JPH05134353A - Optical interchangeable plastic product - Google Patents

Abstract

PURPOSE: To obtain a plastic product used as an article for eyes, such as sunglasses, eyeglasses or a window covering material with photochromic properties such that the product has high visual transmissivity in an unactivated state and significantly turns dark in color when irradiated with ultraviolet rays and shows excellent resistance to fatigue due to light. CONSTITUTION: This plastic product is formed by adding a photochromic compound represented by the formula and a singlet oxygen quencher to a plastic host. In the formula: one of R1 , R2 and R3 is hydrogen, a halogen or a lower alkoxyl group and the others are hydrogen; each of R4 and R5 is hydrogen, a lower alkyl or lower alkoxyl group or a halogen; R6 is a lower alkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic plastic product using a photochromic composition, and more particularly to spiro [indoline-2,3 '-[ 3H ] -naphtho [2,1- b ].
The present invention relates to a photochromic plastic product using an organic photochromic composition containing a [1,4] oxazine] dye (hereinafter sometimes abbreviated as SO dye) and a specific ultraviolet (UV) stabilizer.

[0002]

2. Description of the Related Art A compound that reversibly changes color by light is called a photochromic compound. These photochromic compounds change their transmittance when irradiated with ultraviolet rays or visible rays, but when they are subsequently irradiated with rays of different wavelengths or when the initial light source is removed, the original color state is restored. Return.

Although organic photochromic substances have been known for over 50 years, they have not reached widespread industrial or commercial use. The reason is mainly due to the irreversible decomposition phenomenon generally called light fatigue. That is, when light is repeatedly irradiated, the photochromic substance loses the photochromic property. Light, heat or both light and heat are believed to cause photolysis of organic photochromic compounds,
Many researchers have attempted to improve the resistance to light fatigue (light fatigue resistance) of photochromic compounds by adding many conventional antioxidants and UV absorbers. For example, U.S. Pat. No. 3,212,898 teaches the use of conventional UV absorbers such as benzophenone and benzotriazole to increase the photochromic lifetime of photochromic benzospiropyran compounds. Similarly, U.S. Pat. No. 3,666,352 describes the photochemical nature of photochromic mercury thiocarbazonate-based lenses that transmit light at wavelengths above 4200 angstrom units, but do not transmit light below 4200 angstrom units. It teaches the inclusion of conventional UV absorbers in the photochromic lens to substantially improve resistance to degradation.

A group of organic photochromic compounds, spiro [indoline-2,3 '-[ 3H ] -naphtho [2,1-]
b ] [1,4] oxazoline] (SO) dyes are known to have good light fatigue resistance. Photochromic compounds of this kind are disclosed in U.S. Pat.
578,602 and 4,215,010. Photochromic articles or lenses obtained from this type of compound are more excellent in light fatigue resistance than those obtained from other photochromic compounds, but expand the applications of photochromic articles and It has been desired to further improve the light fatigue resistance in order to extend the period (life). SO dyes with improved light fatigue resistance are believed to be particularly useful in making photochromic sunglasses, opthalmic lenses, ski goggles, window coverings and the like.

The exact mechanism of photodegradation of SO dyes has not yet been fully elucidated. Although some circumstantial evidence implicates oxygen in the photodegradation process, traditional antioxidants (so-called hindered phenols and amines) do not improve the light-fastness of SO dyes. Further, conventional benzophenone and benzotriazole, which are ultraviolet stabilizers, improve the light fatigue resistance of SO dyes, but they effectively protect the SO dyes from the fact that they strongly absorb the ultraviolet rays in the region where they absorb the ultraviolet rays, so that they have a shielding effect. It cannot be used. Thus, by competing with SO dyes that absorb UV light, these conventional UV stabilizers reduce the light intensity available for SO dye activation. In addition, some conventional UV stabilizers can damage SO dyes under certain conditions.

[0006]

OBJECT OF THE INVENTION It is an object of the present invention to produce sunglasses, optical lenses and skis using an SO dye-containing organic photochromic composition having improved light fatigue resistance without impairing its photochromic ability. It is to provide photochromic plastic products such as goggles and window coverings.

[0007]

The above prior art problems have been overcome by the discovery that a group of specific UV stabilizers improve the light fatigue resistance of SO dyes without adversely affecting the photochromic properties thereof. These particular UV stabilizers belong to the class of peroxide decomposers or excited state quenchers.
Preferably the UV stabilizer is a single oxygen scavenger, more preferably a complex of Ni ²⁺ ions and an organic ligand. These Ni ²⁺ complexes are commonly used in polyethylene to protect against photodegradation. These particular UV stabilizers have almost no absorption in the UV region absorbed by SO dyes, and therefore do not impair the photochromic ability of SO dyes. SO dyes and specific UV stabilizers are added to optically clear plastics to make the photochromic elements suitable for photochromic sunglasses, ski goggles and the like.

The organic photochromic composition according to the present invention has the formula

[0009]

[Chemical 2]

Wherein _one of R ₁ , R ₂ and R ₃ is hydrogen, halogen or lower alkoxy, the other is hydrogen, and R ₄ and R ₅ are hydrogen, lower alkyl, lower alkoxy or halogen. And R ₅ is lower alkyl) spiro [indoline-2,3 ′-[3 H ]
-Naphtho [2,1- b ] [1,4] oxazine] (S
O) Includes a dye and a specific UV stabilizer. The specific ultraviolet stabilizer belongs to the class of peroxide decomposition or excited state quenchers, and is preferably a singlet oxygen quencher.

Depending on its solubility, 0.1 to about 15% by weight of SO dye and 0.01 to about 5% by weight of UV stabilizer are optically transparent with increased light fatigue resistance. It is added in the plastic film. The optically transparent matrix preferably has a thickness in the range of 0.0001 to 2 inches. The SO dye and UV stabilizer are mixed in a liquid with an optically clear polymer that is subsequently cast into the film or lens or a polymer that is injection molded or otherwise molded into the film or lens. The pre-polymerized film or lens containing the UV stabilizer may be immersed in a dye bath containing SO dye dissolved in an organic solvent solution such as alcohol, toluene, chlorinated hydrocarbons. Another method of mixing the UV stabilizer with the SO dye and the optically transparent polymer is as follows:
A coating method and a laminating method may be used.

As the ultraviolet stabilizer used in the present invention,
Complexes of Ni ²⁺ ions with organic ligands and cobalt (III)
-Tris-di-n-butyldiocarbamate, iron (II
I) -Tris-di-isopropyldithiocarbamate and cobalt (II) -di-isopropyldithiocarbamate. Preferred UV stabilizers are Ni ²⁺ complexes,
Especially from the American Cyanamide company, Cyasor
b) Formula sold under the trade name of UV1084

[0013]

[Chemical 3]

Having [2,2'-thiobis [4-
(1,1,3,3-Tetramethylbutyl) phenolato]
(Butylamine)] Nickel, a formula sold by Ciba-Geigy under the trade name Irgastab 2002

[0015]

[Chemical 4]

Nickel-bis [0-ethyl (3,5-di-tert-butyl-4-hydroxybenzyl)] phosphonate having E. I. Formula sold by DuPont under the trade name Rylex NBC

[0017]

[Chemical 5]

A nickel-dibutyldithiocarbamate having the formula commercially available from Ferro Corporation under the trade name UV-Chek AM101.

[0019]

[Chemical 6]

Bis [2,2'-thiobis-4- having
(1,1,3,3-Tetramethylbutyl) phenolato]
Nickel, and UV- from Ferro Corporation
Chek AM10, UV-Chek AM126 and UV-
It is another Ni complex sold under the trade name of Chek AM205. A preferred SO dye used in the present invention is one in which the spiro [indoline-2,3 '-[ 3H ] -naphtho [2,1- b ] [1,4] oxazine] moiety in the dye is S.
When abbreviated as O, 1,3,3,4,5-pentamethyl-
9'-methoxy-SO, 1,3,3,5,6-pentamethyl-9'-methoxy-SO, 1,3,3-trimethyl-5'-methoxy-SO, 1,3,3-trimethyl-5
-Methoxy-SO, 1,3,3,4,5-pentamethyl-8'-bromo-SO and 1,3,3,5,6-pentamethyl-8'-bromo-SO. 1,3,3-Trimethyl-SO is also preferably used. 1, 3, 3,
4,5-pentamethyl-9'-methoxy-SO and 1,
3,3,5,6-pentamethyl-9'-methoxy-SO
When using with, the former is 30-45% and the latter is 7
It is preferably 0 to 55%.

Preferably, the transparent plastic host is cellulose acetate butyrate (CAB), CR39, a propylene glycol bisallyl carbonate available from PPG, or Lexan, a polycarbonate product available from GE by condensation of bisphenol A and phosgene. (Lexan), a polymethylmethacrylate commercially available from Rohm and Haas Company Limited (Plexigla
s).

[0022]

The present invention will be further described by the following examples. Example 1 (Comparative) 100 mg of 1,3,3,4,5-pentamethyl-9'-
Methoxy-spiro [indoline-2,3 '-[3H]-
Naphtho [2,1-b] [1,4] oxazine] and 1,
3,3,5,6-Pentamethyl-9'-methoxy-spiro [indoline-2,3 '-[3H] -naphtho [2,1]
-B] [1,4] oxazine] A isomer mixture and 50
A panel of CAB films was cast with 50 g of a 10% cellulose acetate butyrate (CAB) solution in methylene chloride containing mg antioxidant. The antioxidant used was 2,4,6-tri-tert-butyl-phenol, 6
It was -tert-butyl-2,4-dimethyl-phenol and N-phenyl-p-phenylenediamine. A control film without added antioxidant was also obtained by casting.

The four kinds of CAB films were subjected to a 20-hour exposure test using a fade odometer manufactured by Atlas Electric Devices Co., Chicago, Illinois, USA. After a fifth 20 hour period, the photochromism of the CAB films was tested by irradiating them with a mercury lamp for 10 minutes. All CAB films lost the photochromism they possessed. Example 2 (Comparative Example) Example 1 except that a conventional UV absorber was used in place of the antioxidant.
A group of CAB films was prepared and tested according to. The conventional ultraviolet absorber used is 2-hydroxy-4-methoxybenzophenone (commercially available from American Cyanamide under the trade name of Ciasorp UV9), 2,
2'-dihydroxy-4-methoxybenzophenone (commercially available from American Cyanamide under the trade name of Ciasorp UV24) and 2 (2'-hydroxy-
5'-methylphenyl) benzotriazole (commercially available under the trade name of TINUPIN P from Ciba Geigy)
Met.

After 5 exposures with a fade odometer for 20 hours, the control film lost all its photochromism. As is clear from Table 1, in the case of the three types of CAB films containing the conventional ultraviolet absorber, the photochromic ability remaining after 100 hours of exposure was smaller than that of the newly prepared sample. Table 1 also shows that the photochromic ability of the film is reduced by the shielding effect of the conventional ultraviolet absorber.

[0025]

[Table 1]

Example 3 A group of CAB films were prepared and tested according to Example 1 except that a UV stabilizer Ni ²⁺ complex was used in place of the antioxidant. The amount of Relex NBC used as one of the Ni ²⁺ complexes was 0.25 wt% instead of the usual 1 wt%. 5 hours of exposure with a fade odometer
After being run through, the control film lost all of its photochromism. As is clear from Table 2, Ni after 100 hours of exposure
The CAB film incorporating the complex still showed good photochromic properties similar to the freshly prepared samples. When the Ni ²⁺ complex, which is a specific UV stabilizer, was used, the decrease in the photochromic ability of the film was so small that it could be ignored.

[0027]

[Table 2]

Example 4 1,3,3,4,5-pentamethyl-9'-methoxy-
SO and 1,3,3,4,5,6-pentamethyl-9'-
A group of CAs according to Example 3 except that 1,3,3-trimethyl-SO dye was used instead of the methoxy-SO mixed dye.
A B film was made and tested.

Similar to the above example, the control film lost its photochromism within 100 hours of exposure of the fadeometer. As is clear from Table 3, the CAB film containing the Ni ²⁺ complex after 100 hours of exposure still showed as good photochromic properties as the newly prepared film.

[0030]

[Table 3]

Example 5 1,3,3,4,5-pentamethyl-9'-methoxy-
Instead of a mixture of SO and 1,3,3,5,6-pentamethyl-9'-methoxy-SO, 1,3,3-trimethyl-
A group of CAB films were prepared and tested according to Example 1 except that 5'-methoxy-SO dye was used and Cyasorb UV 1084 was used in place of the antioxidant. The control film lost all its photochromism after five 20 hour cycles of exposure in the fade odometer, while the film containing Cyasorb UV 1084 still retained good photochromism. Example 6 A group of films was made according to Example 3 except that the CAB film was replaced with a Rohm and Haas Plexiglas film and the film was applied 4 times instead of 5 times for a 20 hour fade odometer exposure cycle. , Tested. After 4 cycles, the control film lost all its photochromism, while the films incorporating the UV stabilizer Ni ²⁺ complex all showed good photochromic effects. Example 7 The GE Lexan film was used in place of the CAB film, and 1,3,3,4,5-pentamethyl-9'-methoxy-SO and 1,3,3,5,6-pentamethyl-
1,3 instead of the isomer mixture of 9'-methoxy-SO,
3-trimethyl-SO dye was used, and 2 of the film was used.
A group of films were made and tested according to Example 3 except that the 0 hour period fade odometer exposure was changed to 8 instead of 5. The control film lost all its photochromism, but even after 160 hours the UV stabilizer N
The film containing the i-complex retained a good photochromic effect. Example 8 0.02 g of UV-Chek AM105 was added to 20 g of CR-
Dissolve in 39 and add 0.8 g of di-isopropyl peroxydical carbonate (catalyst). The resulting solution was used to cast a 1.14 mm thick CR-39 plate. A control film was also cast without the above base UV-Chek AM105.

UV-CR-containing CR-AM105
CR without 39 plate and UV-Chek AM105
-39 plate to 1,3,3,4,5-pentamethyl-9'-
Immersion in a dye bath containing an isomer mixture of methoxy-SO dye and 1,3,3,5,6-pentamethyl-9'-methoxy-SO dye A, the plate was placed in a fade odometer at 2
It was subjected to a 0-hour cycle exposure test. After the eighth 20 hour cycle, the control film lost 78% of its photochromic activity, but U
Plates loaded with V-Chek AM105 lost only 47% of photochromic capacity.

Although the present invention has been described with reference to its preferred embodiments, those skilled in the art can understand that similar effects can be obtained in other embodiments. Modifications and improvements relating to the present invention are included in the present invention as long as they are obvious to those skilled in the art and do not depart from the present invention.

[0034]

[Effect] As is clear from the above description, the photochromic plastic product of the present invention has sufficient photochromic ability,
Moreover, it has improved light fatigue resistance, and is particularly suitable for photochromic plastic products such as sunglasses, optical lenses, ski goggles, and window covering materials.

Claims (16)

[Claims] 1. (a) a transparent plastic host, (b) a structural formula: (Wherein _one of R ₁ , R ₂ and R ₃ is hydrogen, halogen or lower alkoxy, the other is hydrogen, R ₄
And R ₅ is hydrogen, lower alkyl, lower alkoxy or halogen, and R ₆ is lower alkyl), and (c) a singlet oxygen scavenger. Photochromic plastic products. 2. The photochromic plastic product according to claim 1, wherein the singlet oxygen scavenger comprises a complex of Ni ²⁺ ions and an organic ligand. 3. A photochromic plastic product according to claim 1, wherein the plastic host is cellulose acetate butyrate. 4. The photochromic plastic product according to claim 1, wherein the plastic host is a polycarbonate resin. 5. A photochromic plastic product according to claim 1, wherein the plastic host is polymethylmethacrylate. 6. A photochromic plastic product according to claim 1, wherein the plastic host is diethylene glycol bis (allyl carbonate). 7. Photochromic plastic products 1, 3,
3,4,5-Pentamethyl-9'-methoxyspiro [indoline-2,3 '-[ 3H ] -naphtho [2,1-b]
The photochromic plastic product according to claim 1, comprising [1,4] oxazine. 8. A photochromic compound is 1,3,3,5,6-pentamethyl-9'-methoxyspiro [indoline-2,
The photochromic plastic product according to claim 1, comprising 3 '-[ 3H ] -naphtho [2,1- b ] [1,4] oxazine]. 9. A photochromic compound is 1,3,3-trimethyl-5-methoxyspiro [indoline-2,3 '-[3
The photochromic plastic product according to claim 1, comprising [ H ] -naphtho [2,1- b ] [1,4] oxazine]. 10. A photochromic compound is 1, 3, 3, 5, 6-
Pentamethyl-8'-bromo-spiro [indoline-
2,3 '-[ 3H ] -naphtho [2,1- b ] [1,4]
The photochromic plastic product according to claim 1, comprising oxazine]. 11. A photochromic compound is 1, 3, 3, 4, 5-
Pentamethyl-8'-bromo-spiro [indoline-
2,3 '-[ 3H ] -naphtho [2,1- b ] [1,4]
The photochromic plastic product according to claim 1, comprising oxazine]. 12. (a) Diethylene glycol bis (allyl carbonate), (b) 1,3,3,5,6-pentamethyl-9'-methoxyspiro [indoline-2,3 '-[ 3H ] -naphtho [ The photochromic plastic product according to claim 1, which comprises 2,1- b ] [1,4] oxazine] and (c) a Ni ²⁺ -based singlet oxygen scavenger. 13. (a) Diethylene glycol bis (allyl carbonate), (b) 1,3,3,4,5-pentamethyl-9'-methoxyspiro [indoline-2,3 '-[ 3H ] -naphtho [ The photochromic plastic product according to claim 1, which comprises 2,1- b ] [1,4] oxazine] and (c) a Ni ²⁺ -based singlet oxygen scavenger. 14. (a) Jetylene glycol bis (allyl carbonate), (b) 1,3,3-pentamethyl-5-methoxyspiro [indoline-2,3 '-[ 3H ] -naphtho [2,1]. −
b ) [1,4] oxazine] and (c) a Ni ²⁺ -based singlet oxygen scavenger, The photochromic plastic product according to claim 1. 15. A photochromic plastic product according to any one of claims 1, 12, 13 and 14 wherein the plastic product is a lens. 16. A photochromic plastic product according to any one of claims 1, 12, 13 and 14 wherein the plastic product is eyeglasses.