Non-yellowing part-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers
First Claim
1. A method of stabilizing a material which is subject to degradation by actinic radiation comprising:
- incorporating into the material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises a compound of formula (II);
whereinX is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R1 is C1-C24 alkyl, C1-C24 branched alkyl, C2-C24 alkenyl, a cycloalkyl from 5-24 carbon atoms, an araalkyl from 7-24 carbon atoms, —
COR9, —
CO2R9, —
CONHR9, —
SO2R9, C1-C18 alkyl substituted with at least one hydroxy, C1-C18 alkoxy, C3-C18 alkenoxy, halogen, phenoxy, C1-C18 alkyl-substituted phenoxy, C1-C18 alkoxy-substituted phenoxy, halogen-substituted phenoxy, —
COOH, —
COOR9, —
CONH2, —
CONHR9, —
CON(R9)(R10), —
NH2, —
NHR9, —
N(R9)(R10), —
NHCOR11, —
N(R9)COR11, —
NHCOOR11, —
N(9)COOR11, —
CN, —
OCOR11, —
OC(O)NHR9, —
OC(O)N(R9)(R10), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —
OCOR11, and C2-C50 alkyl interrupted by at least one oxygen atom or carbonyl group and optionally substituted by one or more substituents selected from the group consisting of hydroxy or C1-C12 alkoxy;
wherein R9 and R10 each independently are C1-C12 alkyl, C3-C12 alkoxyalkyl, C4-C16 dialkylaminoalkyl, C5-C12 cycloalkyl, or R9 and R10 taken together are C3-C9 alkylene, C3-C9 oxoalkylene or C3-C9 azaalkylene; and
R11 is C1-C18 alkyl, C2-C18 alkenyl, or phenyl; and
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof.
1 Assignment
0 Petitions
Accused Products
Abstract
This invention relates generally to para-tertiary alkyl phenyl substituted pyrimidines and triazines and the use thereof to protect against degradation by environmental forces, inclusive of ultraviolet light, actinic radiation, oxidation, moisture, atmospheric pollutants and combinations thereof. The new class of para-tertiary alkyl phenyl substituted pyrimidines and triazines includes two tertiary alkylated phenyl groups, and a resorcinol or substituted resocinol group attached to the triazine or pyrimidine ring. These materials may, under the appropriate circumstances, be bonded to formulations comprising coatings, polymers, resins, organic compounds and the like via reaction of the bondable functionality with the materials of the formulation. A method for stabilizing a material by incorporating such para-tertiary alkyl phenyl substituted pyrimidines and triazines is also disclosed.
89 Citations
30 Claims
-
1. A method of stabilizing a material which is subject to degradation by actinic radiation comprising:
-
incorporating into the material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises a compound of formula (II);
wherein X is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R1 is C1-C24 alkyl, C1-C24 branched alkyl, C2-C24 alkenyl, a cycloalkyl from 5-24 carbon atoms, an araalkyl from 7-24 carbon atoms, —
COR9, —
CO2R9, —
CONHR9, —
SO2R9, C1-C18 alkyl substituted with at least one hydroxy, C1-C18 alkoxy, C3-C18 alkenoxy, halogen, phenoxy, C1-C18 alkyl-substituted phenoxy, C1-C18 alkoxy-substituted phenoxy, halogen-substituted phenoxy, —
COOH, —
COOR9, —
CONH2, —
CONHR9, —
CON(R9)(R10), —
NH2, —
NHR9, —
N(R9)(R10), —
NHCOR11, —
N(R9)COR11, —
NHCOOR11, —
N(9)COOR11, —
CN, —
OCOR11, —
OC(O)NHR9, —
OC(O)N(R9)(R10), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —
OCOR11, and C2-C50 alkyl interrupted by at least one oxygen atom or carbonyl group and optionally substituted by one or more substituents selected from the group consisting of hydroxy or C1-C12 alkoxy;
wherein R9 and R10 each independently are C1-C12 alkyl, C3-C12 alkoxyalkyl, C4-C16 dialkylaminoalkyl, C5-C12 cycloalkyl, or R9 and R10 taken together are C3-C9 alkylene, C3-C9 oxoalkylene or C3-C9 azaalkylene; and
R11 is C1-C18 alkyl, C2-C18 alkenyl, or phenyl; and
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22)
an alkyl of 1 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl, carboalkoxy, amide, epoxy, or amino group, and optionally containing at least one carbonyl group, oxygen atom, or nitrogen atom;
an alkenyl of 2 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl, epoxy, or amino group, and optionally containing at least one carbonyl group, oxygen atom, or nitrogen atom;
a cycloalkyl of 5 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl, or amino group, and optionally containing at least one carbonyl group, oxygen atom, or nitrogen atom;
an aralkyl of 7 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl, or amino group, and optionally containing at least one carbonyl, oxygen atom, or nitrogen atom;
a polyoxyalkylene radical of the formula XII
-
-
5. The method according to claim 1, wherein R1 is a hydrocarbyl group having between 4 and 24 carbon atoms.
-
6. The method according to claim 1, wherein one of R3 and R4 is an alkyl group having between 4 and about 24 carbon atoms and the other is hydrogen.
-
7. The method according to claim 1, wherein R3 and R4 are hydrogen.
-
8. The method according to claim 1, wherein the compound of Formula II is present in an amount from about 0.01 to about 20% by weight based on the weight of the material to be stabilized.
-
9. The method according to claim 1, wherein X is hydrogen.
-
10. The method according to claim 1, wherein X is allyl, —
- CORa, —
SO2Rb, —
SiRcRdRe, —
PRfRg, —
PORfRg, or —
CONRh,wherein Ra is substituted or unsubstituted C1-C8 alkyl, halogen, substituted or unsubstituted C5-C12 cycloalkyl, substituted or unsubstituted C2-C, alkenyl, —
CH2—
CO—
CH3, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted phenyl, or substituted or unsubstituted phenoxy, wherein, if present, the substituent is at least one C1-C12 alkyl, C1-C4 alkoxy, halogen, or benzyl;
Rb is C1-C12 alkyl, C6-C10 aryl, or C7-C18 alkylaryl;
Rc, Rd or Re each independently is C1-C18 alkyl, cyclohexyl, phenyl, or C1-C18 alkoxy;
Rf or Rg each independently is substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted phenoxy, wherein, if present, the substituent is at least one C1-C12 alkyl, C1-C4 alkoxy, halogen or benzyl; and
Rh is substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C5-C12 cycloalkyl, substituted or unsubstituted C2-C8 alkenyl, —
CH2—
CO—
CH3, or substituted or unsubstituted phenyl, wherein, if present, the substituent is at least one C1-C12 alkyl, C2-C8 alkenyl, C1-C4 alkoxy, halogen, or benzyl.
- CORa, —
-
11. The method according to claim 1, wherein the material to be stabilized is an organic polymer.
-
12. The method according to claim 11, wherein the organic polymer is a homopolymer, copolymer, or terpolymer.
-
13. The method according to claim 11, wherein the organic polymer is polycarbonate, polyolefin, polyketone, polyester, acrylic urethane, acrylic melamine, polystyrene, halogen-containing polymer, polymer of α
- ,β
-unsaturated acids, polymer of cyclic ethers, polyacetal, polyphenylene oxide, polyphenylene sulfide, polysulfone, polycarbamate, polyurethane, polyamide, polyamine, polyurea, polyether, polyimide, polyamide-imide, alkyd resin, polyketimines, polysiloxanes, cellulose, rubber, gelatin, oils and waxes, organic dye, cosmetic products, cellulose-based paper formulations, or combinations thereof.
- ,β
-
14. The method of claim 13, wherein the organic polymer is polyethylene, polyvinyl, polyacrylate, polymethacrylate, polyalkylene, polystyrene, polyacrylamide, polyacrylonitrile, polybutadiene, polychloroprene, epichlorohydrin polymer, alkylene glycol, alkylene oxide, polyoxymethylene, polyisocyanurate, polycyanate, epoxymelamine resin, polyhydric alcohol, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin, polybenzimidazole, polyester carbonate, polyehter sulfone, polyether ketone, drying and non-drying alkyd resins, unsaturated polyester resin, epoxymelamine resins, photographic film paper, ink, or combinations thereof.
-
15. The method of claim 11, wherein the organic polymer is polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl alcohol, polyallyl amine, polyallyl glycidyl ether, polyallyl phthalate, polyallyl melamine, polyethylene terephthalate, ABS (acrylonitrile-butadiene-styrene), SAN (styrene-acrylonitrile), or a combination thereof.
-
16. The method according to claim 1, wherein the compound of Formula II is incorporated into the material by chemical bonding during and/or subsequent to the preparation of the material.
-
17. The method according to claim 1 further comprising incorporating into the material at least one additional additive, wherein the additional additive is antioxidant, ultraviolet light absorber, ultraviolet light stabilizer, metal deactivator, phosphite, phosphonite, hydroxylamine, nitrone, thiosynergist, peroxide scavenger, polyamide stabilizer, nucleating agent, filler, reinforcing agent, plasticizer, lubricant, emulsifier, pigment, rheological additive, flameproofing agent, antistatic agent, blowing agent, benzofuranone, or indolinone.
-
18. The method according to claim 17, wherein the additional additive is hindered amine light stabilizer.
-
19. The method of claim 18, wherein the hindered amine is at least one bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
- bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonate;
a condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;
a condensate of N,N′
-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate;
1,1′
-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate;
a condensate of N,N′
-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine;
a condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane;
a condensate of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3- aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
a condensate of N,N′
-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine;
a condensate of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines;
or a condensate of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin.
- bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
-
20. The method according to claim 17, wherein the UV light absorber is benzotriazole, triazine, benzophenone, ester of benzoic acids, acrylate, sterically hindered amine, or oxamide.
-
21. The method according to claim 20, wherein said additional additive is a benzotriazole.
-
22. The method according to claim 21, wherein the benzotriazole comprises at least one 2-(2′
- -hydroxy-5′
-methylphenyl)-benzotriazole;
2-(3′
,5′
-di-tert-butyl-2′
-hydroxyphenyl)benzotriazole;
2-(5′
-tert-butyl-2′
-hydroxyphenyl)benzotriazole;
2-(2′
-hydroxy-5′
-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;
2-(3′
,5′
-di-tert-butyl-2′
-hydroxyphenyl)-5-chlorobenzotriazole;
2-(3′
-tert-butyl-2′
-hydroxy-5′
-methylphenyl)-5-chloro-benzotriazole;
2-(3′
-sec-butyl-5′
-tert-butyl-2′
-hydroxyphenyl)-benzotriazole;
2-(2′
-hydroxy-4′
-octoxyphenyl)benzotriazole;
2-(3′
,5′
-di-tert-amyl-2′
-hydroxphenyl)benzotriazole;
2-(3′
,5′
-bis(ana-dimethylbenzyl)-2′
-hydroxyphenyl)-benzotriazole;
a mixture of 2-(3′
-tert-butyl-2′
-hydroxy-5′
-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3′
-tert-butyl-5′
-[2-(2-ethylhexyloxy)-carbonylethyl]-2′
-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′
-tert-butyl-2′
-hydroxy-5′
-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3′
-tert-butyl-2′
-hydroxy-5′
-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′
-tert-butyl-2′
-hydroxy-5′
-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′
-tert-butyl-5′
-[2-(2-ethylhexyloxy)carbonylethyl]-2′
-hydroxyphenyl)benzotriazole, 2-(3 ′
-dodecyl-2′
-hydroxy-5′
-methylphenyl)benzotriazole and 2-(3′
-tert-butyl-2′
-hydroxy-5′
-(2-isooctyloxycarbonylethyl)phenylbenzotriazole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; and
a transesterification product of 2-[3′
-tert-butyl-5′
-(2-methoxycarbonylethyl)-2′
-hydroxyphenyl]benzotriazole with polyethylene glycol.
- -hydroxy-5′
-
23. A method of protecting a substrate against degradation by actinic radiation comprising applying to the substrate a coating containing an actinic radiation stabilizer composition in an amount effective to reduce the amount of actinic radiation impinging on the substrate, wherein the actinic radiation stabilizer composition comprises a compound of formula (II):
-
wherein X is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R1 is C1-C24 alkyl, C1-C24 branched alkyl, C2-C24 alkenyl, a cycloalkyl from 5-24 carbon atoms, an araalkyl from 7-24 carbon atoms, —
COR9, —
CO2R9, —
CONHR9, —
SO2R9, C1-C18 alkyl substituted with at least one hydroxy, C1-C18 alkoxy, C3-C18 alkenoxy, halogen, phenoxy, C1-C18 alkyl-substituted phenoxy, C1-C18 alkoxy-substituted phenoxy, halogen-substituted phenoxy, —
COOH, —
COOR9, —
CONH2, —
CONHR9, —
CON(R9)(R10), —
NH2, —
NHR9, —
N(R9)(R10), —
NHCOR11, —
N(R9)COR11, —
NHCOOR11, —
N(9)COOR11, —
CN, —
OCOR11, —
OC(O)NHR9, —
OC(O)N(R9)(R10), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —
OCOR11, and C2-C50 alkyl interrupted by at least one oxygen atom or carbonyl group and optionally substituted by one or more substituents selected from the group consisting of hydroxy or C1-C12 alkoxy;
wherein R9 and R10 each independently are C1-C12 alkyl, C3-C12 alkoxyalkyl, C4-C16 dialkylaminoalkyl, C5-C12 cycloalkyl, or R9 and R10 taken together are C3-C9 alkylene, C3-C9 oxoalkylene or C3-C9 azaalkylene; and
R11 is C1-C18 alkyl, C2-C18 alkenyl, or phenyl; and
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof.- View Dependent Claims (24)
-
-
25. A method of stabilizing a material which is subject to degradation by actinic radiation comprising:
-
incorporating into the material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises a compound of formula (III);
wherein X is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof;
r is an integer between 2 and 4; and
D, when r is 2, is selected from the group consisting of C2-C16 alkylene, C4-C12 alkenylene, xylylene, C4-C20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is interrupted by one or more oxygen atoms, —
CH2CH(OH)CH2O—
R15—
OCH2CH(OH)CH2—
, —
CO—
R16—
CO—
, —
CO—
NH—
R17—
NH—
CO—
, —
(CH2)s—
COO—
R18—
OCO—
(CH2)s—a polyoxyalkylene bridge member of the formula XX
-
-
26. A method of protecting a substrate against degradation by actinic radiation comprising applying to the substrate a coating containing an actinic radiation stabilizer composition in an amount effective to reduce the amount of actinic radiation impinging on the substrate, wherein the actinic radiation stabilizer composition comprises a compound a compound of formula (III):
-
wherein X is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof;
r is an integer between 2 and 4; and
D, when r is 2, is selected from the group consisting of C2-C16 alkylene, C4-C12 alkenylene, xylylene, C4-C20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is interrupted by one or more oxygen atoms, —
CH2CH(OH)CH2O—
R15—
OCH2CH(OH)CH2—
, —
CO—
R16—
CO—
, —
CO—
NH—
R17—
NH—
CO—
, —
(CH2)s—
COO—
R18—
OCO—
(CH2)s—a polyoxyalkylene bridge member of the formula XX
-
-
27. A method of stabilizing a material which is subject to degradation by actinic radiation comprising:
-
incorporating into the material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises a compound of formula (IV);
wherein each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof;
L is hydrogen, C1-C24 alkyl, C1-C24 branched alkyl, C3-C6 alkenyl, —
COR12, —
COOR12, —
CONHR12, —
SO2R13, C1-C18 alkyl which is substituted with at least one hydroxy, C1-C18 alkoxy, C3-C18 alkenoxy, halogen, phenoxy, C1-C18 alkyl-substituted phenoxy, C1-C18 alkoxy-substituted phenoxy, halogen-substituted phenoxy, —
COOH, —
COOR9, —
CONH2, —
CONHR9, —
CON(R9)(R10), —
NH2, —
NHR9, —
N(R9)(R10), —
NHCOR11, —
N(R9)COR11, —
NHCOOR11, —
N(R9)COOR11, —
CN, —
OCOR11, —
OC(O)NHR9, —
OC(O)N(R9)(R10), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —
OCOR11 or C2-C50 alkyl optionally interrupted by at least one oxygen atom or carbonyl group and optionally substituted by at least one substituents selected from the group consisting of hydroxy and C1-C12 alkoxy,wherein R9 and R10 independently of one another are C1-C12 alkyl, C3-C12 alkoxyalkyl, C4-C16 dialkylaminoalkyl, C5-C12 cycloalkyl, or R9 and R10 taken together are C3-C9 alkylene, C3-C9 oxoalkylene, C3-C9 azaalkylene;
R11 is C1-C18 alkyl, C2-C18 alkenyl or phenyl;
R12 is C1-C18 alkyl, C2-C18 alkenyl, phenyl, C1-C12 alkoxy, phenoxy, C1-C12 alkylamino, phenylamino, tolylamino or naphthylamino; and
R13 is C1-C12 alkyl, phenyl, naphthyl or C7-C14 alkylphenyl;
r is an integer between 2 and 4; and
X′
, when r is 2, is selected from the group consisting of C2-C16 alkylene, C4-C12 alkenylene, xylylene, C4-C20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is interrupted by one or more oxygen atoms, —
CH2CH(OH)CH2OR15—
OCH2CH(OH)CH2—
, —
(CH2)s—
COO—
R18—
OCO—
(CH2)s—a polyoxyalkylene bridge member of the formula XX
-
-
28. A method of protecting a substrate against degradation by actinic radiation comprising applying to the substrate a coating containing an actinic radiation stabilizer composition in an amount effective to reduce the amount of actinic radiation impinging on the substrate, wherein the actinic radiation stabilizer composition comprises a compound a compound of formula (IV):
-
wherein each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R3 and R4 are each independently hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl) and mixtures thereof;
L is hydrogen, C1-C24 alkyl, C1-C24 branched alkyl, C3-C6 alkenyl, —
COR12, —
COOR12, —
CONHR12, —
SO2R13, C1-C18 alkyl which is substituted with at least one hydroxy, C1-C18 alkoxy, C3-C18 alkenoxy, halogen, phenoxy, C1-C18 alkyl-substituted phenoxy, C1-C18 alkoxy-substituted phenoxy, halogen-substituted phenoxy, —
COOH, —
COOR9, —
CONH2, —
CONHR9, —
CON(R9)(R10), —
NH2, —
NHR9, —
N(R9)(R10), —
NHCOR11, —
N(R9)COR11, —
NHCOOR11, —
N(R9)COOR11, —
CN, —
OCOR11, —
OC(O)NHR9, —
OC(O)N(R9)(R10), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —
OCOR11 or C2-C50 alkyl optionally interrupted by at least one oxygen atom or carbonyl group and optionally substituted by at least one substituents selected from the group consisting of hydroxy and C1-C12 alkoxy,wherein R9 and R10 independently of one another are C1-C12 alkyl, C3-C12 alkoxyalkyl, C4-C16 dialkylaminoalkyl, C5-C12 cycloalkyl, or R9 and R10 taken together are C3-C9 alkylene, C3-C9 oxoalkylene, C3-C9 azaalkylene;
R11 is C1-C18 alkyl, C2-C18 alkenyl or phenyl;
R12 is C1-C18 alkyl, C2-C18 alkenyl, phenyl, C1-C12 alkoxy, phenoxy, C1-C12 alkylamino, phenylamino, tolylamino or naphthylamino; and
R13 is C1-C12 alkyl, phenyl, naphthyl or C7-C14 alkylphenyl;
r is an integer between 2 and 4; and
X′
, when r is 2, is selected from the group consisting of C2-C16 alkylene, C4-C12 alkenylene, xylylene, C4-C20 alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is interrupted by one or more oxygen atoms, —
CH2CH(OH)CH2OR15—
OCH2CH(OH)CH2—
, —
(CH2)s—
COO—
R18—
OCO—
(CH2)s—a polyoxyalkylene bridge member of the formula XX
-
-
29. A method of stabilizing a material which is subject to degradation by actinic radiation comprising:
-
incorporating into the material an amount of an actinic radiation stabilizer composition effective to stabilize the material against the effects of actinic radiation, wherein the actinic radiation stabilizer composition comprises a compound of formula (V);
wherein X is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R3 is hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), or —
N(hydrocarbyl)2;
R4 is a straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkyl interrupted by phenylene, benzylidene, —
S—
, —
S—
S—
, —
S—
E—
S—
,—
SO—
, —
SO2—
, —
SO—
E—
SO—
, —
SO2—
E—
SO2—
, —
CH2—
NH—
E—
NH—
CH2—
, andwherein E is selected from the group consisting of alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon atoms; r is an integer between 2 and 4; and
L is selected from a hydrogen, hydrocarbyl, further substituted by halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl), —
N(functional hydrocarbyl)(functional hydrocarbyl), —
S(hydrocarbyl), —
S(functional hydrocarbyl), —
SO2(hydrocarbyl), —
SO3(hydrocarbyl), —
SO2(functional hydrocarbyl), —
SO3(functional hydrocarbyl), —
COO(hydrocarbyl), —
COO(functional hydrocarbyl), —
CO(hydrocarbyl), —
CO(functional hydrocarbyl), —
OCO(hydrocarbyl), —
OCO(functional hydrocarbyl), —
CONH2, —
CONH(hydrocarbyl), —
CONH(functional hydrocarbyl), —
CON (hydrocarbyl)(hydrocarbyl), —
CON(functional hydrocarbyl)(hydrocarbyl), —
CON(functional hydrocarbyl)(functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups.
-
-
30. A method of protecting a substrate against degradation by actinic radiation comprising applying to the substrate a coating containing an actinic radiation stabilizer composition in an amount effective to reduce the amount of actinic radiation impinging on the substrate, wherein the actinic radiation stabilizer composition comprises a compound a compound of formula (V):
-
wherein X is hydrogen or a blocking group;
each R independently is a hydrocarbyl group of 1 to 21 carbon atoms;
R3 is hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), or —
N(hydrocarbyl)2;
R4 is a straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkyl interrupted by phenylene, benzylidene, —
S—
, —
S—
S—
, —
S—
E—
S—
,—
SO—
, —
SO2—
, —
SO—
E—
SO—
, —
SO2—
E—
SO2—
, —
CH2—
NH—
E—
NH—
CH2—
, andwherein E is selected from the group consisting of alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon atoms; r is an integer between 2 and 4; and
L is selected from a hydrogen, hydrocarbyl, further substituted by halogen, hydroxyl, cyano, —
O(hydrocarbyl), —
O(functional hydrocarbyl), —
N(hydrocarbyl)(hydrocarbyl), —
N(functional hydrocarbyl)(functional hydrocarbyl), —
S(hydrocarbyl), —
S(functional hydrocarbyl), —
SO2(hydrocarbyl), —
SO3(hydrocarbyl), —
SO2(functional hydrocarbyl), —
SO3(functional hydrocarbyl), —
COO(hydrocarbyl), —
COO(functional hydrocarbyl), —
CO(hydrocarbyl), —
CO(functional hydrocarbyl), —
OCO(hydrocarbyl), —
OCO(functional hydrocarbyl), —
CONH2, —
CONH(hydrocarbyl), —
CONH(functional hydrocarbyl), —
CON (hydrocarbyl)(hydrocarbyl), —
CON(functional hydrocarbyl)(hydrocarbyl), —
CON(functional hydrocarbyl)(functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups.
-
Specification