636A Withdrawn EP1119572A1 (en) 1998-10-09 1999-10-07 Photochromatic compounds, preparation, use in polymeric materials

Country Status (4)

Country Link
EP (1) EP1119572A1 (it)
AR (1) AR020754A1 (it)
IT (1) IT1302637B1 (it)
WO (1) WO2000021968A1 (it)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7807075B2 (en) 2002-11-04 2010-10-05 Advanced Polymerik Pty Ltd Photochromic compositions and light transmissible articles

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7465415B2 (en) 2004-07-30 2008-12-16 Ppg Industries Ohio, Inc. Photochromic materials derived from ring-opening monomers and photochromic initiators
GB0815109D0 (en) 2008-08-18 2008-09-24 James Robinson Ltd Polydialkylsiloxane-bridged bi-photochromic molecules
CN115160478B (zh) * 2022-07-11 2023-07-14 湖南科技大学 一种光致变色聚合物应用于时间分辨信息动态加密的方法

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JP2856926B2 (ja) * 1991-01-17 1999-02-10 株式会社トクヤマ 有機ケイ素化合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0021968A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7807075B2 (en) 2002-11-04 2010-10-05 Advanced Polymerik Pty Ltd Photochromic compositions and light transmissible articles

Also Published As

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AR020754A1 (es) 2002-05-29
ITMI982175A1 (it) 2000-04-10
WO2000021968A1 (en) 2000-04-20
IT1302637B1 (it) 2000-09-29

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