Feb.
9, 1971 HiSATAKE ONO ET All- 3,562,172
PHOTOCHROMIC COMPOUND AND COMPOSITION CONTAINING THE SAME
Filed Oct. 28, 1969
DENSTY
()
WAVE LENGTH
NVENTORS
HSATAKE ONO
CHAK OSADA
ATTORNEYS
3,562,172
United States Patent Office Patented Feb. 9, 1971
2
We previously discovered the photochromic compound
3,562,172 represented by the above formula, in which R1 is an alkyl
PHOTOCHROMC COMPOUND AND COMPOS group, as disclosed in Japanese patent application No.
TION CONTAINING THE SAME 55,662/67. The photochromic action of the compound
Hisatake Ono and Chiaki Osada, Asaka-shi, Japan, as was remarkable at about 10 C.
signors to Fuji Photo Film Co. Ltd., Tokyo, Japan
Filed Oct. 28, 1969, Ser. No. 871,872 SUMMARY OF THE INVENTION
Claims priority, application Japan, Oct. 28, 1968, Photochromic composition containing, and photo
43/78,465
Int, C. G02b 5/20 chromic compounds per se, represented by the formula:
U.S. C. 252-300 10 Claims
O
ABSTRACT OF THE DISCLOSURE
Photochromic compositions containing, and photo
chromic compounds per se, represented by the formula: 5
wherein R represents -(CH2)COOH, -(CH2)CN or
(CH2)COOR (wherein R is an alkyl group having 1 to
5 carbon atoms; n is 1 to 4); R2 and R3 represent an
20 alkyl group having 1 to 5 carbon atoms or a phenyl
group; and R4 represents a hydrogen atom, an alkyl group
having 1 to 5 carbon atoms, a halogen atom, a nitro
wherein R represents -(CH2)COOH, -(CH2)CN or group, a cyano group or an alkoxyl group having 1 to 5
-(CH)COOR (wherein R is an alkyl group having 1 carbon atoms or a carboxyl group, and said carboxyl
25 group may be substituted with an alkyl group having 1 to
to 5 carbon atoms; n is 1 to 4); R2 and R3 represent an
alkyl group having 1 to 5 carbon atoms or a phenyl group; 5 carbon atoms.
and R represents a hydrogen atom, an alkyl group hav An object of the present invention is to obviate the dis
ing 1 to 5 carbon atoms; a halogen atom, a nitro group, advantages discussed above and to provide a novel com
a cyano group, or an alkoxyl group having 1 to 5 carbon 30
pound having an oxazine ring to replace the conventional
atoms or a carboxyl group, and said carboxyl group may compounds having a pyrane ring.
be substituted with an alkyl group having 1 to 5 carbon Another object of the present invention is to provide a
atOnS. photochromic compound which is not influenced by the
polar nature of the solvent, and which illustrates photo
BACKGROUND OF THE INVENTION 35
chromic action at normal temperatures.
Field of the invention BRIEF DESCRIPTION OF THE DRAWINGS
This invention relates to photochromic materials. The drawing is a plot of density versus Wavelength for
The present invention relates to a photochromic com a compound of the invention before and after irradiation
pound represented by the formula 40
with ultraviolet rays.
DETALED DESCRIPTION OF THE PREFERRED
R EMBODIMENTS
The present invention relates to a photochromic com
pound represented by the formula
45 R
wherein R represents -(CH2)COOH, -(CH2)CN or
-(CH2)COOR (wherein R is an alkyl group having 1
to 5 carbon atoms; n is 1 to 4); R2 and R3 represent an
alkyl group having 1 to 5 carbon atoms or a phenyl group;
50
-0) . . )
wherein R represents -(CH2)COOH, -(CH2)CN or
and R4 represents a hydrogen atom, an alkyl group hav -(CH2)COOR (wherein R is an alkyl group having 1
ing 1 to 5 carbon atoms; a halogen atom, a nitro group, 55 to 5 carbon atoms; n is 1 to 4); R2 and R3 represent an
a cyano group, or an alkoxyl group having 1 to 5 carbon alkyl group having 1 to 5 carbon atoms or a phenyl
atoms or a carboxyl group, and said carboxyl group may group; and R4 represents a hydrogen atom, an alkyl group
be substituted with an alkyl group having 1 to 5 carbon having 1 to 5 carbon atoms; a halogen atom, a nitro group,
atoms. a cyano group, or an alkoxyl group having 1 to 5 carbon
Description of the prior art 60 atoms or a carboxyl group, and said carboxyl group may
be substituted with an alkyl group having 1 to 5 carbon
As used herein, "photochromic' defines a reversible atoms.
change in the color of a substance by the action of light. The compound represented by the above formula is
Typical photochromic compounds, that is, 1,3,3-trimethyl dissolved in a solvent such as benzene, toluene, carbon
6'-nitro-spiro (indolino-2,2'-2H-chromene) and its de 65 disulfide, ethyl acetate, methyl ethyl ketone, acetone,
rivatives, show good photochromic phenomenon in a ethyl alcohol, methyl alcohol, acetonitrile, tetrahydro
non-polar organic solvent. However, in general, the photo furane, dioxane, methyl cellusolve morpholine, ethylene
chromic properties thereof are lost when they are coated glycol, dimethyl formamide, dimethyl sulfoxide, etc. (at
on a film or paper. In essence, they are often influenced normal temperature) to yield the photochromic com
by the polarity of the solvent or the high molecular weight 70 position in a colorless state. When it is irradiated with
substance necessary to make a film, and are thereby ultraviolet rays, the photochromic composition turns blue.
colored before exposure. Further, the compound of the present invention can be
3,562,172
3 4.
dissolved in a solution such as polyvinylacetate-acetone dimethyl-5-methoxy spiro indolino - 2,3'-naphtho(2.1-bl.
solution, nitrocellulose-acetonitrile solution, polyvinyl (1.4)oxane having a melting point of 165 to 167 C.
chloride-methyl ethyl ketone solution, polymethylacrylate The properties thereof were the same as the compound of
acetone solution, cellulose acetate-dimethyl formaldehyde Example 2.
solution, polyvinylpyrrolidone-acetonitrile solution, poly EXAMPLE 4.
styrol-benzene solution, ethyl cellulose-methylene chloride 6.8 g. of 1-y-cyanopropyl-2,3,3-trimethyl-5-chlorindo
solution, etc., to obtain the photochromic composition in
a colorless state, regardless of the kinds of solvents and/or lenium bromide and 3.5 g. of cy-nitroso-6-naphthol were
resins. reacted in the same manner as in Example 1 to obtain
The composition can be coated on a support such as O 2.1 g of the light yellow crystals of 1-y-cyanopropyl-3,3-
baryta paper, cellulose acetate, polyethylene terephthalate, dimethyl - 5 - chlor-spiro indolino-2,3'-naphthoI2.1 - bl
etc., and then dried, and will still turn blue when irradiated (1.4)oxazine which melts at 158 to 160 C. A poly
with ultraviolet rays and, if allowed to stand in the dark ethylene terephthalate film coated with a solution of this
without exposure to ultraviolet rays, will change to color compound dissolved in benzene-polystyrol and dried was
less again. 15 colorless and transparent, but, when irradiated with ultra
The compound represented by the above formula is violet rays, immediately colored blue and, on allowing to
obtained by refluxing a quaternized indolenine deriva stand in the dark turned back to colorless.
tive, c-nitroso-6-naphthol and triethylamine in an approxi We claim:
mate equimolar ratio in ethyl alcohol while passing nitro 1. A photochromic compound represented by the gen
gen gas through the system, followed by cooling, filtering eral formula,
and recrystallizing from an appropriate solvent. R. Rs
The photochromic compositions of the present inven
tion are employed as photochromic materials for photog -N
raphy and printing, which are obtained by coating the R; >-( >
above composition on a high molecular weight film, baryta
paper, etc., photochromic materials for furniture usage
such as curtains, glass, etc., and photochromic materials
?
R1
\ /
for use in filters. wherein R represents -(CH2)COOH, -(CH2)CN,
The figure is a graph showing the change in the visible or -(CH2)COOR; R is an alkyl group having 1 to 5
absorption spectrum of film, before and after irradiation 30
carbon atoms; n is 1 to 4; R2 and R3 represent an alkyl
with ultraviolet rays, which is coated with the photo group having 1 to 5 carbon atoms or a phenyl group;
chromic composition of this invention, then dried. R4 represents a hydrogen atom, an alkyl group having 1
EXAMPLE 1. to 5 carbon atoms; a halogen atom, a nitro group, a
6.2 g. of 1-3-carboxyethyl-2,3,3-trimethyl-indolenium cyano group, an alkoxyl group having 1 to 5 carbon atoms,
bromide and 3.5 g. of cy-nitroso-6-naphthol were dissolved a carboxyl group or a carboxyl group being substituted
in 50 cc. of dehydrated ethanol and, after adding 2 g. with an alkyl group having 1 to 5 carbon atoms.
of triethylamine thereto, were refluxed in a nitrogen at 2. The photochromic compound as claimed in claim 1
mosphere for two hours. After the reaction, excess ethanol
wherein said compound represented by the general for
Was distilled out and the mixture was cooled to produce 40 mula is 1-3-carboxyethyl-3,3-dimethyl-spiroLindolino-2,3'-
a crystal. A small amount of ethanol was added thereto naphtho.2.1-b (1.4) oxazine.
and filtered. The crude crystal thus obtained was recrys 3. The photochromic compound as claimed in claim
tallized from ethanol using active carbon to provide 0.7 wherein said compound represented by the general for
g. of the yellow crystal of 1-6-carboxyethyl-3,3-dimethyl mula is 1-3-carboxyethyl-3,3,5-trimethyl-spiro indolino-2,
spiro indolino-2,3'-naphtho2.1-b (1.4)oxazine) having a 3'-naphtho.2.1-lb (1.4)oxazine.
melting point of 186 to 187° C. The ethanol solution of
45 4. The photochromic compound as claimed in claim 1
wherein said compound represented by the general for
this compound was colorless under the light of a room mula is 1 - carboxyethyl-3,3-dimethyl-5-methoxy-spiro in
lamp, but, when irradiated with ultraviolet rays, immedi dolino-2,3'-naphtho2.1-b (1.4)oxazine.
ately colored blue, and turned back to colorless when 5. The photochromic compound as claimed in claim
allowed to stand in a dark place. 50 wherein said compound represented by the general for
EXAMPLE 2. mula is 1-y-cyanopropyl - 3,3 - dimethyl-5-chloro-spiro
indolino-2,3'-naphthol2.1-b (1.4) oxazine.
3.3 g. of 1-3-carboxyethyl-2,3,3,5-tetramethyl-indoleni 6. A photochromic composition comprising a photo
um bromide and ox-nitroso-3-naphthol were reacted in the chromic compound represented by the general formula,
same manner as in Example 1 to obtain 1.2 g. of the 55
yellow crystals of 1-3-carboxyethyl-3,3,5-trimethyl spiro
indolino - 2,3' - naphthoI2.1-lb (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 ace wherein R represents -(CH2)COOH, -(CH2)CN or
tate and dried was colorless in the ordinary state, but, -(CH2)COOR; R is an alkyl group having 1 to 5 car
when irradiated with ultraviolet rays, immediately colored bon atoms; and n is 1 to 4; R2 and R3 each represents an
blue. Upon discontinuing irradiation with ultraviolet rays, alkyl group having 1 to 5 carbon atoms or a pheny
this material turned colorless. The absorption curve for group; and R4 represents a hydrogen atom, an alkyl group
this material is shown in FIG. 1. Curve 1 is before irradi having 1 to 5 carbon atoms, a halogen atom, a nitro
ation, and curve 2 is after irradiation. group, a cyano group, an alkoxy group having 1 to 5
EXAMPLE 3 O carbon atoms, a carboxyl group or a carboxy group sub
stituted with an alkyl group having 1 to 5 carbon atoms,
6.8 g. of 1-carboxyethyl-2,3,3-trimethyl-5-methoxyin and a solvent.
dolenium bromide and 3.5 g. of c-nitroso-g-naphthol were 7. The photochromic composition as claimed in claim
reacted in the same manner as in Example 1 to obtain 6 wherein said solvent is benzene, toluene, carbon di
2.1 g of the light yellow crystal of 1-carboxyethyl-3,3- Sulfide, chloroform, ethyl acetate, methyl ethyl ketone,
3,562,172
5 6
acetone; methyl alcohol, ethyl alcohol, acetonitrile, tetra group Substituted with an alkyl group having 1 to 5 car
hydrofuran, dioxane, methyl Cellosolve morpholine, eth bon atoms, a binder and a solvent.
ylene glycol, dimethyl formamide or dimethyl sulfoxide. 9. The photochromic composition as claimed in claim
8. A photochromic composition comprising a photo 8 wherein said binder is polyvinyl acetate, nitrocellulose,
chromic compound represented by the general formula, polyvinyl chloride, polymethylmethacrylate, cellulose ace
tate, 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
10 or methylene chloride.
References Cited
UNITED STATES PATENTS
wherein R1 represents -(CH2)COOH, -(CH2)CN or 5 3,395, 145 7/1968 Hansen et al. -------- 260-244
-(CH2)COOR; wherein R is an alkyl group having 1 GEORGE F. LESMES, Primary Examiner
to 5 carbon atoms; n is 1 to 4; Ra and R3 each represents
an alkyl group having 1 to 5 carbon atoms; and R4 rep J. P. BRAMMER, Assistant Examiner
resents a hydrogen atom, an alkyl group having 1 to 5
carbon atoms, a halogen atom, a nitro group, a cyano 20 U.S. C. X.R.
group, an alkoxyl group, a carboxyl group, or a carboxy 260-244
