WO1998004563A1 - Nouvelles spirooxazines homoazaadamantane et leur utilisation dans le domaine de l'optique ophtalmique - Google Patents
Nouvelles spirooxazines homoazaadamantane et leur utilisation dans le domaine de l'optique ophtalmique Download PDFInfo
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- WO1998004563A1 WO1998004563A1 PCT/FR1997/001196 FR9701196W WO9804563A1 WO 1998004563 A1 WO1998004563 A1 WO 1998004563A1 FR 9701196 W FR9701196 W FR 9701196W WO 9804563 A1 WO9804563 A1 WO 9804563A1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000707 boryl group Chemical group B* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003473 flash photolysis reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- FQXSOMJROOSMJJ-UHFFFAOYSA-N methyl 3-hydroxy-4-nitrosonaphthalene-2-carboxylate Chemical compound C1=CC=C2C(N=O)=C(O)C(C(=O)OC)=CC2=C1 FQXSOMJROOSMJJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920001603 poly (alkyl acrylates) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
Definitions
- the subject of the invention is new photochromic compounds, more particularly photochromic compounds from the family of homoazaadamantane spirooxazines, their use in the field of ophthalmic optics, in particular in and / or on ophthalmic lenses, and contact lenses. optical devices.
- Photochromism has been known for many years.
- a compound is said to be photochromic when this compound, irradiated by a light beam, certain wavelengths of which lie in the ultraviolet range, changes color and returns to its original color as soon as the irradiation ceases.
- Such compounds can be used in the manufacture of lenses or glasses for glasses, with a view to filtering light radiation as a function of their intensity.
- photochromic compounds can be used in the field of ophthalmic optics. Indeed, the photochromic compound must meet a certain number of criteria, including among others:
- the organic photochromic compounds known and currently used generally exhibit a decreasing photochromism when the temperature increases, so that the photochromism is particularly marked at temperatures close to 0 ° C., while it is much weaker, even nonexistent, at temperatures of the order of 40 ° C which are temperatures that glasses can reach during exposure to the sun in particular.
- Another problem encountered for the photochromic compounds of the state of the art is their lifetime. In fact, for certain products of the state of the art, there is a relatively short life. In fact, after a certain number of coloring and discoloration cycles, the photochromic compound undergoes chemical degradation and no longer exhibits reversible photochromic properties.
- the document EP-A-0338660 describes photochromic compounds of the spiro family [3H-1,4-oxazines] comprising a ring of the piperidine type grafted on spiranic carbon. These compounds have satisfactory photochromic characteristics with in particular a hypsochromic displacement of the wavelength of absorption in the visible compared to the standard reference series spiro [indoline-naphthoxazine]. On the other hand, the synthesis of compounds of document EP-A-033 660 proves to be difficult, in particular at the level of the piperidine precursor.
- photochromic compounds having higher spectrokinetic constants and therefore better photochromic properties and which are easily synthesizable.
- the applicant company has discovered a new family of spirooxazines with particularly interesting photochromic properties.
- the compounds according to the invention indeed have a high colorability, in particular in the field of pink or gray / green which is particularly useful for ophthalmic optics, these compounds then being able to be used with photochromic compounds giving a yellow or red color. such as chromenes, in order to obtain a natural final coloration when exposed to light.
- the compounds in accordance with the invention moreover exhibit an absence of coloration or a very weak coloration in the initial state and rapid kinetics of coloration and discoloration in a very wide temperature range, in particular between 0 and 40 ° C.
- the compounds according to the invention are more easily synthesizable than the compounds of document EP-A-0338660.
- ophthalmic lenses are called spectacle lenses, in particular sunglasses, contact lenses.
- An object of the invention therefore consists of the new photochromic compounds.
- Another object of the invention is constituted by their use in ophthalmic optics.
- the invention also relates to compositions intended to be used for coating ophthalmic lenses or their incorporation into these lenses and the lenses of optical devices.
- photochromic compounds according to the invention are essentially characterized by the fact that they correspond to the general formula:
- Ri represents a C ⁇ -C 16 alkyl group optionally substituted by one or more hydroxy, halogen, aryl, aroxy, alkoxy, acyloxy, acryloxy, methacryloxy or vinyl substituents; vinyl, allyl, phenyl, arylalkyl, phenyl mono- or disubstituted by alkyl or alkoxy substituents C j -C 6 alkyl or halogen, an optionally substituted alicyclic group, or an aliphatic hydrocarbon group having in its chain one or more heteroatoms from O, N and S;
- R 2 and R 3 denote, independently of one another, a hydrogen atom; an alkyl group; an aryl group; a group - (CH 2 ) m OR, -SR, -COR or -COOR, in which R denotes a hydrogen atom, an alkyl group or an aryl group and m is an integer from 0 to 10; an amino group of formula NR 4 R 5 in which R and R 5 denote, independently of one another, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, R 4 and R 5 can forming with the nitrogen atom, a heterocycle comprising 4 to 7 members and which may additionally contain one or more intracyclic heteroatoms chosen from nitrogen, oxygen and sulfur; a halogen atom; a mono- or polyhaloalkyl group; a group -N0 2 , -CN, -SCN, S0 3 R 'where R' denotes hydrogen or an alkali metal, S0
- an alkyl group preferably denotes a group having 1 to 6 carbon atoms
- a cycloalkyl group preferably denotes a group having 3 to 7 carbon atoms
- the aryl group preferably denotes a phenyl group
- halogen denotes preferably chlorine, bromine, fluorine
- the polyhaloalkyl group preferably designates the group CF 3 .
- alkyl groups represented by R j mention may be made of methyl, ethyl, n-propyl, isopropyl and n-butyl groups.
- R j preferably represents the benzyl group.
- the aromatic heterocycle H is more particularly represented by formula (II):. () n (X) p
- X, Y and Z independently of each other, CR 6 wherein R 6 is hydrogen, alkyl C j -C 6 alkyl or a phenyl group, the carbon atom being linked to the one of the neighboring atoms by a double bond; a nitrogen atom linked to one of the neighboring atoms by a double bond; an oxygen atom or sulfur; n, p and q being integers equal to O or 1;
- R 7 denotes hydrogen, a C 1 -C 6 alkyl group, a phenyl group, or R and X or R 7 and Z may jointly form a 5 or 6-membered ring, aromatic or not, preferably benzene, or a naphthalene nucleus, optionally substituted by one or more groups (Rg) r , R g having the meaning of any of the groups R,, R 2 , R 3 , as defined above and r having an integer value of 1 to 4 when we have a benzene cycle or from 1 to 6 when we have a naphthalene cycle; X, Y, Z and CR 7 being chosen so as to ensure the aromaticity of the heterocycle condensed on the naphthoxazine nucleus.
- the particularly preferred heterocyclic rings are chosen from the groups of formula (II), in which n is equal to 0, X denotes O, S or N and Z denotes CR 7 or X denotes CR 7 and Z denotes O, S or N, R 6 and R 7 having the meanings indicated above. X preferably denotes O or S.
- n + p + q 3
- at least one of the groups X, Y or Z denotes N.
- aromatic rings that H can represent there may be mentioned benzene, hydroxybenzenes, alkoxybenzenes such as methoxybenzene and halobenzenes such as bromobenzene.
- aromatic heterocycles which H may represent there may be mentioned thiophene, benzothiophene, naphthothiophene, furan, pyran, isobenzofuran, pyrrole, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, isoindole, indole, indazole, isoquinoline, quinoline, phthalazine, quinoxaline, quinazoline, cinnaline, these cycles can possibly include one or more substituents.
- the more particularly preferred heterocyclic rings H are chosen from pyridine, pyrimidine, pyrazine and furan rings, optionally con
- Preferred photochromic compounds according to the invention correspond to the formulas: where R j , R 2 , R 3 and R g have the same meaning as above, R 9 is a group as defined for R 2 and R 3 , X j represents -S- or -O-, r is an integer of 0 to 4, s is an integer from 0 to 3 and t is 0, 1 or 2.
- the new compounds according to the invention can be easily synthesized using the method described in J. Org. Chem. 43, 20, The reaction scheme is indicated below.
- a substituted nitrosonaphthol or a substituted aminonaphthol is reacted on the quaternary base c), in the presence of triethylamine, or on the methylene base d) according to the reaction scheme below.
- the photochromic compounds according to the invention can be used to make photochromic ophthalmic lenses.
- the compounds according to the invention can be introduced into a composition intended to be applied to or be introduced into a transparent organic polymer material to obtain a photochromic transparent article. They can also be introduced into solid compositions such as plastic films, plates and lenses for producing usable materials, in particular as ophthalmic lenses, sunglasses, viewfinders, camera optics and filters.
- the liquid compositions which constitute an object of the invention are essentially characterized in that they contain, in dissolved or dispersed form, the compounds according to the invention in a medium based on solvents suitable for being applied or introduced into a polymer material transparent.
- More particularly useful solvents are organic solvents chosen from benzene, toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofuran , dioxane, ethylene glycol methyl ether, dimethylformamide, dimethyl sulfoxide, methylcellosolve, morpholine, and ethylene glycol.
- organic solvents chosen from benzene, toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofuran , dioxane, ethylene glycol methyl ether, dimethylformamide, dimethyl sulfoxide, methylcellosolve, morpholine, and ethylene glycol.
- the medium can also contain water.
- the compounds according to the invention can be introduced and preferably dissolved in colorless or transparent solutions prepared from polymers, copolymers or mixtures of transparent polymers in an appropriate organic solvent.
- Examples of such solutions are inter alia solutions of nitrocellulose in acetonitrile, polyvinylacetate in acetone, polyvinyl chloride in methyl ethyl ketone, polymethyl methacrylate in acetone, cellulose acetate in dimethylformamide, polyvinylpyrrolidone in acetonitrile, polystyrene in benzene, ethylcellulose in methylene chloride.
- These compositions can be applied to transparent supports such as polyethylene glycol terephthalate, boryl paper, cellulose triacetate and dried to obtain a photochromic material which can be colored in the presence of ultraviolet radiation, and which returns to the colorless and transparent state in the absence of the radiation source.
- photochromic compounds of the present invention or the compositions containing them defined above can be applied or incorporated in a solid transparent polymerized organic material suitable for ophthalmic elements such as ophthalmic lenses or materials useful for use in sunglasses , viewfinders, camera optics and filters.
- polyol (allylcarbonate) polymers As transparent solid materials which can be used to produce ophthalmic lenses in accordance with the invention, mention may be made of polyol (allylcarbonate) polymers, polyacrylates, poly (alkylacrylate) such as polymethylmethacrylates, cellulose acetate , cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), polyurethanes, polycarbonates, polyethyleneterephthalates, polystyrenes, (polystyrene-methylmethacrylate) , copolymers of styrene and acrylonitrile, polyvinylbutyrates.
- polyol (allylcarbonate) polymers polyacrylates, poly (alkylacrylate) such as polymethylmethacrylates, cellulose acetate , cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vin
- Transparent copolymers or mixtures of transparent polymers are also suitable for producing such materials. Mention may be made in this connection of materials prepared from polycarbonates such as poly (4,4'-dioxydiphenol-2,2 propane), polymethylmethacrylate, polyol (allylcarbonate) such as in particular diethylene glycol bis (allylcarbonate) and its copolymers such as for example with vinyl acetate. Mention may in particular be made of the copolymers of diethylene glycol bis (allylcarbonate) and of vinyl acetate (80-90 / 10-20) and also the copolymer of diethylene glycol bis (allylcarbonate) with vinyl acetate, of cellulose acetate.
- Polyols (allylcarbonate) are prepared using allyl carbonates of aliphatic or aromatic, linear or branched liquid polyols such as aliphatic glycols of bis-allylcarbonate or alkylene bis (allylcarbonate).
- polyols (allylcarbonatc) which can be used to prepare the transparent solid materials which can be used in accordance with the invention, mention may be made of ethylene glycol bis (allylcarbonatc), diethylene glycol bis (2-methallylcarbonate), diethylene glycol bis (allylcarbonate), ethylene glycol bis (2-chloroallylcarbonate), triethylene glycol bis (allylcarbonate).
- the quantity of photochromic compounds to be used in accordance with the invention is not critical and generally depends on the intensity of the color which the composition can impart to the material after exposure to radiation. In general, the more photochromic compounds are added. the more the coloring under ii ⁇ adiation will be important.
- a sufficient amount is used to give the treated material the property of changing color when exposed to radiation.
- This quantity of photochromic compounds is generally between 0.01 and 2 () 7 ⁇ - by weight and preferably between 0.05 and 107c by weight relative to the total weight of the optical material or of the composition.
- the photochromic compounds according to the invention can also be introduced into a temporary transfer support (such as a varnish forming a coating on a substrate) and then be transferred thermally into the substrate as described in particular in US Pat. No. 4,286. 957 or US-4,880,667.
- a temporary transfer support such as a varnish forming a coating on a substrate
- the invention also relates to a transfer varnish which contains at least one photochromic compound according to the invention.
- photochromic compounds such as photochromic compounds giving give rise to different colors such as yellow or red, known in the state of the art. This is how chromenes well known in the art can be used.
- the compounds in accordance with the invention have the advantage of allowing this change in coloration a large number of times and this at very variable temperatures of between 0 and 40 ° C.
- the expected product is obtained having a melting point of 108 ° C with a yield of 26%.
- the expected product is obtained having a melting point of 159 ° C with a yield of 32%.
- the expected product is obtained having a melting point of 188 ° C with a yield of 29%.
- the expected product is obtained having a melting point of 122 ° C with a yield of 12%.
- the expected product is obtained having a melting point of 128 ° C with a yield of 28%.
- the expected product is obtained having a melting point of 11 ° C. with a yield of 14%.
- This compound is obtained as in Example 3, from compound (c) (R j ⁇ nPr) and 7-methoxy-1-nitroso-2-naphthol.
- the expected product is obtained having a melting point of 106 ° C with a yield of 18%.
- the spectrokinetic parameters of the products of Examples 1-10 and of comparison products 11 and 12 (A 0 , K and ⁇ ma ⁇ ) (K denotes the rate of thermal discoloration rate and A Q the "colorability" determined by the value of l absorbance measured immediately after the irradiation flash) were obtained by flash photolysis coupled to a fast spectrometer of the Warner and Swasey type.
- the experimental conditions are as described in patent application WO-96/04590, using in particular concentrations of 2.5 ⁇ 10 "5 Ml "! in photochromes in toluene and a temperature of 25 ° C.
- a solution is prepared at 10% by weight of polymethyl methacrylate (PMMA) obtained from the company ALDRICH and 3% by weight in photochrome in chloroform.
- PMMA polymethyl methacrylate
- the solution is deposited in a thin layer in a crystallizer. The solvent is allowed to evaporate and then the plastic film is peeled off.
- Products 1 and 2 give good coloring.
- Product 1 1 shows no coloration.
- product 12 is photochromic under these conditions with lower colorability.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Eyeglasses (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10508538A JP2000515876A (ja) | 1996-07-31 | 1997-07-03 | 新規なホモアザアダマンタンスピロオキサジン及び眼科用光学素子分野におけるその使用 |
EP97931863A EP0915886A1 (fr) | 1996-07-31 | 1997-07-03 | Nouvelles spirooxazines homoazaadamantane et leur utilisation dans le domaine de l'optique ophtalmique |
BR9710557A BR9710557A (pt) | 1996-07-31 | 1997-07-03 | Composto fotocr{mico utiliza-ao do composto composi-Æo destinada ser aplicada sobre ou introduzida em um material polimero org nico transparente material sÄlido transparente aproporiado para realizar lentes oft lmicas e verniz de transfer-ncia |
AU35466/97A AU719894B2 (en) | 1996-07-31 | 1997-07-03 | Novel homoazaadamantane spirooxazines and their use in the field of ophthalmic optics |
US09/230,672 US6136968A (en) | 1996-07-31 | 1997-07-03 | Homoazaadamantane spirooxazines and their use in the field of ophthalmic optics |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR96/09659 | 1996-07-31 | ||
FR9609659A FR2751971B1 (fr) | 1996-07-31 | 1996-07-31 | Nouvelles spirooxazines homoazaadamantane et leur utilisation dans le domaine de l'optique ophtalmique |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998004563A1 true WO1998004563A1 (fr) | 1998-02-05 |
Family
ID=9494684
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1997/001196 WO1998004563A1 (fr) | 1996-07-31 | 1997-07-03 | Nouvelles spirooxazines homoazaadamantane et leur utilisation dans le domaine de l'optique ophtalmique |
Country Status (7)
Country | Link |
---|---|
US (1) | US6136968A (fr) |
EP (1) | EP0915886A1 (fr) |
JP (1) | JP2000515876A (fr) |
AU (1) | AU719894B2 (fr) |
BR (1) | BR9710557A (fr) |
FR (1) | FR2751971B1 (fr) |
WO (1) | WO1998004563A1 (fr) |
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WO2012121997A1 (fr) | 2011-03-04 | 2012-09-13 | Ppg Industries Ohio, Inc. | Articles composites à base de polythiouréthane |
US8641933B2 (en) | 2011-09-23 | 2014-02-04 | Ppg Industries Ohio, Inc | Composite crystal colloidal array with photochromic member |
US9133362B2 (en) | 2012-07-16 | 2015-09-15 | Ppg Industries Ohio, Inc. | Coating composition having mechanochromic crystals |
US10866455B2 (en) | 2017-10-19 | 2020-12-15 | Ppg Industries Ohio, Inc. | Display devices including photochromic-dichroic compounds and dichroic compounds |
CN108299447A (zh) * | 2018-03-05 | 2018-07-20 | 天津孚信阳光科技有限公司 | 一种有色变无色金刚烷类光致变色化合物 |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP0388660A2 (fr) * | 1989-02-23 | 1990-09-26 | Showa Denko Kabushiki Kaisha | Composé photochromique |
EP0449669A1 (fr) * | 1990-03-29 | 1991-10-02 | Tokuyama Corporation | Composé photochromique, composition et son utilisation |
EP0489655A1 (fr) * | 1990-12-06 | 1992-06-10 | ESSILOR INTERNATIONAL Compagnie Générale d'Optique | Composés photochromiques de type indolino-spiro-benzoxazine et leur procédé de préparation |
EP0653428A1 (fr) * | 1993-11-17 | 1995-05-17 | Essilor International Compagnie Generale D'optique | Spirooxazines et leur utilisation dans des lentilles opthalmiques |
WO1996004590A1 (fr) * | 1994-07-29 | 1996-02-15 | Essilor International Compagnie Generale D'optique | Composes photochromiques de structure spiro[indoline-[2,3']-benzoxazine] a groupement cyano ou phenylsulfonyl en 6' et comportant un cycle benzenique condense en 7', 8' du noyau benzoxazine, et leur utilisation dans le domaine de l'optique ophtalmique |
WO1996011926A1 (fr) * | 1994-10-13 | 1996-04-25 | Ppg Industries, Inc. | Composes de naphthoxazine photochromique |
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Publication number | Priority date | Publication date | Assignee | Title |
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GB8610709D0 (en) * | 1986-05-01 | 1986-06-04 | Plinkington Bros Plc | Photochromic lenses |
US5186867A (en) * | 1989-12-12 | 1993-02-16 | Enichem Synthesis, S.P.A. | Spiro-indoline oxazine compounds with photochromatic and photosensitizing characteristics and the process for their preparation |
-
1996
- 1996-07-31 FR FR9609659A patent/FR2751971B1/fr not_active Expired - Fee Related
-
1997
- 1997-07-03 BR BR9710557A patent/BR9710557A/pt not_active Application Discontinuation
- 1997-07-03 EP EP97931863A patent/EP0915886A1/fr not_active Withdrawn
- 1997-07-03 WO PCT/FR1997/001196 patent/WO1998004563A1/fr not_active Application Discontinuation
- 1997-07-03 JP JP10508538A patent/JP2000515876A/ja active Pending
- 1997-07-03 US US09/230,672 patent/US6136968A/en not_active Expired - Fee Related
- 1997-07-03 AU AU35466/97A patent/AU719894B2/en not_active Ceased
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0388660A2 (fr) * | 1989-02-23 | 1990-09-26 | Showa Denko Kabushiki Kaisha | Composé photochromique |
EP0449669A1 (fr) * | 1990-03-29 | 1991-10-02 | Tokuyama Corporation | Composé photochromique, composition et son utilisation |
EP0489655A1 (fr) * | 1990-12-06 | 1992-06-10 | ESSILOR INTERNATIONAL Compagnie Générale d'Optique | Composés photochromiques de type indolino-spiro-benzoxazine et leur procédé de préparation |
EP0653428A1 (fr) * | 1993-11-17 | 1995-05-17 | Essilor International Compagnie Generale D'optique | Spirooxazines et leur utilisation dans des lentilles opthalmiques |
WO1996004590A1 (fr) * | 1994-07-29 | 1996-02-15 | Essilor International Compagnie Generale D'optique | Composes photochromiques de structure spiro[indoline-[2,3']-benzoxazine] a groupement cyano ou phenylsulfonyl en 6' et comportant un cycle benzenique condense en 7', 8' du noyau benzoxazine, et leur utilisation dans le domaine de l'optique ophtalmique |
WO1996011926A1 (fr) * | 1994-10-13 | 1996-04-25 | Ppg Industries, Inc. | Composes de naphthoxazine photochromique |
Also Published As
Publication number | Publication date |
---|---|
FR2751971B1 (fr) | 1998-11-20 |
US6136968A (en) | 2000-10-24 |
AU719894B2 (en) | 2000-05-18 |
FR2751971A1 (fr) | 1998-02-06 |
EP0915886A1 (fr) | 1999-05-19 |
BR9710557A (pt) | 1999-08-17 |
AU3546697A (en) | 1998-02-20 |
JP2000515876A (ja) | 2000-11-28 |
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