Red-shifted tris-aryl-s-triazines and compositions stabilized therewith

Claim 2

A compound of formula I, II, III, IV, V or VI according to claim 1 where in the compounds of formula I X and Y are the same or different and are phenyl or phenyl substituted with one to three lower alkyl, halogen, hydroxy or alkoxy; R₁ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, halogen, -SR₃, -SOR₃, or -SO₂R₃; or said alkyl or cycloalkyl substituted by one to eight halogen, -R₄, -OR₅, -N(R₅)₂, =NR₅ =O, -CON(R₅)₂, -COR₅, -COOR₅, -OCOR₅, -CN, -NO₂, -SR₅, -SOR₅, -SO₂R₅, -P(O)(OR₅)₂, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperazinyl groups or combinations thereof; or said alkyl or cycloalkyl interrupted by one to six phenylene, -O-, -NR₅-, -CONR₅-, -COO-, -OCO-, -C(R₅)=C(R₅)- or -CO- groups or combinations thereof; or said alkyl or cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; R₃ is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms; R₄ is aryl of 6 to 10 carbon atoms, or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; or phenylalkyl of 7 to 15 carbon atoms, or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms; R₅ is defined as R₄, or R₅ is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms; or R₅ is a group of the formula where T is hydrogen, oxyl, hydroxyl, alkyl of 1 to 12 carbon atoms, said alkyl substituted by at least one hydroxyl or lower alkoxy, benzyl or alkanoyl of 2 to 18 carbon atoms; R₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or cycloalkyl substituted by one to eight halogen, epoxy, glycidyloxy, furyloxy, -R₄, -OR₅, -N(R₅)₂, -CON(R₅)₂, -COR₅, -COOR₅, -OCOR₅, -OCOC(R₅)=C(R₅)₂, -C(R₅)=C(R₅)-COOR₅, -CN, -NCO, or or combinations thereof; or said alkyl or cycloalkyl interrupted by one to six epoxy, -O-, -NR₅-, -CONR₅-, -COO-, -OCO-, -CO-, -C(R₅)=C(R₅)COO-, -OCOC(R₅)=C(R₅)-, -(R₅)C=C(R₅)-, phenylene, or -phenylene-G-phenylene in which G is -O-, -S-, -SO₂-, -CH₂-, or -C(CH₃)₂-, or combinations thereof; or said alkyl or cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R₂ is -SO₂R₃, or -COR₆; R₆ is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, phenyl, alkoxy of 1 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms or a group -R₇COOH or -NH-R₈-NCO; R₇ is alkylene of 2 to 14 carbon atoms or o-phenylene; R₈ is alkylene of 2 to 10 carbon atoms, phenylene, tolylene, diphenylenemethane or a group with the proviso that when R₂ is hydrogen and R₁ is n-hexyl, X and Y are not each 5-n-hexyl-2,4-dihydroxyphenyl; for the compounds of formula II: X is phenyl or phenyl substituted with one to three lower alkyl, halogen, hydroxy or alkoxy; R₁ and R₁' are the same or different and are defined as R₁ above; R₂ and R₂' are the same or different and are defined as R₂ above; and with the proviso that when R₁ and R₁' are each n-hexyl and R₂ and R₂' are each hydrogen, X is not 5-n-hexyl-2,4-dihydroxyphenyl; for the compounds of formula III: R₁, R₁' and R₁'' are the same or different and are as defined for R₁ above; R₂, R₂' and R₂'' are the same or different and are as defined for R₂ above; and with the proviso that when R₂, R₂' and R₂'' are each hydrogen, R₁, R₁' and R₁'' are not each n-hexyl; for the compound of formula IV: X, X', Y and Y' are the same or different and are phenyl, phenyl substituted by one to three lower alkyl, halogen, hydroxy or alkoxy; L is straight or branched chain alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylene substituted by or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is -S-, -S-S-, -S-E-S-, -SO-, -SO₂-, -SO-E-SO-, -SO₂-E-SO₂-, -CH₂-NH-E-NH-CH₂- or where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms; R₂ and R₂' are the same or different and are defined as R₂ is above; for the compounds of formula V: X, Y, and R₁ are defined as above; n = 2 to 4; when n = 2, Q is straight or branched chain alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to eight -OH; or said alkylene interrupted by one to eight -CH=CH- or -O-; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group -CONH-R₈-NHCO-, -CH₂CH(OH)CH₂O-R₉-OCH₂CH(OH)CH₂-, -CO-R₁₀-CO-, or -(CH₂)m-COO-R₁₁-OOC-(CH₂) m -, where m = 1 to 3; or Q is R₈ is defined as above; R₉ is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by 1 to 10 -O-, phenylene, or a group -phenylene-G-phenylene- in which G is -O-, -S-, -SO₂-, -CH₂-, or -C(CH₂)₂-; R₁₀ is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by 1 to 4 -O-, -S-, or -CH=CH-; or R₁₀ is arylene of 6 to 12 carbon atoms; R₁₁ is alkylene of 4 to 20 carbon atoms, or said alkylene interrupted by 1 to 8 -O-; when n = 3, Q is a group -[(CH₂) m COO]₃-R₁₂ where m = 1 to 3 and R₁₂ is an alkanetriyl of 3 to 12 carbon atoms; when n = 4, Q is a group -[(CH₂) m COO]₄-R₁₃ where m = 1 to 3 and R₁₃ is an alkanetetryl of 4 to 12 carbon atoms; and for the compounds of formula VI: X and Y are as defined above; t is 0 to 9; L is as defined above, with the proviso that at least one L linkage is attached to the phenyl ring in the 5-position; and R₂ is as defined above.

Claim 3

A compound according to claim 1 where X, Y, X' and Y' are phenyl or phenyl substituted with one to three lower alkyl or halogen; R₁ is straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 3 to 12 carbon atoms, -Cl, -SR₃, -SOR₃, or -SO₂R₃; said alkyl substituted by phenyl, -OR₅, -N(R₅)₂, =NR₅, =O and/or interrupted by -O-, -NR₅-, -CO- or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; or phenylalkyl of 7 to 15 carbon atoms; R₂ and R₂' are hydrogen, alkyl of 1 to 24 carbon atoms, or alkyl of 2 to 24 carbon atoms substituted by one or two -OR₅; R₅ is H, alkyl of 1 to 24 carbon atoms, or phenyl; and and L is methylene; benzylidene; or

Claim 4

A compound according to claim 3 where A and A' are phenyl, a group of formula or phenyl substituted with one or two lower alkyl; R₁ is straight or branched chain alkyl of 1 to 18 carbon atoms, propenyl, -Cl, alkylaminoalkyl of 4 to 12 carbon atoms, alkyliminoalkyl of 4 to 12 carbon atoms, alkanoyl of 2 to 18 carbon atoms, benzoyl, -SR₃, -SOR₃, or -SO₂R₃; or C₁-C₇alkyl substituted by phenyl and/or -OH; R₂ and R₂' are hydrogen, alkyl of 1 to 24 carbon atoms, or alkyl of 2 to 12 carbon atoms substituted by one or two -OR₅; R₃ is phenyl; R₅ is H, alkyl of 1 to 12 carbon atoms, or phenyl.

Claim 5

A compound according to claim 2 where X, Y, X' and Y' are phenyl or phenyl substituted with one to three lower alkyl or halogen; R₁, R₁' and R₁'' are straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, or phenylalkyl of 7 to 15 carbon atoms; R₂ and R₂' are straight or branched chain alkyl of 2 to 24 carbon atoms, or said alkyl substituted by one or two -OR₅, where R₅ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, or phenyl; and and L is methylene; benzylidene; or

Claim 6

The compound according to claim 1 which is a. 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; b. 4,6-bis-(2,4-dimethylphenyl)-2-[5-hexyl-2-hydroxy-4-(2-hydroxy-3-phenoxypropoxy)phenyl]-s-triazine; c. 4,6-bis-(2,4-dimethylphenyl)-2-[4-(3-dodecyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-s-triazine; d. 2-(2,4-dihydroxy-5-ethylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; e. 2-[2,4-dihydroxy-5-(1,1-dimethylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine; f. 2-[2,4-dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine; g. 4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine; h. 4,6-bis-(2,4-dimethylphenyl)-2-[4-hexyloxy-2-hydroxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine; i. [2,4-dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazine; j. 2-[2-hydroxy-5-(1-methyl-1-phenylethyl)-4-octyloxyphenyl]-4,6-bis-phenyl-s-triazine; k. 2-(5-chloro-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; l. 2-(2,4-dihydroxy-5-propionylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; m. 2-[2,4-dihydroxy-5-(1-isobutylimino)propylphenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine; n. 2-[2,4-dihydroxy-5-(1-isobutylamino)propylphenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine; o. 4,6-bis-(2,4-dimethylphenyl)-2-[2,4-dihydroxy-5-(1-hydroxypropyl)phenyl]-s-triazine; p. 2-(5-benzoyl-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; q. 4,6-bis-(2,4-dimethylphenyl)-2-[2,4-dihydroxy-5-(α-hydroxybenzyl)phenyl]-s-triazine; r. 2-(2,4-dihydroxy-5-phenylthiophenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; s. 2-(2,4-dihydroxy-5-phenylsulfinylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine; t. 2-(2,4-dihydroxy-5-phenylsulfonylphenyl)- 4,6-bis-(2,4-dimethylphenyl)-s-triazine; u. 2-(5-chloro-2,4-dihydroxyphenyl)-4,6-diphenyl-s-triazine; v. 4,6-diphenyl-2-(5-chloro-4-hexyloxy-2-hydroxyphenyl)-s-triazine; w. 4,6-diphenyl-2-(5-hexyl-4-methoxy-2-hydroxyphenyl)-s-triazine; x. 2-[4-(3-butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-diphenyl-s-triazine; y. 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-methylphenyl)-s-triazine; z. 4,6-bis(4-methylphenyl)-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine; aa. 2-[4-(3-butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-bis(4-methylphenyl)-s-triazine; bb. 2-[4-(3-butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine; cc. 2,4-bis(2,4-dihydroxy-5-hexylphenyl)-6-phenyl-s-triazine; dd. 2,4-bis[4-(3-butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-6-phenyl-s-triazine; ee. 2,4-bis(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-6-phenyl-s-triazine; ff. 2-[2,4-dihydroxy-5-(1-propenyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine; gg. 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-diphenyl-s-triazine; hh. 4,6-diphenyl-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine; ii. 4,6-bis(2,4-dimethylphenyl)-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine; jj. 2-[5-hexyl-2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)phenyl]-4,6-bis-phenyl-s-triazine; kk. 4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-hexyloxy-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine; ll. 1,3-bis{1-[2,4-dihydroxy-5-(3,5-bis(2,4-dimethylphenyl-s-triazinyl))phenyl]-1-methylethyl}benzene; mm. mixture of methylene-bis-2-(2-hydroxy-4-octyloxyphenyl)-4,6-(2,4-dimethylphenyl)-s-triazine; bridged in the 3:5, 5:5 and 3:3 positions in a 5:4:1 ratio; or nn. mixture of benzylidene-bis-2-(2-hydroxy-4-octyloxyphenyl)-4,6-(2,4-dimethylphenyl)-s-triazine; bridged in the 3:5 and 5:5 positions in a 1:1 ratio.

Claim 7

A process for the preparation of a compound of formula I where R₁ is straight or branched chain alkyl of 4 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 8 to 15 carbon atoms, R₂ is hydrogen, and X and Y are the same or different and are phenyl or phenyl substituted by 1 to 3 lower alkyl or by 1 to 3 chloro groups, which comprises reacting a compound of formula A where R₂, X and Y are as defined above, with a two to ten excess equivalent amount of an alkene of 4 to 24 carbon atoms, a cycloalkene of 5 to 12 carbon atoms or an phenylalkene of 8 to 15 carbon atoms, compared to the amount of the compound of formula A neat in the presence of a catalytic amount of a Friedel-Crafts alkylation catalyst at a temperature of 110°C to 250°C.

Claim 8

A process according to claim 7 wherein the catalyst is aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, diisobutylaluminum hydride or aluminum isopropoxide.

Claim 9

A process according to claim 8 wherein the catalyst is aluminum isopropoxide.

Claim 10

A composition stabilized against the deleterious effects of actinic radiation which comprises (a) an organic material subject to degradation when exposed to actinic radiation, and (b) an effective stabilizing amount of a compound of formula A or B according to claim 1.

Claim 11

A composition according to claim 10 wherein the organic material of component (a) is a polymer.

Claim 12

A composition according to claim 10 containing the stabilizer of component (b) in an amount of 0.01 to 20% by weight of the composition.

Claim 13

A composition according to claim 10 wherein the polymer is a high solids thermoset acrylic/melamine resin or an acrylic urethane resin.

Claim 14

A composition according to claim 10 where the composition is a polymer film composition which comprises (a) an electro coat primer in adhesion to a metal substrate, (b) a base or color coat that is in adhesion to the electro coat and which comprises a film-forming binder and an organic pigment or an inorganic pigment or mixtures thereof, (c) a clear coat that is in adhesion to the base coat and which comprises a film-forming binder, and (d) an effective stabilizing amount, of at least one tris-aryl-s-triazine UV absorber contained in either the base coat or the clear coat or both base coat and clear coat.

Claim 15

A composition according to claim 14 wherein component (d) is between 1 and 20% by weight of the film-forming binder.

Claim 16

A composition according to claim 14 wherein component (d) is incorporated into the base coat.

Claim 17

A composition according to claim 14 which additionally contains an effective stabilizing amount of at least one 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or hindered amine light stabilizer or mixtures thereof.

Claim 18

A composition according to claim 14 wherein the film-forming binder is a high solids thermoset acrylic/melamine resin or an acrylic urethane resin.

Claim 19

Use of a compound of formula A or B according to claim 1 as stabiliser for protecting an organic polymer against degradation caused by light, oxygen and/or heat.

Claim 20

A method of protecting an organic polymer against degradation caused by light, oxygen and/or heat, which comprises incorporating in said materials at least one compound of formula A or B according to claim 1.

Claim 21

The method of claim 20, wherein the organic polymer is a binder for a surface-coating composition.