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Publication numberUS3562172 A
Publication typeGrant
Publication dateFeb 9, 1971
Filing dateOct 28, 1969
Priority dateOct 28, 1968
Also published asDE1954220A1
Publication numberUS 3562172 A, US 3562172A, US-A-3562172, US3562172 A, US3562172A
InventorsHisatake Ono, Chiaki Osada
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photochromic compound and composition containing the same
US 3562172 A
Images(1)
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Description  (OCR text may contain errors)

Feb. 9, 1971 v l T 0 0 ETAL 3,562,172

PHOTOCHROMIC COMPOUND AND COMPOSITION CONTAINING THE SAME Filed 001.. 28, 1969 DENSRTY (DI WAVE LENGTH INVENTORS HiSATAKE 0N0 I CHIAKI OSADA s jl w im M ATTORNEYS United States Patent Ofice 3,562,172 Patented Feb. 9, 1971 U.S. Cl. 252-300 10 Claims ABSTRACT OF THE DISCLOSURE Photochromic compositions containing, and photochromic compounds per se, represented by the formula:

wherein R represents (CH ),,COOH, (CH ),,CN or -(CH ),,COOR (wherein R is an alkyl group having 1 to carbon atoms; n is 1 to 4); R and R represent an alkyl group having 1 to 5 carbon atoms or a phenyl group; and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; a halogen atom, a nitro group, a cyano group, or an alkoxyl group having 1 to 5 carbon atoms or a carboxyl group, and said carboxyl group may be substituted with an alkyl group having 1 to 5 carbon atoms.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to photochromic materials. The present invention relates to a photochromic compound represented by the formula wherein R represents -(CH ),,COOH, -(CH ),,CN or -(CH ),,COOR (wherein R is an alkyl group having 1 to 5 carbon atoms; n is 1 to 4); R and R represent an alkyl group having 1 to 5 carbon atoms or a phenyl group; and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; a halogen atom, a nitro group, a cyano group, or an alkoxyl group having 1 to 5 carbon atoms or a carboxyl group, and said carboxyl group may be substituted with an alkyl group having 1 to 5 carbon atoms.

Description of the prior art We previously discovered the photochromic compound represented by the above formula, in which R is an alkyl group, as disclosed in Japanese patent application No. 55,662/67. The photochromic action of the compound was remarkable at about 10 C.

SUMMARY OF THE INVENTION Photochromic composition containing, and photochromic compounds per se, represented by the formula:

wherein R represents -(CH ),,COOH, (CH CN or (CH ),,COOR (wherein R is an alkyl group having 1 to 5 carbon atoms; 11 is 1 to 4); R and R represent an alkyl group having 1 to 5 carbon atoms or a phenyl group; and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a cyano group or an alkoxyl group having 1 to 5 carbon atoms or a carboxyl group, and said carboxyl group may be substituted with an alkyl group having 1 to 5 carbon atoms.

An object of the present invention is to obviate the disadvantages discussed above and to provide a novel compound having an oxazine ring to replace the conventional compounds having a pyrane ring.

Another object of the present invention is to provide a photochromic compound which is not influenced by the polar nature of the solvent, and which illustrates photochromic action at normal temperatures.

BRIEF DESCRIPTION OF THE DRAWINGS The drawing is a plot of density versus wavelength for a compound of the invention before and after irradiation with ultraviolet rays.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a photochromic compound represented by the formula wherein R represents -(CH ),,COOH, (CH CN or (CH ),,COOR (wherein R is an alkyl group having 1 to 5 carbon atoms; is is l to 4); R and R represent an alkyl group having 1 to 5 carbon atoms or a phenyl group; and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; a halogen atom, a nitro group, a cyano group, or an alkoxyl group having 1 to 5 carbon atoms or a carboxyl group, and said carboxyl group may be substituted with an alkyl group having 1 to 5 carbon atoms.

The compound represented by the above formula is dissolved in a solvent such as benzene, toluene, carbon disulfide, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofurane, dioxane, methyl cellusolve morpholine, ethylene glycol, dimethyl formamide, dimethyl sulfoxide, etc. (at normal temperature) to yield the photochromic composition in a colorlas state. When it is irradiated with ultraviolet rays, the photochromic composition turns blue. Further, the compound of the present invention can be dissolved in a solution such as polyvinylacetate-acetone solution, nitrocellulose-acetonitrile solution, polyvinylchloride-methyl ethyl ketone solution, polymethylacrylate acetone solution, cellulose acetate-dimethyl formaldehyde solution, polyvinylpyrrolidone-acetonitrile solution, polystyrol-benzene solution, ethyl cellulose-methylene chloride solution, etc., to obtain the photochromic composition in a colorless state, regardless of the kinds of solvents and/ or resins.

The composition can be coated on a support such as baryta paper, cellulose acetate, polyethylene terephthalate, etc., and then dried, and will still turn blue when irradiated with ultraviolet rays and, if allowed to stand in the dark without exposure to ultraviolet rays, will change to colorless again.

The compound represented by the above formula is obtained by refluxing a quaternized indolenine derivative, u-nitroso-fi-naphthol and triethylamine in an approximate equimolar ratio in ethyl alcohol while passingnitro gen gas through the system, followed by cooling, filtering and recrystallizing from an appropriate solvent.

The photochromic compositions of the present inven tion are employed as photochromic materials for photography and printing, which are obtained by coating the above composition on a high molecular weight film, baryta paper, etc., photochromic materials for furniture usage such as curtains, glass, etc., and photochromic materials for use in filters.

The figure is a graph showing the change in the visible absorption spectrum of film, before and after irradiation with ultraviolet rays, which is coated with the photochromic composition of this invention, then dried.

EXAMPLE 1 6.2. g. of l-B-carboxyethyl-2,3,3-trimethyl-indolenium bromide and 3.5 g. of u-nitroso-B-naphthol were dissolved in 50 cc. of dehydrated ethanol and, after adding 2 g. of triethylamine thereto, were refluxed in a nitrogen atmosphere for two hours. After the reaction, excess ethanol was distilled out and the mixture was cooled to produce a crystal. A small amount of ethanol was added thereto and filtered. The crude crystal thus obtained was recrystallized from ethanol using active carbon to provide 0.7 g. of the yellow crystal of 1- 3-carboxyethyl-3,3-dimethyl spiro[indolino-2,3'-naphtho[2.1-b] (1.4)oxazine] having a melting point of 186 to 187 C. The ethanol solution of this compound was colorless under the light of a room lamp, but, when irradiated with ultraviolet rays, immediately colored blue, and turned back to colorless when allowed to stand in a dark place.

EXAMPLE 2 3.3 g. of l-/3-carb0xyethyl-2,3,3,S-tetramethyl-indolenium bromide and a-nitroso-p-naphthol were reacted in the same manner as in Example 1 to obtain 1.2 g. of the yellow crystals of l-B-carboxyethyl-3,3,5-trimethyl spiro [indolino 2,3 naphtho[2.1-b] (1.4) oxazine] having a melting point of 188 to 190 C. A benzene solution of this compound was colorless, but, when irradiated with ultraviolet rays, colored greenish blue and, on being al lowed to stand in the dark, turned back to colorless. A baryta paper which 'was coated with a solution of this compound dissolved in ethyl acetate ester-polyvinyl acetate and dried was colorless in the ordinary state, but, when irradiated with ultraviolet rays, immediately colored blue. Upon discontinuing irradiation with ultraviolet rays, this material turned colorless. The absorption curve for this material is shown in FIG. 1. Curve 1 is before irradiation, and curve 2 is after irradiation.

EXAMPLE 3 6.8 g. of 1-carboxyethyl-2,3,3-trimethyl-5-methoxyindolenium bromide and 3.5 g. of a-nitroso-B-naphthol were reacted in the same manner as in Example 1 to obtain 2.1 g. of the light yellow crystal of 1-carboxyethyl-3,3-

4 dimethyl-S-methoxy spiro[indolino 2,3'-naphtho[2.l-b]

(1.4)oxane] having a melting point of 165 to 167 C.

The properties thereof were the same as the compound of Example 2.

EXAMPLE 4 6.8 g. of 1-'y-cyanopropyl-2,3,3-trimethyl-5-chlorindolenium bromide and 3.5 g. of oc-nitroso-B-naphthol were reacted in the same manner as in Example 1 to obtain 2.1 g. of the light yellow crystals of 1- -cyanopropyl-3,3- dimethyl 5 chlor-spiro[indolino-2,3'-naphtho[2.1 b] (1.4)oxazine] which melts at 158 to 160 C. A polyethylene terephthalate film coated with a solution of this compound dissolved in benzene-polystyrol and dried was colorless and transparent, but, when irradiated with ultraviolet rays, immediately colored blue and, on allowing to stand in the dark turned back to colorless.

We claim:

1. A photochromic compound represented by the general formula,

R2 Ra wherein R represents -(CH COOH, (CH CN, or -(CH COOR; R is an alkyl group having 1 to 5 carbon atoms; n is 1 to 4; R and R represent an alkyl group having 1 to 5 carbon atoms or a phenyl group; R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; a halogen atom, a nitro group, a cyano group, an alkoxyl group having 1 to 5 carbon atoms, a carboxyl group or a carboxyl group being substituted with an alkyl group having 1 to 5 carbon atoms.

2. The photochromic compound as claimed in claim 1 wherein said compound represented by the general formula is 1- 3-carboxyethyl-3,3-dimethyl-spiro [indolino-2,3 naphtho[2.1-b] (1.4) oxazine] 3. The photochromic compound as claimed in claim 1 wherein said compound represented by the general formula is l-fi-carboxyethyl-3,3,S-trimethyl-spiro[indolino-2, 3-naphtho[2.1-b] (1.4)oxazine].

4. The photochromic compound as claimed in claim 1 wherein said compound represented by the general formula is 1 carboxyethyl-3,3-dimethyl-5-methoxy-spiro [indolino-2,3'-naphtho [2. l-b] (1.4)oxazine].

5. The photochromic compound as claimed in claim 1 wherein said compound represented by the general formula is l-y-cyanopropyl 3,3 dimethyl-S-chloro-spiro [indolino-2,3 '-naphthol[2.1-b] (1.4)oxazine].

6. A photochromic composition comprising a photochromic compound represented by the general formula,

wherein R represents (CH ),,COOH, (CH ),,CN or (CH COOR; R is an alkyl group having 1 to 5 carbon atoms; and n is 1 to 4; R and R each represents an alkyl group having 1 to 5 carbon atoms or a phenyl group; and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 5 carbon atoms, a carboxyl group or a carboxy group substituted with an alkyl group having 1 to 5 carbon atoms, and a solvent.

7. The photochromic composition as claimed in claim 6 wherein said solvent is benzene, toluene, carbon disulfide, chloroform, ethyl acetate, methyl ethyl ketone,

wherein R represents -(CH COOH, (CH CN or (CH COOR; wherein R is an alkyl group having 1 to 5 carbon atoms; n is 1 to 4; R and R each represents an alkyl group having 1 to 5 carbon atoms; and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group, a cyano 20 group, an alkoxyl group, a carboxyl group, or a carboxy group substituted with an alkyl group having 1 to 5 carbon atoms, a binder and a solvent.

9. The photochromic composition as claimed in claim 8 wherein said binder is polyvinyl acetate, nitrocellulose, polyvinyl chloride, polymethylmethacrylate, cellulose acetate, polyvinyl pyrrolidone, polystyrene or ethyl cellulose.

10. The photochromic composition as claimed in claim 9 wherein said solvent is acetone, acetonitrile, methyl ethyl ketone, dimethyl formamide, acetonitrile, benzene or methylene chloride.

References Cited UNITED STATES PATENTS 3,395,145 7/1968 Hansen et al 260244 GEORGE F. LESMES, Primary Examiner J. P. BRAMMER, Assistant Examiner US. Cl. X.R. 260244

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Classifications
U.S. Classification252/600, 544/71
International ClassificationC08L33/00, C08K5/00, C08L27/00, C07D498/10, C09K9/02, C08L1/00, C08K5/3412, C08L33/02, G03C1/685
Cooperative ClassificationG03C1/685, C07D498/10
European ClassificationG03C1/685, C07D498/10