Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
• • 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
• • 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 photochromatic com- pounds.
• the present invention relates to photochromatic compounds bound to a triazine nucleus, 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 to 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 photochromatic compounds bound to a triazine nucleus which have good photochromatic characteristics, good fatigue resistance and good coloura- bility characteristics .
• the present invention therefore relates to photochromatic compounds having general formula (I) :
• R' ⁇ represents a hydrogen atom; an OH group; or a pho- tochromatic compound having general formula (II) .
• R' represents a linear or branched C ⁇ -C ⁇ o alkyl group; a linear or branched C 2 -C ⁇ o acyl group; a hydroxyl group; a linear or branched Ci-C ⁇ alkoxyl group; an amine group, said amine group optionally substituted with a linear or branched C ⁇ C 6 alkyl group; an N-alkyl (C ⁇ -C 6 ) amine group; an N,N-dialkyl (Ci-C ⁇ ) amine group; a pi- peridine, piperazine or morpholine group; a carboxylic acid group; a chloro carbonyl (CO-Cl) group; an amide group; a COOR' a ester group wherein R' a represents a linear or branched Ci-Cio alkyl group; a linear or branched C 2 -C ⁇ o heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium; a
• 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 C ⁇ -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally sub- stituted with linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C ⁇ -C 6 ) amine groups; a 4-N,N
• Ri and R 2 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 (meth) acrylic group; a C 3 -C 8 1- alkenyloxyl group; a linear or branched C 2 -C ⁇ o alkenyl group; a COOR' a ester 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
• R 3 , R 4 , R5 and Re represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci-C ⁇ alkyl group, said alkyl group optionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hy- droxyl groups, linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine 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
• 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 general formula (XII) ; anthracenic represented by general formula (XIII); or a group with general formula (XIV):
• R 8 and R i3 , R i4 and R 21 , R 22 and R 28 , R 30 and R 35 , R 36 and R 41 , R 42 and R 47 , Rs and R 57 , R 58 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 4 , R 5 and R 6 ;
• 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 Ci-Cio alkyl group; Y represents CH or a nitrogen atom.
• Preferred photochromatic compounds having general for- mula (I) for the purposes of the present invention are those wherein:
• R' ⁇ represents an OH group; or a photochromatic compound having general formula (II) ;
• R' represents a linear or branched C ⁇ -C 4 alkyl group; a linear or branched C 2 -C 4 acyl group; a hydroxyl group; a linear or branched C ⁇ -C 6 alkoxyl group; an amine group; an N-alkyl (C ⁇ -C 6 ) amine group; an N,N-dialkyl
• (Ci-C ⁇ ) amine group a piperidine, piperazine or mor- pholine group; a carboxylic acid group; a chloro car- bonyl (CO-Cl) group; 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
• R 3 , R, R5 and R 6 the same or different, rep- resent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-dimethylamine, piperi- dine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, meth- ylketone, phenylketone, phenyl; a linear or branched Ci-C ⁇ alkoxyl group; an amine group; an N-alkyl (C ⁇ -C 6 ) amine group; an N,N- dialkyl (C ⁇ -C 6 ) amine group; a piperidine, piperazine or morpholine group; a carboxylic acid group; an amide group; a chloro carbonyl (CO-Cl) group; a COOR' a
• R13, Ru and R 2i , R 22 and R 28 , R 30 and R 35 , R 36 and R 41 , R 42 and R 47 , R 48 and R 57 , R 58 and R 6 , Res and R 75 in- dependently represent the condensation points with the oxazine or pyran ring; and the other substituents each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, 2- (meth) allyl, (meth)acryl, hydroxyl, methoxyl, 2- hydroxyethyl, amine, N-methylamine, N-ethylamine, N,N-dimethylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, ethylketone, phenylke- tone, methylthiol;
• a further object of the present invention relates to a process for the preparation of the 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) :
• X represents a halogen atom such as fluorine, chlorine, bromine or iodine, in the presence of an inert organic solvent such as, for example, acetone, ethyl alcohol, iso- propanol, toluene, dioxane, or of a mixture of these solvents, at a temperature ranging from 20°C to 100°C, preferably from 20°C to 40°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 5 hours.
• the reaction product thus obtained is generally purified on a silica col- umn, with subsequent crystallization from a solvent such as, for example, acetone, toluene, pentane, heptane, diethyl ether.
• 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 having general formula (XIX) , with nitroso compounds or aldehyde compounds having general formula (XX) , or with hydroxy- aryl compounds having general formula (XXI), to give the respective photochromatic compounds having general formula (XVIa) , (XVIIa) and (XVIIIa) , indicated in Schemes 1-4:
• the condensation reaction is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, acetonitrile, or of a mixture of these 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, titanium (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 of a mixture of these solvents
• the reaction product thus obtained is gen- erally 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, chlQrides, 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 U.S. patents 5,585,042 and 5,238,981.
• 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.
• 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 general formula (XVI), or indoline compounds having general formula (XVII), are the following:
• aldehyde compound having general formula (XX) is the following: #
• the compounds having general formula (XV) are generally products which are commercially available.
• the photochromatic compounds having general formula (I) of the present invention are colourless or slightly yellow- coloured, 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.
• Some 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, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
• the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
• 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 meth (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 meth (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
• the 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 impregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing one or more of the photochromatic compounds having general formula (I) , operating according to a method described, for example, in U.S. patent 5,130,353.
• a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate
• 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 tech- niques described above, into various organic polymers such as, for example, high density polyethylene (HOPE), 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, polycarbonate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, polystyrene, polyvinylchloride, polyethy- lacrylate, siliconic polymers.
• HOPE high density polyethylene
• LDPE low density polyethylene
• ethylene-vinylacetate copolymer polyether amides
• polypropylene polymethyl methacrylate
• polyvinyl alcohol polyviny
• a further object of the present invention therefore re- lates to polymeric compositions comprising the above polymeric 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 weight, preferably between 0.1% and 2% by weight, with respect to the weight of said polymeric compositions.
• the photochromatic compounds having general formula (I) of the present invention can also be added 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.
• a further object of the present invention consequently relates 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, comprising said photochromatic compounds .
• the photochromatic compounds having general formula (I) of the present invention are added to the above coating compositions 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. Nogami, 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 conven- tional 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 slightly yellow-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 U.S. patent 5,066,818, are particularly useful for the purpose.
• the product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 23.5 g.
• a quantity equal to 23.5 g of the above product is charged into a 100 ml stainless steel autoclave together with 20 ml of toluene and 16 g of methyliodide.
• the autoclave is heated to 85 °C and the whole mixture 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.
• 35 g of product are obtained, corresponding to 1, 1, 2, 4, 7-pentamethyl-3-methylene-isoindoline iodide having formula (XVI 1 ) -A.
• the solvent is eliminated by distillation under vacuum and 40 ml of toluene and 2.0 g of activated carbon are subsequently added. This mixture is heated to 70 °C for 15 minutes: the reaction raw product is filtered, concentrated and cooled.
• This mixture is subsequently cooled to room temperature and the reaction raw product obtained is poured into an aqueous solution 2M of NH 4 C1 (100 ml) and heated to 80 °C for an hour. At the end, the mixture is cooled again to room temperature and, after filtration of the titanium (IV) tetra- ethoxide, the organic phase is separated, washed with water and dried on magnesium sulfate. The solvent is partially removed at reduced pressure and the resulting solution is cooled to 0°C.
• reaction raw product After 2 hours at room temperature, the reaction raw product is filtered and the solvent is eliminated by evapo- ration under vacuum. A light blue solid is obtained which is purified by repeated washings with 10 ml of diethyl ether and dried by evaporation under vacuum.
• reaction raw product After 1 hour at room temperature, the reaction raw product is filtered and the solvent is eliminated by evaporation under vacuum. A light green solid is obtained, which is purified by repeated washings with 10 ml of diethyl ether and dried by evaporation under vacuum.
• reaction raw product is filtered and the solvent is eliminated by evapo- ration under vacuum.
• a light orange solid is obtained, which is purified by repeated washings with 10 ml of diethyl ether and dried by evaporation under vacuum.
• the photochromatic activity is evaluated in ethanol, at 25°C, of Compounds (Ia)-(Ic) obtained as described in Examples 5-7.
• 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 .

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