JPH0343315B2 - - Google Patents

Abstract

An organic photochromic composition comprises spiro [indoline-2,3'- [3H] -napht [2,1-b] [1,4] oxazine] dye (spirooxazine dye) and unconventional ultraviolet stabilizers. The ultraviolet stabilizers provide for a good light fatigue resistance of the spirooxazine (S.O.) dye and will not hinder the photocolorability of the photochromic composition. The unconventional ultraviolet stabilizers belong to the class of hindered amine light stabilizers (HALS) and excited state quenchers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photochromic compositions, and more particularly, spiro[indoline-2,3'-[ 3H ]-naphtho[2,1- b ][1,4] Oxazine〕(SO)
An organic photochromic composition comprising a dye and an unconventional ultraviolet (UV) stabilizer. Compounds that undergo a reversible light-induced hue change are called photochromic compounds. When exposed to ultraviolet or visible light, the photochromic compounds change their transmittance. When the compound is exposed to light of a different wavelength or when the initial light source is removed, it immediately returns to its original hue state. Although organic photochromic materials have been known for over 50 years, they have not had widespread industrial or commercial utility. This is primarily due to the irreversible degradation phenomenon commonly known as photofatigue. Upon repeated exposure to light, photochromic materials lose their photochromic properties. Light or heat or both light and heat are believed to cause photodegradation of organic photochromic compounds. Therefore, many people have attempted to increase the photofatigue resistance of the compounds by adding a large number of conventional antioxidants or UV absorbers. For example, US Pat. No. 3,212,898 teaches the use of conventional UV absorbers such as benzophenones and benzotriazoles to increase the photochromic lifetime of photochromic benzospiropyran compounds. Similarly, U.S. Pat. No. 3,666,352
To substantially increase the persistence of photochromic thiocarbazonate mercury lenses (lenses that transmit radiation with wavelengths greater than 4200 angstrom units and do not transmit radiation with wavelengths below) against photochemical degradation. teaches the use of conventional UV light absorbers in the lens. One class of organic photochromic compounds, namely spiro[indoline-2,3'-[ 3H ]-naphtho[2,1-
b] [1,4]oxazine] dye (SO dye) is
It is known for having good light fatigue resistance.
In general, the photofatigue resistance of the spirooxazine compounds is about 100 times superior to the spiropyrans to which they are closely related. Photochromic compounds of this class are disclosed in U.S. Pat. No. 3,562,172; U.S. Pat. No. 3,578,602; U.S. Pat. The exact mechanism of photodegradation of SO dyes is still not fully understood. Conventional antioxidants (arylamines and hindered phenols) do not improve the photofatigue resistance of SO dyes, although there is some circumstantial evidence that oxygen affects the photodegradation process. Conventional UV stabilizers, namely substituted benzophenones and benzotriazoles, slightly improve the photofatigue resistance of SO dyes;
They cannot be used effectively because they cause a screening effect in which they strongly absorb UV radiation within the UV radiation absorbing range. By competing with the SO dye to absorb UV light, these conventional stabilizers substantially reduce the effective light intensity for SO dye activation. Furthermore, conventional UV
Some stabilizers can be harmful to SO dyes under certain conditions. In addition, the presence of acids has a detrimental effect on SO compounds. Acids are used to produce photochromic products.
May be present in plastic host materials such as PVC or cellulosic materials. Acids are typically generated either thermally during the molding process or photochemically during use of photochromic products. SO dye solutions become pinkish to reddish in the presence of even trace amounts of acid, and the solutions no longer exhibit photochromic effects. The pinkish to reddish color is thought to be due to the formation of a complex between the SO compound and the acid. A base must be used to neutralize the acid and restore the original colorless or light blue color. US Pat. No. 4,440,672 discloses the use of organo-nickel complex stabilizers to improve the photofatigue resistance of photochromic compounds. However, the organo-nickel complex does not have the ability to neutralize any acids that may be present. The problems of the prior art have been overcome by the discovery of a group of unconventional UV stabilizers that can improve the photofatigue resistance of SO dyes without affecting their photochromic properties. The unconventional UV stabilizers belong to the class of hindered amine light stabilizers (HALS) and excited state quenchers. Hindered amine light stabilizers offer advantages over organometallic complex stabilizers in their ability to neutralize acids, thus improving the light fatigue resistance of SO dyes and protecting the original hue. It is preferred to use an excited state quencher together with a hindered amine light stabilizer in the organic photochromic compounds of the invention. That is, in this case, they have a synergistic effect in improving the photofatigue resistance of the SO compound. Since the UV stabilizer has minimal absorption within the absorption range of the SO dye, it does not impede the photochromic properties of the SO dye. SO dye and UV stabilizer,
They can be incorporated into visually transparent plastics to make photochromic components suitable for photochromic sunglasses, ski goggles or other plastic products to make them photochromic. It is therefore an object of the present invention to improve the photofatigue resistance of organic photochromic compositions containing SO dyes. Another object of the present invention is to improve the photofatigue resistance of the photochromic composition without impairing its photochromic properties. It is further an object of the present invention to use such improved photochromic compositions for making photochromic products such as sunglasses, ophthalmic lenses, ski goggles, window coverings, toys, textiles, etc. be. Other objects and scope of further applicability of the invention will become apparent from the detailed description below. The organic photochromic composition of the present invention has: a) Structural formula (In the formula, one of R ₁ , R ₂ and R ₃ is hydrogen, halogen, lower alkyl, or lower alkoxy, and the others are hydrogen; R ₄ and R ₅ are hydrogen, lower alkyl, lower alkoxy, halogen , or trifluoromethyl; and R ₆ is lower alkyl).
H]-naphtho[2,1- b ][1,4]oxazine] dye (spirooxazine dye), and b) an unconventional single or plural UV stabilizer. As used herein, "lower"
means up to 12 carbon atoms (n=1-12) in a group of free alkyl or alkoxy groups, where the group of alkyl groups has the structural formula C _o H _2o+1
and the alkoxy radical group has the structural formula C _o H _2o+1
It is O. Preferably, the UV stabilizer includes hindered amine light stabilizers (HALS). Preferred hindered amine light stabilizers include derivatives of tetramethylpiperidine. Most preferably, the UV stabilizer consists of a blend of a hindered amine light stabilizer and an excited state quencher. Preferably, the excited state quencher includes an organo-nickel complex light stabilizer. For a description of hindered amine light stabilizers and excited state quenchers, see the Modern Plastics Encyclopedia.
Please refer to the following four items. Among these are:
1) Shute, Raymond, "Antioxidants" Vol.
pp. 102-103 (1983-1984); 2) Li;
S. S. , “Ultraviolet stabilizer
174-177 (1983-1984)
); 3) Patel, A. , “Antioxidants” pp. 106-107 (1984-)
1985); and 4) Stretanski, J.A. A. , "Ultraviolet Stabilizers", pp. 179-180 (1984-1985). Depending on solubility, 0.1 to about 15% SO by weight
Dyes and 0.01 to about 5% by weight of HALS stabilizers or blended UV stabilizers can be incorporated into plastic articles with enhanced light fatigue resistance. The SO dye and UV stabilizer can be mixed in a solution with a visually clear polymer, and this solution can then be cast as a film, sheet, lens or fixture, or injection molded into a film or lens. or the UV stabilizer-containing prepolymer film or lens is molded in alcohol, toluene,
It may also be immersed in a dye bath consisting of a solution of SO dye dissolved in an organic solvent such as a halogenated hydrocarbon. Other methods of mixing the UV stabilizer with the SO dye and polymer can also be used, such as coating or lamination. Certain hindered amine light stabilizers useful in the organic photochromic compositions of the present invention have the structural formula (In the formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and
R ₁₀ is lower alkyl; R ₃ and R ₈ are lower alkyl or hydrogen; and n=1-12. ); in particular, the hindered amine light stabilizer consists of bis(2,2,6,6-tetramethyl-
4-piperidinyl) sebacate (here, R ₁ ,
R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are methyl, R ₃ and R ₈ are hydrogen, and n=8
It is. ), marketed under the trademark Tinuvin 770, and manufactured by Ciba-Geigy.
Corporation); and especially also:
The hindered amine light stabilizer is bis(1,2,
2,6,6-pentamethyl-4-piperidinyl)
Sebacate (here, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ ,
R ₇ .R ₉ and R ₁₀ are methyl, R ₃ and R ₈ are methyl, and n=8. ) and
It is commercially available under the trademark Tinuvin 765 and is obtained from Ciba-Geigy Corporation. Another hindered amine light stabilizer useful in the organic photochromic compositions of the present invention has the structure (In the formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are lower alkyl; and R ₃ and R ₈ are lower alkyl or hydrogen. ); In particular, the hindered amine light stabilizer consists of di(1,2,2,
6,6-pentamethyl-4-piperidinyl)-butyl (3',5'-ditert-butyl-4-hydroxybenzyl) malonate (here R ₁ , R ₂ , R ₄ ,
R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
R ₁₆ and R ₁₇ are methyl, R ₁₁ is butyl, and R ₃
and R ₈ is methyl. ) and Tinuvin144
It is marketed under the trademark Ciba Geigy
-Geigy Corporation). Another hindered amine light stabilizer useful in the organic photochromic compositions of the present invention has the structure (In the formula, R ₁ , R ₄ , R ₅ , R ₁₁ and R ₁₆ are lower alkyl or hydrogen; R ₂ , R ₃ , R ₆ , R ₇ ,
R ₈ , R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ and
R ₁₈ is lower alkyl; n ₁ = 1-12; and
n ₂ =1 to 15. ); In particular, the hindered amine light stabilizer consists of poly[(6-[(1,1,3,
3-tetramethylbutyl)amino]-1,3,5
-triazine-2,4-diyl)(1,6-[2,
2,6,6-tetramethyl-4-piperidinyl]
amino-hexamethylene)] (here, R ₂ , R ₃ ,
R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
R ₁₇ and R ₁₈ are methyl, R ₁ , R ₄ , R ₅ , R ₁₁
and R ₁₆ is hydrogen and n ₁ =6. )
is commercially available under the trademark Chimassorb944,
Ciba-Geigy Corporation
It is taken from. Another hindered amine light stabilizer useful in the organic photochromic compositions of the present invention has the structural formula (In the formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and
R ₁₀ is lower alkyl; R ₃ and R ₈ are lower alkyl or hydrogen; n ₁ = 1-12; and
n ₂ =1 to 15. ); in particular, the hindered amine light stabilizer comprises poly[[6-(morpholino)-S-triazine-2,4-diyl][1,6
-(2,2,6,6-tetramethyl-4-piperidyl)amino]hexamethylene] (here,
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are methyl, R ₃ and R ₈ are hydrogen, and n ₁
=6. ), marketed under the trademark Cyasorb3346, and manufactured by American Cynamid
Cyanamid Corporation). Another hindered amine light stabilizer useful in the organic photochromic compositions of the present invention has the structure (wherein R ₁ , R ₂ , R ₃ and R ₄ are lower alkyl; and n=1 to 15); in particular, the hindered amine light stabilizer is 4-hydroxy-2,2, Dimethyl succinate polymer with 6,6-tetramethyl-1-piperidineethanol (here R ₁ , R ₂ , R ₃ and
R ₄ is methyl. ), marketed under the trademark Tinuvin 622, and manufactured by Ciba-Geigy
Corporation). Other hindered amine light stabilizers useful in _the organic photochromic compositions of the present invention are hindered amine light stabilizers having the structural formula ( _C26H52N4 ) _o , where n= _1-15 . encompasses,
It is commercially available under the trademark Spinuvex A-36 and is available from Borg-Warner.
Corporation);
A hindered amine light stabilizer is commercially available under the trademark HostavinTMN20 and is obtained from American Hoechst Corporation. UV stabilizers belonging to the class of excited state quenchers useful in the organic photochromic compounds of the present invention include complexes of certain organic ligands with Ni ²⁺ ions, cobalt()tris-di-n- Includes butyl dithiocarbamate, cobalt () diisopropyldithiocarbamate (Co DIPDTP), and nickel diisopropyldithiophosphate (Ni DIPDTP). Preferred excited state quenchers are singlet oxygen quenchers, especially complexes of Ni ²⁺ ions with certain organic ligands. The Ni ²⁺ complex is commonly used in polyolefins to protect them from photodegradation. The most preferred Ni ²⁺ complex is: Structural formula [2,2′-thiobis[4-(1,1,
3,3-tetramethylbutyl)phenolate](butylamine)]nickel, Cyasorb
Marketed under the trademark UV1084, American
American Cyanamid
Company); Structural formula Nickel [O-ethyl (3,5-di-
tert-butyl-4-hydroxybenzyl)] phosphonate, commercially available under the trademark Irgastab 2002 and manufactured by Ciba-Geigy.
Corporation); Structural formula is a nickel dibutyl dithiocarbamate with
E.I. Dupont de. Nemours & Co.
Company); Structural formula Bis[2,2'-thiobis-4-(1,
1,3,3-Tetramethylbutethyl)phenolate]nickel, marketed under the trademark UV-Chek AM101 and manufactured by Ferro
Corporation); Structural formula and other Ni ²⁺
The complex is UV-Chek AM 105, UV-Chek
It is marketed under the trademarks AM126 and UV-Chek AM205, which are also manufactured by Ferro.
Corporation). A preferred SO dye for use according to the invention is 1,3,3,4,5-pentamethyl-9'-methoxy-spiro[indoline-2,3'-[ 3H ]-
Naphtho[2,1- b ][1,4]oxazine; 1,
3,3,5,6-pentamethyl-9'-methoxy-
Spirooxazine; 1,3,3-trimethyl-
5'-methoxy spirooxazine; 1,3,3-
Trimethyl-5-methoxy spirooxazine;
1,3,3,4,5-pentamethyl-8'-bromo spirooxazine; 1,3,3,5,6-pentamethyl-8'-bromo spirooxazine; 1,
2,3,3,4,5-hexamethyl-9'-methoxy spirooxazine; 1,2,3,3,5,6
-hexamethyl-9'-methoxy spirooxazine; 1,3,3-trimethyl-4-trifluoromethyl-9'-methoxy spirooxazine; 1,
3,3-trimethyl-6-trifluoromethyl-
9′-Methoxy-spirooxazine; 1,3,3-
trimethyl-4-trifluoromethyl-5'-methoxy spirooxazine; and 1,3,3-trimethyl-6-trifluoromethyl-5'-methoxy spirooxazine. Preferred plastic hosts are cellulose acetate butyrate (CAB); CR-39 ^™ , diethylene glycol bis(allyl carbonate);
PPG Industries, Inc.
Inc.); Lexan ^TM , bisphenol-A
and phosgene, obtained from General Electric; Lexan ^™ , polycarbonate resin concentrate of bisphenol-A and phosgene, obtained from General Electric;
Plexiglas ^TM , polymethyl methacrylate, Rohm and Haas
Company); polyvinyl chloride; and polyolefins. The invention will be further illustrated by the following non-limiting examples. Examples 1-8 have a thickness of 17-19 mils, 1, 2, 3, 3, 4,
5 and 1,2,3,3,5,6-hexamethyl-
Eight samples of cellulose acetate butyrate (CAB) containing 0.4% by weight of a mixture of 9'-methoxy SO isomers without or with the addition of hindered amine light stabilizers (HALS) were poured into a solution of CAB in methylene chloride. Prepared by mold. 4 to obtain the desired thickness and with good visual appearance.
Continuous casting was required. The above included a control sample without the addition of HALS. The other seven samples contained various hindered amine light stabilizers in any amount within 0.4% by weight. The samples were subjected to a 20 hour cycle exposure test on a Fadeometer. After 5 cycles, the control sample without HALS lost its total photochromism, while the sample with HALS still showed good photochromism. Table 1 shows the individual HALS used in the CAB samples after 100 hours exposure on a Fadeometer and the percentage of residual photochromism of the samples. [Table] Examples 9-10 Two sheet samples of CAB (60
mill) was manufactured. One sample of the CAB sheet samples contained 0.2% by weight of 1,2,3,3,4,5 and 1,2,3,3,5,6-hexamethyl-9'-
Mixture of methoxy spirooxazine isomers and 0.2% by weight of UV-Chek as excited state quencher
AM-205 was included. The other sample contained 0.2% by weight of Tinuvin as a hindered amine light stabilizer in addition to the SO dye and UV-Chek AM-205.
622 was also included. Samples without HALS were tested in the fademeter after 15 20-hour exposure cycles.
It has lost all of its photochromism. However, H.A.L.S.
The sample containing still retained 40% of its original photochromism. Examples 11-13 Control samples were prepared from 31% diisodecyl phthalate,
3% octyl epoxytalate, 3% control stabilizer, 63% PVC and 0.1% 1,3,3,4,
5- and 1,3,3,5,6-pentamethyl-
Casting was performed from a plastisol solution consisting of a 9'-methoxy SO dye mixture in an oven at 160°C for 20 minutes. Two additional samples were prepared as follows: one sample contained the components of the control sample plus 0.2% by weight of UV-
Chek AM-205 was included; other samples included 0.2 wt.% UV-Chek AM-205 and 1.0 wt.% UV-Chek AM-205.
Included Tinuvin622. The control sample lost all its photochromic effects after 20 hours of exposure on the Fadeometer; UV-Chek
Samples containing AM-205 lasted for 80 hours before losing their photochromic effect and UV-Chek AM-205
and Tinuvin622 lasted for 180 hours before losing its photochromic effect. Examples 14-18 13.1 mg of 1,3,3- in 100 ml of ethanol
An ethanol solution of 1,3,3-trimethyl SO dye was prepared by dissolving the trimethyl SO dye. Five 10.0 ml volumetric flasks were each filled with 2 ml of the solution. Then add 0.01ml to each flask.
1NHCl was added and each solution was diluted to 10.0 ml with ethanol. Each solution was initially colorless, but turned pinkish and lost its photochromic effect as soon as HCl was added. Approximately 3 mg of Tinuvin770, Tinuvin765,
Either Cyasorb 1084 or UV-Chek AM-205 was added. The solution containing Tinuvin and Cyasorb compounds returned to a colorless solution and regained the photochromic effect, while the other solutions remained pinkish in color and showed no photochromic effect. Although the invention has been described in terms of preferred embodiments, other embodiments can achieve the same results. Changes and modifications of this invention will be apparent to those skilled in the art and it is intended that all such modifications and equivalents be included within the scope of the claims.

Claims (1)

[Scope of Claims] 1. A spirooxazine photochromic composition and a hindered amine light stabilizer for increasing the photofatigue resistance of the spirooxazine photochromic composition.
Photochromic composition. 2 Structural formula (In the formula, one of R ₁ , R ₂ and R ₃ is hydrogen, halogen,
selected from the group consisting of lower alkoxy and lower alkyl, the others being hydrogen; R ₄ and R ₅ are hydrogen;
selected from the group consisting of lower alkyl, lower alkoxy, halogen and trifluoromethyl; and R ₆ is lower alkyl. 2. A composition according to claim 1, comprising at least one photochromic compound having the following: ) and a hindered amine light stabilizer. 3. The composition according to claim 1 or 2, further comprising a singlet oxygen quencher ultraviolet stabilizer. 4. The composition of claim 3, wherein the singlet oxygen quencher UV stabilizer is a Ni ²⁺ ion complex with an organic ligand. 5 The singlet oxygen quencher ultraviolet stabilizer is [2,
2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenolate](butylamine)]nickel, nickel[0-ethyl(3,5-di-tert)
-butyl-4-hydroxybenzyl)] phosphonate, nickel dibutyl dithiocarbamate,
Nickel di-isopropyldithiophosphate,
Bis[2,2'-thiobis-4-(1,1,3,3
-tetramethylbutyl)phenolate]nickel,
4. The composition of claim 3, wherein the composition is selected from cobalt() tris-di-n-butyldithiocarbamate and cobalt()diisopropyldithiocarbamate. 6 The hindered amine light stabilizer has the following formula: (In the formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and
R ₁₀ is lower alkyl, R ₃ and R ₈ are selected from lower alkyl and hydrogen, and n is 1-12); (In the formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are lower alkyl, R ₃ and R ₈ are selected from lower alkyl and hydrogen); (wherein R ₁ , R ₄ , R ₅ , R ₁₁ and R ₁₆ are selected from lower alkyl and hydrogen, R ₂ , R ₃ , R ₇ , R ₈ ,
R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ and R ₁₈ are lower alkyl, n is 1-12, and
n ₂ is 1 to 15); (In the formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and
_R10 is lower alkyl, _R3 and _R8 are selected from lower alkyl and hydrogen, _n1 is 1-12, and _n2 is 1-15); (wherein R ₁ , R ₂ , R ₃ and R ₄ are lower alkyl and n1-15); and (C ₂₆ H ₅₂ N ₄ ) _o (wherein n is 1-15); ). 6. A composition according to any one of claims 1 to 5 selected from one or more compounds of. 7 The hindered amine light stabilizer is bis(2,
2,6,6-tetramethyl-4-piperidinyl)
Sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, di(1,2,2,6,6-pentamethyl-4-piperidinyl)-butyl(3',5'-di tert-butyl-4
-hydroxybenzyl)malonate, poly[(6
-[(1,1,3,3-tetramethylbutyl)-amino]1,3,5-triazine-2,4-diyl)(1,6-[2,2,6,6-tetramethyl-
4-piperidinyl]amino-hexamethylene)],
Poly[[6-(morpholino)-S-triazine-
2,4-diyl][1,6-(2,2,6,6-tetramethyl-4-piperidyl)amino]-hexamethylene], and 4-hydroxy-2,2,6,
7. The composition of claim 6 selected from one or more of dimethyl succinate polymers with 6-tetramethyl-1-piperidineethanol. 8. The composition of claim 6, further comprising a plastic host. 9. The composition of claim 8 containing from about 0.1 to about 15% by weight of said photochromic compound and from about 0.01 to about 5% by weight of said stabilizer(s).