Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-04-17
2001-06-12
Higel, Floyd D. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C524S090000, C544S132000, C544S366000, C546S199000, C548S260000, C548S261000
Reexamination Certificate
active
06245915
ABSTRACT:
The instant invention pertains to novel asymmetrical bisbenzotriazole compounds which are red-shifted, are particularly soluble due to that asymmetry and which are useful in a host of end-use applications.
BACKGOUND OF THE INVENTION
Although benzotriazoles with just hydrogen at the 5-position of the benzo ring are photostable and useful in adhesive formulations, they lack red-shifted absorbance toward longer UV wavelengths which would make them more useful in giving added protection to the substrates. U.S. Pat. No. 5,319,091 and U.S. Pat. No. 5,410,071 described the preparation of benzotriazoles substituted at the 5-position of the benzo ring with alkyl- or aryl-sulfonyl moieties. It is taught in U.S. Pat. No. 5,280,124 that by introducing a higher alkyl or aryl sulfoxide or sulfone at the 5-position of the benzo ring of the benzotriazole, the resulting benzotriazole exhibits enhanced absorption in the near visible range (over 350 nm). Such sulfone substituted products were shown to be useful in automotive coatings applications. Copending patent applications Ser. Nos. 08/961,127 and 09/234,880 teach that an electron withdrawing moiety at the 5-position of the benzo ring of the benzotriazole is advantageous for similar reasons. Additionally, these copending patent applications teach that such an electron withdrawing group dramatically increases the photostability of these benzotriazole UV absorbers in automotive coatings.
It is known in the art that the concomitant use of a hindered amine light stabilizer with a UV absorber such as a benzotriazole provides excellent stabilization in many polymer compositions as summarized by G. Berner and M. Rembold, “New Light Stabilizers for High Solids Coatings”, Organic Coatings and Science and Technology, Vol. 6, Dekkar, New York, pp 55-85.
The benzotriazole UV absorbers represent a special class of commercial UV absorbers as described above. Only a few references refer to substitution on the benzo ring by an aryl or alkyl sulfoxide or sulfonyl moiety. U.S. Pat. No. 3,218,332 discloses benzotriazoles substituted at the 5-position of the benzo ring by a lower alkyl sulfonyl moiety. However, this patent deals with putting reactable groups, namely alkenyl groups, at the 3-position on the phenyl ring and is of little relevance to the instant application. U.S. Pat. No. 5,268,450 and U.S. Pat. No. 5,319,091 disclose polymer compositions and a process for the production of substituted aryl thio and aryl sulfonyl benzotriazoles which are covalently bound to polymers, such as poly(phenylene sulfide), RYTON®, Phillips Petroleum. U.S. Pat. No. 5,280,124 discloses benzotriazoles with only higher alkyl or aryl sulfinyl or sulfonyl moieties at the 5-position of the benzo ring which are useful for protecting thermoset automotive coatings. The copending patent applications mentioned above teach the use of certain electron withdrawing groups including some sulfonyl groups at the 5-position of the benzo ring for the stabilization of automotive coatings.
Japanese Patent No. 92-352228 discloses the use of 5-ethylsulfonyl benzotriazoles with the 3-position of the phenyl ring being unsubstituted or substituted by methyl for the UV protection of dust proof poly(vinyl chloride) resin films. These compounds when studied in the instant adhesive compositions were found to be quite insoluble and totally useless for the instant adhesive compositions. By contrast, when a tertiary alkyl group is inserted at the 3-position of the phenyl ring, the solubility of the thus substituted benzotriazole in adhesive composition is surprisingly enhanced.
The instant compounds exhibit enhanced broadened absorption characteristics particularly in the long wavelength UV region (over 350 nm) when compared with compounds of the prior art. Additionally, the instant compounds have surprising and unexpectedly high solubility in adhesives making them especially well suited for use in adhesive formulations.
The effect of UV light on laminated articles that are exposed to the sun or other sources of UV light are of great concern to the manufacturers of such articles. Over time, constant or repeated exposure to UV light can result in dye and/or pigment fade for dyes and/or pigments used in such articles and in the degradation or breakdown of the adhesives, polymers or other materials used in the construction of the articles. The aforementioned fading and degradation shorten the useful life of the articles in question, making protection from UV light exposure an issue of great importance to the manufacturers of such articles.
Molecules known as UV absorbers are generally known in the art. However, due to the differences discussed above between the various UV absorber classes, it is the benzotriazoles and articles containing them which will be discussed here. Due to the incompatibility and low solubility of certain benzotriazoles, a need exists for selected benzotriazoles that are highly soluble and which would provide added protection in the 350 to 400 nm region of the ultraviolet. T. Nagashima et al., J. Non-Cryst. Solids, 178 (1994), 182, report “Recently ultraviolet light (UV) shielding glass, which is UV absorbing over the range of long wavelengths (320-400 nm) to avoid sunburn effects, has become an important issue because of the possible hazard of skin cancer due to depletion of the ozone layer.”
In addition, articles which incorporate the selected benzotriazoles of the instant invention are useful in protecting interior structures, textiles and fabrics from UV induced photodegradation such as in automotive applications.
Bisbenzotriazoles such as 2,2′-methylene-bis[4-tert-octyl-6-(2H-benzotriazolyl-2-yl)phenol], TINUVIN® 360 (Ciba) are are described in U.S. Pat. No. 5,299,521. While useful, these compounds are not red-shifted.
German 1,670,951 describes generically both symmetrical and asymmetrical alkylene-bisbenzotriazoles, but specifically only some symmetical bisbenzotriazoles which are outside of the scope of the instant claims. None of the compounds described in German 1,670,951 are substituted by a perfluroalkyl moiety, such as by CF
3
, and as is -seen in instant Example 6, these symmetrical bisbenzotriazoles are insoluble in adhesive compositions.
U.S. Pat. No. 4,812,498 describes symmetrical bisbenzotriazoles as stabilizers for polycarbonate resins. The bisbenzotriazoles are symmetrical in structure, do not contain perfluoroalkyl moieties, and are clearly outside the scope of the instant compounds.
EP 924,203 A1 describes bisbenzotriazole compounds each containing a polymerizable moiety and polymers made therefrom. None of these prior art bisbenzotriazoles is red-shifted or contains a perfluoroalkyl group. The instant compounds are clearly distinguished from these prior bisbenzotriazoles.
U.S. Pat. No. 5,977,219, British patent application 2,319,035, copending application Ser. Nos. 09/234,880 and 09/303,583 all describe both symmetrical and asymmetrical red-shifted bisbenzotriazoles. Quite surprisingly, these red-shifted benzotriazoles are amazingly soluble in adhesives making them especially well-suited for the instant applications. Copending application Ser. No. 09/234,880 also teaches symmetrical bisbenzotriazoles which are substituted on the both benzo rings by a perfluoroalkyl moiety and asymmetrical bisbenzotriazoles which is substituted on one benzo ring by a perfluoroalkyl moiety and where the other benzo ring is unsubstituted. There is a clear line of demarcation between the instant bisbenzotriazoles are also asymmetrical but where one benzo ring is subsituted by a perfluoroalkyl moiety, and the other benzo ring is substituted by a different electron withdrawing moiety.
DETAILED DISCLOSURE
The instant invention pertains to compounds of formula I
wherein
G
1
and G
1
′ are independently hydrogen or halogen;
G
2
is halogen, nitro, cyano, —COOG
3
, —P(O)(C
6
H
5
)
2
, —CO—G
3
, —CO—NH—G
3
, —CO—N(G
3
)
2
, —N(G
3
)—CO—G
3
, E
3
S—, E
3
SO— or E
3
SO
2
—;
G
2
′ is perfluoroalkyl of 1 to 12 carbon atoms;
G
3
is hydrogen, straight or branched c
Lau Jacqueline
Ravichandran Ramanathan
Wood Mervin
Ciba Specialty Chemicals Corporation
Hall Luther A. R.
Higel Floyd D.
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