US3505352A - Halogen-5 trimethyl-1,3,3 indoline 2-spiro-3' nitro 8' naphtho (1,2-b) pyrannes - Google Patents

Halogen-5 trimethyl-1,3,3 indoline 2-spiro-3' nitro 8' naphtho (1,2-b) pyrannes Download PDF

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Publication number
US3505352A
US3505352A US433315A US3505352DA US3505352A US 3505352 A US3505352 A US 3505352A US 433315 A US433315 A US 433315A US 3505352D A US3505352D A US 3505352DA US 3505352 A US3505352 A US 3505352A
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United States
Prior art keywords
photochrome
nitro
naphtho
indoline
color
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Expired - Lifetime
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US433315A
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English (en)
Inventor
Rene Lucien Gautron
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Compagnie de Saint Gobain SA
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Compagnie de Saint Gobain SA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • 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

  • This invention relates to the photochrome and phototrope sciences.
  • photochrome and phototrope are used more or less interchangeably to describe a phenomenon associated with actinic light in which substances change color, become opaque, or absorb one wave length and issue another when affected by the light.
  • the most notable of such compounds are those which respond to the invisible forms of radiation such as infrared and ultraviolet.
  • Known types of these materials have been made use of in the manufacture of variable transmission windows for buildings and vehicles, the purpose of which has been to exclude the heat of the day, automatically and to a degree commensurate with the intensity of the radiation involved, and to regulate the amount of light admitted through the window.
  • the methods of use which have been proposed are to coat an ordinary sheet of window glass with a transparent lacquer containing a photochrome, and to dissolve a photochrome in a suitable solvent and sandwich the solvent between two layers of glass.
  • photochromes which remain transparent while becoming colored, being thus suitable for windows of vehicles as well as for those of stationary structures. Another object is to provide a class of photochromes among the members of which are a number which yield different colors under excitation, thus providing scope for the efforts of artists and decorators. Another object is to provide a class of photochromes, some members of which color and decolor at different speeds, thus providing rates of change adapted to different conditions.
  • Another object is to provide a class of photochromes which can be used in liquid or solid solution, which are compatible with typical resins, for instance the vinyls, and which can be embodied in useful solutions, films, and solid objects, such embodiments being capable of wide variation in change of coloration and time of recovery.
  • Other objects are to make such novel photochromic means by simple methods which do not degrade the resins.
  • photochromic means embodying at least one of the photochromic compounds represented by Formula l, in which at least one of R1, R2, and R3 is from the group consisting of lower alkyl, lower alkoxy, halogen, nitro, hydroxy, cyano, triuoromethyl, and phenyl, the alkoxy, alkyl and phenyl groups of which may bear substituents from the class consisting of halogen, nitro and amino, and R4 is one of the group consisting of lower alkyl and phenyl, and a carrier therefor.
  • Lower alkyl means from 1 to about 10 C atoms.
  • photochromic means meet the requirements above stated except that they remain transparent and do not become opaque. When they are incorporated in solutions and irradiated by ultraviolet light, they reveal a band at about 5900 A., the exact position of the band varying according to the nature of the substituents attached to the nucleus. This is a very valuable quality because the location of the spectrum band can be changed by changing the substituents.
  • a preferred group of these photochromes is as follows:
  • the principal properties which are desired in variable transmission windows are high speeds of coloration and decoloration; coloration and decoloration operating as a function of the quantity of radiation; stability of the photochrome under conditions of use for long periods; when the object is to exclude or extensively limit the passage of radiation, a maximum absorption of light, that is to say practically complete opacity when the radiation received reaches a predetermined peak value; an absorption spectrum covering, so far as possible, the whole wave length of visible light from 4000 to 7500 in general the coloration or decoloration should take Vplace within a few minutes and preferably within a few seconds following a change in the intensity of the radiation received. Not all of these properties are to be expected of any one photochrome and, indeed, some of them are mutually inconsistent. The art seeks to find photochrome with properties which satisfy particular needs.
  • At least one of R1, R2, R3 should be other than hydrogen.
  • photochromes have the power to change color under irradiation when they are dissolved in asolvent, or when they are in a dissolved state in a solid solution in a plastic mass such as a lacquer film, and this property of maintaining their phototropic power after undergoing a change in state is of material value in the construction of variable transmission windows.
  • photochromes may be dissolved in solvents and the solution can be entrapped between two sheets of glass to act as a light lter which changes under the impact of different dosages of actinic light.
  • the preferred solvents arethose which have low polarity, for instance hexane and toluene, and because these solvents are compatible with numerous polymers used in the manufacture of lacquers the solutions are valuable for incorporation in films and lacquers.
  • photochrome in a plastic mass, for instance in a plate or sheet of polyvinyl butyral, which is merely illustrative. This particular resin is useful in making sandwich glass and it is even more useful for that purpose when the photochrome has been incorporated in it.
  • a method of incorporating the photochrome in the film is suggested above and explained in more detail in the following examples.
  • the first color is that before irradiation and the second is that during irradiation.
  • the time expressed in seconds is the time required to resume its origina-l form from its excited state. When only a single color appears it indicates that the irradiation did not substantially change the color and that a different solvent should be used with that photochrome. A blank indicates that the particular photochrome was not tried with that particular solvent.
  • Carmine. Carmine Carmino..-- Vio1et-.... Violet
  • Formula l is a general formula for the class of chemical compounds to which the new photochromes belong;
  • Formula 3 represents the preferred reaction, the use of which produces the compound of Formulas l and 2.
  • the rst compound is dimethyl-3,3- methylene-Z-indoline.
  • the second reactant is formly l hydroxy 2 naphthalene.
  • the product of this reaction is Formula 1 plus water, the water passing olf as vapor.
  • Tests have been carried out on solutions in the usual INCORPORATED IN POLYVINYL BUTYRAL A sheet of polyvinyl butyral plasticized by butyl sebacate is immersed for 3 to 5 minutes in a benzene solution of 5% photochrome and 5% butyl sebacate. The sheet is then drained and dried to eliminate the benzene. Test pieces of the sheet thus obtained are colorless or faintly yellow regardless of the photochrome employed. The test pieces were submitted at 20 C. to the action of photo flash having an output of 350 joules. The tests consisted in noting the coloration acquired by the test piece as a result of the flash and the length of time required to return to its original color. This is expressed in the following tables:
  • the resin When it is desired to make thick sheets, or for that matter thin sheets, in which a photochrome is uniformly dispersed throughout, the resin may be dissolved in a suitable solvent, the photochrome may be dissolved in the same solvent, and the two may be mixed.
  • TEST Y Trimethyl1,3,3 indoline 2spiro3' nitro-8 naphtho (1,2-b) pyran was dissolved in toluene at room temperature. Its color was as in Test X. After seconds of irradiation with the same lamp the solution became violet and took 1 second to return to its original color after excitation ceased.
  • photochromie composition which include the photochrome and a support or carrier which may tbe a solvent, liquid or solid in which the photochrome is, in effect, in solid solution.
  • These novel manufactures may be colored or colorless in their inert state but they have the general property of changing color when excited by actinic light, especially ultraviolet light. They remain transparent under all conditions. The depth of the color produced is proportioned to the intensity of the exciting source.v
  • the colors produced vary according to the solvent employed. Recovery is extremely rapid in solution in a solvent, is slower when the solvent contains a resin, and is much more retarded when the resin is solid.
  • This class of photochromic materials is characterized by good selectivity as to color and high selectivity as to time of recovery, and this selectivity makes the materials suited to different uses. They have long life without degradation or loss of activity.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US433315A 1964-02-18 1965-02-17 Halogen-5 trimethyl-1,3,3 indoline 2-spiro-3' nitro 8' naphtho (1,2-b) pyrannes Expired - Lifetime US3505352A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR964157A FR1394163A (fr) 1964-02-18 1964-02-18 Compositions photochromes notamment pour la fabrication de vitrages à transmission variable

Publications (1)

Publication Number Publication Date
US3505352A true US3505352A (en) 1970-04-07

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Country Status (7)

Country Link
US (1) US3505352A (no)
BE (1) BE659801A (no)
DE (1) DE1286713B (no)
FR (1) FR1394163A (no)
GB (1) GB1092124A (no)
LU (1) LU47994A1 (no)
NL (1) NL6501950A (no)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652285A (en) * 1968-07-01 1972-03-28 Agfa Gevaert Nv Photochromic-photopolymerization compositions
CN109207140A (zh) * 2018-09-10 2019-01-15 苏州健雄职业技术学院 一种萘并螺吡喃类光致变色化合物

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4945064B1 (no) * 1969-03-18 1974-12-02
US4215010A (en) * 1978-09-08 1980-07-29 American Optical Corporation Photochromic compounds
US4342668A (en) * 1978-09-08 1982-08-03 American Optical Corporation Photochromic compounds
US4699473A (en) * 1983-08-08 1987-10-13 American Optical Corporation Trifluoromethyl substituted spirooxazine photochromic dyes
DE3345639A1 (de) * 1983-12-16 1985-07-04 Optische Werke G. Rodenstock, 8000 München Optisches element mit phototropem ueberzug
CA1246565A (en) * 1984-07-06 1988-12-13 Shinichi Yamamoto Spiro-oxazine compounds and preparation thereof and photochronic shaped article
GB9315584D0 (en) * 1993-07-28 1993-09-08 Mckee Frederick B Improvements in or relating to energy saving windows & cladding

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB887958A (en) * 1959-04-03 1962-01-24 Ncr Co Derivatives of 1,3,3 trimethyl-spiro(2 h-1-benzopyran-2,2-indoline)
US3149120A (en) * 1959-07-16 1964-09-15 Ncr Co 3, 3'-dimethyl-6'-nitro-spiro
US3197475A (en) * 1962-03-12 1965-07-27 Du Pont Certain 2-(o-aminophenyl)-tetrahydrobenzotriazole compounds
US3218332A (en) * 1961-06-16 1965-11-16 Geigy Ag J R 2-phenyl-benztriazole compounds
US3231584A (en) * 1959-07-16 1966-01-25 Ncr Co 1-phenyl-3, 3-dimethylspiro[(2'h-1'-benzopyran)-2', 2'-indoline] compound
US3272646A (en) * 1963-04-16 1966-09-13 American Cyanamid Co Impregnated porous photochromic glass
US3290331A (en) * 1964-03-30 1966-12-06 Ncr Co 6'no2, 7'-methoxy indolino-benzospiropyrans
US3299079A (en) * 1963-08-14 1967-01-17 Polaroid Corp Chelatable spiro [benzopyran-2, 2'-indoline] derivatives
US3321491A (en) * 1964-12-14 1967-05-23 American Cyanamid Co Photochromic benzofuran compounds
US3331854A (en) * 1964-12-14 1967-07-18 American Cyanamid Co Novel furan and thiophene compounds

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB887958A (en) * 1959-04-03 1962-01-24 Ncr Co Derivatives of 1,3,3 trimethyl-spiro(2 h-1-benzopyran-2,2-indoline)
US3149120A (en) * 1959-07-16 1964-09-15 Ncr Co 3, 3'-dimethyl-6'-nitro-spiro
US3231584A (en) * 1959-07-16 1966-01-25 Ncr Co 1-phenyl-3, 3-dimethylspiro[(2'h-1'-benzopyran)-2', 2'-indoline] compound
US3218332A (en) * 1961-06-16 1965-11-16 Geigy Ag J R 2-phenyl-benztriazole compounds
US3197475A (en) * 1962-03-12 1965-07-27 Du Pont Certain 2-(o-aminophenyl)-tetrahydrobenzotriazole compounds
US3272646A (en) * 1963-04-16 1966-09-13 American Cyanamid Co Impregnated porous photochromic glass
US3299079A (en) * 1963-08-14 1967-01-17 Polaroid Corp Chelatable spiro [benzopyran-2, 2'-indoline] derivatives
US3290331A (en) * 1964-03-30 1966-12-06 Ncr Co 6'no2, 7'-methoxy indolino-benzospiropyrans
US3321491A (en) * 1964-12-14 1967-05-23 American Cyanamid Co Photochromic benzofuran compounds
US3331854A (en) * 1964-12-14 1967-07-18 American Cyanamid Co Novel furan and thiophene compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652285A (en) * 1968-07-01 1972-03-28 Agfa Gevaert Nv Photochromic-photopolymerization compositions
CN109207140A (zh) * 2018-09-10 2019-01-15 苏州健雄职业技术学院 一种萘并螺吡喃类光致变色化合物

Also Published As

Publication number Publication date
FR1394163A (fr) 1965-04-02
LU47994A1 (no) 1965-08-17
NL6501950A (no) 1965-08-19
BE659801A (no) 1965-08-17
DE1286713B (de) 1969-01-09
GB1092124A (en) 1967-11-22

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