CA2174411C - 2-(2-hydroxy-3-.alpha.-cumyl-5-alkylphenyl)-2h benzotriazoles - Google Patents
2-(2-hydroxy-3-.alpha.-cumyl-5-alkylphenyl)-2h benzotriazoles Download PDFInfo
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- CA2174411C CA2174411C CA002174411A CA2174411A CA2174411C CA 2174411 C CA2174411 C CA 2174411C CA 002174411 A CA002174411 A CA 002174411A CA 2174411 A CA2174411 A CA 2174411A CA 2174411 C CA2174411 C CA 2174411C
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
Abstract
Benzotriazole UV absorbers typified by those of formula I
(see formula I) where R is tert-octyl, nonyl or dodecyl or -CH m CH2m COOR4 where R4 is alkyl and m is 1 to 4, provide excellent light stability protection to organic substrates.
(see formula I) where R is tert-octyl, nonyl or dodecyl or -CH m CH2m COOR4 where R4 is alkyl and m is 1 to 4, provide excellent light stability protection to organic substrates.
Description
2-(2-HYDROXY-3-a-CU MYL-5-ALKYLPH ENYL)-2H-BENZOTRfAZOLES
The instant invention pertains to new 2-(2-hydroxy-3-a-cumyl-5-alkylphenyl)-2H-benzotriazoles which are particularly effective in stabilizing organic materials.
U.S. Patent No. 4,278,589 describes the preparation of 2-(2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole and 2-(2-hydroxy-3-tert-octyl-5-a-cumylphenyl)-2H-benzotriazole.
U.S. Patent No. 4,278,589 also describes the preparation of 2-(2-hydroxy-3,5-di-a-cumyl-phenyl)-2H-benzotriazole. This latter compound is a very effective UV
absorber, but unfortunately is relatively insoluble being soluble only at about the 14% (by weight) level in xylene. Since such aromatic solvents are threatened with banning because of environmental concerns, a diligent search for an effective benzotriazole which has the general light stabilizing effectiveness of 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole and which is soluble in environmentally approved solvents is required.
Japanese Kokai 75/158588 describes the preparation of 2-(2-hydroxy-3-a-cumyl-5-methyl-phenyl)-2H-benzotriazole and 2-(2-hydroxy-3-methyl-5-a-cumylphenyl)-2H-benzotriazole as effective UV absorbers.
U.S. Patent No. 4,283,327 discloses the preparation of 2-(2-hydroxy-3,5-di-tert-octylphenyl)--2H-benzotriazole and 5-chloro-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole. U.S.
Patent Nos. 4,587,346; 4,675,352; 4,973,701; 5,095,062 and 5,240.975 describe the preparation of liquid benzotriazole mixtures by the post alkylation of preformed benzotriazoles using higher alkenes and an acid catalyst. Such products are complex liquid mixtures of various related benzotriazoles and are soluble in the environmentally acceptable solvents.
However, while these UV absorbers are quite soluble in environmentally acceptable solvents, they do not have the thermal stability of the benzotriazole compounds which are substituted in the 3-position by an a-cumyl moiety.
The instant benzotriazole compounds are substituted in the 3-position with a a-cumyl group and in the 5-position with either an alkyl group or an alkyl group substituted by a carboxyalkyl group. These materials are more soluble in common coatings solvents than the tris-aryl-s-triazines that are functionalized with simple alkyl groups. Common coatings solvents include xylene, methyl amyl ketone, butyl cellosolve, butyl carbitol and methyl isobutyl ketone.
The object of this invention is to provide new soluble 2-(2-hydroxy-3-a-cumyl-5-alkylphenyl)--2H-benzotriazoles.
Still another object of this invention is to provide organic compositions stabilized against the deleterious effects of actinic light using the new soluble benzotriazoles substituted in the 3-position of the phenyl ring by an a-cumyl moiety.
The instant invention pertains to a new soluble crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole.
The compound 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole is disclosed in US 4,278,589 in Example 18 as being an off-white powder melting at 88-90°C. As such, the powdery product has defects in terms of handling and apparent density, exhibiting poor flowability, meterability and storage stability.
It has now been found that the compound 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole can be obtained in a different crystalline modification as purified crystalline particles which exhibit acceptable.properties in respect to handling, apparent density, flowability, meterability and storage stability.
The new modification is characterized by a novel crystalline form as off-white crystals melting in the range of 109-111°C; and by an X-ray diffraction pattern obtained using Cu-Ka radiation which exhibits diffraction angles (20) as seen below:
The instant invention pertains to new 2-(2-hydroxy-3-a-cumyl-5-alkylphenyl)-2H-benzotriazoles which are particularly effective in stabilizing organic materials.
U.S. Patent No. 4,278,589 describes the preparation of 2-(2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole and 2-(2-hydroxy-3-tert-octyl-5-a-cumylphenyl)-2H-benzotriazole.
U.S. Patent No. 4,278,589 also describes the preparation of 2-(2-hydroxy-3,5-di-a-cumyl-phenyl)-2H-benzotriazole. This latter compound is a very effective UV
absorber, but unfortunately is relatively insoluble being soluble only at about the 14% (by weight) level in xylene. Since such aromatic solvents are threatened with banning because of environmental concerns, a diligent search for an effective benzotriazole which has the general light stabilizing effectiveness of 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole and which is soluble in environmentally approved solvents is required.
Japanese Kokai 75/158588 describes the preparation of 2-(2-hydroxy-3-a-cumyl-5-methyl-phenyl)-2H-benzotriazole and 2-(2-hydroxy-3-methyl-5-a-cumylphenyl)-2H-benzotriazole as effective UV absorbers.
U.S. Patent No. 4,283,327 discloses the preparation of 2-(2-hydroxy-3,5-di-tert-octylphenyl)--2H-benzotriazole and 5-chloro-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole. U.S.
Patent Nos. 4,587,346; 4,675,352; 4,973,701; 5,095,062 and 5,240.975 describe the preparation of liquid benzotriazole mixtures by the post alkylation of preformed benzotriazoles using higher alkenes and an acid catalyst. Such products are complex liquid mixtures of various related benzotriazoles and are soluble in the environmentally acceptable solvents.
However, while these UV absorbers are quite soluble in environmentally acceptable solvents, they do not have the thermal stability of the benzotriazole compounds which are substituted in the 3-position by an a-cumyl moiety.
The instant benzotriazole compounds are substituted in the 3-position with a a-cumyl group and in the 5-position with either an alkyl group or an alkyl group substituted by a carboxyalkyl group. These materials are more soluble in common coatings solvents than the tris-aryl-s-triazines that are functionalized with simple alkyl groups. Common coatings solvents include xylene, methyl amyl ketone, butyl cellosolve, butyl carbitol and methyl isobutyl ketone.
The object of this invention is to provide new soluble 2-(2-hydroxy-3-a-cumyl-5-alkylphenyl)--2H-benzotriazoles.
Still another object of this invention is to provide organic compositions stabilized against the deleterious effects of actinic light using the new soluble benzotriazoles substituted in the 3-position of the phenyl ring by an a-cumyl moiety.
The instant invention pertains to a new soluble crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole.
The compound 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole is disclosed in US 4,278,589 in Example 18 as being an off-white powder melting at 88-90°C. As such, the powdery product has defects in terms of handling and apparent density, exhibiting poor flowability, meterability and storage stability.
It has now been found that the compound 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole can be obtained in a different crystalline modification as purified crystalline particles which exhibit acceptable.properties in respect to handling, apparent density, flowability, meterability and storage stability.
The new modification is characterized by a novel crystalline form as off-white crystals melting in the range of 109-111°C; and by an X-ray diffraction pattern obtained using Cu-Ka radiation which exhibits diffraction angles (20) as seen below:
Peak No. 20 Peak 20 Peak 20 Peak No. 20 No. No.
1 9.6 2 10.2 3 10.4 4 10.8 12.8 6 13.8 7 14.2 8 14.8 9 15.0 10 16.4 11 16.8 12 17.8 13 18.0 14 18.6 15 19.0 16 19.4 17 19.8 18 20.2 19 20.6 20 21.2 21 21.4 22 23.0 23 23.4 24 24.6 25 26.0 26 28.0 27 29.0 28 30.4 29 31.0 The instant compound 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole can also be obtained as in an amorphous modification having excellent solubility characteristics.
Furthermore, the instant invention also pertains to the compounds 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl-5-dodeylphenyl)-2H-benzotriazole and H
'N~ / a-cumyl to compounds of the formula \ \ /N
N
R
where R is -CHmCH2mCOOR4 , R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
Preferred compounds of the above formula are those, where R is nonyl, dodecyl or -CHmCH2mCOOR4, R4 is alkyl of 1 to 12 carbon atoms and m is 2.
Alkyl of 1 to 18 carbon atoms are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and the corresponding branched isomers.
The instant invention also relates to a process for the preparation of the novel soluble crystalline modification of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole which comprises dissolving said compound in an aromatic solvent and precipitating the compound by the addition of a lower alkanol; or by crystallizing or recrystallizing the compound from a lower alkanol alone or in conjunction with a minor amount of an aromatic solvent.
Preferably, the process comprises crystallizing or recrystallizing said compound from an alkanol of 1 to 4 carbon atoms either alone or in conjunction with a minor amount of an aromatic solvent.
Aromatic solvents which can be used in the above process are, for example, toluene or xylene.
When used in a minor amount, such minor amount may be, for example, up to 15%
or, preferably, 5-15% by volume of the total volume of solvent used.
Some alkanols useful in the instant process are, for example, methanol, ethanol, n-propanol, isopropanol, 1-butanol, sec-butyl alcohol or isobutyl alcohol. Preferably the alkanol is an alkanol of 2, 3 or 4 carbon atoms; most preferably isopropanol or 1-butanol.
The instant invention also pertains to a composition stabilized against actinic induced degradation comprising (a) an organic material subject to actinic induced degradation, and (b) the amorphous or crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as described above, 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl-5-dodeylphenyl)-2H-benzotriazole or a compound of the formula H
~N~
a-cumyl w wN/N \ ~ , R
where R is -CHmCH2mCOOR4, R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
In general the benzotriazole according to the present invention are used from 0.01 to 20% by weight of the stabilized composition.
1 9.6 2 10.2 3 10.4 4 10.8 12.8 6 13.8 7 14.2 8 14.8 9 15.0 10 16.4 11 16.8 12 17.8 13 18.0 14 18.6 15 19.0 16 19.4 17 19.8 18 20.2 19 20.6 20 21.2 21 21.4 22 23.0 23 23.4 24 24.6 25 26.0 26 28.0 27 29.0 28 30.4 29 31.0 The instant compound 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole can also be obtained as in an amorphous modification having excellent solubility characteristics.
Furthermore, the instant invention also pertains to the compounds 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl-5-dodeylphenyl)-2H-benzotriazole and H
'N~ / a-cumyl to compounds of the formula \ \ /N
N
R
where R is -CHmCH2mCOOR4 , R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
Preferred compounds of the above formula are those, where R is nonyl, dodecyl or -CHmCH2mCOOR4, R4 is alkyl of 1 to 12 carbon atoms and m is 2.
Alkyl of 1 to 18 carbon atoms are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and the corresponding branched isomers.
The instant invention also relates to a process for the preparation of the novel soluble crystalline modification of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole which comprises dissolving said compound in an aromatic solvent and precipitating the compound by the addition of a lower alkanol; or by crystallizing or recrystallizing the compound from a lower alkanol alone or in conjunction with a minor amount of an aromatic solvent.
Preferably, the process comprises crystallizing or recrystallizing said compound from an alkanol of 1 to 4 carbon atoms either alone or in conjunction with a minor amount of an aromatic solvent.
Aromatic solvents which can be used in the above process are, for example, toluene or xylene.
When used in a minor amount, such minor amount may be, for example, up to 15%
or, preferably, 5-15% by volume of the total volume of solvent used.
Some alkanols useful in the instant process are, for example, methanol, ethanol, n-propanol, isopropanol, 1-butanol, sec-butyl alcohol or isobutyl alcohol. Preferably the alkanol is an alkanol of 2, 3 or 4 carbon atoms; most preferably isopropanol or 1-butanol.
The instant invention also pertains to a composition stabilized against actinic induced degradation comprising (a) an organic material subject to actinic induced degradation, and (b) the amorphous or crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as described above, 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl-5-dodeylphenyl)-2H-benzotriazole or a compound of the formula H
~N~
a-cumyl w wN/N \ ~ , R
where R is -CHmCH2mCOOR4, R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
In general the benzotriazole according to the present invention are used from 0.01 to 20% by weight of the stabilized composition.
The benzotriazole UV absorbers have long been a mainstay in this area with 2-[2-hydroxy-3,5-di(a-cumyl)phenyl]-2H-benzotriazole being the workhorse and epitomy of what the benzotriazole UV absorbers can deliver. Unfortunately, this compound has only limited solubility (about 14% by weight) in toluene or xylene, and is sparingly soluble in environmentally more friendly solvents. This is becoming a severe limitation since the aromatic solvents are on their way out because of environmental concerns.
Fortunately, there are soluble and thermally stable benzotriazole UV
absorbers, chiefly the new soluble crystalline modification of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, which has the same low volatility and superior light stabilization effectiveness of 2-[2-hydroxy-3,5-di(a-cumyl)phenyf]-2H-benzotriazole, but which are soluble in environmentally friendly solvents.
Such environmentally friendly solvents are, for example, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, propyl acetate, oxohexyl acetate, oxo-octyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol phenyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, n-amyl propionate, diisobutyl ketone, cyclohexanone, methyl isoamyl ketone, methyl amyl ketone, diisoamyl ketone, methyl hexyl ketone, ethanol, 2-ethylhexanol, diacetone alcohol, ethyl amyl alcohol, propanol, isobutanol, isotridecyl alcohol, butoxy ethoxy propanol, isobutyl isobutyrate, pentanedioic acid dimethyl ester, 3-methoxy-n-butyl acetate, n-amyl propionate.
The instant compositions also pertain to a composition which additionally comprises a tris-aryl-s-triazine, a hindered amine or a benzofurane-2-one light stabilizer or a mixture thereof.
The instant compositions further pertain to a composition which additionally comprises a phenolic antioxidant, a light stabilizer, a processing stabilizer or a mixture thereof.
Preferably such compositions contain additionally an effective stabilizing amount of 2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-[3-(pentadecyloxy)-2-hydroxypropoxy]-s-triazine; bis-(1-octyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) sebacate; bis-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide; or N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide.
Fortunately, there are soluble and thermally stable benzotriazole UV
absorbers, chiefly the new soluble crystalline modification of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, which has the same low volatility and superior light stabilization effectiveness of 2-[2-hydroxy-3,5-di(a-cumyl)phenyf]-2H-benzotriazole, but which are soluble in environmentally friendly solvents.
Such environmentally friendly solvents are, for example, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, propyl acetate, oxohexyl acetate, oxo-octyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol phenyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, n-amyl propionate, diisobutyl ketone, cyclohexanone, methyl isoamyl ketone, methyl amyl ketone, diisoamyl ketone, methyl hexyl ketone, ethanol, 2-ethylhexanol, diacetone alcohol, ethyl amyl alcohol, propanol, isobutanol, isotridecyl alcohol, butoxy ethoxy propanol, isobutyl isobutyrate, pentanedioic acid dimethyl ester, 3-methoxy-n-butyl acetate, n-amyl propionate.
The instant compositions also pertain to a composition which additionally comprises a tris-aryl-s-triazine, a hindered amine or a benzofurane-2-one light stabilizer or a mixture thereof.
The instant compositions further pertain to a composition which additionally comprises a phenolic antioxidant, a light stabilizer, a processing stabilizer or a mixture thereof.
Preferably such compositions contain additionally an effective stabilizing amount of 2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-[3-(pentadecyloxy)-2-hydroxypropoxy]-s-triazine; bis-(1-octyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) sebacate; bis-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide; or N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide.
A preferred embodiment of the instant invention is to a composition stabilized against the deleterious effects of actinic light which comprises (a) an organic material subject to the deleterious effects of actinic light, and (b) a benzotriazole UV absorber which is 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-benzotriazole or 2-(2-hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole.
To attain maximum light stabilization, the concurrent use of other conventional light stabilizers can be advantageous. Examples of such stabilizers are UV absorbers of the benzophenone, benzotriazole, cyanoacrylate or oxanilide type, or metal-containing light stabilizers, for example, organic nickel compounds, or hindered amine light stabilizers.
In general organic materials (polymers) which can be stabilized include 1. Polymers of monoolefins and diolefins, for example polyethylene (which optionally can be crosslinked), polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene.
2. Mixtures of 'the polymers mentioned under 1 ), for example mixtures of polypropylene with polyisobutylene.
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, propylene/butene-1, propylene/isobutylene, ethyl-ene/butene-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethyl-ene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbomene.
4. Polystyrene, poly-(a-methylstyrene).
~1"~~4~~.
To attain maximum light stabilization, the concurrent use of other conventional light stabilizers can be advantageous. Examples of such stabilizers are UV absorbers of the benzophenone, benzotriazole, cyanoacrylate or oxanilide type, or metal-containing light stabilizers, for example, organic nickel compounds, or hindered amine light stabilizers.
In general organic materials (polymers) which can be stabilized include 1. Polymers of monoolefins and diolefins, for example polyethylene (which optionally can be crosslinked), polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene.
2. Mixtures of 'the polymers mentioned under 1 ), for example mixtures of polypropylene with polyisobutylene.
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, propylene/butene-1, propylene/isobutylene, ethyl-ene/butene-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethyl-ene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbomene.
4. Polystyrene, poly-(a-methylstyrene).
~1"~~4~~.
5. Copolymers of styrene or methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/ethyl methacrylate, styrene/butadiene/ethyl acrylate, styrene/acrylonitr7le/methyl acrylate;
mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block polymers of styrene, such as, for example, styrene/butadiene/styrene, /isoprene/styrene, /ethylene/butyl-enelstyrene or styrene/ethylene/propylene/styrene.
6. Graft copolymers of styrene, such as, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MBS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrin homo- and copolymers, polymers from halogen-containing vinyl compounds, as for example, polyvinylchloride, polyvinylidene chloride, poly-vinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate, vinylidene chloride/vinyl acetate copolymers, or vinyl fluoride/vinyl ether copolymers.
mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block polymers of styrene, such as, for example, styrene/butadiene/styrene, /isoprene/styrene, /ethylene/butyl-enelstyrene or styrene/ethylene/propylene/styrene.
6. Graft copolymers of styrene, such as, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MBS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrin homo- and copolymers, polymers from halogen-containing vinyl compounds, as for example, polyvinylchloride, polyvinylidene chloride, poly-vinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate, vinylidene chloride/vinyl acetate copolymers, or vinyl fluoride/vinyl ether copolymers.
8. Polymers which are derived from a,~3-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile.
9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturated monomers, such as, for instance, acrylonitrile/butadiene, acrylonitrile/alkyl acrylate, acrylonitr7le/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylo-nitrile/alkyl methacrylate/butadiene terpolymers.
10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, _g_ polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.
11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, poly-ethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.
12. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as comonomer.
13. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene.
14. Polyurethanes which are derived from polyethers, polyesters or polybutadienes with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof (polyisocyanates, polyols or prepolymers).
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4-trimethyl-hexamethylene terephthalamide, poly-p-phenylene terephthalamide or poly-m-phenylene isophthalamide, as well as copolymers thereof with polyethers, such as for instance with poly-ethylene glycol, polypropylene glycol or polytetramethylene glycols.
16. Polyureas, polyimides and polyamide-imides.
17. Polyesters which are derived from dicarboxylic acids and diols and/or from hydroxy-carboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutyl-ene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate and polyhydroxybenzoates as well as block-copolyether-esters derived from polyethers having hydroxyl end groups.
18. Polycarbonates.
_g_ 19. Polysulfones, polyethersulfones and polyetherketones.
_g_ 19. Polysulfones, polyethersulfones and polyetherketones.
20. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenoUformaldehyde resins, urealformaldehyde resins and melamine/formaldehyde resins.
21. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
23. Thermosetting acrylic resins, derived from substituted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester acrylates.
24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, polyisocyanates or epoxide resins as crosslinking agents.
25. Crosslinked epoxide resins which are derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.
26. Natural polymers, such as cellulose, rubber, gelatin and derivatives thereof which are chemically modified in a polymer homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl cellulose.
27. Mixtures of polymers as mentioned above, for example PP/EPDM, Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.
28. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, which materials may be used as plasticizers for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.
29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S.
Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S.
Patent No. 4,355,147.
Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S.
Patent No. 4,355,147.
31. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.
32. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
33. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).
In general, the compounds of the present invention are employed from 0.01 to 20% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from 0.1 to 5%; preferably 1 to 5%.
The resulting stabilized compositions of the instant invention may optionally also contain from about 0.01 to about 10%, preferably from about 0.025 to about 5%, and especially from about 0.1 to about 1 % by weight of various conventional additives, such as the materials listed below, or mixtures thereof.
Other compositions of special interest include those which additionally contain a UV absorber selected from the group consisting of the benzophenones, benzotriazoles, cyanoacrylic acid derivatives, hydroxyaryl-s-triazines, organic nickel compounds and oxanilides.
Preferred UV absorbers are selected from the group consisting of 2-[2-hydroxy-3,5-di-(a,oc-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(w-hydroxy-octalethyleneoxy)carbonyl)ethylphenyl]--2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)phenyl]-benzotriazole, 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyl-oxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'ethyloxanilide, 2,6-bis(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl-s-triazine, 2,6-bas(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl}-s-triazine, 2,4-bas(2,4-dihydroxyphenyl}-6-(4-chlorophenyl)-, 2,6-bis(2,4-dimethylphenyl)-4-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropanoxy)phenyl]-s-triazine and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
Additional compositions of interest include those which additionally contain an effective stabilizing amount of a phenolic antioxidant; those which additionally contain a hindered amine derivative; or which additionally contain a phosphate or phosphonite stabilizer.
Compositions of special interest also include those wherein the organic material is an enamel of high solids content used for an industrial finish; is used as a coil coating; is used as a penetrating wood finish or is used as a film-forming wood finish.
When the instant compounds also contain a reactive functional group, said compounds can be chemically bonded by either condensation or free radical addition reaction to the polymer substrate. This provides for a non-migrating, non-sublimable UV absorber stabilizer. Such reactive functional groups include hydroxy, carboxyl and ethylenically unsaturated moieties.
1. Antioxidants 1.1. Alkylated mono~henols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-~~~~4~~.
methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tart-butyl-4-methoxymethylphenol 1.2. Alk~ late ed h~rdroguinones for example 2,6-di-tart-butyl-4-methoxyphenol, 2,5-di-tart-butyl-hydroquinone, 2,5-di-tart-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol 1.3. Hv dr roxylated thiodiphenyl ethers for example 2,2'-thio-bis-(6-tart-butyl-4-methyfphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3-methylphenol), 4,4'-thio-bis-(6-tart-butyl-2-methylphenol) 1.4. Alkylidene-bi_sphenols for example 2,2'-methylene-bis-(6-tart-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tart-butyl-4-ethylphenol), 2,2'-methylene-bis-[4-methyl-6-(a-methylcyctohexyl)-phenol], 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-[6-(a,a-dimethylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-(4,6-di-tart-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(6-tart-butyl-4-isobutylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 4,4'-methylene-bis-(6-tart-butyl-2-methylphenol), 1,1-bis-(5-tart-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-tart-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris-(5-tart-butyl-4-hydroxy-2-methylphenyl)-, 1,1-bis-(5-tart-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethyleneglycol bis-[3,3-bis-(3'-tart-butyl-4'-hydroxyphenyl)-butyrate], di-(3-tart-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, di-[2-(3'-tart-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tart-butyl-4-methylphenyl] terephthalate.
1.5. Benzyl compounds for example 1,3,5-tri-(3,5-di-tart-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tart-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tart-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tart-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris-(3,5-di-tart-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(4-tart-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tart-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt 1.6. Acylaminophenols for example 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate 1.7. Esters of (3-(3,5-di-tert-butyl-4-by di rox\,~phenyly-propionic acid with monohydric or polyhydric alcohols, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl isocyanurate thiodiethylene glycol di-hydroxyethyl oxalic acid diamide 1.$. Esters of fi-(5-tert-butv I-r 4-hydroxy-3-meth~~phern~~propionic acid with monohydric or polyhydric alcohols, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl isocyanurate thiodiethylene glycol di-hydroxyethyl oxalic acid diamide 19. Amides of ti-(3 5-di-tert-butt I-~ 4-by di rox)~phen~L~propionic acid for example, N, N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine N, N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl}-trimethylenediamine N, N'-di-(3,5-di-tert-butyl-4-hyd roxyphenylpropionyl)-hydrazine 2. UV absorbers and light stabilizers 2.1. 2~2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-, 3',5'-di-tart-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tart-butyl-, 5-chloro-3'-tart-butyl-5'-methyl-, 3'-sec-butyl-5'-tart-butyl-, 4'-octoxy, 3',5'-di-tart-amyl-, 3',5'-bis-(a,a-dimethylbenzyl), 3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-, and dodecylated-5'-methyl derivatives.
2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy; 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tart-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tart-butyl-4-hydroxybenzoic acid 2,4-di-tart-butylphenyl ester and 3,5-di-tart-butyl-4-hydroxybenzoic acid hexadecyl ester.
2.4. Acr)ilates, for example, a-cyano-[i,~i-diphenylacrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-~i-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, oc-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(~i-carbomethoxy-a-cyanovinyl)-2-methyl-indoline.
2.5. Nickel compounds, for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethyl-butyl)-phenoll, such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tart-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. Ster7cally hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-hydroxyethyl--2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1'(1,2-ethanediyl)-bas-(3,3,5,5-tetramethyl-piperazinone).
2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
2.$. Hydroxyphen~il-s-triazines, for example 2,6-bas-(2,4-dimethylphenyl)-4-{2-hydroxy-4--octyloxyphenyl)-s-triazine; 2,6-bas-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-; 2,4-bis(2,4-di-hydroxyphenyl)-6-(4-chlorophenyl)-; 2,4-bas[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chloro-phenyl)-s-triazine; 2,4-bas[2-hydroxy-4-(2-hydroxy-4-{2-hydroxyethoxy)phenyl]-6-(2,4-dimethyl-phenyl)-s-triazine; 2,4-bas[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;
2,4-bas[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-di-hydroxyphenyl)-6-(2,4-dimethylphenyl)-; 2,4-bas-(2,4-dimethylphenyl)-6-{2-hydroxy-4-[3-(2--ethylhexyloxy)-2-hydroxypropoxy]phenyl}-s-triazine; 2,4-bas-(2,4-dimethylphenyl)-6-(2-hydroxy--4-[3-(pentadecyloxy)-2-hydroxypropoxy]phenyl}-s-triazine.
~. Metal deaciivators, for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl-hydrazine, N,N'-bas-salicyloylhydrazine, N,N'-bas-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)--hydrazine, 3-salicyloylamino-1,2,4-triazole, bas-benzylidene-oxalic acid dihydrazide.
4. Phosehites and phosphonites, for example, triphenyl phosphate, diphenylalkyl phosphates, phenyldialkyl phosphates, tri-(nonylphenyl) phosphate, trilauryl phosphate, trioctadecyl phosphate, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphate, di-iso-decylpentaerythritol diphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol trfphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4'-diphenylylenediphosphonite.
5. Compounds which destroy~~aeroxide, for example, esters of [3-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-((3-dodecylmercapto)-propionate.
6. Hydrox\ilamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-di-hexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
~. Polvamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.
11. Fillers and reinforcing a, ents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.
The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert--butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tr7s(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl- 4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxy-benzyl)isocynurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-tent-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5--di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl--4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N'-bis(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6--tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
The hindered amine compound of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butyl-malonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, tris(2,2,6,6-tetramethyl-piperidin-4-yl) nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetra-_18_ methylpiperidine), polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethyfpiperidine) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl} 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-di-chloro-6-morpholino-s-trlazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethyl-piperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yU[3,[3,(3',[3°-tetra-methyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yU[i,(i,(3',(i'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate), 4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetra-methylpiperidin-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecyl-succinimlde, N-1-acetyl-2,2,6,6-tetramethyfpiperidin-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetra methylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl} succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{(6-tert-octylamino-s-triazin-2,4-diyl](2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy--2,2,6,6-tetramethylpiper7din-4-yl}imino], 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)-n-butylamino]-s-triazine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiper-idin--4-yl)-n-butylamino)-6-[di-(2-hydroxyethyl)amino]-s-triazine, and 2,4-bis[N-(1-octyloxy-2,2,6,6--tetramethylpiperidin-4-yl}-n-butylamino]-6-(di-(2-hydroxyethyl)amino]-s-triazine.
A most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)- s-triazine-2-yl]-1,10-diamino-4,7-diazadecane, di-(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl](2--(1-cyclohexyloxy-2,2, 6,6-tetramethyl pi peridi n-4-yl)imino-hexamethylene-[4-( 1-cyclohexyloxy---1~-2,2,6,6-tetramethylpiperidin-4-yl)imino], or 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)-n-butylaminoj-s-triazine.
A further object of this invention is to provide a process for stabilizing an organic material against actinic-induced degradation, which comprises incorporating therein or applying thereto the amorphous or crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as defined in claims 1 and 2, respectively, 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl-5-dodeylphenyl)-2H-benzotriazole or a compound of the formula H
~N~
N ~ a-cumyl N
R
where R is -CHmCHZmCOOR4, R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
Still another object of this invention is to provide a method for protecting organic material against actinic-induced degradation for longer than 3000 hours, when subjected to a QUV
testing apparatus (cycle: 8 hours light and 70°C; 4 hours dark, 50°C and 100% rel. humidity), characterized by incorporating in the organic material or applying thereto the amorphous or crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as defined in claims 1 and 2, respectively, 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3--a-cumyl-5-dodeylphenyl)-2H-benzotriazole or a compound of the formula ~N~
N
where R is -CHmCH2mCOOR4 , R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
X-ray diffraction patterns are recorded on a Philips Norelco X-ray Diffractometer unit, using Cu-Ka radiation with a nickel filter. All samples have a uniform particle size of 40 to 75 microns.
The following examples are presented for the purpose of illustration only and are not to be construed to limit the nature or scope of the instant invention in any manner whatsoever.
Example 1: 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole To a 5-liter 3-necked flask fitted with a stirrer, thermometer, reflux condenser and nitrogen inlet is charged 380 g (0.8 mol) of 2-nitro-2'-hydroxy-3'-a,a-dimethylbenzyl-5'-tert-octylazobenzene and 1200 ml of toluene. To the resulting solution is added 240 ml of isopropanol and 240 ml of water. A nitrogen atmosphere is imposed and 160 ml of 50.1 % aqueous sodium hydroxide is added. A flask containing 158.2 g (2.42 gramatoms) of zinc is connected to the reaction flask and the zinc dust is added portionwise to the reaction mixture over a 90-minute period. The internal temperature is kept between 40 and 45° C during the adition and for an additional hour and then the mixture is heated for 3 hours at 70°C. The mixture is cooled to room temperature and acidified with 600 ml of concentrated hydrochloric acid. The zinc sludge is removed by filtration. The product is contained in the organic layer, which is washed with 4 340 ml portions of dilute hydrochloric acid, and then dried over anhydrous sodium sulfate. The organic solvent was removed in vacuo to yield a crude product as a viscous syrup.
A 300 g sample of the crude product is dissolved in 300 mL of xylene. To this solution is then added with stirring 600 mL of ethanol to afford 254 g of the novel soluble crystalline modification of the compound of formula I having a melting point of 109-111 °C; and exhibiting only one spot in thin layer chromatography.
Analysis:
Calcd for C2gH35N3O: C, 78.9; H, 8.0; N, 9.5.
Found: C, 78.7; H, 8.1; N, 9.6.
This product has an X-ray diffraction pattern obtained using Cu-Ka radiation which exhibits diffraction angles (20) as seen below:
Peak No. 20 Peak No. 20 Peak 20 Peak No. 20 No.
1 9.6 2 10.2 3 10.4 4 10.8 12.8 6 13.8 7 14.2 8 14.8 9 15.0 10 16.4 11 16.8 12 17.8 13 18.0 14 18.6 15 19.0 16 19.4 17 19.8 18 20.2 19 20.6 20 21.2 21 21.4 22 23.0 23 23.4 24 24.6 25 26.0 26 28.0 27 29.0 28 30.4 29 31.0 Example 2: 2-(2-Hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole Comparative Example The title compound is prepared as described in Example 18 of U.S. Patent No.
4,278,589 as off-white crystals melting at 88-90°C. This compound exhibits an X-ray diffraction pattern obtained using Cu-Ka radiation which exhibits diffraction angles (20) as seen below:
Peak No. 20 Peak No. 20 Peak 20 Peak No. 20 No.
1 5.2 2 6.2 3 6.8 4 9.2 5 9.7 6 11.0 7 12.0 8 12.2 9 13.0 10 13.6 11 14.6 12 15.4 13 15.6 14 16.4 15 17.8 16 18.8 17 19.4 18 19.8 19 20.4 20 21.0 21 22.4 22 22.8 23 23.4 24 24.2 25 25.0 26 25.4 , 27 26.0 28 27.6 29 29.4 30 30.8 31 31.2 32 32.4 A comparison of the X-ray diffraction pattern of the instant crystalline modification as seen in Example 1 with the X-ray diffraction pattern of the prior art compound of Example 18 of U.S.
Patent No. 4,278,589 clearly indicates that the two materials are not the same.
21'~42I1 Example 3: Amorphous form of 2-(2-hydroxy-3-a,-cumyl-5-tert-octylphenyl)-2H-benzotriazole The compound prepared in Example 1 is heated to a melt and then allowed to resolidify. The amorphous material obtained has a melting point of 59-74°C. Thin layer chromatography exhibits one spot identical to that obtained from the product of Example 1.
X-ray diffraction shows a featureless pattern confirming the amorphous nature of the compound obtained in this example.
Example 4: 2-(2-Hydroxy-3-oc-cumyl-5-nonylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin, but where the reduction of the corresponding o-nitroazobenzene intermediate is carried out using catalytic hydrogenation.
Analysis:
Calcd for C3oH3,N3O: C, 79.1; H, 8.2; N, 9.2.
Found: C, 79.5; H, 8.5; N, 9Ø
Example 5: 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole The title compound is prepared by the catalytic hydrogenation of the o-nitroazobenzene compound used in Example 1 as an off-white solid. A 100 g sample of said solid is recrystallized from 100 mL of isopropanol, again from 100 mL of 19:1 isopropanolaoluene and finally from 100 mL of 9:1 isopropanolaoluene to afford 78 g of the title compound melting at 109-111 °C and having the same crystalline modification and X-ray diffraction pattern as the compound prepared in Example 1.
Example 6: 2-(2-Hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin.
Example 7: 2-(2-Hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin.
H-NMR data in CDC13 [ppm]: 0.8-0.9 triplets; 1.3-1.42 singlets; 1.9 singlets;
7.14-7.30 complex;
7.44 complex; 7.48-7.64 meta doublets; 7.86 complex; 8.20-8.34 meta doublets;
11.38-11.46 singlet; the data is consistent with the title compound.
Example 8: 2-(2-Hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin, but where the reduction of the corresponding o-nitroazobenzene compound is carried out using catalytic hydrogenation.
Examples 9 and 10' Following the general procedure of Examples 1 and 5, the following compounds of the formula H
~N~
/N / a-cumyl are prepared.
N ~
R
21'74411 Example ;
; -CH2CH2COOC8H1~
Example 11: Solubility in Organic Solvents In order to incorporate a UV absorber stabilizer into the high solids thermoset acrylic resin systems, the UV absorber must be soluble in an appropriate organic solvent. To date solvents such as the aromatic hydrocarbons, toluene or xylene, have provided ample solubility for such UV absorbers, even the sparingly soluble 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzo-triazole.
However, the possible phasing out of such aromatic hydrocarbon solvents for environmental reasons, the trend to higher solids coatings, and the increasing demands of the automobile industry for automotive coatings that will last for up to 10 years means that a more soluble, non-volatile, but equally effective UV absorber will be required.
Additionally, the UV absorber must be soluble in an environmentally friendly solvent.
The relative solubility of three different benzotriazole UV absorbers in a five typical organic solvents is measured by dissolving the benzotriazole UV absorber in 50-100 mL
of five different solvents till the solutions become supersaturated. This is seen when the benzotriazole begins to settle to the bottom of the test flask. The supersaturated solutions are allowed to remain undisturbed overnight. Then, the top layer is decanted and filtered.
The resulting filtrate containing the benzotriazole dissolved in the solvent is tested in triplicate for percent solids using ASTM Test Method D 2369-81. The higher the percent solids found indicates a more soluble benzotriazole. The results are seen in the table below.
Solubility in grams/100 solvent*
Solvent A B C D
xylene 14 76 >50 >50 butyl acetate 6 33 >50 >50 methyl amyl ketone 4 33 >50 >50 acetone n.d. n.d. >50 >50 EXXATE~ 600 4 22 >50 >50 PM acetate 3 14 >50 >50 PM solvent n.d. 4 n.d. n.d.
*A is 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotrlazole (for comparision).
B is the compound of Example 5.
C is the compound of Example 4.
D is the compound of Example 8.
EXXATE~ 600 is hexyl acetate from Exxon.
PM acetate is 1-methoxy-2-propyl acetate.
PM solvent is 1-methoxy-2-propanol.
n.d. : not determined Xylene is now a regulated solvent and is listed as a HAP's solvent (Hazardous Air Pollutant).
As such, xylene is rapidly becoming phased out as a solvent for all types of coatings and an appropriate solvent substitute is becoming mandatory.
The other solvents listed in the table above are not currently targeted far regulation or removal and are becoming more common in the coatings industry.
The recent trend in the coatings industry is to higher solids coatings which means even less solvent to dissolve the UV absorber. The need for a more soluble, non-volatile UV absorber is most evident.
Inspection of the data in the table shows that UV absorber A is clearly less soluble in each of the solvents than is UV absorber B-D. In fact, the solubility of UV absorber A
in any solvent ~~.~44~.~, other than xylene essentially removes it from consideration as a practical stabilizer in the new long term automotive coatings under the constraints listed above.
UV absorbers B-D have also the excellent non-volatility exhibited by UV
absorber A. This combination of properties makes UV absorbers B-D prime candidates for use in long-term automotive high solids coatings.
Example 12:
The amorphous modification of 2-(2-hydroxy-3-oc-cumyl-5-tert-octylphenyl)-2H-benzotriazole as prepared in Example 3 exhibits essentially the same solubility parameters in the various solvents as seen in Example 11 for the new crystalline modification of 2-(2-hydroxy-3-a-cumyl-5-tert octylphenyl)-2H-benzotriazofe prepared in Example 1 or 5 except that the amorphous form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole dissolves much more easily and rapidly in the non-HAPS solvents. This is a distinct advantage for using the amorphous compound of Example 3 in practical applications.
Examplel3~
Compounds used:
A. 2-(2-hydroxy-3-oc-cumyl-5-tert-octylphenyl)-2H-benzotriazole, compound of Example 5;
B. 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, compound of Example 4;
C. 2-(2-hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole, compound of Example 8;
D. 2-(2-hydroxy-3,5-di-oc-cumylphenyl)-2H-benzotriazole, commercially available as Tinuvin~
900 from Ciba-Geigy Corporation (for comparision);
The clear coat is prepared by mixing 60 parts of acrylic polyol with 40 parts of Resimene~ 747 (hexamethoxymethylmelamine, Monsanto) along with an acid catalyst and flow aids. The base coat is an acrylic melamine. The silver metallic acrylic melamine base coat is sprayed to about 0.6 mil thickness. The clear coat is sprayed onto the base coat while the base coat is still wet to give a clear coat of a 2 mil thickness.
21'~~411 The test Compounds A-D are added to a model high solids thermoset acrylic urethane resin used as the clear coat using butyl acetate (a non-HAPS solvent).
The following values for the Distinction of Image are obtained after exposure of the samples in a QUV (FD40 Bulbs) for the hours stated in the tables below.
Distinction of Image Hours Sam* of Exposure I 93 23 8 6 3 4 3 3**
II 93 69 38 34 25 29 21 7**
*I is unstabilized blank;
II has 0.24% by weight of Compound D;
III has 1.2% by weight of Compound A;
IV has 3% by weight of Compound C; and V has 3% by weight of Compound B.
**The coating has failed at this point by cracking.
In this test method the UV absorber is dissolved in a non-HAPS solvent butyl acetate and then added to the resin system as is normally done in the industry. The limited solubility of Compound D in butyl acetate allows only 0.24% by weight of Compound D based on resin solids to be present in the coating. The greater solubility of Compound A in butyl acetate allows 1.2% by weight of Compound A based on resin solids to be present in the coating. The still greater solubility of Compounds B and C in butyl acetate allows 3% by weight of Compound B or Compound C based on resin solids to be present in the coating.
In each case, the more soluble Compound A, B or C afforded far greater Distinction of Image than the less soluble Compound D.
In general, the compounds of the present invention are employed from 0.01 to 20% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from 0.1 to 5%; preferably 1 to 5%.
The resulting stabilized compositions of the instant invention may optionally also contain from about 0.01 to about 10%, preferably from about 0.025 to about 5%, and especially from about 0.1 to about 1 % by weight of various conventional additives, such as the materials listed below, or mixtures thereof.
Other compositions of special interest include those which additionally contain a UV absorber selected from the group consisting of the benzophenones, benzotriazoles, cyanoacrylic acid derivatives, hydroxyaryl-s-triazines, organic nickel compounds and oxanilides.
Preferred UV absorbers are selected from the group consisting of 2-[2-hydroxy-3,5-di-(a,oc-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(w-hydroxy-octalethyleneoxy)carbonyl)ethylphenyl]--2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)phenyl]-benzotriazole, 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyl-oxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'ethyloxanilide, 2,6-bis(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl-s-triazine, 2,6-bas(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl}-s-triazine, 2,4-bas(2,4-dihydroxyphenyl}-6-(4-chlorophenyl)-, 2,6-bis(2,4-dimethylphenyl)-4-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropanoxy)phenyl]-s-triazine and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
Additional compositions of interest include those which additionally contain an effective stabilizing amount of a phenolic antioxidant; those which additionally contain a hindered amine derivative; or which additionally contain a phosphate or phosphonite stabilizer.
Compositions of special interest also include those wherein the organic material is an enamel of high solids content used for an industrial finish; is used as a coil coating; is used as a penetrating wood finish or is used as a film-forming wood finish.
When the instant compounds also contain a reactive functional group, said compounds can be chemically bonded by either condensation or free radical addition reaction to the polymer substrate. This provides for a non-migrating, non-sublimable UV absorber stabilizer. Such reactive functional groups include hydroxy, carboxyl and ethylenically unsaturated moieties.
1. Antioxidants 1.1. Alkylated mono~henols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-~~~~4~~.
methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tart-butyl-4-methoxymethylphenol 1.2. Alk~ late ed h~rdroguinones for example 2,6-di-tart-butyl-4-methoxyphenol, 2,5-di-tart-butyl-hydroquinone, 2,5-di-tart-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol 1.3. Hv dr roxylated thiodiphenyl ethers for example 2,2'-thio-bis-(6-tart-butyl-4-methyfphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3-methylphenol), 4,4'-thio-bis-(6-tart-butyl-2-methylphenol) 1.4. Alkylidene-bi_sphenols for example 2,2'-methylene-bis-(6-tart-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tart-butyl-4-ethylphenol), 2,2'-methylene-bis-[4-methyl-6-(a-methylcyctohexyl)-phenol], 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-[6-(a,a-dimethylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-(4,6-di-tart-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(6-tart-butyl-4-isobutylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 4,4'-methylene-bis-(6-tart-butyl-2-methylphenol), 1,1-bis-(5-tart-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-tart-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris-(5-tart-butyl-4-hydroxy-2-methylphenyl)-, 1,1-bis-(5-tart-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethyleneglycol bis-[3,3-bis-(3'-tart-butyl-4'-hydroxyphenyl)-butyrate], di-(3-tart-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, di-[2-(3'-tart-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tart-butyl-4-methylphenyl] terephthalate.
1.5. Benzyl compounds for example 1,3,5-tri-(3,5-di-tart-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tart-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tart-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tart-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris-(3,5-di-tart-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(4-tart-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tart-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt 1.6. Acylaminophenols for example 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate 1.7. Esters of (3-(3,5-di-tert-butyl-4-by di rox\,~phenyly-propionic acid with monohydric or polyhydric alcohols, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl isocyanurate thiodiethylene glycol di-hydroxyethyl oxalic acid diamide 1.$. Esters of fi-(5-tert-butv I-r 4-hydroxy-3-meth~~phern~~propionic acid with monohydric or polyhydric alcohols, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl isocyanurate thiodiethylene glycol di-hydroxyethyl oxalic acid diamide 19. Amides of ti-(3 5-di-tert-butt I-~ 4-by di rox)~phen~L~propionic acid for example, N, N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine N, N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl}-trimethylenediamine N, N'-di-(3,5-di-tert-butyl-4-hyd roxyphenylpropionyl)-hydrazine 2. UV absorbers and light stabilizers 2.1. 2~2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-, 3',5'-di-tart-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tart-butyl-, 5-chloro-3'-tart-butyl-5'-methyl-, 3'-sec-butyl-5'-tart-butyl-, 4'-octoxy, 3',5'-di-tart-amyl-, 3',5'-bis-(a,a-dimethylbenzyl), 3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-, and dodecylated-5'-methyl derivatives.
2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy; 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tart-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tart-butyl-4-hydroxybenzoic acid 2,4-di-tart-butylphenyl ester and 3,5-di-tart-butyl-4-hydroxybenzoic acid hexadecyl ester.
2.4. Acr)ilates, for example, a-cyano-[i,~i-diphenylacrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-~i-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, oc-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(~i-carbomethoxy-a-cyanovinyl)-2-methyl-indoline.
2.5. Nickel compounds, for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethyl-butyl)-phenoll, such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tart-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. Ster7cally hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-hydroxyethyl--2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1'(1,2-ethanediyl)-bas-(3,3,5,5-tetramethyl-piperazinone).
2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
2.$. Hydroxyphen~il-s-triazines, for example 2,6-bas-(2,4-dimethylphenyl)-4-{2-hydroxy-4--octyloxyphenyl)-s-triazine; 2,6-bas-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-; 2,4-bis(2,4-di-hydroxyphenyl)-6-(4-chlorophenyl)-; 2,4-bas[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chloro-phenyl)-s-triazine; 2,4-bas[2-hydroxy-4-(2-hydroxy-4-{2-hydroxyethoxy)phenyl]-6-(2,4-dimethyl-phenyl)-s-triazine; 2,4-bas[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;
2,4-bas[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-di-hydroxyphenyl)-6-(2,4-dimethylphenyl)-; 2,4-bas-(2,4-dimethylphenyl)-6-{2-hydroxy-4-[3-(2--ethylhexyloxy)-2-hydroxypropoxy]phenyl}-s-triazine; 2,4-bas-(2,4-dimethylphenyl)-6-(2-hydroxy--4-[3-(pentadecyloxy)-2-hydroxypropoxy]phenyl}-s-triazine.
~. Metal deaciivators, for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl-hydrazine, N,N'-bas-salicyloylhydrazine, N,N'-bas-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)--hydrazine, 3-salicyloylamino-1,2,4-triazole, bas-benzylidene-oxalic acid dihydrazide.
4. Phosehites and phosphonites, for example, triphenyl phosphate, diphenylalkyl phosphates, phenyldialkyl phosphates, tri-(nonylphenyl) phosphate, trilauryl phosphate, trioctadecyl phosphate, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphate, di-iso-decylpentaerythritol diphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol trfphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4'-diphenylylenediphosphonite.
5. Compounds which destroy~~aeroxide, for example, esters of [3-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-((3-dodecylmercapto)-propionate.
6. Hydrox\ilamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-di-hexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
~. Polvamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.
11. Fillers and reinforcing a, ents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.
The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert--butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tr7s(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl- 4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxy-benzyl)isocynurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-tent-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5--di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl--4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N'-bis(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6--tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
The hindered amine compound of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butyl-malonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, tris(2,2,6,6-tetramethyl-piperidin-4-yl) nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetra-_18_ methylpiperidine), polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethyfpiperidine) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl} 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-di-chloro-6-morpholino-s-trlazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethyl-piperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yU[3,[3,(3',[3°-tetra-methyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yU[i,(i,(3',(i'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate), 4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetra-methylpiperidin-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecyl-succinimlde, N-1-acetyl-2,2,6,6-tetramethyfpiperidin-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetra methylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl} succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{(6-tert-octylamino-s-triazin-2,4-diyl](2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy--2,2,6,6-tetramethylpiper7din-4-yl}imino], 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)-n-butylamino]-s-triazine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiper-idin--4-yl)-n-butylamino)-6-[di-(2-hydroxyethyl)amino]-s-triazine, and 2,4-bis[N-(1-octyloxy-2,2,6,6--tetramethylpiperidin-4-yl}-n-butylamino]-6-(di-(2-hydroxyethyl)amino]-s-triazine.
A most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)- s-triazine-2-yl]-1,10-diamino-4,7-diazadecane, di-(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl](2--(1-cyclohexyloxy-2,2, 6,6-tetramethyl pi peridi n-4-yl)imino-hexamethylene-[4-( 1-cyclohexyloxy---1~-2,2,6,6-tetramethylpiperidin-4-yl)imino], or 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)-n-butylaminoj-s-triazine.
A further object of this invention is to provide a process for stabilizing an organic material against actinic-induced degradation, which comprises incorporating therein or applying thereto the amorphous or crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as defined in claims 1 and 2, respectively, 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl-5-dodeylphenyl)-2H-benzotriazole or a compound of the formula H
~N~
N ~ a-cumyl N
R
where R is -CHmCHZmCOOR4, R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
Still another object of this invention is to provide a method for protecting organic material against actinic-induced degradation for longer than 3000 hours, when subjected to a QUV
testing apparatus (cycle: 8 hours light and 70°C; 4 hours dark, 50°C and 100% rel. humidity), characterized by incorporating in the organic material or applying thereto the amorphous or crystalline form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as defined in claims 1 and 2, respectively, 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3--a-cumyl-5-dodeylphenyl)-2H-benzotriazole or a compound of the formula ~N~
N
where R is -CHmCH2mCOOR4 , R4 is alkyl of 1 to 18 carbon atoms and m is 1 to 4.
X-ray diffraction patterns are recorded on a Philips Norelco X-ray Diffractometer unit, using Cu-Ka radiation with a nickel filter. All samples have a uniform particle size of 40 to 75 microns.
The following examples are presented for the purpose of illustration only and are not to be construed to limit the nature or scope of the instant invention in any manner whatsoever.
Example 1: 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole To a 5-liter 3-necked flask fitted with a stirrer, thermometer, reflux condenser and nitrogen inlet is charged 380 g (0.8 mol) of 2-nitro-2'-hydroxy-3'-a,a-dimethylbenzyl-5'-tert-octylazobenzene and 1200 ml of toluene. To the resulting solution is added 240 ml of isopropanol and 240 ml of water. A nitrogen atmosphere is imposed and 160 ml of 50.1 % aqueous sodium hydroxide is added. A flask containing 158.2 g (2.42 gramatoms) of zinc is connected to the reaction flask and the zinc dust is added portionwise to the reaction mixture over a 90-minute period. The internal temperature is kept between 40 and 45° C during the adition and for an additional hour and then the mixture is heated for 3 hours at 70°C. The mixture is cooled to room temperature and acidified with 600 ml of concentrated hydrochloric acid. The zinc sludge is removed by filtration. The product is contained in the organic layer, which is washed with 4 340 ml portions of dilute hydrochloric acid, and then dried over anhydrous sodium sulfate. The organic solvent was removed in vacuo to yield a crude product as a viscous syrup.
A 300 g sample of the crude product is dissolved in 300 mL of xylene. To this solution is then added with stirring 600 mL of ethanol to afford 254 g of the novel soluble crystalline modification of the compound of formula I having a melting point of 109-111 °C; and exhibiting only one spot in thin layer chromatography.
Analysis:
Calcd for C2gH35N3O: C, 78.9; H, 8.0; N, 9.5.
Found: C, 78.7; H, 8.1; N, 9.6.
This product has an X-ray diffraction pattern obtained using Cu-Ka radiation which exhibits diffraction angles (20) as seen below:
Peak No. 20 Peak No. 20 Peak 20 Peak No. 20 No.
1 9.6 2 10.2 3 10.4 4 10.8 12.8 6 13.8 7 14.2 8 14.8 9 15.0 10 16.4 11 16.8 12 17.8 13 18.0 14 18.6 15 19.0 16 19.4 17 19.8 18 20.2 19 20.6 20 21.2 21 21.4 22 23.0 23 23.4 24 24.6 25 26.0 26 28.0 27 29.0 28 30.4 29 31.0 Example 2: 2-(2-Hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole Comparative Example The title compound is prepared as described in Example 18 of U.S. Patent No.
4,278,589 as off-white crystals melting at 88-90°C. This compound exhibits an X-ray diffraction pattern obtained using Cu-Ka radiation which exhibits diffraction angles (20) as seen below:
Peak No. 20 Peak No. 20 Peak 20 Peak No. 20 No.
1 5.2 2 6.2 3 6.8 4 9.2 5 9.7 6 11.0 7 12.0 8 12.2 9 13.0 10 13.6 11 14.6 12 15.4 13 15.6 14 16.4 15 17.8 16 18.8 17 19.4 18 19.8 19 20.4 20 21.0 21 22.4 22 22.8 23 23.4 24 24.2 25 25.0 26 25.4 , 27 26.0 28 27.6 29 29.4 30 30.8 31 31.2 32 32.4 A comparison of the X-ray diffraction pattern of the instant crystalline modification as seen in Example 1 with the X-ray diffraction pattern of the prior art compound of Example 18 of U.S.
Patent No. 4,278,589 clearly indicates that the two materials are not the same.
21'~42I1 Example 3: Amorphous form of 2-(2-hydroxy-3-a,-cumyl-5-tert-octylphenyl)-2H-benzotriazole The compound prepared in Example 1 is heated to a melt and then allowed to resolidify. The amorphous material obtained has a melting point of 59-74°C. Thin layer chromatography exhibits one spot identical to that obtained from the product of Example 1.
X-ray diffraction shows a featureless pattern confirming the amorphous nature of the compound obtained in this example.
Example 4: 2-(2-Hydroxy-3-oc-cumyl-5-nonylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin, but where the reduction of the corresponding o-nitroazobenzene intermediate is carried out using catalytic hydrogenation.
Analysis:
Calcd for C3oH3,N3O: C, 79.1; H, 8.2; N, 9.2.
Found: C, 79.5; H, 8.5; N, 9Ø
Example 5: 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole The title compound is prepared by the catalytic hydrogenation of the o-nitroazobenzene compound used in Example 1 as an off-white solid. A 100 g sample of said solid is recrystallized from 100 mL of isopropanol, again from 100 mL of 19:1 isopropanolaoluene and finally from 100 mL of 9:1 isopropanolaoluene to afford 78 g of the title compound melting at 109-111 °C and having the same crystalline modification and X-ray diffraction pattern as the compound prepared in Example 1.
Example 6: 2-(2-Hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin.
Example 7: 2-(2-Hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin.
H-NMR data in CDC13 [ppm]: 0.8-0.9 triplets; 1.3-1.42 singlets; 1.9 singlets;
7.14-7.30 complex;
7.44 complex; 7.48-7.64 meta doublets; 7.86 complex; 8.20-8.34 meta doublets;
11.38-11.46 singlet; the data is consistent with the title compound.
Example 8: 2-(2-Hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole The title compound is prepared according to the general procedure of Example 1 as an amber resin, but where the reduction of the corresponding o-nitroazobenzene compound is carried out using catalytic hydrogenation.
Examples 9 and 10' Following the general procedure of Examples 1 and 5, the following compounds of the formula H
~N~
/N / a-cumyl are prepared.
N ~
R
21'74411 Example ;
; -CH2CH2COOC8H1~
Example 11: Solubility in Organic Solvents In order to incorporate a UV absorber stabilizer into the high solids thermoset acrylic resin systems, the UV absorber must be soluble in an appropriate organic solvent. To date solvents such as the aromatic hydrocarbons, toluene or xylene, have provided ample solubility for such UV absorbers, even the sparingly soluble 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzo-triazole.
However, the possible phasing out of such aromatic hydrocarbon solvents for environmental reasons, the trend to higher solids coatings, and the increasing demands of the automobile industry for automotive coatings that will last for up to 10 years means that a more soluble, non-volatile, but equally effective UV absorber will be required.
Additionally, the UV absorber must be soluble in an environmentally friendly solvent.
The relative solubility of three different benzotriazole UV absorbers in a five typical organic solvents is measured by dissolving the benzotriazole UV absorber in 50-100 mL
of five different solvents till the solutions become supersaturated. This is seen when the benzotriazole begins to settle to the bottom of the test flask. The supersaturated solutions are allowed to remain undisturbed overnight. Then, the top layer is decanted and filtered.
The resulting filtrate containing the benzotriazole dissolved in the solvent is tested in triplicate for percent solids using ASTM Test Method D 2369-81. The higher the percent solids found indicates a more soluble benzotriazole. The results are seen in the table below.
Solubility in grams/100 solvent*
Solvent A B C D
xylene 14 76 >50 >50 butyl acetate 6 33 >50 >50 methyl amyl ketone 4 33 >50 >50 acetone n.d. n.d. >50 >50 EXXATE~ 600 4 22 >50 >50 PM acetate 3 14 >50 >50 PM solvent n.d. 4 n.d. n.d.
*A is 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotrlazole (for comparision).
B is the compound of Example 5.
C is the compound of Example 4.
D is the compound of Example 8.
EXXATE~ 600 is hexyl acetate from Exxon.
PM acetate is 1-methoxy-2-propyl acetate.
PM solvent is 1-methoxy-2-propanol.
n.d. : not determined Xylene is now a regulated solvent and is listed as a HAP's solvent (Hazardous Air Pollutant).
As such, xylene is rapidly becoming phased out as a solvent for all types of coatings and an appropriate solvent substitute is becoming mandatory.
The other solvents listed in the table above are not currently targeted far regulation or removal and are becoming more common in the coatings industry.
The recent trend in the coatings industry is to higher solids coatings which means even less solvent to dissolve the UV absorber. The need for a more soluble, non-volatile UV absorber is most evident.
Inspection of the data in the table shows that UV absorber A is clearly less soluble in each of the solvents than is UV absorber B-D. In fact, the solubility of UV absorber A
in any solvent ~~.~44~.~, other than xylene essentially removes it from consideration as a practical stabilizer in the new long term automotive coatings under the constraints listed above.
UV absorbers B-D have also the excellent non-volatility exhibited by UV
absorber A. This combination of properties makes UV absorbers B-D prime candidates for use in long-term automotive high solids coatings.
Example 12:
The amorphous modification of 2-(2-hydroxy-3-oc-cumyl-5-tert-octylphenyl)-2H-benzotriazole as prepared in Example 3 exhibits essentially the same solubility parameters in the various solvents as seen in Example 11 for the new crystalline modification of 2-(2-hydroxy-3-a-cumyl-5-tert octylphenyl)-2H-benzotriazofe prepared in Example 1 or 5 except that the amorphous form of 2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole dissolves much more easily and rapidly in the non-HAPS solvents. This is a distinct advantage for using the amorphous compound of Example 3 in practical applications.
Examplel3~
Compounds used:
A. 2-(2-hydroxy-3-oc-cumyl-5-tert-octylphenyl)-2H-benzotriazole, compound of Example 5;
B. 2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole, compound of Example 4;
C. 2-(2-hydroxy-3-a-cumyl-5-dodecylphenyl)-2H-benzotriazole, compound of Example 8;
D. 2-(2-hydroxy-3,5-di-oc-cumylphenyl)-2H-benzotriazole, commercially available as Tinuvin~
900 from Ciba-Geigy Corporation (for comparision);
The clear coat is prepared by mixing 60 parts of acrylic polyol with 40 parts of Resimene~ 747 (hexamethoxymethylmelamine, Monsanto) along with an acid catalyst and flow aids. The base coat is an acrylic melamine. The silver metallic acrylic melamine base coat is sprayed to about 0.6 mil thickness. The clear coat is sprayed onto the base coat while the base coat is still wet to give a clear coat of a 2 mil thickness.
21'~~411 The test Compounds A-D are added to a model high solids thermoset acrylic urethane resin used as the clear coat using butyl acetate (a non-HAPS solvent).
The following values for the Distinction of Image are obtained after exposure of the samples in a QUV (FD40 Bulbs) for the hours stated in the tables below.
Distinction of Image Hours Sam* of Exposure I 93 23 8 6 3 4 3 3**
II 93 69 38 34 25 29 21 7**
*I is unstabilized blank;
II has 0.24% by weight of Compound D;
III has 1.2% by weight of Compound A;
IV has 3% by weight of Compound C; and V has 3% by weight of Compound B.
**The coating has failed at this point by cracking.
In this test method the UV absorber is dissolved in a non-HAPS solvent butyl acetate and then added to the resin system as is normally done in the industry. The limited solubility of Compound D in butyl acetate allows only 0.24% by weight of Compound D based on resin solids to be present in the coating. The greater solubility of Compound A in butyl acetate allows 1.2% by weight of Compound A based on resin solids to be present in the coating. The still greater solubility of Compounds B and C in butyl acetate allows 3% by weight of Compound B or Compound C based on resin solids to be present in the coating.
In each case, the more soluble Compound A, B or C afforded far greater Distinction of Image than the less soluble Compound D.
Claims (9)
1. The crystalline form of 2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole, characterized by melting in the range of 109-111°C and by an X-ray diffraction pattern obtained using Cu-K.alpha.-radiation which exhibits diffraction angles (2.theta.) as seen below:
2. A process for the preparation of the crystalline form of the compound 2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as defined in claim 1, which comprises dissolving said compound in an aromatic solvent and precipitating the compound by the addition of an alkanol of 1 to 4 carbon atoms; or by crystallizing or recrystallizing the compound from an alkanol of 1 to 4 carbon atoms alone or in conjunction with up to 15% by volume of the total volume of solvent used of an aromatic solvent.
3. The process according to claim 2 wherein the alkanol is an alkanol of 2, 3 or 4 carbon atoms.
4. A composition stabilized against the deleterious effects of actinic light which comprises (a) an organic material subject to the deleterious effects of actinic light, and (b) the crystalline form of 2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole, as defined in claim 1.
5. The composition according to claim 4 wherein the organic material is a natural, semi-synthetic or synthetic polymer.
6. The composition according to claim 5 wherein the polymer is a thermoplastic polymer.
7. The composition according to claim 5 wherein the polymer is a polyolefin.
8. The composition according to any one of claims 4 to 7, which further comprises a phenolic antioxidant, a light stabilizer, a processing stabilizer or a mixture thereof.
9. The composition according to any one of claims 4 to 7, which further comprises a tris-aryl-s-triazine, a hindered amine or a benzofuran-2-one light stabilizer or a mixture thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/424843 | 1995-04-19 | ||
| US08/424,843 US5574166A (en) | 1995-04-19 | 1995-04-19 | Crystalline form of 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2174411A1 CA2174411A1 (en) | 1996-10-20 |
| CA2174411C true CA2174411C (en) | 2007-02-20 |
Family
ID=23684097
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002174411A Expired - Fee Related CA2174411C (en) | 1995-04-19 | 1996-04-17 | 2-(2-hydroxy-3-.alpha.-cumyl-5-alkylphenyl)-2h benzotriazoles |
| CA002174412A Abandoned CA2174412A1 (en) | 1995-04-19 | 1996-04-17 | Coatings and recording materials stabilized with benzotriazole uv absorbers |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002174412A Abandoned CA2174412A1 (en) | 1995-04-19 | 1996-04-17 | Coatings and recording materials stabilized with benzotriazole uv absorbers |
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| AU (2) | AU707202B2 (en) |
| BE (1) | BE1010550A3 (en) |
| BR (2) | BR9601992A (en) |
| CA (2) | CA2174411C (en) |
| DE (1) | DE19615000A1 (en) |
| ES (1) | ES2130930B1 (en) |
| FR (1) | FR2733239B1 (en) |
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| WO2023205221A2 (en) | 2022-04-21 | 2023-10-26 | Covestro (Netherlands) B.V. | Low-volatility radiation curable compositions for coating optical fibers |
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| JPS4967378A (en) * | 1972-11-02 | 1974-06-29 | ||
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| EP0006564B1 (en) * | 1978-06-26 | 1981-12-30 | Ciba-Geigy Ag | 2-(3.5-disubstituted-2-hydroxyphenyl)-2h-benzotriazoles and stabilized compositions containing them |
| US4278589A (en) * | 1978-06-26 | 1981-07-14 | Ciba-Geigy Corporation | 2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole and stabilized compositions |
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| DE3328771A1 (en) * | 1983-08-10 | 1985-02-28 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF OXYGEN-CONTAINING COMPOUNDS |
| US4587346A (en) * | 1985-01-22 | 1986-05-06 | Ciba-Geigy Corporation | Liquid 2-(2-hydroxy-3-higher branched alkyl-5-methyl-phenyl)-2H-benzotriazole mixtures, stabilized compositions and processes for preparing liquid mixtures |
| US4675352A (en) * | 1985-01-22 | 1987-06-23 | Ciba-Geigy Corporation | Liquid 2-(2-hydroxy-3-higher branched alkyl-5-methyl-phenyl)-2H-benzotriazole mixtures, stabilized compositions and processes for preparing liquid mixtures |
| US4760148A (en) * | 1985-09-03 | 1988-07-26 | Ciba-Geigy Corporation | 5-aralkyl substituted 2H-benzotriazoles and stabilized compositions |
| JPS62262777A (en) * | 1986-05-09 | 1987-11-14 | Kansai Paint Co Ltd | Formation of corrosion preventive coated film |
| US5096977A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing polymer bound UV stabilizers |
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| US5240975A (en) * | 1988-04-11 | 1993-08-31 | Ciba-Geigy Corporation | Liquid substituted 2H-benzotriazole mixtures, stabilized compositions |
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-
1995
- 1995-04-19 US US08/424,843 patent/US5574166A/en not_active Expired - Lifetime
- 1995-06-06 US US08/466,851 patent/US5554760A/en not_active Expired - Lifetime
- 1995-06-06 US US08/466,850 patent/US5563242A/en not_active Expired - Lifetime
-
1996
- 1996-04-05 US US08/628,433 patent/US5607987A/en not_active Expired - Lifetime
- 1996-04-10 EP EP96810220A patent/EP0738718A1/en not_active Withdrawn
- 1996-04-10 GB GB9607427A patent/GB2299957B/en not_active Expired - Lifetime
- 1996-04-10 SE SE9601345A patent/SE509606C2/en not_active IP Right Cessation
- 1996-04-16 DE DE19615000A patent/DE19615000A1/en not_active Ceased
- 1996-04-17 CA CA002174411A patent/CA2174411C/en not_active Expired - Fee Related
- 1996-04-17 KR KR1019960012131A patent/KR100426626B1/en not_active IP Right Cessation
- 1996-04-17 CA CA002174412A patent/CA2174412A1/en not_active Abandoned
- 1996-04-17 BE BE9600333A patent/BE1010550A3/en not_active IP Right Cessation
- 1996-04-17 AU AU50731/96A patent/AU707202B2/en not_active Ceased
- 1996-04-18 IT IT96MI000751A patent/IT1283615B1/en active IP Right Grant
- 1996-04-18 AU AU50784/96A patent/AU706957B2/en not_active Ceased
- 1996-04-18 CN CN96105141A patent/CN1059899C/en not_active Expired - Lifetime
- 1996-04-18 KR KR1019960012170A patent/KR100378233B1/en not_active IP Right Cessation
- 1996-04-18 CN CN96105137A patent/CN1066181C/en not_active Expired - Lifetime
- 1996-04-18 ES ES009600874A patent/ES2130930B1/en not_active Expired - Fee Related
- 1996-04-18 AT AT0070596A patent/AT405936B/en not_active IP Right Cessation
- 1996-04-18 FR FR9604847A patent/FR2733239B1/en not_active Expired - Lifetime
- 1996-04-19 BR BR9601992A patent/BR9601992A/en not_active IP Right Cessation
- 1996-04-19 JP JP8122465A patent/JPH08291151A/en active Pending
- 1996-04-19 NL NL1002904A patent/NL1002904C2/en not_active IP Right Cessation
- 1996-04-19 BR BR9601991A patent/BR9601991A/en not_active IP Right Cessation
- 1996-04-19 JP JP12246696A patent/JP3309153B2/en not_active Expired - Lifetime
- 1996-05-14 TW TW085105661A patent/TW419497B/en not_active IP Right Cessation
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