Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/357—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
  • C08K5/3417—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/353—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
  • C08K5/47—Thiazoles

Definitions

• a further object of the present invention relates to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysilo- xanes and/or silica gel, compositions based on plastic materials, containing said photochromatic composi- tions.
• 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.
• 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.
• Photochromatic compounds have a limited existence as their capacity for changing colour and/or degree of light transmission when exposed to light radiation, as already mentioned above, is made irreversible as a result of decomposition due to light fatigue. Repeated exposure to light is therefore responsible for a loss in the photochromatic properties of these compounds which, at times, have undesired colouring.
• Light stabilizers are used, among others, to overcome this phenomenum.
• U.S. patent 3.212.898 describes the use of ultraviolet light stabilizers, such as benzo- phenones and benzotriazoles, to improve the light
• U.S. patent 4.720.356 discloses photochromatic compositions endowed with light fatigue resistance which comprise a spiro-oxazine combined with a sterically hindered amine selected from those normally used for the ultraviolet light stabilization of organic polymers.
• European patent application EP 195.898 describes the use of sterically hindered amines associated with UV quenchers of excited states based on nickel .
• Photochromatic compounds (a) belonging to the group of spiro-indolino-oxazines which can be used for the purposes of the present invention are selected from compounds having general formula (I) :
• R 1 and R 2 represent a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched C,-C 5 alkyl or haloalkyl group; a linear or branched C.,-C 5 alkoxyl group; a nitro group; a cyano group ;
• R 3 and R 4 represent a linear or branched C,-C 5 alkyl group; a phenyl group; a benzyl group; or, R 3 and R 4 considered jointly wich the carbon atom co which they are
• groups R 1 and R 2 do not represent a hydrogen atom, they can be bound to any of positions 4, 5, 6 and 7 of the indolinic part of the
• group R 7 does not represent a hydrogen atom or a condensed aromatic or heterocyclic ring, it can be present in any of positions 7', 8', 9' and 10' of the naphthenic part of the molecule.
• Preferred compounds having general formula (I) for the purposes of the present invention are those wherein:
• R 1 and R 2 each independently represent a hydrogen atom; or a methyl group; - R 3 and R 4 both represent a methyl group; or, considered jointly, represent a cyclohexyl group;
• R 5 represents a methyl group
• R 6 represents a hydrogen atom; or an -NR 8 R 9 group wherein groups R 8 and - ⁇ , together with the nitro- gen atom to which they are bound, represent a piperidyl, morpholyl , pyrrolidyl or hexamethylene- imine ring structure;
• R 7 represents a hydrogen atom; or a methoxyl group ; and - X represents CH.
• photochromatic compounds having general formula (I) which can be used for the purposes of the present invention but which in no way limit the scope of the invention itself, are: - 1,3,3,4,5 or 1 , 3 , 3 , 5 , 6-pentamethyl spiro- [indol- ino-2 , 3 ' - [3H] -naphtho- (2,l-b) - (l,4) -oxazine] , having the formula:
• photochromatic compounds having general formula (I) are prepared as described, for example, in U.S. patent 5.180.524.
• Photochromatic compounds (a) belonging to the group of spiro-pyrans which can be used for the purposes of the present invention are selected from compounds represented by the following general formulae : indolino-spiro-pyrans having general formula (II) :
• R 10 and R each independently, represent linear cr branched C.,-C 10 alkyl groups or C 6 -C 14 aryl grou s,-
• R 12 represents a linear or branched C- j -C- ⁇ alkyl group, said alkyl group optionally substituted with one or more halogen atoms selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C 2 ⁇ c ⁇ o carboalkoxyl groups, linear or branched C ⁇ C ⁇ alkoxyl groups, amine groups ; or an aryl group ;
• R 1 represents a hydrogen atom; a linear or branched C ⁇ C- ⁇ alkyl group; a linear or branched c ⁇ _c ⁇ o a lk° ⁇ yJ group; an aryl group;
• R 13 and R 15 each independently, represent a hydrogen atom; mono- or polysubstitution groups selected from C. J -C- JQ alkyl groups optionally substituted; halogen atoms selected from fluorine, chlorine and bromine; nitro groups; C ⁇ C ⁇ alkoxyl groups.
• Photochromatic compounds (a) belonging to the group of spiro-isoindolino-oxazines which can be used for the purposes of the present invention are selected from those having general formula (VI) :
• R' represents a linear or branched C j -C- jg alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched C.,- ⁇ alkoxyl groups, carboxyl groups, cyano groups, or with a 2 , 2 , 6 , 6-tetrame- thylpiperidine group; a linear or branched 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched C 1 -C ⁇ alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C,-C 6 ) amine groups; a benzyl group; b) R'- !
• R' 2 represent a linear or branched C j -C- ⁇ alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bro- mine, or with hydroxyl groups, linear or branched
• N,N-dialkyl (C 1 -C 6 ) amine groups an N,N-dialkyl (C 1 -C 6 ) amine group; a piperidine, piperazine or morpholine group; a C,-C 6 carboxyalkyl group; a C 2 -C 6 carboxyalkenyl group; a carboxyamide group; an N-alkyl (C 1 -C 6 ) carboxya- mide group; an N,N-dialkyl (C.,- ⁇ ) carboxyamide group; a cyano group; a nitro group; a sulfonic group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N-dialkyl (C 1 -C 6 ) amine groups, linear or branched C 1 -C 6 alkoxyl groups, hydroxyl groups, linear or branched C,- ⁇ alkyl groups; an acyl group of the
• -14- P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: benzenic represented by general formula (VII) ,- naphthalenic represented by general formula (VIII) ; quinolinic represented by general formula (IX) ; isoquinolinic represented by general formula (X) ; cumarinic represented by general formula (XI) ; quinazolinic represented by general formula (XII) ; phenanthrenic represented by general formula (XIII) ; anthracenic represented by general formula (XIV) :
• reaction product is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these solvents, at a temperature ranging from 50°C to 100°C, preferably between 60 °C and 75 °C, for a time ranging from 1 hour to 10 hours, preferably between 2 hours and 5 hours.
• an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these solvents.
• reaction product is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these solvents, and in the presence of aqueous ammonia at 30%, at a temperature ranging from 50°C to 100°C, preferably between 60°C and 75°C, for a time ranging from 1 hour to 10 hours, preferably between 2 hours and 3 hours.
• 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, heptane.
• the isoindolinic compounds having general formula (VI') can be prepared according to processes known in the art 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 isoindolinic compounds having general formula (VI') are usually kept in the form of salts such as,
• nitroso compounds having general formula (VII') can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent 1.176.858.
• aromatic 1,2-quinones having general formula (VIII') can be prepared as described, for example, in: "Journal of American Chemical Society” (1952) , Vol. 74, page 278; Chemical Abstract Nr. 103-104923q; in European patent EP 245.020 and in U.S. patent 5.446.150.
• photochromatic compounds having general formula (VI) which can be used for the purposes of the present invention, but which in no way limit its scope, are:
• R' ' o m n wherein: m represents an integer from 1 to 3 , extremes included; n represents an integer from 1 to 4 , extremes included;
• R''- ! represents a triazine having one of the following general formulae (XVI) , (XVII) or (XVIII) :
• R > - 5 wherein R'' 5 represents a hydrogen atom; a linear or branched C ⁇ C- ⁇ alkyl group; an -NHR'' 6 amine group or an -SR' ' 6 group wherein R' ' 6 represents a hydrogen atom or a linear or branched C- j -C ⁇ alkyl group ;
• R''-, and R'' 2 represent a hydrogen atom; a linear or branched C,-C 18 alkyl group; a linear or branched C 2 -C 8 alkoxyalkyl group; a C 5 -C 8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C 6 -C 18 aryl group; a C 7 -C 2Q arylalkyl or alkylaryl group; a group having general formula (XIX) :
• R'' 7 represents a hydrogen atom; a linear or branched C ⁇ C- ⁇ alkyl group, said alkyl group optionally substituted with an -NHR' ' 8 group or an -0R'' 3 group wherein R'' 8 represents a hydrogen atom, a linear or branched C ⁇ C- jg alkyl group, or a C 6 -C 18 aryl group; an -0R'' 9 group wherein R'' 9 represents a hydrogen atom, or a linear or branched C ⁇ - ⁇ & alkyl group; or, R' ⁇ and R, ' 2 considered jointly with the nitrogen atom, represent a C 5 -C 8 heterocyclic group optionally containing a second heteratom selected from oxygen, nitrogen and sulfur;
• R'' 3 and R'' 4 represent a linear or branched C-,-C 18 alkyl group; a C 6 -C 18 aryl group; a C 7 -C 20 alkylaryl or arylalkyl group; a linear or branched C ⁇ C ⁇ alkoxyl group; a linear or branched C 2 -C 18 alkyleneoxyl group; a C 6 -C 18 aryloxyl group; or, R'' 4 represents a group having general formula (XX) : i
• R'' 7 has the same meanings defined above; or, R' ' 4 represents an NR'' 10 R' ' ⁇ group wherein R'' 10 and R'' , the same or different, represent a hydrogen atom; a linear or branched C,-C 18 alkyl group; a linear or branched C 2 -C 8 alkoxyalkyl group; a C 5 -C 8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C ⁇ -C 18 aryl group; a C 7 -C 20 arylalkyl or alkylaryl group; a triazine having one of the following general formulae (XVI) , (XVII) or
• R'' 5 has the same meanings defined above; a group having general formula (XIX) :
• R'' 7 has the same meanings defined above; or, R'' 10 an ⁇ ⁇ R ''n considered jointly with the nitrogen atom, represent a C 5 -C 8 heterocyclic group optionally containing a second heteroatom selected from oxygen, nitrogen and sulfur; or R'' 4 represents a group having one of the following general formulae (XXI) , (XXII) or (XXIII) :
• R' ' 2 represents a hydrogen atom; or a linear or branched ⁇ -C ⁇ alkyl group
• R' ' 3 represents a linear or branched 0,,-C ⁇ alkyl group
• a -C0CH 2 C0CH 3 group or a direct
• R'' ⁇ R'' 2 ' R '' ⁇ o anc R ''n g rou P s i n addition to a hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl , 4- (2, 2 , 6, 6-tetramethyl) piperidinyl, 4- (2,2,6, 6-tetramethyl) -1-butoxy- ethylpiperidinyl , 4- (2 , 2, 6, 6-tetramethyl) -1-butoxypipe- ridinyl , 4- (2 , 2 , 6, 6-tetramethyl) -1-methylpiperidinyl, 3 , 5-dioctylaminotriazine, 3 , 5-dibutylaminotriazine, etc.
• C 8 -C 8 heterocyclic groups when R''., and R'' 2 or R' ' 0 and R'' ⁇ are considered jointly with the nitrogen atom, are: morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, benzothiazolidine, etc.
• R'' 3 and R'' 4 groups are: methyl, ethyl, propyl, isopropyl, phenyl, oxymethyl, oxyethyl, oxybutyl, oxyoctyl, oxyoctadecyl , oxyallyl, phenoxyl, etc.
• R'' 4 groups when R'' 4 represents a group having general formula (XX), are: 4- (2,2,6,6- tetramethyl) piperidinoxy, N-methyl-4- (2,2,6, 6-tetramethyl) piperidinoxy, N-methoxyethyl-4- (2,2,6, 6-tetramethyl) piperidinoxy, N-methylaminoethyl-4- (2,2,6,6- tetramethyl) piperidinoxy, etc.
• R'' 4 groups when R'' represents a group having general formula (XXI) , (XXII) or (XXIII) and n is 2, are:
• R'' 4 groups when R'' represents a group having general formula (XXI) , (XXII) or (XXIII) and n is 3, are:
• R'' 4 groups when R'' 4 represents a
• R' ' 7 groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, ⁇ -hydroxyethyl , -methoxyethyl , ⁇ -butoxyethyl, methylaminoethyl , etc.
• R" 5 , R ' R' R" 9 , R '' ⁇ 2 and R ''i 3 groups when said groups represent a linear or branched C j -C jg alkyl group, are: methyl, ethyl, propyl, isopropyl, butyl, octyl, etc.
• Specific examples of compounds (a) having general formula (XV) which can be used for the purposes of the present invention but which should in no way be considered as limiting its scope are:
• a process for the synthesis of the compounds having general formula (XV) comprises the reaction of 1-4 moles of a primary or secondary, aliphatic or aromatic amine, having general formula (XXIV) :
• R' ' 3 , R' ' 4 and n have the same meanings defined above .
• the above reaction takes place in the presence of an inert organic solvent, preferably a hydrocarbon, in particular toluene, at a temperature ranging from 60°C to 160°C, preferably from 115°C to 150°C, at atmospher- ic pressure, and for a time ranging from 0.5 to 24
• an inert organic solvent preferably a hydrocarbon, in particular toluene
• Acetic acid can optionally be added as catalyst to this reaction.
• reaction water is released which is separated by azeotropic distillation using an apparatus for azeotropic distillation, whereas the organic solvent is recycled.
• the desired compound having general formula (XV) is purified from the raw product thus obtained, by fractionated distillation, operating under vacuum, at a pressure ranging from 0.1 mm/Hg to 50 mm/Hg and a temperature ranging from 40 °C to 200 °C. Or, said compound having general formula (XV) is separated by crystallization using techniques known in the art .
• Examples of primary or secondary, aliphatic or aromatic amines, having general formula (XXIV) which can be used for the purposes of the above process are : cyclohexylamine, n-butylamine, tert-butylamine, n-octy- lamine, tert-octylamine, n-octadecylamine, n-dodecylam- ine, benzylamine, 2-methoxyethylamine, 2-furfurylamine, pyrrolidine, piperidine, morpholine, dibenzylamine, aniline, diphenylamine, melamine, 4-amino-2 , 2 , 6 , 6-te- tramethylpiperidine, 4-amino-2 , 2 , 6 , 6-tetramethyl-l-me-
• Examples of ⁇ -keto-esters or ⁇ -keto-amides, or 1, 3-diketones having general formula (XXV) which can be used for the purposes of the above process are: ethyl acetoacetate, allyl acetoacetate, phenyl acetoacetate, ethyl benzoylacetate, acetylacetone, benzoylacetone, p-toluylacetone, 4- (2,2,6, 6-tetramethyl) piperidinyl acetoacetate, N-methyl-4- (2,2,6, 6-tetramethyl) piperid- inyl acetoacetate, acetoaceta ide, acetoacet-4- (2, 2, - 6, 6-tetramethylpiperidine) amide, acetoacet- (3 , 5-dibu- tyltriazine) -1-amide, etc.
• Preferred photochromatic compounds (a) for the purposes of the present invention are:
• Preferred compounds belonging to the group of enamines (b) for the purposes of the present invention are - enamine having general formula (a.,) :
• R c wherein R b represents one of the following groups:
• R c represents a hydrogen atom, or a CH 3 ; enamine having general formula (a 3 ) :
• R represents a hydrogen atom, or a CH 3 ;
• the ratio between the photochromatic compound (a) and the compound belonging to the group of enamines (b) is between 1:1 and 1:10, preferably between 1:2 and 1:6.
• the photochromatic compounds of the present invention can be applied to the surface or incorporated in mass into the desired articles, using techniques already known in the art and described hereunder.
• the photochromatic compounds (a) and the compounds belonging to the group of enamines (b) can also be applied or incorporated separately into the desired articles.
• polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which the composition of the present invention or its components (a) and (b) separately, is homogeneously dispersed in mass.
• moulding techniques such as, for example, injection or compression moulding, starting from polymers in which the composition of the present invention or its components (a) and (b) separately, is homogeneously dispersed in mass.
• said composition or said components such as, for example, injection or compression moulding
• -37- (a) and (b) 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, polysil- oxane, urethane resin.
• the mixture thus obtained is deposited on a transparent support to form, after evaporation of the solvent, a photochromatic coating.
• (b) 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 (isobutyronitrile) in the case of the meth (acrylic) monomer or a peroxyketal 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 (isobutyronitrile) in the case of the meth (acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer
• composition or compounds (a) and (b) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethylene glycol bis (allyl carbonate), by surface impregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing the mixture or compounds (a) and (b) , 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 polydiethylene glycol bis (allyl carbonate
• the photochromatic compositions of the present invention or compounds (a) and (b) 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, polymethylmethacrylate, polyvinyl alcohol, polyvinyl butyral , cellulose acetate butyrate, epoxy, polysiloxane or urethane resins, polycarbonate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, etc.
• HDPE high density polyethylene
• LDPE low density polyethylene
• ethylene-vinylacetate copolymer polyether amides
• polypropylene polymethylmethacrylate
• polyvinyl alcohol polyvinyl butyral
• cellulose acetate butyrate cellulose acetate butyrate
• epoxy polysilox
• a further object of the present invention therefore relates to polymeric compositions comprising the above organic polymers and the above photochromatic compositions and the photochromatic articles obtained from their processing.
• the photochromatic compositions of the present invention or compounds (a) and (b) are added to the above polymeric compositions in such a quantity that the photochromatic compound (a) is present in a quantity of 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, and the compound belonging to the group of enamines (b) is present in a quantity ranging from 0.1% to 10% by weight, preferably between 0.1% and
• photochromatic compositions 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 compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, containing said photochromatic compositions.
• the photochromatic compositions of the present invention or compounds (a) and (b) are added to the above coating compositions in such a quantity that the photochromatic compound (a) is present in a quantity of 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, and the compound belonging to the group of enamines (b) is present in a quantity ranging from 0.1% to 15% by weight, preferably between 0.1% and 8% by weight .
• 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,
• 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 compositions of the present invention can be combined, as already mentioned above, with other conventional additives or their mixtures. These additives are added in a quantity ranging from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example. 1.
• Antioxidants 1.1 Alkylated monophenols such as, for example: 2, 6-di-t-butyl-4-methylphenol; 2-t-butyl-4, 6-dimethylphenol; 2, 6-di-t-butyl-4-ethylphenol; 2, 6-di-t-butyl-4-n-butylphenol; 2, 6-di-t-butyl-4-isobutylphenol;
• Alkylthiomethylphenols such as, for example: 2 , 4-dioctylthiomethyl-6-t-butylphenol ;
• Hydroquinones and alkylated hydroquinones such as, for example :
• Tocopherols such as, for example: ⁇ .-tocopherol , ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and their mixtures (Vitamin E) .
• Hydroxylated thiophenyl ethers such as, for example:
• Hydroxybenzylated malonates such as, for example: dioctadecyl-2 , 2-bis (3 , 5-di-t-butyl-2 -hydroxybenzyl) malonate; dioctadecyl-2- (3 -t-butyl -4 -hydroxy- 5 -methylben- zyl) malonate; didodecylmercaptoethyl-2 , 2-bis (3 , 5-di-t-butyl-4- hydroxybenzyl ) malonate ; bis [4- (1,1, 3, 3 - tetramethylbutyl ) phenyl] -2,2- bis (3, 5 -di-t -butyl -4 -hydroxybenzyl) malonate.
• Aromatic hydroxybenzyl compounds such as, for example :
• Triazine compounds such as, for example:
• Benzylphosphonates such as, for example: dimethyl-2, 5-di-t-butyl -4 -hydroxybenzylphosphona- te; diethyl-3 , 5-di-t-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3 , 5-di-t-butyl-4 -hydroxybenzylphospho- nate; dioctadecyl - 5 - 1 -butyl -4 -hydroxy- 3 -methylbenzylpho- sphonate ; calcium salts of monoethyl ester of 3,5-di-t- butyl-4-hydroxybenzylphosphonic acid.
• -46- 1.12 Acylaminophenols such as, for example: 4 -hydroxylauranilide ; 4-hydroxystearanilide; octyl-N- (3 , 5-di-t-butyl-4-hydroxyphenyl) carbamate.
• esters of ⁇ - (3 , 5-di-t-butyl-4 -hydroxyphenyl ) pro- pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1, 6-hexandiol, 1, 9-nonandiol , ethylene glycol, 1, 2-propanediol , neopentyl glycol, thiodiethylene glycol, diethylene glycol, trie- thylene glycol, pentaerythritol , tris (hydroxy- ethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxami- de, 3-thioundecanol, 3-thiopentadecanol, trime- thylhexandiol , trimethylolpropane, 4-hydroxyme- thyl-l-phospho-2, 6, 7-trio
• esters of ⁇ - (5-t-butyl-4-hydroxy-3 -methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1, 6-hexandiol, 1,9-nonan- diol, ethylene glycol, 1, 2-propanediol , neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy- ethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxami- de, 3-thioundecanol, 3 -thiopentadecanol , trime- thylhexandiol, trimethylolpropane, 4-hydroxyme-
• esters of ⁇ - (3 , 5 -dicyclohexyl -4 -hydroxyphenyl) pro- pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1, 6-hexandiol , 1, 9-nonandiol , ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triet- hylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3- thioundecanol , 3-thiopentadecanol , trimethylhexan- diol, trimethylolpropane, 4-hydroxymethyl-l- phospho-2 , 6, 7-trioxabicyclo [2.2.2]
• esters of (3 , 5 -di-t-butyl -4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1 , 6-hexandiol , 1 , 9-nonandiol , ethylene glycol, 1, 2-propanediol , neopentyl glycol, thiodiethylene glycol, diethylene glycol, trie- thylene glycol, pentaerythritol, tris (hydroxye- thyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3 -thioundecanol , 3 -thiopentadecanol , trimethyl- hexandiol, trimethylolpropane, 4-hydroxymethyl-l- phospho-2 , 6 , 7-trio
• 2- (2 ' -hydroxyphenyl) benzotriazoles such as, for example: 2- (2' -hydroxy-5 'methylphenyl) benzotriazole;
• 2-hydroxybenzophenones such as, for example: 4 -hydroxy-; 4-methoxy-; 4-octyloxy- ; 4- decyloxy- ; 4-dodecyloxy- ; 4-benzyloxy- ; 4, 2', 4'- trihydroxy- ; 2 ' -hydroxy-4 , 4 ' -dimethoxy .
• esters of benzoic acids optionally substituted, such as, for example: phenyl salicylate, 4-t- butylphenyl salicylate, octylphenyl salicylate, benzoyl-resorcinol , bis (4-t-butylbenzoyl) -resor- cinol, dibenzoyl-resorcinol , 2 , 4-di-t-butylphenyl- 3 , 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3 , 5- di-t-butyl-4-hydroxybenzoate, octadecyl-3 , 5-di-t- butyl -4 -hydroxybenzoate , 2 -methyl-4 , 6-di-1-butyl - phenyl -3 , 5-di-t-butyl -4 -hydroxybenzoate .
• Acrylates such as, for example, ethyl or isoctyl ⁇ .-cyano- ⁇ , ⁇ -diphenylacrylate; methyl ⁇ -carbometho- xycinnamate, methyl or butyl ⁇ -cyano- ⁇ -methyl-p- methoxycinnamate, methyl ⁇ .-carbomethoxy-p-methoxy- cinnamate, N- ( ⁇ -carbomethoxy- ⁇ -cyanovinyl) -2 - methylindoline .
• Nickel compounds such as, for example, complexes of 2,2' -thio-bis- [4- (1, 1, 3 , 3-tetramethylbutyl) phenol] , for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3 , 5-di-t-butyl- benzyl-phosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2- hydroxy-4 -methylphenyl undecyl ketoxime, nickel
• Sterically hindered amines such as, for example: bis (2,2,6, 6-tetramethyl-piperidyl) sebacate; bis (2,2,6, 6-tetramethyl -piperidyl) succinate; poly-methylpropyl-3-oxy [4- (2,2,6, 6-tetramethyl) pi- peridinyl] siloxane; poly-methylpropyl-3 -oxy [4- (1,2,2,6, 6 -pentame - thyl) piperidinyl] siloxane; bis (1,2,2,6, 6-pentamethyl-piperidyl) sebacate; bis (1,2,2,6, 6 -pentamethyl-piperidyl) n-butyl-3, 5- di-t-butyl-4 -hydroxybenzylmalonate ; condensation product between 1- (2 -hydroxyethyl) -
• Oxamides such as, for example:
• Metal -deactivators such as, for example: N,N- diphenyloxamide, N-salicylal-N' -salicyloyl-hydra- zine, N,N' -bis (salicyloyl) hydrazine; N,N' -bis (3 , 5- di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3- salicyloylamino-1, 2 , 4-triazole, bis (benzylidene) o- xalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diace- tyladipoyl dihydrazide, N,N' -bis (salicyloyl) oxal- lyl dihydrazide, N,N' -bis (salicyloyl) thio
• Phosphites and phosphonites such as, for example: triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2 , 4-di-t-butyl- phenyl) pentaerythritol diphosphite, bis (2 , 5-di-t- butyl -4 -methylphenyl ) pentaerythritol diphosphite , diisodecyloxypentaerythritol diphosphi
• Agents which are capable of destroying peroxides such as, for example, esters of ⁇ -thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole, zinc dibutyldithiocarbama- te, dioctadecyldisulfide pentaerythritol tetrakis ( ⁇ -dodecylmercapto) propionate .
• Stabilizers of polyamides such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts. 7.
• Basic co-stabilizers such as, for example: mela- mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, polyure- thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids such as, for example: mela- mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, polyure- thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids such as, for example: mela- mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, polyure- thanes, salt
• Nucleating agents such as, for example: 4-t-butyl- benzoic acid, adipic acid, diphenylacetic acid.
• Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
• reaction mass is maintained under stirring and reflux heated for 4 hours, to a temperature ranging from 115°C to 118°C. During this period there is the formation of reaction water which is separated by azeotropic distillation: 1.5 g of reaction water are separated.
• the solvent and acetic acid are removed by distil - lation and the raw residue thus obtained is subjected to fractionated distillation.
• This distillation is carried out in a distiller consisting of a 100 ml boiler equipped with a thermometer, stirrer, column, condenser and device for the collection of fractions.
• Amine 4-amino-2 , 2 , 6 , 6-tetramethylpiperidine; 31.25 g (0.2 moles) .
• Carbonyl compound ethyl aceto-acetate
• Carbonyl compound 2 , 2 , 6, 6-tetramethyl-4-piperidi- nylacetoacetate; 48.5 g (0.2 moles).
• Reaction time and temperature 3.5 hours at 114°C- 128°C.
• the raw residue obtained is not subjected to fractionated distillation as the end- product crystallizes in the reaction medium at room temperature.
• the product obtained is filtered, washed with toluene and dried.
• Solvent toluene; 50 g.
• Catalyst acetic acid; 0.3 g Reaction water separated: 3.50 g - Reaction time and temperature: 1 hour 45 minutes at 118°C-130°C.
• Compound Nr. 4 is characterized by NMR analysis which confirms its enamine structure.
• Reaction water separated 20.20 g - Reaction time and temperature: 4 hours at 130°C-
• Tinuvin 770 sold by Ciba.
• the quantities of compounds added in (b) and (c) are equal to 3 x 10 "4 M (equal to a ratio of 1:3 between photochromatic compound/stabilizing compound) .
• the deterioration of the photochromatic activity was determined by measuring the ⁇ Y which corresponds to
• Y corresponds to the value of the tristimulus colorimetry which indicates the Luminous Transmittance value in the visible region, as defined in Regulation CIE 1931 (this value is obtained by mathematical processing of the absorption spectra of the two activated and deactivated forms) .
• Table 2 indicates the ⁇ Y at time 0 and after 40' of radiation in a reactor as described in Example 6.
• Three photochromatic lenses are prepared according to the process described in patent application MI 92/A 002492.
• the product thus obtained is a complex mixture containing: bis (allyl carbonate) of neopentyl glycol, monomer and oligomers; tris (allyl carbonate) of tris (hydroxyethyl) isocyanurate, monomer and oligomers; mixed allyl carbonates of neopentyl glycol and tris (hydroxyethyl) isocyanurate .
• the above product has the following physico- chemical characteristics:
• Viscosity 25°C (cst) 80. Density, 20°C (g/ml) : 1.1411. n D 20 : 1.4595
• the polymerizable liquid compositions are prepared by mixing and homogenizing allyl carbonate (98.4%), perketal 1, 1-di (ter-butylperoxy) -3,3, 5-trimethylcyclo- hexane (1.5%), the photochromatic compound Variacrol Red PNO ® and compounds Nr . 1 , Nr . 2 , Nr . 3 and Nr . 4 , obtained as described above.
• compositions thus obtained are transformed by polymerization into lenses with a thickness of 2 mm, using the conventional "casting" technique.
• the liquid composition containing the catalyst is poured into the cavity of a mould consisting of two glass elements, with a seal made of plastic- ized polyvinylchloride or ethylene-vinyl acetate (EVA) copolymer .
• the liquid composition is subjected to polymerization in the mould by means of thermal treatment, in a forced circulation oven, for 5 hours at 85°C, over 15 hours at 90 °C and a further 7 hours at 100 °C.
• the moulds are opened, the polymerized products are recovered and the photochromatic properties are determined on the photochromatic lenses thus obtained, by recording the UVA-visible spectra at 23 °C of the deactivated and activated forms, using a Hewlett Packard HP8452A spectrophotometer (activation for 60 seconds of radiation with a UVA lamp having 9W/m 2 of irradiance) .
• the luminous transmittance values (Y) of the deactivated and activated forms ( ⁇ Y) are recorded.
• the photochromatic activity of the lenses expressed as ⁇ Y is measured again at various intervals of time and the percentage loss of photochromatic activity itself is determined (% loss of ⁇ Y) .
• the % loss of ⁇ Y is indicated in Table 3.

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• 1998
  • 1998-02-26 IT IT98MI000377A patent/IT1298452B1/it active IP Right Grant
• 1999
  • 1999-02-18 ZA ZA9901290A patent/ZA991290B/xx unknown
  • 1999-02-25 AU AU29284/99A patent/AU2928499A/en not_active Abandoned
  • 1999-02-25 WO PCT/EP1999/001179 patent/WO1999043666A1/en active Application Filing

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