CH693032A5 - Benzotriazole UV absorbent with increased durability. - Google Patents

Description

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CH 693 032 A5

description

Benzotriazole UV absorbers, which are substituted on the benzo ring with electron-withdrawing residues, show increased durability and low loss rates if they are incorporated into motor vehicle coatings.

The benzotriazoles have long been an important class of UV absorbers (UVA) and have gained wide commercial importance and acceptance in many industrial applications. There is a large number of publications in the prior art which deal with their production and use. However, as the demands continue to increase, the search for even more stable and durable benzotriazoles continues. The gradual exclusion of HAPS solvents, such as xylene, due to environmental concerns and their replacement with non-HAPS solvents, such as esters, ethers or ketones, and the higher durability requirements for automotive coatings make this search more urgent. Indeed, the automotive industry is concerned about UVA losses from automotive paints and coatings, as disclosed in the J.L. Gerlock et al., Proc. 36th Annual Tech. Sym. (Cleveland Coating Society), May 18, 1993, outlined, very concerned.

Vysokomol Soedin, Ser. A. 18 (3), 553 (1976) describes the linear dependence on hydrogen bond strength and photostability in benzotriazoles.

J.E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995), describe the degradation of benzotriazole UV absorbers in poly (methyl methacrylate) films by light. A structural change generally caused little difference in degradation rates unless the substitution broke the intramolecular hydrogen bonds that are critical to stability. Pickett et al. did not study benzotriazoles which, as in the present invention, have both electron-withdrawing and electron-donating groups.

The prior art leads to the conclusion that strengthening the hydrogen bond leads to a more stable benzotriazole, but does not find out how this can be done. The present invention discloses benzotriazoles which show increased durability, but surprisingly, this increased durability is not always associated with greater hydrogen bond strength. Indeed, compounds with increased durability often have weaker, not stronger hydrogen bonds.

U.S.-A-4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 describe selected benzotriazoles which are substituted in the 3-position of the hydroxyphenyl ring with an a-cumyl group and show very good durability in motor vehicle coatings. These benzotriazoles represent the current state of the art. The present invention is directed to the production of benzotriazoles which exhibit even better durability and lower loss rates than the prior art benzotriazoles.

US-A-5 278 314; 5,280,124; 5,436,349 and 5,516,914 describe red-shifted benzotriazoles. These benzotriazoles are substituted in the 5-position of the benzo ring with thioether, alkylsulfonyl or phenylsulfonyl radicals. The red shift of the benzotriazoles is desirable for spectral reasons. An electron-withdrawing group in the 5-position provides further advantages in terms of low loss rates and durability, as set forth in the present invention.

The present invention relates to benzotriazole UV absorbers with increased stability and durability and a low loss rate when incorporated in automotive coatings.

In particular, the present invention relates to a coating composition stabilized with a benzotriazole, the benzotriazole having increased durability and a low loss rate when incorporated into the coating, the composition comprising

(a) a resin selected from the group consisting of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin crosslinked with melamine with side carbamate groups or an acrylic polyol resin crosslinked with melamine containing carbamate groups, and

(b) 0.01 to 5 weight percent, based on the resin solids, of a benzotriazole of formula A, B, C or D.

oh g

r

(A)

r,

'2

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CH 693 032 A5

(B)

(D)

wherein

Gì, G2 or T represents an electron-withdrawing radical,

Gì represents hydrogen or halogen,

G2 halogen, nitro, cyano, R3SO-, R3SO2-, -COOG3, CF3-, -P (O) (C6H5) 2, -CO-G3, -CO-NH-G3, -CO-N (G3) 2, -N (G3) -CO-G3,

/

co-

■ N

\

co-

-G

3

or

/

co-

-n

\

co-1

shown,

G3 is hydrogen, straight-chain or branched-chain alkyl having 1 to 24 carbon atoms, straight-chain or branched-chain alkenyl having 2 to 18 carbon atoms, cycioalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group on the phenyl ring with 1 to 4 alkyl with 1 to 4 carbon atoms,

Ri is hydrogen, straight or branched chain alkyl having 1 to 24 carbon atoms, straight or branched chain alkenyl having 2 to 18 carbon atoms, cycioalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group on the phenyl ring with 1 to 4 alkyl with 1 to 4 carbon atoms,

R2 straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycioalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on the phenyl ring with 1 to 3 alkyl having 1 to 4 carbon atoms; or R2 hydroxyl or -OR4, where R4 is straight3

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CH 693 032 A5

or represents branched chain alkyl of 1 to 24 carbon atoms; or this alkyl group substituted with one or more groups -OH, -OCO-Rn, -NCO or -NH2 or mixtures thereof; or this alkyl or alkenyl group, interrupted by one or more groups -O- -NH- or -NR4- or mixtures thereof, and which may be unsubstituted or substituted by one or more groups -OH or -IMH2 or mixtures thereof; or R2 represents -SR3, -NHR3 or -N (R3) 2;

wherein R3 alkyl with 1 to 20 carbon atoms, hydroxyalkyl with 2 to 20 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycioalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, aryl with 6 to 10 carbon atoms or this aryl group, substituted with one or two alkyl having 1 to 4 carbon atoms, or 1, 1, 2, 2-tetrahydroperfluoroalkyl, in which the perfluoroalkyl radical has 6 to 16 carbon atoms,

or R2

- (CH2) m-CO-X- (Z) p-Y-R, 5, in which X represents -O- or -N (Ri6) -,

Y represents -O- or -N (Ri7) -,

Z represents C2-Ci2-alkylene, C4-Ci2-alkylene, interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C3-Ci2-alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group .

R16 and R17 independently represent hydrogen, Ci-Ci2-alkyl, C3-Ci2-alkyl, interrupted by 1 to 3 oxygen atoms, or represent cyclohexyl or C7-Ci5-aralkyl and R16 together with R17 in the case when Z represents ethylene, likewise Forms ethylene

m is zero, 1 or 2,

p is 1 or p is also zero if X and Y represent -N (Ri6) - and -N (Ri7) -,

R15 represents a group -CO-C (Ris) = C (H) Ri9 or, if Y represents -N (Ri7) - together with R17 represents a group -CO-CH = CH-CO-, where Rie is hydrogen or methyl and R19 represents hydrogen, methyl or -CO-X-R20, where R20 represents hydrogen, Ci-Ci2-alkyl or a group of the formula

wherein the symbols Gì, G2, Ri, X, Z, m and p have the meanings defined above n is 1 or 2,

when n is 1, R5 is Cl, OR6 or NR7Rs or R5 is -PO (ORi2) 2, -OSi (Rn) 3 or -OCO-R11, or straight-chain or branched-chain Ci -C24-alkyl, which is represented by -O- , -S- or -NRu is interrupted and which may be unsubstituted or substituted by -OH or -OCO-Rn, Cs-Ci2-cycloalkyl which is unsubstituted or substituted by -OH, straight-chain or branched-chain C2-cis-alkenyl, which is unsubstituted or substituted by -OH, C7-cis-aralkyl, -CH2-CHOH-R13 or glycidyl,

Rö represents hydrogen, straight-chain or branched-chain Ci-C24-alkyl which is unsubstituted or substituted by one or more groups OH, OR4 or NH2 or -ORö - (OCH2CH2) wOH or - (OCH2CH2) wOR2i, where w is 1 to 12 is and R21 is alkyl of 1 to 12 carbon atoms, R7 and Rß are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3-Ci8-alkyl which is interrupted by -O-, -S- or -NRn- Represent Cs-Ci2-cycloalkyl, C6-Ci4-aryl or C1-C-3-hydroxylalkyl, or R7 and Rs together with the N atom represent a pyrrolidine, piperidine, piperazine or morpholine ring,

when n is 2, R5 represents one of the divalent radicals -O-R9-O- or -N (Rn) -Rio-N (Rn) -, Rg C2-C8-alkylene, C4-C8-alkenylene, C4-alkynylene, Cyclohexylene, straight-chain or branched-chain C4-C10-AI-kylene which is interrupted by -O- or by -CH2-CHOH-CH2 -O-R14-O-CH2-CHOH-CH2-, R10 represents straight-chain or branched-chain C2-Ci2-alkylene is represented by -O-, cyclohexylene or

OH

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CH 693 032 A5

may be interrupted, or Rio and Rn form a piperazine ring with the two nitrogen atoms, Rh straight-chain or branched-chain C2-C8-alkylene, straight-chain or branched-chain C4-Cio-alkylene, which may be interrupted by -O-, cycloalkylene, arylene or or represents, in which R7 and Rs independently represent hydrogen, alkyl having 1 to 18 carbon atoms, or R7 and Rs together represent alkylene having 4 to 6 carbon atoms, 3-oxapenta-methylene, 3-iminopentamethylene or 3-methyliminopentamethylene,

R11 represents hydrogen, straight-chain or branched-chain Ci-Cie-alkyl, C5-Ci2-cycloalkyl, straight-chain or branched-chain C3-C8-alkenyl, C6-Ci4-aryl or C7-cis-aralkyl,

R12 represents straight-chain or branched-chain Ci-Cis-alkyl, straight-chain or branched-chain C3-Cis-alkenyl, Cs-Cio-Cyc-loalkyl, C6-Ci6-aryl or C? -Ci5-aralkyl,

R13 is H, straight-chain or branched-chain Ci-cis-alkyl which is substituted by -PO (ORi2) 2, phenyl which is unsubstituted or substituted by OH, C7-cis-aralkyl or -CH20Ri2,

L represents alkylene having 1 to 12 carbon atoms, alkylidene having 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and

T -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CO-, -CO-E-CO-, -COO-E-OCO-, -CO-NG3- Represents E-NG3-CO- or -NG3-CO-E-CO-NG3-,

wherein E represents alkylene with 2 to 12 carbon atoms, cycloalkylene with 5 to 12 carbon atoms or alkylene, interrupted by or terminated with cyclohexylene with 8 to 12 carbon atoms,

wherein the benzotriazole exhibits increased durability and low loss rate values when the coating is exposed to actinic radiation, confirmed by a loss of less than 0.22 absorbance units after 1200 hours of exposure, or less than 0.27 absorbance units after 1500 hours of exposure, or less than 0.40 absorbance units after 2500 hours of exposure in a Xe-Nonbogen Weather-O-meter.

Component (b) is preferably a compound of the formula A '

(A ')

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CH 693 032 A5

wherein

G2 represents fluorine, chlorine, cyano, R3SO2-, CF3-, -CO-G3, -COO-G3 or -CO-N (G3) 2,

G3 represents alkyl having 1 to 12 carbon atoms,

R 1 represents hydrogen, alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or this phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups having 1 to 4 carbon atoms,

R2 alkyl with 1 to 12 carbon atoms, phenyl, phenylalkyl with 7 to 15 carbon atoms or -CH2CH2COOG4, in which G4 represents hydrogen, alkyl with 1 to 24 carbon atoms or this alkyl group, substituted by OH, interrupted by one to six atoms -O- or both substituted with OH and interrupted by one to six atoms -O-, and

R3 represents alkyl having 1 to 18 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms.

More preferred is in the compound of formula A '

G2 fluorine, chlorine, cyano, R3SO2-, CF3-, -COO-G3 or -CO-N (G3) 2,

G3 alkyl with 1 to 8 carbon atoms,

Ri is hydrogen, phenyl or a-cumyl,

R2 alkyl with 4 to 12 carbon atoms or phenyl and R3 phenyl or alkyl with 8 to 12 carbon atoms.

In particular, compounds of the formula A 'in which G2 is phenyl-S02, 0ctyl-S02-, fluorine or CF3-, Ri is a-cumyl or phenyl and R2 is tert-butyl or tert-octyl are preferred.

Preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.

Examples of these various residues are as follows:

If one of the radicals R 1 to R 21 represents alkyl, such groups are, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, tert-octyl, lauryl, tert- Dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; if one of the radicals is alkenyl, such groups are, for example, allyl or oleyl; when one of the radicals is cycioalkyl, such groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; if one of the radicals is phenylalkyl, such groups are, for example, benzyl, phenethyl, a-methylbenzyl and a, a-dimethylbenzyl; and when one of the radicals is aryl they are for example phenyl, naphthyl or, when substituted with alkyl, they are for example tolyl and xylyl. If R6 is alkyl substituted with one or more groups -O- and / or substituted with one or more groups -OH, the radical -OR6 can be, for example - - (OCH2CH2) wOH or - (OCH2CH2) wOR2i, where w is 1 to 12 and R21 represents alkyl of 1 to 12 carbon atoms.

When E represents alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, octamethylene, decamethylene and dodecamethylene; when E is cycloalkylene it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E represents alkylene interrupted by or terminated with cyclohexylene, it is, for example, the saturated diyl radical derived from limonene, herein called dihydrolimony diyl.

A further preferred embodiment of the invention is a compound of the formula III, in which Fti is tert-butyl, n is 1, R3 is phenyl and R5 is -OR6, in which R6 is a straight-chain or substituted octyl group. A further preferred embodiment of the present invention is furthermore a compound of the formula C, in which n is 2, R i is tert-butyl, R3 is phenyl and R5 is -O-R9-O-, in which Rs is C2-C24-alkylene, interrupted by -O- or by -CH2-CHOH-CH2-O-R14-O-CH2-CHOH-CH2-.

If the present compounds contain a free carboxyl radical in which R2 represents -CH2CH2COOR6, in which Rô is hydrogen, the alkali metal or amine salts of the acids are also conceivable as part of this invention, such UV absorbers due to the increased water solubility of the present compounds in aqueous systems can be used.

R6, R7 and Rs can be the following C3-cis-alkyl radicals which are interrupted by -O-, -S- or -NRn- and can be substituted by OH: methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl, CH3OCH2CH2OCH2CH2- , CH3CH2OCH2CH2OCH2CH2-, C4H9OCH2CH2OCH2CH2-, ethylthiopropyl, Octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, -CH2CH2-NH-C4H9, -CH2CH2CH2NH-C8H17 and -CH2CH2CH2-N (CH3) -CH2CH (C2H5) C4Hg,

R6, R7, Rb, R11 and R12 can be the following C5-Ci2-cycloalkyl radicals: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In the case of R6, the radical can also be substituted with -OH.

R7, Rs and R11 can be the following alkenyl radicals: allyl, methallyl, 2-n-hexenyl or 4-n-octenyl.

When R6 is alkenyl, it can have the same meaning as R7, Rs and Rh as alkenyl radicals, but it can also be -CH = CH2, n-undec-10-enyl or n-octadec-9-enyl and it is also possible that the radical R6 is substituted with -OH.

R7 and Rs can be the following C7-Ci5 aralkyl radicals: benzyl, a-phenethyl, 2-phenethyl or 4-tert-butylbenzyl.

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CH 693 032 A5

If Rn, R13 or R12 are aralkyl, they can independently have the same meanings as for R7 or Rs.

Independently of one another, R7, Rs and R11 can be the following C6-Ci4-aryl radicals: phenyl, a-naphthyl or β-naphthyl.

When R7 and Rs represent CrC3-hydroxyalkyl, they can be the following radicals: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.

As C2-C8 alkylene, Rg and Rm can be the following radicals: ethylene, propylene, butylene, hexylene or octylene.

As alkylene, R10 can denote the following radicals, but can additionally also represent groups of relatively high molecular weight, such as decylene or dodecylene.

When Rg is C4-C8 alkenylene, the following is an example of a suitable group: butenylene.

In the case of Rg and R14, suitable straight or branched chain C4-Cio-alkylene groups which are interrupted by -O- are the following groups: -CH2CH2OCH2CH2-, -CH (CH3) -CH2-0-CH2-CH (CHs) , -CH2CH2OCH2CH2OCH2CH2- and -CH2CH2OCH2CH2OCH2CH2OCH2CH2-.

When R14 represents a cycloalkylene group, the following groups are included: 1,3-cyclohexylene and 1,4-cyclohexylene.

If R14 represents arylene, this can in particular be the following groups: 1,3-phenylene or 1,4-phenylene.

As C2-C-12 alkylene, Z is a straight or branched chain. It is, for example: ethylene, propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene, 2,2-amylidene or 2-ethylhexamethylene. C2-C6 alkylene groups are preferred.

If Z represents C4-Ci2-A! Kylene which is interrupted by oxygen, then it is, for example: -CH2-CH2-O-CH2-CH2-, -CH2-CH2-O-CH2-CH2-CH2, CH2-CH2 -O-CH2-CH2-O-CH2-CH2 or -CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-CH2- and if alkylene is interrupted by nitrogen this means a group - N (i6) -, in which R16 is as defined above, for example -CH2-CH2-NH-CH2-CH2-CH2-CH2, -CH2-CH2-CH2-NH2) 8 - or -CH2-CH2-CH2-N ( CH3) -CH2-CH (C2H5) (CH2) 4-.

As C3-Ci2-alkylene, substituted with a hydroxyl group, Z represents 2-hydroxytetramethylene, 2-hydroxy-hexamethylene and in particular 2-hydroxytrimethylene.

Z represents, for example, 1,4-cyclohexylene and in particular 1,2-cyclohexylene as cyclohexylene.

Z represents phenylene, for example, m-phenylene or p-phenylene.

m can be zero, 1 or 2, but is preferably 2.

p is preferably 1, but can be zero if both X and Y are attached via nitrogen.

As Ci-Cs-alkyl, Ri is, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-hexyl, n-heptyl, n- Octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.

As Ci-Ci2-alkyl, R16, R17 and R20 can have the same meaning as that given above for Ri, and can also represent a straight or branched chain nonyl, decyl, undecyl or dodecyl group.

When R16 and R17 are alkyl interrupted by oxygen atoms, the examples in question are the same as those described for Z above.

Examples of R16 and R17 as aralkyl are: benzyl, a-methylbenzyl, 1-phenylethyl, a, a-dimethylbenzyl or 1-phenylpropyl.

When Z represents ethylene, R16 and R17 together can also form ethylene, which is equivalent to bridging by a piperazine group.

When Y represents a group -N (Ri7) -, R15 and R17 together form a group -CO-CH = CH-CO- and thus form the substituent

O

O

on the group -X- (Z) P-.

However, the preferred meaning for R15 is -CO-C (Ri8) = CHRi4, where Ria and Rig are preferably methyl and in particular hydrogen.

R2 is -CH2-CH2-C0-0-C (G) = CH2 and G is hydrogen or methyl.

The procedure for the preparation of the present compounds is described in the prior art. The intermediates required for the preparation of the present compounds are largely commercial items.

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Preferred compounds are those wherein X and Y are -O-; especially those in which both X and Y are -O-.

Generally, polymers that can be stabilized include:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and polymers of cycloolefins, for example cyclopentene or norbornene, polyethylene (which may optionally be crosslinked ), e.g. high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), branched low-density polyethylene (BLDPE).

Polyolefins, i.e. Polymers of monoolefins, which have been given by way of example in the preceding paragraph, preferably polyethylene and polypropylene, can be produced by different, in particular by the following processes:

a) Free radical polymerization (usually under high pressure and at elevated temperature).

b) Catalytic polymerization using a catalyst which normally contains one or more metals from groups IVb, Vb, Vlb or VIII of the Periodic Table of the Elements. These metals usually have one or more ligands, generally oxides, halides, alcohols, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either n- or a-coordinated. These metal complexes can be in free form or fixed to substrates, generally activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon dioxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used as such in the polymerization or additional activators can be used, generally metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups la, IIa and / or purple of the periodic table of the elements. The activators can expediently be modified with additional ester, ether, amine or silyl ether groups. These catalyst systems are commonly called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of polymers listed under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers, for example ethylene / propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene Copolymers, ethylene / but-1-en copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers , Ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, di- cyclopentadiene or ethylidene-norbornene and mixtures of such copolymers with one another and with polymers which were mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vin ylacetate copolymers (EVA), LDPE / ethylene acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, e.g. Polyamides.

4. Hydrocarbon resins (e.g. C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly- (p-methylstyrene), poly- (a-methylstyrene).

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; Mixtures of high impact strength from styrene copolymers and other polymer, for example polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene, for example styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene / propylene / diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers and mixtures thereof with the copolymers listed under 6) , for example the copolymer blends known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homopolymers and copolymers, in particular polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinyl chloride / vinyl chloride / vinyl acetate or vinyl chloride / vinyl acetate copolymers.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates

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CH 693 032 A5

and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact modified with butyl acrylate.

10. Copolymers of monomers listed under 9) with one another or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene -T polymer.

11. Polymers derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine and their copolymers with olefins mentioned under 1) above were.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived on the one hand from polyethers, polyesters or polybutadienes with terminal hydroxyl groups and on the other hand from aliphatic or aromatic polyisocyanates and precursors thereof.

16. 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, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides, starting from m-xylene diamine and adipic acid; Polyamides made from hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally with an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above-mentioned polyamides with polyolefins, olefin copolymers, ionomeric or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides, modified with EPDM or ABS, and polyamides that are condensed during production (RIM polyamide systems).

17. Polyureas, polyimides, polyamide imides, and polybenzimidazoles.

18. Polyesters which are derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethyl-cyclohexane terephthalate and polyhydroxybenzoates as well as block copolyether esters, derived from polyethers having hydroxyl end groups and also polyester, modified with polycarbonate or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and also halogen-containing modifications thereof with low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins, crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof such as cellulose acetates, cellulose propionates and cellulose butyrates or the cellulose ethers such as methyl cellulose; and natural resins and their derivatives.

28. Mixtures of polymers mentioned above (polymer blends), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP , PA / PPO.

29. Naturally occurring and synthetic organic materials that are purely 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 (for example phthalates, adipates) , Phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratio, in general those used as spin agents, and aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, for example natural latex or latices of carboxylated styrene / butadiene copolymers.

31. Polysiloxanes, such as the soft hydrophilic polysiloxanes described, for example, in US Pat

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No. 4,259,467 and the hard polyorganosiloxanes described, for example, in U.S. Patent No. 4,355,147.

32. 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 acrylic copolymers with unsaturated side groups and the acrylated melamines. The polyketimines are made from polyamines and ketones in the presence of an acid catalyst.

33. Radiation-curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxy melamine resins, such as light-stable epoxy resins, crosslinked with an epoxy-functional, cover-ether melamine resin with a high solids content, such as LSE 4103 (Monsanto).

In general, the compounds of the present invention are used in an amount of about 0.01 to about 5% by weight of the stabilized mass, although this will vary with the particular substrate and application. An advantageous range is about 0.05 to about 3%, especially

0.05 to about 1%.

The stabilizers of the present invention can be readily incorporated into organic polymers by conventional techniques at any suitable stage prior to making the molded articles thereof. For example, the stabilizer can be mixed with the polymer in dry powder form or a suspension or emulsion of the stabilizer can be mixed with a solution, suspension or emulsion of the polymer. The stabilized polymer compositions of the invention obtained can optionally also contain about 0.01 to about 5%, preferably about 0.025 to about 2%, in particular about 0.1 to about 1% by weight, of various conventional additives, such as the materials listed below or Mixtures of these.

1. Antioxidants

1.1. Alkalized monophenols.

for example

2,6-di-tert-butyl-4-methyl phenol

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-iso-butyl phenol

2,6-cyclopentyl-4-methyl phenol

2- (a-methylcyclohexyl) -4,6-dimethylphenol

2,6-dioctadecyl-4-methyl phenol

2,4,6-tricyclohexylphenol

2,6-di-tert-butyl-4-methoxymethyl phenol.

1.2. Alkaline hydroquinones.

for example

2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone

2.5-di-tert-amylhydroquinone

2.6-diphenyl-4octadecyloxyphenol.

1.3 Hydroxylated thiodiphene ethers.

for example

2,2'-thiobis (6-tert-butyl-4-methylphenol)

2,2'-thiobis (4-octylphenol)

4,4'-thiobis (6-tert-butyl-3-methylphenol)

4,4'-thiobis (6-tert-butyl-2-methylphenol).

1.4. Alkvlidenbisphenole.

for example

2,2'-methylenebis (6-tert-butyl-4-methylphenol)

2,2'-methylenebis (6-tert-butyl-4-ethylphenol)

2,2'-methylenebis [4-methyl-6- (a-methylcyclohexyl) phenol]

2,2'-methylenebis (4-methyl-6-cyclohexylphenol)

2,2'-methylenebis (6-nonyl-4-methylphenol)

2,2'-methylenebis [6- (cx-methylbenzyl) -4-nonylphenol]

2,2'-methylene bis [6- (a, a-dimethylbenzyl) -4-nonylphenol]

2,2'-methylene bis (4,6-di-tert-butylphenol)

2,2'ethylidenebis (4,6-di-tert-butylphenol)

2,2'-ethylidenebis (6-tertbutyl-4-isobutylphenol)

4,4'-methylene bis (2,6-di-tert-butylphenol)

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4,4'-methylenebis (6-tertbutyl-2-methylphenol)

1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane

2,6-di (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol

1,1,3-T ris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane

1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane

Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate]

Di (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene

Di [2- (3'-tert-butyl-2'-hydroxy-5'-methyIbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.

1.5. Benzvlverbindunaen.

for example

1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene di (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert.butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester bis (4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate 1,3,5-T ris- (3,5-di-tert. butyl-4-hydroxybenzyl) isocyanurate 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid dioctadecyl ester calcium salt of 3,5-di-tert.butyl-4-hydroxybenzylphosphoric acid monoethyl ester

1.6. Acvlaminophenole.

for example

Lauric acid 4-hydroxyanilide stearic acid 4-hydroxyanilide

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 B- (3,5-di-tert.butvl-4-hvdroxvphenvli-propionic acid with mono- or polyhydric alcohols,

e.g. With

Methanol diethylene glycol

Octadecanol triethylene glycol

1.6-Hexanediol pentaerythritol neopentyl glycol tris (hydroxyethyl) isocyanurate thiodiethylene glycol dihydroxyethyl oxalic acid diamide triethanolamine triisopropanolamine.

1.8. Esters of B- (5-tert-butvl-4-hvdroxv-3-methvlphenvnpropionic acid with mono- or polyhydric alcohols, e.g. with methanol diethylene glycol

Octadecanol triethylene glycol

1,6-hexanediol pentaerythritol

Neopentyl glycol tris (hydroxyethyl) isocyanurate

Thiodiethylene glycol Dihydroxyethyloxalsäurediamid Triethanolamine Triisopropanolamin.

1.9. Amides of β-f3.5-di-tert.butvl-4-hvdroxvphenvlipropionic 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-hydroxyphenylpropionyl) hydrazine.

1.10. Diarvlamine.

for example diphenylamine, n-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, 4,4'-di-tert-octyldiphenylamine, reaction product of N-phenylbenzylamine and 2,4,4-trimethylpentene , Reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1.2- (2'-Hvdroxvphenvl'lbenzotriazole. For example, the 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1, 3,3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-, 3'-sec.butyl-5 '-tert.-

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butyl-, 4'-octoxy-, 3 ', 5'-di-tert.amyl-, 3', 5'-bis (a, a-dimethylbenzyl), 3'-tert-butyl-5 '- (2- (cû-hydroxyocta- (ethy-lenoxy) carbonyl) -ethyl) -, 3'-dodecyl-5'-methyl-, 3'-tert-butyl-5 '- (2-octyloxycarbonyl) ethyl- and dodecylated 5'- methyl derivatives.

2.2. 2-Hvdroxybenzophenone. for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-do-decyloxy, 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-butylphenylsalicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert.butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4-hydroxybenzoic acid 4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4. Acrvlate. for example, a-cyano-ß, ß-diphenylacrylate or isooctyl ester, a-carbomethoxy-xycinnamic acid methyl ester, a-cyano-ß-methyl-p-methoxycinnamic acid methyl ester or -butyl ester, a-carbomethoxy-p-methoxycinnamate (methyl ester) carbomethoxy-ß-cyanovinyl) -2-methylindoline.

2.5. Nickelverbindunoen. for example nickel complexes of 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phe-nol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n- Butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert. butylbenzylphosphonic acid monoalkyl esters, e.g. the methyl, ethyl or butyl esters, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, for example bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pen-tamethylpiperidyl) sebacate, bis (1,2,2,6,6 pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylma-lonat, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N '(2,2,6,6-tetramethyl! piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, tris- (2,2,6,6-tetramethylpiperidyl) ) nitrilotriacetate, tetrakis (2,2,6,6-tet-ramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '- (1,2-ethanediyl) bis- (3, 3,5,5-tetramethylpiperazi-non), bis (1-octyl-oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert.butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert.butyloxanilide, 2-ethoxy- 2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and their mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert.butyl-oxanilide and mixtures of ortho- and paramethoxy- as well as of o- and p-ethoxydisubstituted oxanilides.

2.8. Hvdroxvphenvl-s-triazines. for example 2,6-bis (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) s triazine; 2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-triazine; 2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (2,4-dimethylphenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydro-xyethoxy) phenyl] -6- (4-bromophenyl) -s-triain; 2,4-bis [2-hydroxy-4- (2-acetoxyethoxy) phenyl] -6- (4-chlorphe-phenyl) -s-triazine; 2,4-bis (2,4-dihydroxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine.

3. Metal deactivators. for example, N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl ) hydrazine, 3-salicyloylamino-1,2, 4-triazole, bis (benzylidene) oxalic acid dihydrazide.

4. Phosphites and Phosnhonites. for example triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tri (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritoldiphosphite, tris (2,4-di-tert.butylphenyl) phosphite, diisertecitophosphite .-butylphe-nyl) pentaerythritol diphosphite, di (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, di (2,4-di-tert-bu-tylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, T etrakis (2,4-di-tert-butylphenyl) -4,4'-diphenyl-nylylendiphosphonit.

5. Compounds which remove peroxide, for example esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentane dodecylmercapto) propionate.

6. Hvdroxvlamine. for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-di-octadecylhydroxylamine, N- Hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Nitrons. for example N-benzyl-u-phenylnitron, N-ethyl-a-methyinitron, N-octyl-a-heptylnitron, N-Lau-

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ryl-a-undecylnitron, N-tetradecyl-a-tridecylnitron, N-hexadecyl-a-pentadecylnitron, N-octadecyl-a-hepta-decylnitron, N-hexadecyl-a-heptadecylnitron, N-octadecyl-a-pentadecylnitron Heptadecyl-a-heptade-cylnitron, N-octadecyl-a-hexadecylnitron, nitrone, derived from N, N-dialkylhydroxylamine, derived from hydrogenated tallow amine.

8. Polvamide stabilizers. for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

9. Basic costabilizers. 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 ricinrocateolate and antimony pate or zinc pyrocatecholate.

10. Nuclear imaging agent. for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

11. Fillers and reinforcing agents. 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, flame retardants, antistatic agents and blowing agents and thiosynergists, such as dilauryl thiodipropionate or distearyl thiodipropionate.

13. Benzofuranones and indolinones. for example, that disclosed in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert. -butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert .-Butyl-3- (4- [2-hydroxyethoxy) phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3 - (4-Acetoxy-3,5-dimethylpheny!) - 5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyI) -5,7-di tert-butylbenzo-furan-2-one.

The costabilizers, with the exception of the benzofuranones listed under 13, are added, for example, in concentrations of 0.01 to 10%, based on the total weight of the material to be stabilized.

In addition to components (a) and (b), further preferred compositions comprise further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hindered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list) and peroxide-destroying compounds (item 5 of the list).

Further additives (stabilizers), which are also particularly preferred, are benzofuran-2-ones, as described, for example, in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312.

The phenolic antioxidant of particular interest is selected from the group consisting of 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid n-octadecyl ester, tetrakis (3,5-di-tert-butyl-4-hydroxyhydro-cinnamic acid) neopentanetetraylester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid di-n-octadecyl ester, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylene bis (3,5- di-tert-butyl-4-hydroxyhydro-cinnamate), 1,3,5-trimethyl-2,4,6-tris (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-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert -butylphenyl) -butane, 1,3,5-T ris [2- (3,5-di-tert-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-) hydroxybenzylphosphonate), ethylene bis [3,3-di (3-tert-butyl-4-hydroxyphenyl) butyrate], 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid octyl ester, 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 tetrakis (3,5-di-tert-butyl-4-hydroxyhydro-cinnamic acid) neopentanetetrayl ester, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid n-octadecyl ester, 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) butylmalonate, 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-tetramethylpiperidin-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] heneicosan, poly-condensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4 ' -Hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hy-hydroxypi-

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peridine and succinic acid, polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxy-lat, tetrakis (1,2,2,6,6-penta-methylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4- Dichloro-6-morpholino-s-triazine and 4,4'-hexamethylbenbis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N ", N"' - T etrakis [(4,6- bis (butyl-1,2,2,6,6-pentamethylpiperidin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, mixed [2,2, 6,6-tetramethylpiperidin-4-yl / beta, beta, beta ', ß' -tetramethyl-3,9- (2,4,8,10-tetra-oxaspiro [5.5] -undecane) diethyl] 1.2, 3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl / ß, ß, ß ', ß'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) diethyl] -1,2,3,4-butanetetracarboxylate, octa-methylenebis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4'-ethylenebis (2,2,6, 6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n- dodecyl succinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecyl succinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-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-tetramethylpiperidin-4-yl) seba-cat, di- (1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1 -octyloxy-2,2,6,6-tetramethyl- 4-hydoxypiperidine, poly - {[6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene- [4- (1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] and 2,4,6-tris [N- (1-cyc-lohexyloxy-2,2,6,6- tetramethylpiperidin-4-yl) -n-butylamino] -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-tetra-methyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-oc-tylamino-s-triazine and 4,4'-hexamethylene bis (amino-2,2,6,6- tetramethylpiperidine), N, N ', N ", N"' - tetrakis [(4,6-bis (butyl- (1,2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-triazine 2-yl] -1,10-diamino-4,7-diazadecane, di- (1-oc-tyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyloxy-2 , 2,6,6-tetramethylpiperidin-4-yl) suc-cinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 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-tetramethyl-piperidine 4-yl) imino] or 2,4,6-tris [N- (1-cyclo hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine.

The present composition can additionally contain a further UV absorber selected from the group consisting of the s-triazines, the oxanilides, the hydroxybenzophenones, benzoates and the a-cyanoacrylates.

In particular, the present composition can additionally contain an effectively stabilizing amount of at least one further 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or hindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole; 2- [2-hydroxy-3,5-di (a, a-dimethylbenzyl) phenyl] -2H-benzotriazole; 2- [2-hydroxy-3- (a, a-dimethylbenzyl) -5-octylphenyl] -2H-benzotriazole; 2- {2-hydroxy-3-tert-butyl-5- [2- (co-hydroxyocta (ethyleneoxy) carbonyl) ethyl] phenyl} -2H-benzotriazole; and 2- {2-hydroxy-3-tert-butyl-5- [2- (octyloxy) carbonyl) ethyl] phenyl} -2H-benzotriazole.

Preferably the other tris-aryl-s-triazine is selected from the group consisting of 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,4-diphenyl-6- (2-hydroxy-4-hexyloxy-phenyl) -s-triazine; 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-do- / tri-decyloxy-2-hydroxypropoxy) phenyl] -s-triazine; and 2- (2-hydroxyethylamino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -s-triazine.

The alkyd resin lacquers which can be stabilized against the action of light and moisture according to the present invention are customary stoving lacquers which are particularly suitable for coating motor vehicles (car topcoats), for example lacquers based on alkyd / melamine resins and alkyd / acrylic / melamine resins ( see H. Wagner and HF Sarx, "Lackkunstharze" (1977), pages 99-123). Other crosslinking agents are glycouril resins, blocked isocyanates or epoxy resins.

The lacquers stabilized according to the invention are suitable both for metal topcoats and solid shading topcoats, in particular in the case of touch-up lacquers and for various coil coating applications. The lacquers stabilized according to the invention are preferably applied in a customary manner by two processes, either by the one-coat process or the two-coat process. In the latter process, the pigment-containing base coat is applied first and then a top coat of clear lacquer over it.

It must also be noted that the compounds of the invention are applicable for use with non-acid catalyzed thermosetting resins, e.g. in epoxy, epoxy polyesters, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicone, isocyanates or isocyanurates. The epoxy and epoxy polyester resins are crosslinked with conventional crosslinking agents such as acids, acid anhydrides, amines and the like. Thus, the epoxies can be used as crosslinking agents for various acrylic or polyester resin systems that have been modified by the presence of reactive groups on the framework structure.

When used in two-layer topcoats, the compounds according to the invention can be incorporated into the clearcoat or both into the clearcoat and into the pigmented primer.

If water-soluble, water-miscible or water-dispersible coatings are desired,

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ammonium salts are formed from acid groups present in the resin. The powder coating composition can be made by reacting glycidyl methacrylate with selected alcohol components.

The present benzotriazoles are produced by conventional methods for making such compounds. The usual procedure involves diazotizing a substituted o-nitraniline, followed by coupling the resulting diazonium salt with a substituted phenol and reducing the azo-benzene intermediate to the corresponding desired benzotriazole. Most of the starting materials for these benzotriazoles are commercially available or can be prepared by normal methods of organic synthesis.

Although the present benzotriazoles with their increased durability are particularly suitable for automotive coating applications, it is conceivable that they are also particularly useful in other applications in which their increased durability is required, such as sun films and the like.

The examples below are for illustrative purposes only.

example 1

Preparation of 5-trifluoromethvl-2- (2-hvdroxv-3-o.-cumvl-5-tert-octvlphenvB-2H-benzotriazole a) Diazotization of 4-amino-3-nitro-benzotrifluoride

41.2 g of 4-amino-3-nitrobenzotrifluoride, 52 ml of concentrated hydrochloric acid and 100 ml of distilled water are added to a 500 ml three-necked flask equipped with a mechanical stirrer. The stirred solution is cooled to 5 ° C. and 17.3 g sodium nitrite, dissolved in 50 ml water, are added. The solution is stirred at 0 to 5 ° C for two hours, then filtered and stored at -10 ° C.

b) Monoazo adduct

40 g of sodium hydroxide, dissolved in 200 ml of methanol, and 32.4 g of 2-a-cumyl-4-tert-octylphenol in 50 ml of xylene are added to a 1000 ml flask equipped with a mechanical stirrer. The solution is cooled to 5 ° C and the diazo solution of 4-amino-nitro-benzotrifluoride, prepared in part a, is added at 0 to 5 ° C over a period of two hours. Then 100 ml of xylene are added and the organic layer is washed with water, aqueous hydrochloric acid, water, aqueous sodium bicarbonate solution and finally water. The solvent is removed under reduced pressure and the residue is purified by chromatography (silica gel, heptane: ethyl acetate 95: 5) to give 42.1 g of the adduct product as a dark red paste.

c) Reduction of the monoazo adduct

A 1000 ml flask is charged with 20 g sodium hydroxide, 40 ml water, 42.1 g monoazo adduct, prepared in part b, and 400 ml ethanol. The mixture is heated to 80 ° C. and 27 g of formamidine sulfinic acid are added in portions with stirring. After 1.5 hours the solution is cooled to room temperature and 100 ml of water are added. The pH is adjusted to pH 7 with concentrated hydrochloric acid. The ethanol is removed under vacuum and the water layer extracted with methylene chloride. The solvent is then evaporated in vacuo and the residue is purified by chromatography (silica gel, heptane: toluene 9: 1) and crystallized from ethanol. The title compound is obtained in a yield of 5.6 g as a pale yellow solid which melts at 119-121 ° C.

Example 2

Preparation of 5-fluoro-2- (2-hvdroxv-3-a-cumvl-5-tert-octvlphenvn-2H-benzotriazole

The title compound is prepared according to the general procedure of Example 1 using 31.2 g of 4-fluoro-2-nitraniline. In part c of the process, a further 9 g of formamidine sulfinic acid are required to complete the reduction. Purification of the crude product on silica gel (hep-tan: toluene 1: 1) gives 4.5 g of the title compound as an off-white solid. Further purification by recrystallization from acetonitrile / toluene provides 1.1 g of the title compound, which melts at 93-96 ° C.

Example 3

Preparation of 5-chloro-2-f2-hydroxy-3-g-cumyl-5-tert-octylphenvh-2H-benzotriazole

According to the general procedure of Example 1, parts a and b, the monoazo intermediate of the title compound is prepared from 339.3 g of 4-chloro-2-nitraniline. The crude product is purified by recrystallization from methanol to obtain 70.9 g of deep red monoazo adduct.

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c) Reduction of the monoazo adduct

A mixture of 11.8 g sodium hydroxide and 138 g 2-butanol is heated to 95 ° C. A solution of 60.1 g of the above monoazo adduct and 1.3 g of 2,3-dichloro-1,4-naphthoquinone in 90 g of 2-butanol is added with stirring over a period of 90 minutes. The reaction mixture is heated to remove the 2-butanone by-product, with additional 2-butanol being added to replace the distillate. The reaction mixture is cooled to 85 ° C., washed with 2.5N sulfuric acid and brine and then concentrated. The residue is recrystallized from methanol xylene to give 45.6 g of the title compound as a light yellow solid which melts at 104-105 ° C.

Example 4

Preparation of 5-Phenvlthio-2- (2-hvdroxv-3-a-cumvl-5-tert-octvlphenvn-2H-benzotriazole

To a stirred mixture of 75 g of 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotri-azole and 105 g of N-methylpyrrolidone, heated to 90 ° C. initially 44.3 g of 45% aqueous potassium hydroxide solution over a period of 15 minutes, then 20.4 g of thiophenol added over a further 15 minutes. The reaction mixture is then heated to 170-175 ° C for four hours, the water being removed by distillation. After cooling to 100 ° C., xylene and water are added and the mixture obtained is acidified with 15% aqueous hydrochloric acid solution. The organic layer is separated, washed with water and then concentrated. The crude product residue is recrystallized from methanol to give 82 g of the title product as a pale yellow solid which melts at 124-125 ° C.

Example 5

Preparation of 5-benzenesulfonvl-2- (2-hvdroxv-3-a-cumyl-5-tert-octvlphenvn-2H-benzotriazole

A 1000 ml flask is made with 75.2 g of 5-phenylthio-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-ben-zotriazole, prepared in Example 4, 102 g of xylene , 0.9 g of sodium tungstate dihydrate and 18.4 g of formic acid. The mixture is heated to 50 ° C. 36.3 g of 50% hydrogen peroxide are slowly added to the stirred mixture so that the temperature does not exceed 85 ° C. Additional xylene and water are then added. The organic layer is separated off, washed with aqueous sodium sulfite, then twice with water and concentrated. The crude product residue is recrystallized from methanol to give 75.2 g of the title compound as a pale yellow solid which melts at 170-171 ° C.

Example 6

Preparation of 5-Nonvlthio-2-f2-hvdroxv-3-a-cumvl-5-tert-octvlphenvl) -2H-benzotriazole

Using the procedure of Example 4, the title compound is prepared with 30 g 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 17.6 g nonyl mercaptan.

Example 7

Preparation of 5-Nonvlsulfonvl-2- (2-hvdroxv-3-a-cumvl-5-tert-octvlDhenvn-2H-benzotriazole

5-Nonylthio-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole, prepared in Example 6, is added to the sulfone without purifying the thio intermediate using 8.7 g of formic acid, 0.7 g of sodium tungstate dihydrate and 17.6 g of 50% hydrogen peroxide oxidized to give the title compound as a yellow resin which showed a molecular ion of m / e 631.

Example 8

Preparation of 5-chloro-2-f2-hvdroxv-3-phenvl-5-tert-octvlphenvD-2H-benzotriazole

The general procedure of Example 1, Parts a and b, is used to prepare the monoazo intermediate of the title compound from 4-chloro-2-nitraniline and 2-phenyl-4-tert-octylphenol. The crude product is purified by recrystallization from methanol to give a deep red monoazo adduct.

The title compound is prepared according to the reduction procedure of Example 3 from 65 g of the monoazo adduct prepared above, 19.9 g of sodium hydroxide and 2.4 g of 2,3-dichloro-1,4-naphthoquinone. The crude product is purified by chromatography on silica gel (hexane: ethyl acetate 5: 1)

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nigt to obtain a fraction which is predominantly the title compound, which shows a molecular ion of m / e 433.

Example 9

Preparation of 5-phenvthio-2-f2-hvdroxv-3-phenvl-5-tert-octvlphenvD-2H-benzotriazole

The title compound is prepared according to the procedure of Example 4 from 20 g of the compound of Example 8, 20.4 g of 45% aqueous potassium hydroxide, 10.3 g of thiophenol and 100 g of N-methylpyrrolidone. The title compound is an oil purified by chromatography on silica gel using toluene as the eluent.

Example 10

Preparation of 5-benzenesulfonvl-2- (2-hvdroxv-3-phenvl-5-tert-octvlphenvlV2H-benzotriazole

The title compound is prepared according to the procedure of Example 5 from 20 g of the thio compound of Example 9, 6.4 g of formic acid, 15.0 g of 50% hydrogen peroxide and 0.6 g of sodium tungstate dihydrate. Recrystallization of 2.5 g of raw material from xylene / methanol gives 2.0 g of the purified title compound as a light yellow powder, which melts at 204-206 ° C.

Example 11

Preparation of a mixture of 5-chloro-2- (2-hvdroxv-3.5-di-alkvlphenyB-2H-benzotriazole (Alkvl is independently Ca. Cr. Ci? And Cift)

A mixture of 65.4 g of 5-chloro-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole, 45 ml of dodecene and 13 ml of methanesulfonic acid is heated to 170 ° C. under nitrogen. Another 135 ml of dodecene is added over a period of 4.5 hours. The reaction mixture is allowed to cool to 100 ° C. and then quenched with 400 g of crushed ice and extracted three times with ethyl acetate. The organic layers are combined, washed with water, aqueous sodium bicarbonate solution, again water and brine, dried over anhydrous magnesium sulfate and finally concentrated. The polymeric residue is removed by bulb-to-bulb distillation under vacuum at 0.2 mm and up to 210 ° C. The unreacted starting material is then removed by distillation (at 0.01 mm, 160 ° C.), 45 g of the title mixture being obtained as a yellow oil.

Example 12

Preparation of a mixture of 5-phenvlthio-2- (2-hvdroxv-3.5-dialkvlphenvB-2H-benzotriazole (Alkvl is independently C4. Cr. Ci? And Ciqi

The title mixture is prepared according to the procedure of Example 4 using 40 g of the mixture of Example 11, 11.2 g of potassium hydroxide and 12.3 ml of thiophenol.

Example 13

Preparation of a mixture of 5-benzenesulfonvl-2- (2-hvdroxv-3.5-dialkvlphenvh-2H-benzotriazole (Alkvl is independently approx. Cr. Ci? And Cm)

A mixture of the crude product of Example 12, 350 ml of isopropanol, 14.7 ml of formic acid and 1.8 ml of concentrated sulfuric acid are heated under reflux and 30 ml of 50% hydrogen peroxide are added dropwise over a period of two hours. After a further three hours under reflux, the reaction mixture is cooled and 10% aqueous sodium sulfite and aqueous sodium bicarbonate solution are added. The isopropanol is evaporated and the residue extracted with methylene chloride. The organic layer is washed with water and then dried over anhydrous magnesium sulfate. The solution is concentrated as a viscous orange oil, leaving 45 g of crude product. About 30 g of the crude product are purified by chromatography on silica gel (heptane: ethyl acetate 4: 1) to obtain 28.9 g of the title mixture as a yellow oil.

Example 14

5-Diphenvlphosphinvl-2- (2-hvdroxv-3.5-tert-butvlphenvl) -2H-benzotriazole

To a flame-dried 500 ml three-necked round bottom flask equipped with a cooler, mag-

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stirrer and thermometer, 100 ml of dimethyl sulfoxide, 7.41 g (0.066 mol) of potassium tert-butoxide and 11.17 g (0.060 mol) of diphenylphosphine are added via a syringe. A slurry of 10.56 g (0.030 mol) of 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole in 50 ml of dimethyl sulfoxide is added all at once to the red mixture. The brown solution obtained is stirred at 135 ° C. for 3.5 hours and then cooled to room temperature.

The mixture is quenched with a portion of saturated ammonium chloride solution and then ethyl acetate is added. The organic layer is separated and washed three times with water, once with brine and then dried over anhydrous magnesium sulfate. 50% hydrogen peroxide is added to the solution under exothermic conditions. The mixture is allowed to settle for 30 minutes, then washed once with 10% sodium metabisulfite solution, three times with saturated sodium bicarbonate solution, once with brine and finally dried over anhydrous magnesium sulfate. The mixture is filtered through a pad of silica gel and the solvent removed under reduced pressure to give 8.0 g of a dirty yellow solid. The crude product is treated by medium pressure chromatography using 1: 1 heptane: ethyl acetate to provide 4.2 g (27% yield) of the title compound as a yellow solid which melts at 98-100 ° C.

Example 15

5-Diphenvlphosphinvl-2- (2-hvdroxv-3-re-cumvl-5-tert-octylphenvn-2H-benzotriazole

The title compound is prepared according to the procedure of Example 14 when 5-chloro-2- (2-hydro-xy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole is used as the starting benzotriazole intermediate.

Examples 16-26

The following further 2H-benzotri-azoles of the formula I 'are prepared according to the general procedure of Example 1.

example

Gì

egg

E2

16

CFs

Phenyl tert-octyl

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CFs a-cumyl tert-butyl

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CN

a-cumyl tert-octyl

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CN

a-cumyl

nonyl

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CN

a-cumyl tert-butyl

21

COOCHs a-cumyl

dodecyl

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F

Phenyl tert-octyl

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cf3

a-cumyl

nonyl

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CFs a-cumyl

dodecyl

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CON (Bu) 2

a-cumyl tert-octyl

26

COOCHs

Phenyl tert-octyl

Example 27

Preparation of 5-octvthio-2- (2-hvdroxv-3 - «- cumvl-5-tert-octvlphenvl) -2H-benzotriazole

Using the procedure of Example 6, the title compound is prepared with 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl) -2H-benzotriazole and octyl mercaptan.

Example 28

Production of 5-octvlsulfonvl-2- (2-hvdroxv-3-a-cumvl-5-tert-octvlphenvn-2H-benzotriazole

5-Octylthio-2- (2-hydroxy-3 - «- cumyl-5-tert-octyiphenyl) -2H-benzotriazole, prepared in Example 27, is oxidized to the sulfone without purification of the thio intermediate using the general procedure of Example 7 ,

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Example 29

Preparation of 5-chloro-2- (2.4-dihvdroxvphenvlì-2H-benzotriazole

Following the general procedure of Example 1, Parts a and b, the monoazo intermediate of the title compound is prepared from 17.3 g of 4-chloro-2-nitraniline to give 34.7 g of a deep red, moist cake of the monoazo adduct.

Reduction of the monoazo adduct

A mixture of 20 g of sodium hydroxide, 500 ml of water and 26.3 g of the previously prepared moist cake of the monoazo adduct is heated to 30 ° C. Zinc powder (33.0 g) is added in portions over two hours. At the end of this addition, 180 g of 40% aqueous sodium hydroxide solution are added dropwise over an hour. The mixture is stirred at ambient temperature for 96 hours. The zinc residue is removed by filtration. The aqueous solution is neutralized to pH 5-6 and the slurry obtained is filtered. The filter cake obtained is washed well with water and dried to 22.5 g of crude product. The crude product is purified by Soxhlet extraction with acetone to give 9.6 g of the title compound.

Example 30

Preparation of 5-chloro-2-f2-hvdroxy-4-octvloxvphenyh-2H-benzotriazole

A mixture of 6.5 g of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 7.1 g of 1-bromooctane, 5.2 g of aqueous potassium carbonate and 100 ml of acetone is heated under reflux for 24 hours. About 100 ml of water and ethyl acetate are added to the resulting mixture and 10.6 g of crude product are isolated. Column chromatography using petroleum ether gives 0.9 g of the title compound, the structure of which is confirmed by H-NMR and mass spectrometry.

Example 31

Preparation of 5-trifluoromethvl-2- (2,4-dihvdroxvphenvh-2H-benzotriazole

According to the general procedure of Example 29, the title compound is prepared from 10.3 g of 4-amino-3-nitrobenzotrifluoride to obtain 6.4 g of the title compound, the structure of which is confirmed by H-NMR.

Example 32

Preparation of 5-trifluoromethvl-2- (2-hvdroxv-4-octvloxvphenvn-2H-benzotriazole

The title compound is prepared according to the general procedure of Example 30 from 5.6 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole. The crude product is purified by column chromatography to give 1.1 g of the title compound as a white solid which melts at 79-81 ° C. The structure is confirmed by H-NMR and mass spectrometry.

Example 33

Production of 5-trifluoromethvl-2-f2-hvdroxv-4-f3-butoxv-2-hvdroxvpropoxviphenvl1-2H-benzotriazole

A mixture of 2.3 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, prepared in Example 31, 1.3 ml of butylglycidyl ether and 100 mg of ethyl triphenylphosphonium bromide in 50 ml of xylene is refluxed under nitrogen for 14 hours heated. Water (25 ml) and 25 ml of ethyl acetate are added and 3 g of the crude product are isolated. Recrystallization from heptane gives 2.1 g of the title compound, the structure of which is confirmed by NMR.

Example 34

Preparation of 5-trifluoromethvl-2- (2-hvdroxv-4-aminophenvlV2H-benzotriazole

The title compound is prepared according to the general procedures of Example 1 and Example 29, starting from 4-amino-3-nitrobenzotrifluoride and 3-aminophenol. The structure of the product is confirmed by NMR.

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Example 35

Preparation of 5-trifluoromethvl-2- | 2-hvdroxv-4-f2-ethvlhexanolvamino) phenvll-2H-benzotriazole

A mixture of 2-ethylhexanoyl chloride in 125 ml of toluene is added dropwise to a mixture of 4 g of 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2H-benzotriazole and 1.4 g of triethylamine in 75 ml of toluene. The resulting mixture is washed with 100 ml of water and the crude product formed is purified by column chromatography to give 1.9 g of the title compound, which melts at 179-181 ° C. The structure is confirmed by NMR.

Example 36

Preparation of 5-carbomethoxv-2- (2-hvdroxv-3- (t-cumvl-5-tert-octylphenvl1-2H-benzotriazole a) Esterification of 4-amino-3-nitrobenzoic acid

700 ml of methanol, 20 g of xylene, 14 g of concentrated sulfuric acid and 100 g of 4-amino-3-nitrobenzoic acid are added to a 2 l three-necked flask equipped with a mechanical stirrer. The solution is refluxed for 33 hours. The mixture is cooled to 35 ° C. and neutralized to pH 7.8. Water (1 l) is added, the solid collected and washed with 500 ml to give 100.9 g of 4-amino-3-nitrobenzoic acid methyl ester after drying overnight.

b) Diazotization of methyl 4-amino-3-nitrobenzoate

To a 1 liter three-necked flask equipped with a mechanical stirrer are added 177 g of 96% sulfuric acid and then slowly 11 g of sodium nitrite within 90 minutes. The mixture is heated to 30 ° C to start the reaction, the temperature is kept below 70 ° C. The mixture is then cooled to 15 ° C. and 30 g of methyl 4-amino-3-nitrobenzoate are added over the course of two hours while maintaining the temperature between 15 and 20 ° C. The mixture is cooled to 0 ° C and 200 g of ice are added to make the solution suitable for the coupling reaction to form a monoazo compound.

c) Monoazo adduct

52 g of 2-a-cumyl-4-tert-octylphenol, 20 g of water, 315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide are added to a 2 -) - three-necked flask equipped with a mechanical stirrer and an addition funnel. The mixture is cooled to -5 ° C and the diazonium salt solution prepared in step b is added over a period of two hours with cooling to keep the temperature below 3 ° C. After the diazonium salt solution is added, the pH is adjusted to 6.5-7.0. The mixture is poured into 500 ml of xylene and washed three times with 500 ml of water at 60 ° C. The xylene is removed by distillation to give 186 g of the monoazo adduct containing residual xylene.

d) Reduction of the monoazo adduct

To a 500 ml flask equipped with a mechanical stirrer, 186 g of monoadduct, prepared in step c, 125 g of 2-butanol and 1.7 g of 2,3-dichloro-1,4-naphthoquinone are added. The mixture is heated to 90 ° C. and the solution obtained is then added to the addition funnel on a separate flask. 175 g of 2-butanol and 18.6 g of sodium hydroxide are added to the second flask. The flask is heated to 95 ° C and the monoazo solution is added within two hours while distilling off methyl ethyl ketone and 2-butanol. 2-Butanol (100 g) is added and an azeotrope is distilled off. The mixture is then cooled and 300 g of xylene and 200 ml of water are added. The pH is adjusted to 7-7.5 with 20% sulfuric acid. The aqueous phase is separated off at 60 ° C. and the organic phase is washed twice with 200 ml of water. The xylene is removed by distillation and the residue formed crystallizes from methanol to give 8.8 g of the title compound, which melts at 141-143 ° C.

Example 37

Preparation of 5-fN.N-di-n-butvlcarbamovl-2- (2-hvdroxv-3 - «- cumvl-5-tert-octvDphenvl1-2H-benzotriazole a) Saponification of 5-carbomethoxy-2- (2-hydroxy -3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole.

1.8 g of potassium hydroxide and 40 ml of methanol are added to a 250 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser and nitrogen inlet. The mixture will

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CH 693 032 A5

heated to 40 ° C to dissolve the potassium hydroxide. 2.7 g of 5-carbomethoxy-2- (2-hydroxy-3-β-cumyl-5-tert-octylphenyl) -2H-benzotriazole, prepared in Example 36, in 40 ml of methanol are added to the solution. The reaction mixture is heated under reflux for six hours. The mixture is then cooled and acidified with hydrochloric acid. Ether and ethyl acetate are added and the organic layer is separated and dried over anhydrous sodium sulfate. After vacuum stripping of the solvent, 2.5 g of 5-carboxy-2- (2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl) -2H-benzotriazole are isolated.

b) 5-chlorocarbonyl-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole

The 2.5 g of 5-carboxy-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole, prepared in step a, are placed in a 250 ml flask equipped with a Stirrer, thermometer, reflux condenser, Dean-Stark trap and nitrogen inlet. Toluene (100 ml) is added and the mixture is heated under reflux to remove traces of water. The mixture is then cooled and 0.76 g of oxalyl chloride in 15 ml of toluene are added. The reaction mixture is then slowly warmed to 60 ° C and held at 60-65 ° C for eight hours until the hydrogen chloride gas is expelled to give the acid chloride title compound.

c) 5- [N, N-Di-n-butylcarbamoyl-2- (2-hydroxy-3-cc-cumyl-5-tert-octyl) phenyl] -2H-benzotriazole

0.8 g of di-n-butylamine, 6 ml of pyridine and 25 ml of toluene are added to a 500 ml flask equipped with a mechanical stirrer, drying tube, thermometer and dropping funnel. The mixture is cooled to 0 ° C and the acid chloride solution prepared in step b is added to the dropping funnel and added to the reaction mixture over a period of 30 minutes at -5 ° C to -10 ° C. The reaction mixture is stirred at the temperature for 1.5 hours and then kept at ambient temperature overnight. The mixture is filtered and then vacuum stripped to give 3.0 g of crude solids. The crude product is chromatographed to provide 1.2 g of the title compound as a brown solid which melts at 131-133 ° C. The structure is confirmed by NMR and mass spectrometry, m / z 596.

Example 38

5-Trifluormethvl-2- (2-hvdroxv-5-tert-octvlDhenvli-2H-benzotriazole

The title compound is prepared according to the general procedure of Example 1, the diazo compound of 4-amino-3-nitrobenzotrifluoride and 4-tert-octylphenol, and purified by silica gel chromatography. Recrystallization of the product from either heptane or methanol gives the title compound as an almost white solid that melts at 80-81 ° C.

Application example 39

In order to evaluate the effect of thermal durability and the loss rate from a high-solids thermosetting acrylic coating of various 2H-benzotriazole UV absorbers substituted with a variety of electron-withdrawing and electron-donating groups, the following tests were carried out.

A clear varnish based on thermosetting acrylic resin with a high solids content is produced by mixing an experimental acrylic polyol resin and hexamethoxymethylmelamine (Resimene® 747, Monsanto) at a solids ratio of 60/40. The dodecylbenzenesulfonic acid catalyst (Nacure® 5225; King Industries) is added at 0.70 percent by weight. A flow aid Moda-flow® (Monsanto) is added at 0.25 percent by weight to produce an acrylic melamine resin model system.

The model clear coat is mixed with xylene to a viscosity of 26-27 seconds using a type 2 spout (tooth cup # 2) and with a conventional air spray device at 50 psi (3.5 kg / cm2) over a quartz disc with the Dimensions of 1 "x 3" (2.54 cm x 7.62 cm) plotted. Hardening is achieved by baking the disc for 30 minutes at 260 ° F (127 ° C). The clearcoat is stabilized with 1 percent by weight of a hindered amine light stabilizer, bis (1-octyl-oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123, Ciba-Geigy). The various test benzotriazole UV absorbers are incorporated into the clearcoat with 5 mmol weight percent. The film thickness of the quartz disks is in the range of 1.15 to 1.41 ml (0.029 to 0.036 mm).

The films on the quartz disks are weathered according to the conditions below in a xenon arc weather meter with controlled radiation of 6500 W using a filter of the type (quartz inside and borosilicate glass outside). The irradiation cycle is as follows: 40 minutes of direct irradiation without water spraying, followed by 20 minutes of light plus spraying from the front, followed by 60 minutes of light irradiation and finally 60 minutes of dark plus spraying from the rear (condensation). Curing takes place at 0.55 W / m2 at 340 nm, 1.98 kJ / hour. In which

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CH 693 032 A5

Light cycle, the black panel temperature is regulated at 70 ± 2 ° C. The relative humidity in the light cycle is in the range of 50-55% and 100% in the dark cycle. The absorbance of the long-wave UV band as a function of the xenon arc exposure time in hours is recorded in the table below.

In order to track the loss of UV absorber from the clearcoats, UV spectra are measured initially and then after weathering at regular time intervals. The UV spectrophotometer linearly measures the absorbance up to 5.5 absorbance units using the reference beam attenuation method.

The degradation products from the UV absorber are believed not to contribute to the UV spectrum. This is checked by monitoring the extinction ratio of the band at about 300 nm and the band at about 340 nm. The ratio does not change after weathering the sample. This shows that the UV spectrum of the weathered films corresponds to the amount of UV absorber that remained in the film, contributing very little, if any, to the spectrum from photodegradation products.

The data in the table below are based on structural formula A after 1211 hours of exposure to the clear lacquers which contain the test benzotriazole UV absorbers.

connection

Extinktionseinheitenverlust

G2

ri r2

A

1.7982

hydrogen

-PO (OEt) 2

tert-octyl

B

1.6300

hydrogen

Nitro tert-octyl

C

1.4863

Phenyl-S-

tert-butyl

CH2-CH2COOC8H17

D

1.4002

hydrogen

hydrogen

CH2-CH2COOCH3

e

1.1872

Methoxy tert-butyl

methyl

F

.5259

Hydrogen tert-butyl

CH2-CH2COOCH3

G

.4527

hydrogen

Hydrogen a-cumyl

H

.4420

Hydrogen tert-butyl

CH2-CH2COOC8H17

I

.4299

Hydrogen tert-octyl a-cumyl

J

.4134

hydrogen

Hydrogen tert-octyl k

.3777

Hydrogen tert-octyl tert-octyl l

.3712

Hydrogen tert-butyl

-CH2CH2CH2OH

M

.3433

Hydrogen a-cumyl

CH2-CH2COOCH3

N

.3098

Cyano tert-butyl tert-butyl

O

.2689

Phenyl-S02-

tert-butyl

CH2-CH2COOC8H17

P

.2576

Hydrogen a-cumyl a-cumyl q

.2492

Hydrogen a-cumyl tert-octyl

Reviewing these data leads to a fairly clear conclusion about the photostability of 2H-benzotriazole UV absorbers and the nature of the substitution that affects photostability.

Increased photostability occurs when Ri is a-cumyl or phenyl and when G2 is an electron-withdrawing group such as phenylsulfonyl or cyano.

The nature of group R2 has less influence on the photostability of the benzotriazole UV absorbers.

From these observations, an idealized benzotriazole UV absorber could be theoretically designed, in which G2 is an electron-withdrawing group, Ri is an effective bulky group and R2 is a thermally stable group. Such an idealized compound could be a benzotriazole, where G2 is phenylsulfonyl, Ri is a-cumyl and R2 is tert-octyl. This benzotriazole is generiseli claimed in US-A-5 280 124. The data in Example 40 below confirm this prediction and this “idealized” connection actually shows a very low loss rate, well below the present state of the art.

Example 40

According to the general procedure of Example 39, a large number of additional benzotri-azole test compounds are concentrated in a thermosetting acrylic melamine resin with a high solids content.

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CH 693 032 A5

tions between 1.93 and 3 percent by weight at the same molar concentrations of testbenzotriazole at the same film thickness and sufficient to provide an initial absorbance of about 2.0 extinction units.

The test panes are exposed in a xenon arc weather meter at X180 cycle (0.45 watt / m2). The initial UV absorbance is measured, followed by measurement at about 250 hour intervals for the first 2000 hours and 500 hours after each. Each clear coat also contains 1% by weight of a hindered amine light stabilizer, namely bis (1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-y!) Sebacate.

The data in the table below are based on compounds of formula A after 1253 hours of exposure to the clearcoats containing the test benzotriazole UV absorbers.

connection

Extinktionseinheitenverlust

G2

Ri r2

R

0.2424

hydrogen

Phenyl a-cumyl

Q

.2351

Hydrogen a-cumyl tert-octyl

S

.1271

cf3

a-cumyl tert-octyl

T

.1827

Phenyl-SC> 2

tert-butyl tert-butyl

The data in the table below are based on compounds of Formula A after 1489 hours of exposure to the clearcoats containing the test benzotriazole UV absorbers.

connection

Extinktionseinheitenverlust

G2

Ri r2

R

.3724

hydrogen

Phenyl a-cumyl

Q

0.287

Hydrogen a-cumyl tert-octyl

S

.1547

cf3

a-cumyl tert-octyl

T

.2654

Phenyl-SC> 2

tert-butyl tert-butyl

The data in the table below are based on compounds of Formula A after 2521 hours of exposure to the clearcoats containing the test benzotriazole UV absorbers.

connection

Extinktionseinheitenverlust

G2

Ri r2

R

.4824

hydrogen

Phenyl a-cumyl

Q

.4054

Hydrogen a-cumyl tert-octyl

S

.2192

CFs a-cumyl tert-octyl

T

.3570

Phenyl-SC> 2

tert-butyl tert-butyl

It is clear from the three tables above that compounds S and in particular T which have an electron-withdrawing group in the 5-position of the benzo ring are significantly more durable than benzotriazoles which do not have such a group on the benzo ring.

The data in the table below are based on compounds of Formula A after 1264 hours of exposure to the clearcoats containing the test benzotriazole UV absorbers.

connection

Extinktionseinheitenverlust

G2

ri r2

Q

.2293

Hydrogen a-cumyl tert-octyl

S

.0921

CFs a-cumyl tert-octyl

T

0.1965

Phenyl-S02

tert-butyl tert-butyl

U

.0944

Phenyl-S02

a-cumyl tert-octyl

V

.1719

Chlorine a-cumyl tert-octyl w

.1655

Fluor a-cumyl tert-octyl

X

0.1796

hydrogen

Phenyl tert-octyl

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The data in the table below are based on compounds of Formula A after 1518 hours of exposure to the clearcoats containing the test benzotriazole UV absorbers.

Connection extinction- G2 Ri R2

unit loss

Q

.2662

Hydrogen a-cumyl tert-octyl

S

.1116

cf3

a-cumyl tert-octyl

T

.2423

Phenyl-SC> 2

tert-butyl tert-butyl

U

0.1114

Phenyl-SC> 2

a-cumyl tert-octyl

V

0.1955

Chlorine a-cumyl tert-octyl w

.1668

Fluor a-cumyl tert-octyl

X

.2220

hydrogen

Phenyl tert-octyl

The data in these tables clearly show that benzotriazoles substituted by an electron-withdrawing group on the benzo ring, especially a group such as trifluoromethyl or phenylsulfonyl, are particularly durable as measured by low loss rate extinction values after exposure to actinic radiation. Connections S, U, V and W are particularly durable and fit into the profile proposed above. The requirement that compound U would be particularly durable can actually be gathered from the above data. Examination of the data for compounds T and U shows the additional beneficial effect of having an effective bulky group, such as a-cumyl, in the R i position compared to an ordinary alkyl group such as tert-butyl at that point.

Claims (4)

claims 1. A coating composition stabilized with a benzotriazole, the benzotriazole having increased durability and a low loss rate when incorporated into the coating, the composition comprising (a) a resin selected from the group consisting of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin crosslinked with Me-laminate having carbamate side groups or an acrylic polyol resin crosslinked with carbamate group-containing melamine, and (b) 0.01 to 5 weight percent, based on the resin solids, of a benzotriazole of formula A, B, C or D. (A) r2 24 5 10 15 20 25 30 35 40 45 50 55 60 65 CH 693 032 A5 wherein Gì, G2 or T represents an electron-withdrawing radical, Gì represents hydrogen or halogen, G2 halogen, nitro, cyano, R3SO-, R3SO2-, -COOG3, CF3-, -P (0) (C6H5) 2, -CO-G3, -CO-NH-G3, -CO-N (G3) 2, -N (G3) -CO-G3, co- / -n \ co-3 or / CO -n \ co-1 represents, G3 is hydrogen, straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group substituted on the phenyl ring with 1 to 4 alkyl with 1 to 4 carbon atoms, Ri is hydrogen, straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycioalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group substituted on the phenyl ring with 1 to 4 alkyl with 1 to 4 carbon atoms, R2 straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycioalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on the phenyl ring with 1 to 3 alkyl having 1 to 4 carbon atoms; or R2 hydroxyl or -OR4, wherein R4 represents straight or branched chain alkyl having 1 to 24 carbon atoms; or this alkyl group substituted with one or more groups -OH, -OCO-R11, -NCO or -NH2 or mixtures thereof; or this alkyl or alkenyl group, interrupted by one or more groups -O-, -NH- or -NR4- or mixtures thereof, and which may be unsubstituted or substituted by one or more groups -OH or -Nhfc or mixtures thereof ; or R2 represents -SR3, -NHR3 or -N (R3) 2; wherein R3 is alkyl with 1 to 20 carbon atoms, hydroxyalkyl with 2 to 20 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycioalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, aryl with 6 to 10 carbon atoms or this aryl group, substituted with one or two alkyl having 1 to 4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, in which the perfluoroalkyl radical has 6 to 16 carbon atoms, or R2 - (CH2) m-CO-X- (Z) p-Y-Ri5 represents, wherein X represents -O- or -N (Ri6) -, 25 5 10 15 20 25 30 35 40 45 50 55 60 65 CH 693 032 A5 Y represents -O- or -N (Ri7) -, Z represents C2-Ci2-alkylene, C4-Ci2-alkylene, interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C3-C12-alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group . R16 and R17 independently represent hydrogen, Ci-Ci2-alkyl, C3-Ci2-alkyl, interrupted by 1 to 3 oxygen atoms, or represent cyclohexyl or C7-cis-aralkyl and R16 together with R17 in the case when Z represents ethylene, likewise Forms ethylene m is zero, 1 or 2, p is 1 or p is also zero if X and Y represent -N (Ri6) - and -N (Ri7) -, R15 represents a group -CO-C (Ri8) = C (H) Ri9 or, if Y represents -N (Ri7) - together with R17 represents a group -CO-CH = CH-CO-, in which Ris is hydrogen or methyl represents and R19 represents hydrogen, methyl or -CO-X-R20, wherein R20 represents hydrogen, Ci-Ci2-alkyl or a group of the formula (Chj-co-x (z) m represents wherein the symbols Gì, G2, Ri, X, Z, m and p have the meanings defined above n is 1 or 2, when n is 1, R5 is Cl, ORe or NR7R8 or R5 is -PO (ORi2) 2, -OSi (Rii) 3 or -OCO-R11, or straight-chain or branched-chain Ci-C24-alkyl which is interrupted by -O-, -S- or -NR11 and which may be unsubstituted or substituted by -OH or -OCO-R11, Cs-Ci2-cycloalkyl which is unsubstituted or is substituted with -OH, represents straight-chain or branched-chain C2-cis-alkenyl which is unsubstituted or substituted with -OH, C7-Ci5-aralkyl, -CH2-CHOH-R13 or glycidyl, R6 represents hydrogen, straight-chain or branched-chain Ci-C24-alkyl which is unsubstituted or substituted by one or more groups OH, OR4 or NH2 or -OR6 - (OCH2CH2) wOH or - (OCH2CH2) wOR2i, where w is 1 to 12 is and R2i is alkyl of 1 to 12 carbon atoms, R7 and Rs are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3-Ci8-alkyl which is interrupted by -O-, -S- or -NR11- Represent C5-Ci2-cycloalkyl, C6-Ci4-aryl or C1-C3-hydroxyialkyl, or R7 and Rs together with the N atom represent a pyrrolidine, piperidine, piperazine or morpholine ring if n is 2, R5 represents one of the divalent radicals -O-R9-O- or -N (Rii) -Rio-N (Rii) -, R9 C2-C8-alkylene, C4-Cs-alkenylene, C4-alkynylene, cyclohexylene, straight- or branched-chain C4-C10-AI-kylene, which can be replaced by -O- or by -CH2-CHOH-CH2- (0-Ri4- 0-CH2-CHOH-CH2- is interrupted, R10 represents straight-chain or branched-chain C2-Ci2-alkylene which is substituted by -O-, cyclohexylene or ~ ° which can be interrupted, or R10 and Rn form a piperazine ring with the two nitrogen atoms, R14 straight-chain or branched-chain C2-C8-alkylene, straight-chain or branched-chain C4-Cio-alkylene, which by -O-, cycloalkylene, arylene or 26 5 10 15 20 25 30 35 40 45 50 55 60 65 CH 693 032 A5 CH3 < \ - or ch3 ch3 ( H > - c H > CH, may be interrupted, in which R7 and Rs independently represent hydrogen, alkyl having 1 to 18 carbon atoms, or R7 and Rs together represent alkylene having 4 to 6 carbon atoms, 3-oxapenta-methylene, 3-iminopentamethylene or 3-methyliminopentamethylene, R11 represents hydrogen, straight-chain or branched-chain Ci-Cis-alkyl C5-Ci2-cycloalkyl, straight-chain or branched-chain C3-C8-alkenyl, C6-C-u-aryl or C7-Ci5-aralkyl, R12 represents straight-chain or branched-chain Ci-Cie-alkyl, straight-chain or branched-chain C3-Cis-alkenyl, C5-C10-cycloalkyl, C6-Cie-aryl or C7-Cis-aralkyl, R13 is H, straight-chain or branched-chain Ci-Cis-alkyl which is substituted by -PO (ORi2) 2, phenyl which is unsubstituted or substituted by OH, Cr-Cis-aralkyl or -CH2OR12, L represents alkylene having 1 to 12 carbon atoms, alkylidene having 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and T -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CO-, -CO-E-CO-, -COO-E-OCO-, -CO-NG- 3-E-NG3-CO- or -NG3-CO-E-CO-NG3-, wherein E represents alkylene with 2 to 12 carbon atoms, cycloalkylene with 5 to 12 carbon atoms or alkylene interrupted by or terminated with cyclohexylene with 8 to 12 carbon atoms, the benzotriazole showing increased durability and low loss rates when the coating is exposed to actinic radiation is confirmed by loss of less than 0.22 absorbance units after 1200 hours exposure, or less than 0.27 absorbance units after 1500 hours exposure, or less than 0.40 absorbance units after 2500 hours exposure in a xenon arc weather O-meter, according to SAE J 1960. 2. The composition of claim 1, wherein component (b) is a compound of formula A ' represents what G2 represents fluorine, chlorine, cyano, R3SO2-, CF3-, -CO-G3, -COO-G3 or -CO-N (G3) 2, G3 represents alkyl having 1 to 12 carbon atoms, R 1 represents hydrogen, alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or this phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups having 1 to 4 carbon atoms, R2 alkyl with 1 to 12 carbon atoms, phenyl, phenylalkyl with 7 to 15 carbon atoms or -CH2CH2COOG4, in which G4 represents hydrogen, alkyl with 1 to 24 carbon atoms or this alkyl group, substituted by OH, interrupted by one to six atoms -O- or both substituted with OH and interrupted by one to six atoms -O-, and r, '2 27 5 10 15 20 25 30 35 40 45 50 55 60 65 CH 693 032 A5 R3 represents alkyl having 1 to 18 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms. 3. The composition of claim 2, wherein in the compound of formula A ' G2 represents fluorine, chlorine, cyano, R3SO2-, CF3-, -COO-G3 or -CO-N (G3) 2, G3 represents alkyl with 1 to 8 carbon atoms, Ri represents hydrogen, phenyl or a-cumyl, R2 represents alkyl of 4 to 12 carbon atoms or phenyl and R3 represents phenyl or alkyl of 8 to 12 carbon atoms. 4. The composition of claim 3, wherein G2 represents phenyl-SC> 2-, octyl-S02-, fluorine or CF3-, Ri represents a-cumyl or phenyl and R2 represents tert-butyl or tert-octyl. 28