KR100488744B1 - Durable Benzotriazole UV Absorber - Google Patents

Abstract

The benzotriazole UV absorber, in which the 5-position of the benzo ring is substituted by the electron removal component, is highly durable when incorporated into automotive paints and exhibits a very low loss rate.

Description

Durable benzotriazole shock absorbers

The present invention relates to a durable benzotriazole UV absorber.

The benzotriazole UV absorbers substituted in the benzo ring by electron removal components have enhanced durability and exhibit low loss rates when incorporated into automotive paints.

Benzotriazole has long been an important class of UV absorbers and has been approved for a wide range of commercial significance and many industrial applications. The prior art is rich in their preparation and use. However, as the requirements become more stringent, studies of benzotriazoles, which are much more stable and durable, have continued. Due to environmental concerns, the gradual pattern of replacing HAPS solvents such as xylene with their esters, ethers, or non-HAPS solvents such as ketones and the enhanced durability requirements for automotive paints make this study more urgent. Indeed, the automotive industry is based on J.L.Gerlock's group, Proc. 36th Annual Tech. Most attention is paid to UVA losses from automotive paints and paints, as described in Sym. (Cleaveland Coating Society), May 18, 1993.

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

JE Pickett et al., Angew. Makromol. Chem. 232 , 229 (1995) describe the photolysis of benzotriazole UV absorbers in poly (methyl methacrylate) films. Structural diversity generally results in only slight differences in degradation rates unless the substitution destroys the hydrogen bonds between molecules that are critical for stabilization. Pickett et al. Did not test any benzotriazoles containing both electron removers and electron donor groups as in the present invention.

Prior art has led to the conclusion that the strengthening of hydrogen bonds results in more stable benzotriazoles, but it does not suggest how it can be done. The present invention describes benzotriazoles having enhanced durability, but surprisingly this enhanced durability is not always associated with stronger hydrogen bond strengths. Indeed, durable compounds are often weaker and have less strong hydrogen bonds.

US Patent No. 4,226,763; No. 4,278,589; No. 4,315,848; No. 4,275,004; No. 4,347,180; 5,554,760; 5,554,760; 5,563,242; 5,563,242; 5,574,166 and 5,607,987 describe selected benzotriazoles that are highly durable in automotive paints, where the 3-position of the hydroxyphenyl ring is substituted with an α-cumyl group. Such benzotriazoles represent the state of the art. The present invention is directed to the preparation of benzotriazoles with better durability and lower loss rates than the benzotriazoles of the prior art.

US Patent No. 5,278,314; 5,280,124; 5,280,124; 5,436,349 and 5,516,914 describe red shifted benzotriazoles. These benzotriazoles are substituted at the 5-position of the benzo ring with thio ether, alkylsulfonyl or phenylsulfonyl moieties. Red shifting benzotriazole is preferred for spectral reasons. Electron-removable 5-position groups provide additional advantages in terms of durability and low loss rate as can be seen in the present invention.

It is an object of the present invention to provide benzotriazole UV absorbers having enhanced stability and durability and low loss rates when incorporated into automotive paints.

In particular, the present invention

(a) a group consisting of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin having a carbamate pendant group crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing a carbamate group Resin selected from, and

(b) 0.01 to 5% by weight, based on the resin solid, of the benzotriazole of formula (1), (2), (3), or (4),

The paint may be exposed to actinic radiation, as evidenced by an absorbance loss of less than 0.22 after 1200 hours of exposure in the Xenon-Arc Weather-Ometer, or an absorbance loss of less than 0.27 after 1500 hours of exposure, or less than 0.40 after 2500 hours of exposure. A coating composition stabilized with benzotriazole having enhanced stability and durability when exhibiting a low loss rate value and a low loss rate when incorporated into automotive paints;

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In the above formula

G ₁ , G ₂ or T is an electron removing radical,

G ₁ is hydrogen or halogen,

또는

이고,G ₂ is halogen, nitro, cyano, R ₃ SO-, R ₃ SO _2- , -COOG ₃ , CF _3- , -P (O) (C ₆ H ₅ ) ₂ , -CO-G ₃ , -CO -NH-G ₃ , -CO-N (G ₃ ) ₂ , -N (G ₃ ) -CO-G ₃ ,

or

ego,

G ₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, Phenyl or said phenyl or phenylalkyl substituted by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring,

R ₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, Phenyl or said phenyl or phenylalkyl substituted by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring,

R ₂ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, Or said phenyl or said phenylalkyl substituted by 1 to 3 alkyl having 1 to 4 carbon atoms on the phenyl ring; Or R ₂ is hydroxy or -OR ₄ , R ₄ is straight or branched chain alkyl of 1 to 24 carbon atoms; Or said alkyl substituted by one or more -OH, -OCO-R ₁₁ , -OR ₄ , -NCO or -NH ₂ groups or mixtures thereof; Or in the middle comprising one or more —O—, —NH—, or —NR ₄ groups or mixtures thereof, and unsubstituted or by one or more —OH, —OR ₄ , or —NH ₂ groups or mixtures thereof The alkyl or the alkenyl which may be substituted; Or R ₂ is —SR ₃ , -NHR ₃ or —N (R ₃ ) ₂ ; Or R ₂ is-(CH ₂ ) _m -CO-X- (Z) _p -YR ₁₅ ,

X is -O- or -N (R ₁₆ )-,

Y is -O- or -N (R ₁₇ )-

Z is C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkylene comprising 1 to 3 nitrogen atoms, oxygen atoms or mixtures thereof in between, or C ₃ -C each substituted by a hydroxy group ₁₂ -alkylene, butenylene, butynylene, cyclohexylene or phenylene,

m is 0, 1 or 2,

p is 1 or p is 0 when X and Y are -N (R ₁₆ )-, and -N (R ₁₇ )-, respectively,

의 기이며,R ₁₅ is —CO—C (R ₁₈ ) ═C (H) R ₁₉ groups or, when Y is —N (R ₁₇ ) —, together with R ₁₇ forms a —CO—CH═CH—CO group, R ₁₈ is hydrogen or methyl and R ₁₉ is hydrogen, methyl or CO-XR ₂₀ and R ₂₀ is hydrogen, C ₁ -C ₁₂ -alkyl or a formula

Is the flag of,

R ₁₆ and R ₁₇ are independently of each other hydrogen, C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -alkyl containing 1 to 3 oxygen atoms in between, or cyclohexyl or C ₇ -C ₁₅ -aral K ₁ and R ₁₆ together with R ₁₇ form ethylene when Z is ethylene,

n is 1 or 2,

when n is 1, R ₅ is Cl, OR ₆ or NR ₇ R ₈ , or

R ₅ is —PO (OR ₁₂ ) ₂ , -OSi (R ₁₁ ) ₃ or -OCO-R ₁₁ , or contains -O-, -S- or -NR ₁₁ in the middle and is unsubstituted or -OH or Straight or branched C ₁ -C ₂₄ -alkyl, unsubstituted or substituted by C ₅ -C ₁₂ cycloalkyl, unsubstituted or substituted by -OH, which may be substituted by -OCO-R ₁₁ or Side chain C ₂ -C ₁₈ alkenyl, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-R ₁₃ or glycidyl,

R ₆ is hydrogen, unsubstituted or straight or branched C ₁ -C ₂₄ alkyl substituted by one or more OH, OR ₄ , or NH ₂ groups, or —OR ₆ is — (OCH ₂ CH ₂ ) _w OH or — ( OCH ₂ CH ₂ ) _w OR ₂₁ , w is 1 to 12, and R ₂₁ is alkyl of 1 to 12 carbon atoms,

R ₇ and R ₈ independently of one another are hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched C ₃ -C ₁₈ alkyl, C _5- , comprising -O-, -S- or -NR ₁₁ -in the middle; C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxyalkyl, or R ₇ and R ₈ , taken together with the N atom, are a pyrrolidine, piperidine, piperazine or morpholine ring,

when n is 2, R ₅ is one of the divalent radicals -OR ₉ -O- or N (R ₁₁ ) -R ₁₀ -N (R ₁₁ )-,

R ₉ is C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, in between -O- or -CH ₂ -CHOH-CH ₂ -OR ₁₄ -O-CH ₂ Straight or branched C ₄ -C ₁₀ alkylene comprising -CHOH-CH _2- ;

또는

를 포함할 수 있는 직쇄 또는 측쇄 C_2-C₁₂ 알킬렌이고, 또는 R₁₀ 및 R₁₁은 2개의 질소 원자와 합쳐져 피페라진 고리를 형성하며,R ₁₀ is —O—, cyclohexylene, or

or

Straight chain or branched C ₂ -C ₁₂ alkylene, or R ₁₀ and R ₁₁ may combine with two nitrogen atoms to form a piperazine ring,

또는

를 포함하는 직쇄 또는 측쇄 C₄-C₁₀ 알킬렌이고,R ₁₄ is straight or branched C ₂ -C ₈ alkylene, in the middle -O-, cycloalkylene, arylene or

or

Straight or branched C ₄ -C ₁₀ alkylene comprising a,

R ₇ and R ₈ are independently of each other hydrogen, alkyl of 1 to 18 carbon atoms or R ₇ and R ₈ together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopenta Methylene or 3-methyliminopentamethylene,

R ₁₁ is hydrogen, straight or branched C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched C ₃ -C ₁₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl,

R ₁₂ is straight or branched C ₁ -C ₁₈ alkyl, straight or branched C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₅ aralkyl,

R ₁₃ is H, straight or branched C ₁ -C ₁₈ alkyl substituted by -PO (OR ₁₂ ) ₂ , unsubstituted or phenyl substituted by OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OR ₁₂ ,

R ₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, of 7 to 15 carbon atoms 1,1,2 wherein the aryl or perfluoroalkyl moiety substituted by phenylalkyl, aryl of 6 to 10 carbon atoms or one or two alkyl having 1 to 4 carbon atoms is 6 to 16 carbon atoms , 2-tetrahydroperfluoroalkyl,

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

T is -SO-, -SO _2- , -SO-E-SO-, -SO ₂ -E-SO _2- , -CO-, -CO-E-CO-, -COO-E-OCO-,- CO-, NG ₃ -E-NG ₃ -CO- or -NG ₃ -CO-E-CO-NG ₃

E is alkylene having 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or cyclohexylene having 8 to 12 carbon atoms in the middle or at the end.

Preferably, component (b) is a compound of formula (1a):

[Formula 1a]

In the above formula

G ₂ is fluoro, chloro, cyano, R ₃ SO _2- , CF _3- , -CO-G ₃ , -COO-G ₃ or -CO-N (G ₃ ) ₂ ,

G ₃ is alkyl of 1 to 12 carbon atoms,

R ₁ is phenyl or phenyl substituted on the phenyl ring by hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or 1 to 2 alkyl groups having 1 to 4 carbon atoms Alkyl,

R ₂ is substituted by alkyl of 1 to 12 carbon atoms, phenyl, phenyl alkyl of 7 to 15 carbon atoms or CH ₂ CH ₂ COOG ₄ , wherein G ₄ is hydrogen, alkyl of 1 to 24 carbon atoms or OH; , Said alkyl comprising 1 to 6 -O- atoms in the middle or substituted with OH and containing 1 to 6 -O- atoms in the middle, and

R ₃ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted with one or two alkyls having 1 to 4 carbon atoms.

G ₂ is fluoro, chloro, cyano, R ₃ SO _2- , CF _3- , -COO-G ₃ or -CO-N (G ₃ ) ₂ ,

G ₃ is alkyl of 1 to 8 carbon atoms,

R ₁ is hydrogen, phenyl or α-cumyl,

R ₂ is alkyl or phenyl of 4 to 12 carbon atoms, and

Most preferred are compounds of formula (1a), wherein R ₃ is phenyl or alkyl of 8 to 12 carbon atoms.

Formula (1a), wherein G ₂ is phenyl-SO _2- , octyl-SO _2- , fluoro or CF _3- , R ₁ is α-cumyl or phenyl, and R ₂ is tert-butyl or tertiary octyl Compounds of are particularly preferred.

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

Examples of such various radicals are as follows:

If either of R ₁ to R ₂₁ is alkyl, such groups are for example methyl, ethyl, isopropyl, n-butyl, isobutyl, secondary-butyl, tert-butyl, tert-amyl, 2-ethylhexyl , Tert-octyl, lauryl, tert-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; If either of the radicals is alkenyl, this group is for example allyl or oleyl; If any of the radicals is cycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; If any of the radicals is phenylalkyl such groups are for example benzyl, phenethyl, α-methylbenzyl and α, α-dimethylbenzyl; And if either of the radicals is aryl they are, for example, phenyl, naphthyl, or when substituted by alkyl, for example, tolyl, xylyl. When R ₆ is alkyl substituted by one or more —O— groups and / or substituted by one or more OH, the OR ₆ moiety is — (OCH ₂ CH ₂ ) _w OH or — (OCH ₂ CH ₂ ) _w OR ₂₁ (Eg, w is 1 to 12 and R ₂₁ is alkyl of 1 to 12 carbon atoms).

When E is alkylene it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, heptamethylene, octamethylene, decamethylene and dodecamethylene; When E is cycloalkylene it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; And when E is an alkylene comprising cyclohexylene in the middle or at the end, it is, for example, a saturated diyl radical derived from limonene named dihydrolimonediyl herein.

Preferred embodiments of the invention are compounds of formula (7), wherein R ₁ is tert-butyl, n is 1, R ₃ is phenyl, and R ₅ is OR ₆ , and R ₆ is a straight or substituted octyl group to be. Another preferred embodiment of the invention is n is 2, R ₁ is tert-butyl, R ₃ is phenyl, and R ₅ is -OR ₉ -O-, and R ₉ is -O- or Is C ₂ -C ₂₄ alkylene comprising —CH ₂ —CHOH—CH ₂ —OR ₁₄ —O—CH ₂ —CHOH—CH ₂ —.

When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, heptamethylene, octamethylene, decamethylene and dodecamethylene; When E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; And when E is an alkylene comprising cyclohexylene in the middle or at the end, it is, for example, a saturated diyl radical derived from limonene named dihydrolimonediyl herein.

When the compound of the present invention contains a free carboxy moiety wherein R ₂ is CH ₂ CH ₂ COOR ₆ and R ₆ is hydrogen, the alkali metal or amine salt of the acid is a UV absorber due to the enhanced water solubility of this compound of the invention. It is also regarded as part of the present invention as it allows use in aqueous systems.

R ₆ , R ₇ and R ₈ may be the following C ₃ -C ₁₈ alkyl radical which contains —O—, —S—, or —NR ₁₁ — in the middle and may be substituted by OH: methoxy Ethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl, CH ₃ OCH ₂ CH ₂ OCH ₂ CH _2- , CH ₃ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2- , C ₄ H ₉ OCH ₂ CH ₂ OCH ₂ CH _2- , ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, -CH ₂ CH ₂ -NH-C ₄ H ₉ , -CH ₂ CH ₂ CH ₂ NH-C ₈ H ₁₇ and -CH ₂ CH ₂ CH ₂ N (CH ₃ ) -CH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ .

R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ may be the following C ₅ -C ₁₂ cycloalkyl radicals: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In the case of R ₆ , the radical may be substituted by OH.

R ₇ , R ₈ and R ₁₁ may be alkenyl radicals: allyl, metallyl, 2-n-hexenyl or 4-n-octenyl.

When R ₆ is alkenyl, it may have the same meaning as alkenyl radicals R ₇ , R ₈ and R ₁₁ . However, it may be -CH = CH ₂ , n-undec-10-enyl or n-octadec-9-enyl, and also the radical R ₆ may be substituted by -OH.

R ₇ and R ₈ may be the following C ₇ -C ₁₅ aralkyl radicals: benzyl, α-phenethyl, 2-phenethyl or 4-tert-butylbenzyl.

When R ₁₁ , R ₁₃ or R ₁₂ are aralkyl, they may each independently have the same meaning as R ₇ or R ₈ .

Each independently R ₇ , R ₈ and R ₁₁ may be the following C ₆ -C ₁₄ aryl radicals: phenyl, α-naphthyl or β-naphthyl.

When R ₇ and R ₈ are C ₁ -C ₃ hydroxyalkyl they can be the following radicals: hydroxymethyl, 2-hydroxymethyl or 2-hydroxypropyl.

As C ₂ -C ₈ alkylene, R ₉ and R ₁₄ can be the following radicals: ethylene, propylene, butylene, hexylene or octylene.

As alkylene, R ₁₀ may be the same radical, but may also be a polymer group, such as decylene or dodecylene.

When R ₉ is a C ₄ -C ₈ alkenylene radical, an example of a suitable group is butenylene.

For R ₉ and R ₁₄ , suitable straight or branched C ₄ -C ₁₀ alkylene groups comprising -O- in the middle are the following groups: -CH ₂ CH ₂ OCH ₂ CH _2- , -CH (CH ₃ )- CH ₂ —O—CH ₂ —CH (CH ₃ ) —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ — and CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —.

When R ₁₄ is a cycloalkylene radical, it contains the following groups: 1,3-cyclohexylene and 1,4-cyclohexylene.

When R ₁₄ is arylene, it may be the following groups: 1,3-phenylene, 1,4-phenylene.

C ₂ -C ₁₂ alkylene, Z is straight or branched. This is for example ethylene, propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene, 2,2-amidene or 2-ethylhexamethylene. Preferred are C ₂ -C ₆ alkylene groups.

When Z is C ₄ -C ₁₂ alkylene containing oxygen in the middle, this is for example -CH ₂ -CH ₂ -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH _{2 -O-CH 2 -CH 2 -} , and also to the alkylene contains a nitrogen in the middle, -N (R ₁₆₎ - group, for (R ₁₆ is as defined above) is for example -CH ₂ - CH ₂ -NH-CH ₂ -CH ₂ -CH ₂ -CH _2- , -CH ₂ -CH ₂ -CH ₂ -NH- (CH _{2) 8} -or -CH ₂ CH ₂ -CH ₂ -N (CH ₃ -CH ₂ -CH (C ₂ H ₅ ) (CH ₂ ) _4- .

With C ₃ -C ₁₂ alkylene substituted by a hydroxy group, Z is 2-hydroxytetramethylene, 2-hydroxyhexamethylene and especially 2-hydroxytrimethylene.

As cyclohexylene, Z is for example 1,4-cyclohexylene and especially 1,2-cyclohexylene.

As phenylene, Z is, for example, m-phenylene or p-phenylene.

m may be 0, 1 or 2, but 2 is preferred.

p is preferably 1, but may be zero if both X and Y are combined with nitrogen.

As C ₁ -C ₈ alkyl, R ₁ is for example methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, tert-butyl, n-pentyl, tert-amyl, n- Hexyl, n-heptyl, n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.

C ₁ -C ₁₂ alkyl, R ₁₆ , R ₁₇ and R ₂₀ may have the meanings described above for R ₁ and may additionally be straight or branched nonyl, decyl, undecyl or dodecyl.

R ₁₆ and When R ₁₇ is alkyl containing an oxygen atom in the middle, the corresponding example is as defined in Z above.

As aralkyl R ₁₆ and Examples of R ₁₇ are benzyl, α-methylbenzyl, 1-phenylethyl, α, α-dimethylbenzyl or 1-phenylpropyl.

If Z is ethylene, then R ₁₆ and R ₁₇ may be combined to form ethylene corresponding to the bridge through the piperazine group.

를 형성한다.When Y is an N- (R ₁₇ )-group, R ₁₅ and R ₁₇ together form a —CO—CH═CH—CO— group, and thus a substituent on the —X (Z) _p − group

To form.

However, the preferred meaning of R ₁₅ is —CO—C (R ₁₈ ) ═CHR ₁₄ , and R ₁₈ and R ₁₉ is preferably methyl, in particular hydrogen.

R ₂ is —CH ₂ —CH ₂ —CO—OC (G) —CH ₂ and G is hydrogen or methyl.

The invention also relates to novel benzotriazoles of formula (5), (6), (7) or (8):

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In the above formula

G ₁ is hydrogen or halogen,

G ₂ is cyano, E ₃ SO-, E ₃ SO _2- , -COOG ₃ , CF _3- , -P (O) (C ₆ H ₅ ) ₂ , -CO-G ₃ , -CO-NHG ₃ or -CO-N (G ₃ ) ₂ ,

G ₃ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl or Said phenyl or phenylalkyl substituted by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring,

E ₁ is hydrogen, phenylalkyl of 7 to 15 carbon atoms, phenyl or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring,

E ₂ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl or Said phenyl or phenylalkyl substituted by 1 to 3 alkyl having 1 to 4 carbon atoms on the phenyl ring; Or E ₂ is hydroxy or —OE ₄ , wherein E ₄ is straight or branched alkyl of 1 to 24 carbon atoms; Or said alkyl substituted by one or more -OH, -OCO-E ₁₁ , -OE ₄ , NCO or -NH ₂ groups or mixtures thereof; Or in the middle may comprise one or more —O—, —NH— or —NE ₄ — groups or mixtures thereof and may be unsubstituted or substituted by one or more —OH, —OE ₄ or NH ₂ groups or mixtures thereof. The alkyl or the alkenyl; Or E ₂ is -SE ₃ , -NHE ₃ or -N (E ₃ ) ₂ ; Or E ₂ is- (CH ₂ ) _m -CO-X- (Z) _p -YE ₁₅ ,

At this time,

X is -O- or -N (R ₁₆ )-

Y is -O- or -N (R ₁₇ )-,

Z is C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkylene comprising 1 to 3 nitrogen atoms, oxygen atoms or mixtures thereof in between, or C ₃ -C each substituted by a hydroxy group ₁₂ -alkylene, butenylene, butynylene, cyclohexylene or phenylene,

m is 0, 1 or 2,

p is 1, or p is 0 when X and Y are -N (R ₁₆ )-and -N (R ₁₇ )-, respectively,

의 기이며,E ₁₅ is —CO—C (E ₁₈ ) = C (H) E ₁₉ , or when Y is —N (E ₁₇ ) —, together with E ₁₇ form a —CO—CH═CH—CO group, E ₁₈ is hydrogen and methyl, E ₁₉ is hydrogen, methyl or CO-XE ₂₀ , E ₂₀ is hydrogen, C ₁ -C ₁₂ -alkyl or a formula

Is the flag of,

E ₁₆ and E ₁₇ independently of one another are hydrogen, C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -alkyl containing 1 to 3 oxygen atoms in between, or cyclohexyl or C ₇ -C ₁₅ -aralkyl And when Z is ethylene, E ₁₆ forms ethylene with E ₁₇ ,

n is 1 or 2,

when n is 1, E ₅ is Cl, OE ₆ or NE ₇ E ₈ , or

E ₅ is -PO (OE ₁₂ ) ₂ , -OSi (E ₁₁ ) ₃ or -OCO-E ₁₁ , or contains -O-, -S- or -NE ₁₁ in the middle and is unsubstituted or -OH, Straight or branched chain C ₁ -C ₂₄ alkyl which may be substituted by —OCO—E ₁₁ C ₅ -C ₁₂ cycloalkyl substituted by unsubstituted or —OH, straight or branched chain C which may be substituted by -OH ₂ -C ₁₈ alkenyl, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-E ₁₃ or glycidyl,

E ₆ is hydrogen, unsubstituted or straight or branched C ₁ -C ₂₄ alkyl substituted by one or more OH, OE ₄ or NH ₂ groups, or —OE ₆ is — (OCH ₂ CH ₂ ) _w OH or — (OCH ₂ CH ₂ ) _w OE ₂₁ , w is 1 to 12, E ₂₁ is alkyl of 1 to 12 carbon atoms,

E ₇ and E ₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched C ₃ -C ₁₈ alkyl comprising -O-, -S- or -NE ₁₁ in the middle, C ₅ -C ₁₂ Cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxyalkyl, or E ₇ and E ₈ combine with the N atom to form a pyrrolidine, piperidine, piperazine or morpholine ring,

when n is 2, E ₅ is one of the divalent radicals -OE ₉ -O- or -N (R ₁₁ ) -E ₁₀ -N (E ₁₁ )-,

E ₉ is C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, in between -O- or -CH ₂ -CHOH-CH ₂ -OE ₁₄ -O-CH ₂ Straight or branched C ₄ -C ₁₀ alkylene comprising -CHOH-CH _2- ,

또는

를 포함할 수 있는 직쇄 또는 측쇄 C₂-C₁₂ 알킬렌이거나, 또는 E₁₀ 및 E₁₁은 2개의 질소 원자와 합쳐져서 피페라진 고리를 형성하며,E ₁₀ is -O-, cyclohexyl or

or

Straight chain or branched C ₂ -C ₁₂ alkylene, or E ₁₀ and E ₁₁ may be combined with two nitrogen atoms to form a piperazine ring,

또는

를 포함하는 직쇄 또는 측쇄 C₄-C₁₀ 알킬렌이고,E ₁₄ is straight or branched C ₂ -C ₁₂ alkylene, in the middle -O-, cyclohexyl, arylene or

or

Straight or branched C ₄ -C ₁₀ alkylene comprising a,

E ₇ and E ₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or E ₇ and E ₈ together are alkylene, 3-oxapentamethylene, 3-iminopentamethylene or 4 to 6 carbon atoms or 3-methyliminopentamethylene,

E ₁₁ is hydrogen, straight or branched C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched C ₃ -C ₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl,

E ₁₂ is straight or branched C ₁ -C ₁₈ alkyl, straight or branched C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl,

E ₁₃ is straight chain or branched C ₁ -C ₁₈ alkyl substituted by H, —PO (OR ₁₂ ) ₂ , unsubstituted or phenyl substituted by OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OE ₁₂ ,

E ₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, of 7 to 15 carbon atoms 1,1,2 wherein the aryl or perfluoroalkyl moiety substituted by phenylalkyl, aryl of 6 to 10 carbon atoms or one or two alkyl having 1 to 4 carbon atoms is 6 to 16 carbon atoms , 2-tetrahydroperfluoroalkyl,

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

T is -SO-, -SO _2- , -SO-E-SO-, -SO ₂ -E-SO _2- , -CO-, -CO-E-CO-, -COO-E-OCO-, or -CO-NG ₅ -E-NG ₅ -CO-,

E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene comprising cyclohexylene of 8 to 12 carbon atoms in the middle or terminal;

G ₅ is G ₃ or hydrogen, and

Provided that when G ₂ is E ₃ SO- or E ₃ SO _2- , E ₁ is not phenylalkyl.

Preferably the new benzotriazole is a compound of formula (5a);

[Formula 5a]

In the above formula,

G ₂ is cyano, E ₃ SO _2- , CF _3- , -COO-G ₃ , -CO-NHG ₃ or -CO-N (G ₃ ) ₂ ,

G ₃ is alkyl of 1 to 12 carbon atoms,

E ₁ is hydrogen, phenyl, phenylalkyl of 7 to 15 carbon atoms or the phenyl or the phenylalkyl substituted by 1 to 2 alkyl groups having 1 to 4 carbon atoms on the phenyl ring,

E ₂ is alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or CH ₂ CH ₂ COOG ₄ , G ₄ is substituted by hydrogen, alkyl of 1 to 24 carbon atoms or OH Or an alkyl comprising one to six -O- atoms in the middle, or substituted by OH and one to six -O- atoms in the middle,

E ₃ is alkyl of 8 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted with one or two alkyls having 1 to 4 carbon atoms, provided that G ₂ is E ₃ SO- or When E ₃ SO _2- , E ₁ is not phenylalkyl.

G ₂ is cyano, E ₃ SO _2- , CF _3- , -CO-G ₃ or -CO-N (G ₃ ) ₂ ,

G ₃ is alkyl of 1 to 8 carbon atoms,

E ₁ is hydrogen, phenyl or α-cumyl,

E ₂ is alkyl of 4 to 12 carbon atoms, and

E ₃ is phenyl or octyl provided that, when G _{2 is} E ₃ SO-, the compound of formula (5a) where E ₁ is not α-cumyl is most preferred.

Particular preference is given to compounds of the formula (5a) wherein G ₂ is CF _3- , E ₁ is α-cumyl and E ₂ is tert-butyl or tert-octyl.

The invention also

(a) organic materials susceptible to thermal, oxidation and light induced degradation, and

(b) A composition comprising a stabilized amount of heat, oxidation and photoinduced decomposition, comprising an effective stable amount of a compound of formula (5), (6), (7) or (8).

Preferably, the organic material is a natural, semisynthetic or synthetic polymer, in particular a thermoplastic polymer.

Most preferably, the polymer is polyolefin or polycarbonate, in particular polyethylene or polypropylene; Especially most preferably polypropylene.

In another preferred embodiment of the invention, the organic material contains a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin having a carbamate pendant group crosslinked with melamine or a carbamate group Resin selected from the group consisting of melamine and acrylic polyol resins crosslinked.

Most preferred resins are thermosetting acrylic melamine resins or acrylic urethane resins.

In another preferred embodiment of the invention, the organic material is a recording material.

The recording material according to the present invention is suitable for a reduced pressure radiation system, a photocopy system using microcapsules, a thermal radiation system, a photographic material and inkjet printing.

The recording material according to the invention is characterized in that it is unexpectedly improved in terms of quality, especially light fastness.

The recording material according to the present invention has a structure known for special use. These consist of conventional carriers, for example paper or plastic films coated with one or more layers. Depending on the type of material, these layers contain appropriately necessary ingredients, in the case of photographic materials, for example silver halide emulsions, dye colorants, dyes and the like. Particularly suitable materials for ink jet printing have a layer which in particular absorbs ink on a conventional carrier. Uncoated paper can be used for ink jet printing. In this case the paper simultaneously serves as the carrier material and the ink absorbing layer. Suitable materials for ink jet printing are described, for example, in US Pat. No. 5,073,448 (incorporated herein by reference).

The recording material may be transparent as in the case of, for example, a projection film.

The compounds of the formulas (5), (6), (7) or (8) can be initially incorporated into the cardboard material, such as by initial paper making, for example by addition to paper pulp. A second method of use is to spray an aqueous solution of the compound of formula (5), (6), (7) or (8) onto the cardboard material or to add the compound to the coating composition.

Paint compositions for use in transparent recording materials suitable for projection may not contain any particles that scatter light, such as pigments and fillers.

Dye-linked coating compositions include a number of other additives, such as antioxidants, light stabilizers (including UV absorbers not belonging to the UV absorbers according to the invention), viscosity modifiers, fluorescent brighteners, biotoxins and / or charging It may contain an inhibitor.

Paint compositions are typically prepared as follows:

The water soluble component, for example the binder, is dissolved in water and stirred together. Solid components such as fillers and other additives already mentioned above are dispersed in the aqueous medium. Dispersions can be advantageously handled by devices such as ultrasonic samples, turbine stirrers, homogenizers, colloid mills, bead mills, sand mills, high speed stirrers and the like. Compounds of formula (5), (6), (7) or (8) can be readily incorporated into paint compositions.

Record material according to the invention preferably 1 to 5000mg / m ^2, in particular containing 50 to 1200mg / m ² of the compound of formula (5).

As already mentioned, the recording material according to the present invention covers a wide range of fields.

Compounds of formula (5), (6), (7) or (8) can be used, for example, in a reduced pressure radiation system. These may be introduced into the paper to protect the microencapsulated dye precursor from light, or may be introduced into the binder of the developer layer to protect the formed dye.

Photographic radiometers using photosensitive microcapsules developed by pressure are described in US Pat. No. 4,416,966; 4,483,912; 4,483,912; No. 4,352,200; No. 4,535,050; 4,5365,463, 4,551,402, 4,562,137 and 4,608,330 and EP-A 139,479; EP-A 162,664; EP-A 164,931; EP-A 237,024; EP-A 237,025; Or EP-A 260,129. In all such systems the compound may be present in the dye-receiving layer. However, the compound may also be present in the donor layer to protect the color former from light.

Photographic materials that can be stabilized are photographic dyes and layers comprising dyes or precursors thereof, such as photographic paper and films. Suitable materials are described, for example, in US Pat. No. 5,364,749 (incorporated herein by reference). Compounds of formula (5), (6), (7) or (8) herein serve as UV filters against electrostatic flashes. Colorants and dyes in color photographic materials are also protected from photochemical degradation.

The compounds of the present invention can be used in all types of color photographic materials. For example, they can be used in color, color reversal paper, direct-positive color materials, color negative film, color positive film, color reversal film, and the like. These are preferably used in photographic color materials which contain, among them, a reversal component or form a positive.

The color-photographic recording material typically contains a blue-sensitive and / or green-sensitive and / or red-sensitive silver-halide emulsion layer and, if necessary, a protective layer, on a support, and the compound is preferably green- It is present in the sensitive or red-sensitive layer or in the layer between the green-sensitive and red-sensitive or in the upper layer of the silver-halide emulsion layer.

Compounds of formulas (5), (6), (7) or (8) can be used for photopolymerization, photoplasticization or rupture or thermosensitive and photosensitive diazonium salts of microcapsules, leuco dyes or Lewis acids containing oxidizing agents in recording materials. Containing dye lactones can be used based on the Winchix used.

Moreover, they can be used as recording materials for dye diffusion transfer printing, thermal wax transfer printing and non-matrix printing and recording materials for electrostatic, electrographic, electrophoretic, magnetic field recording and laser-electrophotographic printing and pen-graphic composers. Among the above, for example, a recording material for dye diffusion transfer printing is preferable, as described in EP-A-507,734.

These can preferably be used as ink jet printing inks as described, for example, in US Pat. No. 5,098,477 (incorporated herein by reference).

The compounds of the present invention, when present in stabilized compositions, exhibit excellent hydrolysis stability, handling and storage stability as well as good resistance to extraction rates.

Processes for the preparation of the compounds of the present invention are described in the prior art. The intermediates required to prepare the compounds of the present invention are largely trade names.

Preferred compounds are those in which one of X and Y is -O-; And especially X and Y are both —O—.

Common polymers that can be stabilized include:

1. Polymers of monoolefins and diolefins (such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1ene, polyisoprene or polybutadiene) as well as cycloolefins (such as cyclopentene Or norbornene), optionally crosslinked polyethylene such as high density polyethylene (HDPE), low density polyethylene (LDPE), straight chain low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

The polymers of polyolefins, ie monoolefins exemplified above, preferably polyethylene and polypropylene, can be prepared in different ways and in particular in the following way:

a) radical reaction (typically at high pressure and elevated temperature).

b) Catalytic reaction using a catalyst which usually contains one or more than one of the IVb, Vb, VIb or Group VIII metals of the periodic table. The metals usually have one or more than one ligand, which can bind π- or σ-coordination such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls. The metal complex may be in free form or immobilized on a substrate such as active magnesium chloride, titanium (III) chloride, alumina or silicon oxide. The catalyst may be soluble or insoluble in the polymerization reaction medium. The catalyst may be used alone in the polymerization process or other activators such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being groups Ia, IIa and IIIa of the periodic table. Is an element of. The activator can be advantageously modified by other ester, ether, amine or silyl ether groups. The catalyst system is commonly named Philips, standard oil Indiana, Ziegler (-Natta), TNZ (Dupont), metallocene or single site catalyst (SSC).

2. Mixtures of the polymers described in 1), such as polypropylene and polyisobutylene, polypropylene and polyethylene (such as PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LPDE / HDPE).

3. Copolymers of monoolefin and diolefins with one another or with other vinyl monomers, such as ethylene / propylene copolymers, straight chain low density propylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene air Copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer Isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and salts thereof (Ionomer) as well as ethylene with propylene and dienes (such as hexadiene, dicyclopentadiene or ethylidene-norbornene) Body; And mixtures of the copolymers with each other or with the polymers described above in 1), such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and cross or random polyalkylene / carbon monoxide copolymers and mixtures of these with other polymers such as polyamides.

4. Hydrocarbon resins (such as C ₅ -C ₉ ) and mixtures of polyalkylenes and starches, including hydrogenation modifiers (such as tackifier resins).

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

6. For example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl Styrene such as acrylate or a copolymer of α-methylstyrene with diene or acrylic acid derivatives; High impact strength mixtures consisting of styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene trimers; And block copolymers of styrene such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, styrene on polybutadiene and acrylonitrile (or methacrylonitrile); Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene, styrene and maleic acid on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene / propylene / diene trimers; 6) Graft copolymers of styrene or a-methylstyrene, such as styrene and acrylonitrile on polyalkylacrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers Mixtures of listed copolymers (eg copolymer mixtures known as ABS, MBS, ASA or AES polymers).

8. chlorinated or brominated copolymers of polychloroprene, chlorinated rubber, isobutyrene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, In particular halogen-containing polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as polymers of halogen-containing vinyl compounds, for example vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate Or copolymers thereof such as vinylidene chloride / vinyl acetate copolymer.

9. polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; Polymethyl methacrylate, polyacrylamide and polyacrylonitrile impact-modified with butyl acrylate.

10. Copolymers between monomers described above in 9) or between other unsaturated monomers. For example acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate copolymer or acrylonitrile / vinyl halide copolymer or acrylonitrile / alkyl methacrylate / butadiene 3 coalescence.

11. From unsaturated alcohols such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate or polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl melamine and amines or acyl derivatives thereof Derived polymers; As well as the olefins and copolymers thereof described above in 1).

12. Homogeneous polymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers thereof with bisglycidyl ethers.

13. polyacetals such as polyoxymethylene and polyoxymethylene containing for example ethylene oxide as comonomers; 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 from polyethers, polyesters or polybutadienes with hydroxyl groups at one end and aliphatic or aromatic polyisocyanates at the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / Aromatic polyamides derived from 12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene diamine and adipic acid; Hexamethylene diamine and isophthalic acid or / and terephthalic acid and, optionally, as a modifier, for example polys made from elastomers such as poly-2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenyleneisophthalamide amides; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or branched elastomers; Or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; As well as polyamides or copolyamides modified with EPDM or ABS; And polyamides condensed during processing ("reactant injection molding (RIM) polyamide systems.)."

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

18. Polyesters derived from dicarboxylic and diols and / or hydroxycarboxylic acids such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoate or Block-copolyether esters derived from polyethers having hydroxy end groups as well as the corresponding lactones; And polyesters modified with polycarbonates or MBS.

19. Polycarbonates and Polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

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

22. Dry and undry 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 their halogen-containing modifiers which are inflammable.

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, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides such as bisglycidylether or cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified cognate derivatives thereof such as cellulose acetate, cellulose propionate and cellulose ethers such as cellulose butyrate or methyl cellulose; As well as rosin and derivatives thereof.

28. Mixtures of the aforementioned polymers (composites), such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

29. Natural and synthetic organic materials that are pure monomer compounds or mixtures of these compounds, such as mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters (eg phthalates, adipates, phosphates or trimellitates) and various weight ratios Fats and waxes based on mixtures of mineral oils with synthetic esters, such as materials used in spinning compositions, as well as aqueous emulsions of these materials.

30. Aqueous emulsions of natural or synthetic rubbers, such as natural latices or latices of carboxylated styrene / butadiene copolymers.

31. Polysiloxanes, such as, for example, the soft hydrophilic polysiloxanes described in US Pat. No. 4,259,467 and the hard polyorganosaloxanes described, for example, in US Pat. No. 4,355,147.

32. Polyketimines, unsaturated acrylic resins combined with unsaturated acrylic polyacetoacetate resins or unsaturated acrylic resins, include urethane acrylates, polyether acrylates, vinyl or acrylic copolymers with pendant unsaturated groups, and acrylated melamine. Polyketimines are prepared from polyamines and ketones under acid catalysts.

33. A radiation curable composition containing an unsaturated monomer or oligomer of ethylene and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinked with an epoxy functional coetherified solid solid melamine resin such as LSE-4103 (Monsanto).

Generally, the compounds of the present invention use from about 0.01% to about 5% by weight based on the stabilized composition, but can be used in various ways depending on the particular substrate and use. Advantageous ranges are from about 0.05 to about 3%, in particular from 0.05 to about 1%. The content of the above defined compounds is sufficiently supported by the examples described later in the present invention as the optimum values selected by the inventors through many experiments.

Stabilizers of the present invention can be readily incorporated into organic polymers in conventional techniques at any advantageous stage prior to the manufacture of the molded article. For example, the stabilizer may be mixed with the polymer in dry powder form, or the suspension or emulsion of the stabilizer may be mixed with a solution, suspension, emulsion of the polymer. Compositions of the stabilized polymers of the present invention optionally contain from about 0.01 to about 5 weight percent, preferably from about 0.025 to about 2 weight percent, and especially from about 0.1 to about 5 weight percent of various conventional additives such as the following materials or mixtures thereof It may comprise 1% by weight.

1. Antioxidant

 1.1. Alkylated monophenols such as

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

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

2,6-di-octadecyl-4-methylphenol

2,4,6-tricyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones such as

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

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers such as

2,2'-thio-bis- (6-tert-butyl-4-methylphenol)

2,2'-thio-bis- (4-octylphenol)

4,4'-thio-bis- (6-tert-butyl-3-methylphenol)

4,4'-thio-bis- (6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols such as

2,2'-methylene-bis- (6-tert-butyl-4-methylphenol)

2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) -phenol]

2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis- (6-nonyl-4-methylphenol)

2,2'-methylene-bis- [6- (α-methylbenzyl) -4-nonylphenol]

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

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

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

2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol)

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

4,4'-methylene-bis- (6-tert-butyl-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-tris- (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'-methyl-benzyl) -6-tert-butyl-4-methylphenyl] terephthalate.

1.5. Benzyl compounds such as

1,3,5-tris- (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-hydroxybenzyl-mercapto-acetic acid isooctyl ester

Bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate

1,3,5-tris- (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-hydroxybenzyl-phosphate dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphate monoethyl ester, calcium-salt.

1.6. Acylaminophenols such as

4-hydroxy-lauric acid anilide

4-hydroxy-stearic anilide

2,4-bis-octylmercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine

Octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate.

1.7. Mono or polyhydric alcohols such as

Methanol Diethylene Glycol

Octadecanol triethylene glycol

1,6-hexanediol pentaerythritol

Neopentyl Glycol Tris-hydroxyethyl Isocyanurate

Thiodiethylene glycol di-hydroxyethyl oxalic acid diamide

Triethanolamine Triisopropanolamine

And esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid .

1.8. Mono or polyhydric alcohols such as

Methanol Diethylene Glycol

Octadecanol triethylene glycol

1,6-hexanediol pentaerythritol

Neopentyl Glycol Tris-hydroxyethyl Isocyanurate

Thiodiethylene glycol di-hydroxyethyl oxalic acid diamide

Triethanolamine Triisopropanolamine

And ester of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid

1.9. amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid , such as

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. Diarylamines , for example

Diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, 4,4'-di-tert-octyl-diphenylamine, N- Reaction product of phenylbenzylamine with 2,4,4-trimethylpentene, reaction product of diphenylamine with 2,4,4-trimethylpentene, N-phenyl-1-naphthylamine with 2,4,4-trimethylpentene Reaction product.

2. UV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) -benzotriazole such as 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'-secondary-butyl- 5'-tert-butyl-, 4'-octoxy-, 3 ', 5'-di-tert-amyl-, 3', 5'-bis- (α, α-dimethylbenzyl), 3'-tertiary- Butyl-5 '-(2- (omega-hydroxy-octa- (ethyleneoxy) carbonyl-ethyl)-, 3'-dodecyl-5'-methyl and 3'-tert-butyl-5'-(2 '-Octyloxycarbonyl) ethyl- and dodecylated-5'-methyl derivatives.

2.2. 2-hydroxy-benzophenones such as 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acid such as phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) -resorcinol, Benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl-4-hydroxybenzoic acid and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester .

2.4. Acrylates such as α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid Methyl ester or butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indolin.

2.5 2,2'-thio-bis- [4- (1,1,3,3 with optionally ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine -Tetramethylbutyl) -phenol] mono (eg 1: 1 or 1: 2 complex), mono di of nickel dibutyl dithiocarbamate, 4-hydroxy-3,5-di-tert-butylbenzyl phosphonic acid Nickel salts of alkyl esters (such as methyl, ethyl or butyl esters), nickel complexes of ketoximes (such as 2-hydroxy-4-methyl-phenyl undecylketoxime), 1-phenyl-4 optionally with additional ligands Nickel complexes of lauroyl-5-hydroxy pyrazole.

2.6. Sterically hindered amines such as bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl- 3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis- (1,2,2,6,6-pentamethylpiperidyl) ester, 1-hydroxyethyl-2,2,6, Condensation product of 6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N '-(2,2,6,6-tetramethylpiperidyl) -hexamethylenediamine and 4-tert-octylamino- Condensation product of 2,6-dichloro-s-triazine, tris (2,2,6,6-tetramethylpiperidyl) -nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl- 4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '(1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazage Nons), bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides such as 4,4'-di-octyloxy-oxanide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di -Dodecyloxy-5,5'-di-tert-butyl-oxanide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) -oxala Mid, 2-ethoxy-5-tert-butyl-2'-ethyloxanide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p-methoxy as well as o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines such as 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-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (2,4-dimethylphenyl) -s-triazine; 2 , 4-bis- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-bromophenyl) -s-triazine; 2,4-bis- [2-hydroxy -4- (2-acetoxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine; 2,4-bis (2,4-dihydroxyphenyl) -6- (2,4 -Dimethylphenyl) -s-triazine.

3. Metal deactivators such as N, N'-diphenyloxalic acid diamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis-salicyloylhydrazine, 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 phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di- Stearyl pentaerythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, di-isodecyl pentaerythritol diphosphite, di- (2,4,6-tri-tert-butylphenyl ) Pentaerythritol diphosphite, di- (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, di- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Tristearyl-sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-diphenylenediphosphonite.

5. Peroxide decomposing compounds such as esters of β-thiodipropionic acid, such as lauryl-, stearyl-, myristyl- or tridecyl esters, mercapto-benzimidazoles or zinc salts of 2-mercaptobenzimidazoles, Dibutyl-dithiocarbamate zinc, dioctadecyl disulfide, pentaerythritol tetrakis- (β-dodecylmercapto) -propionate.

6. Hydroxyamines such as N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N Ditetradecylhydroxyamine, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N- Octadecylhydroxyamine, N, N-dialkylhydroxyamine derived from hydrogenated resin amine.

7. Nitrons such as N-benzyl-alpha-phenyl nitron, N-ethyl-alpha-methyl nitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecyl nitron, N- Tetradecyl-alpha-tridecyl-nitron, N-hexadecyl-alpha-pentadecyl nitron, N-octadecyl-alpha-heptadecyl nitron, N-hexadecyl-alpha-heptadecyl nitron, N-octa From decyl-alpha-pentadecyl nitron, N-heptadecyl-alpha-heptadecyl nitron, N-octadecyl-alpha-hexadecyl nitron, N, N'-dialkylhydroxyamine derived from hydrogenated resin amine Induced nitron.

8. Polyamide stabilizers such as copper salts in combination with iodine and / or phosphorus compounds and salts of divalent magnesium.

9. Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of high fatty acids, Such as calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol or zinc pyrocatechol.

10. Nucleating agents such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

11. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

12. Other additives such as plasticizers, lubricants, emulsifiers, pigments, fluorescent brighteners, flame retardants, antistatic agents, blowing agents and sulfur synergists such as diauryl thiodipropionate or distearyl thiodipropionate.

13. benzofuranone and indolinones such as US-A-4,325,863; US-A-4,338,244; Or disclosed in US Pat. No. 5,175,312 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-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-acet Methoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di Tert-butyl-benzofuran-2-one.

Co-stabilizers other than benzofuranone as listed in claim 13 are added at a concentration of 0.01 to 10% relative to the total weight of the material to be stabilized.

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

Particularly preferred additives are the phenolic antioxidants described in paragraph 1, the hindered amines described in section 2.6, the phosphites and phosphonites (described in section 4) and the peroxide decomposing compounds (see section 5). Described).

Also particularly preferred additives (stabilizers) are benzofuran-2-ones as described, for example, in US Pat. No. 4,325,863, US Pat. No. 4,338,244 or US Pat. No. 5,175,312.

Particularly important phenolic antioxidants are n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis (3,5-di-tert-butyl-4- Hydroxyhydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) isocyanurate, thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert-butyl-4-hydroxyhydrocinna Mate), 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-tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] isocy Nurate, 3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydro Cinnamate), 1- (3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnaamide), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis [3 , 3-di (3-tert-butyl-4-hydroxyphenyl) butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis (3,5-di- Tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide, and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) -ethyl ] -Oxamide is selected from the group consisting of.

Most preferred phenolic antioxidants are neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4 -Hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis (4,6 Di-tert-butylphenol).

Particularly important sterically hindered amine compounds are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidine-4- (I) 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-oxodisspiro [5.1.11.2] heneicoic acid, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6, Poly-condensation product of 6-tetramethyl-piperidine), of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid Polycondensation products, polycondensation products of 4,4'-hexamethylenebis- (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis (2,2 , 6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butane-tetracarboxylate, tetrakis (1,2,2,6,6, -pentamethylpiperidine- 4-yl) 1,2,3,4-butanetetracarboxylate, 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis (amino-2,2, Polycondensation product of 6,6-tetramethylpiperidine), N, N ', N ", N'"-tetrakis [(4,6-bis (butyl-1,2,2,6,6-penta) Methyl-piperidin-4-yl) -amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecan, mixed [2,2,6,6-tetra Methylpiperidin-4-yl / β, β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] -undecane) diethyl] 1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl / β, β, β ', β'-tetramethyl- 3,9- (2,4,8,10-tetraoxaspiro [5,5] ound ) Diethyl] 1,2,3,4-butanetetracarboxylate, octamethylenebis (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-dodecylsuccinimide, N-1 , 2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, 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) sebacate, di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine -4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazine-2 , 4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy -2,2,6,6-tetramethylpiperidin-4-yl) Mino] and 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine It is selected from the group consisting of.

Most preferred sterically hindered amine compounds are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidine-4- (I) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 1- Polycondensation product of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 2,4-dichloro-6-tert-octylamino-s-triazine And polycondensation products of 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethyl-piperidine), N, N ', N ", N'"-tetrakis [(4, 6-bis (butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl) -amino) -s-triazin-2-yl] -1,10-diamino-4, 7-diazadecan, di- (1-octyloxy-2,2,6,6-tetramethylpiperazin-4-yl) sebacate, di- (1-cyclohexyloxy-2,2,6 , 6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-jade Til-A Mino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino-hexamethylene- [4 -(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] or 2,4,6-tris [N- (1-cyclohexyloxy-2 , 2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine.

The composition of the present invention may additionally contain other UV absorbers selected from the group consisting of s-triazine, oxanilide, hydroxybenzophenone, benzoate and α-cyanoacrylate.

In particular, the compositions of the present invention additionally comprise one or more other 2-hydroxyphenyl-2H-benzotriazoles; Other tris-aryl-s-triazines; Or an effective stabilizing amount of sterically hindered amine or mixtures thereof.

Preferred 2-hydroxyphenyl-2H-benzotriazole is

2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole;

2- [2-hydroxy-3,5-di (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole;

2- [2-hydroxy-3- (α, α-dimethylbenzyl) -5-octylphenyl] -2H-benzotriazole;

2- {2-hydroxy-3-tert-butyl-5- [2- (omega-hydroxy-octa (ethyleneoxy) carbonyl) ethyl] -phenyl} -2H-benzotriazole; And

2- {2-hydroxy-3-tert-butyl-5- [2- (octyloxy) carbonyl) ethyl] phenyl} -2H-benzotriazole.

Preferred other tris-aryl-s-triazines are

2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine;

2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine;

2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-degree- / tri-decyloxy-2-hydroxy-propoxy) phenyl] -s-tri Azine; And

2- (2-hydroxyethylamino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4yl) amino] -s-triazine is selected from the group consisting of.

Alkyd resin lacquers which can be stabilized from the action of light and moisture in accordance with the invention are particularly suitable for automotive coatings (such as lacquers for automotive finishing) such as lacquers based on alkyd / melamine resins and alkyd / acrylic / melamine resins. Common heat-drying lacquers used (see H. Wagner and HFSarx, "Lackkunstharze" (1977), 99-123). Other crosslinkers include glycouril resins, blocked isocyanates or epoxy resins.

The lacquers stabilized according to the invention are suitable not only for the coating of metal finishes and for the solid color finish, but also for various coil coatings, especially in the case of retouching finishes. The lacquer stabilized according to the invention is preferably applied in a conventional manner by two methods, namely one layer coating or two layer coating. In the latter method, the pigment containing the undercoat is first applied and then transparent lacquer is applied thereon.

It is also possible that the compounds of the present invention can be used in non-acid catalyzed thermosetting resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified silicones, isocyanates or isocyanurates. It is important. Epoxy and epoxy-polyester resins can be crosslinked with conventional crosslinkers such as acids, acid anhydrides, amines and the like. Thus, epoxides can be used as crosslinkers for various acrylic or polyester resins modified by the presence of a reactor in the main chain structure.

When used in a two layer coating method, the compounds of the present invention can be incorporated into transparent paints or transparent paints and colored undercoats.

When water soluble, paints that are miscible with or dispersed in water require an ammonium salt of the acid moiety present in the resin formed. Powder coating compositions can be prepared by reacting glycidyl methacrylate with those selected from alcohol components.

The benzotriazoles of the present invention can be prepared by conventional methods for preparing these compounds. The usual method involves producing the corresponding desired benzotriazoles by diazolation of substituted o-nitroanilines, followed by coupling of the resulting diazonium salts with substituted phenols and reduction of the azobenzene intermediates. Starting materials for these benzotriazoles are mostly trade names or can be prepared by the usual methods of organic synthesis.

Although the benzotriazoles of the present invention with enhanced durability are particularly suitable for automotive paints, they can be considered particularly useful in other applications where their enhanced durability is required, such as in solar films and the like.

The following examples are intended to illustrate the invention in detail.

Example 1

5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-

Preparation of 2H-benzotriazole

a) Diazolation of 4-amino-3-nitro-benzotrifluoride

To a 500 mL three-necked flask equipped with a mechanical stirrer, 41.2 g of 4-amino-3-nitro-benzotrifluoride, 52 mL of concentrated hydrochloric acid and 100 mL of distilled water were added. The stirred solution was cooled to 5 ° C, and 17.3 g of nitrile chloride was dissolved in 50 mL of water and added. The solution was stirred for 2 h at 0-5 ° C., filtered and stored at −10 ° C.

b) monoazo adducts

To a 1000 mL flask equipped with a mechanical stirrer, 40 g of sodium hydroxide dissolved in 200 mL of methanol and 32.4 g of 2-α-cumyl-4-tert-octylphenol dissolved in 50 mL of xylene were added. The solution was cooled to 5 ° C. and a diazo solution of 4-amino-3-nitro-benzotrifluoride prepared in a) was added at 0-5 ° C. for 2 hours. Then 100 mL of xylene was added and the organic phase was washed with water, aqueous hydrochloric acid, water, aqueous sodium carbonate solution and finally water. The solvent was removed under reduced pressure and the residue was purified by chromatography (silica gel, heptane: ethyl acetate 95: 5) to give 42.1 g of adduct as a black red paste.

c) reduction of the monoazo adduct

In a 1000 mL flask was placed 42.1 g of monoazo adduct prepared in 20 g of sodium hydroxide, 40 mL of water, b) and 40 mL of ethynol. The mixture was warmed to 80 ° C. and 27 g of formamidine sulfinic acid was added little by little with stirring. After 1.5 hours the solution was cooled to room temperature and 100 mL of water was added. The pH was adjusted to 7 with concentrated hydrochloric acid. Ethanol was removed under vacuum and the aqueous phase was extracted with methylene chloride. The solvent was evaporated in vacuo and the residue was purified by chromatography (silica gel, heptane: toluene 9: 1) to crystallize from ethanol. The title compound was obtained in 5.6 g yield as a pale yellow solid with a melting point of 119-121 ° C.

Example 2

Preparation of 5-fluoro-2- (2-hydroxy-3α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

The title compound was prepared according to the conventional method of Example 1 using 31.2 g of 4-fluoro-2-nitroaniline. In part c) of the above method, additionally 9 g of formamidine sulfinic acid is required for complete reduction. The crude product was purified on silica gel (heptane: toluene, 1: 1) to give 4.5 g of the title compound as a white solid. Purification by recrystallization from acetonitrile: toluene gave 1.1 g of the title compound having a melting point of 93-96 ° C.

Example 3

Preparation of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

Monoazo intermediate for the title compound was prepared by the general method of a) and b) of Example 1 from 339.3 g of 4-chloro-2-nitroaniline. The crude product was purified by recrystallization from methanol to give 70.9 g of dark red monoazo adduct.

c) reduction of the monoazo adduct

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

Example 4

Preparation of 5-phenylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

To a stirred mixture of 75 g of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 105 g of N-methylpyrrolidone heated at 90 ° C. 44.3 g of 45% aqueous potassium hydroxide solution was added and added over 15 minutes, followed by addition of 20.4 g of thiophenol for another 15 minutes. The reaction mixture was removed by distillation while heating at 170-175 ° C. for 4 hours. After cooling to 100 ° C., xylene and water were added and the resulting mixture was acidified with 15% aqueous hydrochloric acid solution. The organic phase was separated, washed with water and then concentrated. The crude residue was recrystallized from methanol to give 82 g of the title compound as a pale yellow solid at melting point 124-125 ° C.

Example 5

Preparation of 5-benzenesulfonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

75.2 g of 5-phenylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in Example 4 in a 1000 mL flask, 102 g of xylene, tungstic acid 0.9 g of sodium dihydrate and 18.4 g of formic acid were added. This mixture was heated to 50 ° C. 36.3 g of 50% hydrogen peroxide was slowly added to the stirred mixture so that the temperature did not exceed 85 ° C. Additionally xylene and water were added. The organic phase was separated and washed with aqueous sodium sulfite and concentrated by washing twice with water. The crude residue was recrystallized from methanol to yield 75.2 g of the title compound as a pale yellow solid at melting point 170-171 ° C.

Example 6

Preparation of 5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

The title compound in the manner of Example 4 using 30 g of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 17.6 g of nonyl mercaptan. Prepared.

Example 7

Preparation of 5-nonylsulfonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

8.7 g of formic acid and sodium tungstate dihydrate were prepared with 5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in Example 6. Oxidation with sulfone without the thio intermediate identity using g and 17.6 g of 50% hydrogen peroxide afforded the title compound as a yellow resin exhibiting molecular ions of m / e 631.

Example 8

Preparation of 5-chloro-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole

The monoazo intermediate for the title compound was prepared from 4-chloro-2-nitroaniline and 2-phenyl-4-tert-octylphenol by the general method of example a) and b). The crude product was purified by recrystallization from methanol to give a dark red monoazo addition product.

The title compound was prepared according to the reduction method 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 was purified by chromatography on silica gel (hexanes: ethyl acetate, 5: 1) to give a fraction with the majority of the title compound exhibiting molecular ions of m / e 433.

Example 9

Preparation of 5-phenylthio-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole

The title compound was prepared according to the method 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 eluent.

Example 10

Preparation of 5-benzenesulfonyl-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole

The title compound was prepared according to the method 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. 2.5 g of unpurified material was recrystallized from xylene / methanol to give 2.0 g of the title compound which was purified as a pale yellow powder with a melting point of 204-206 ° C.

Example 11

5-chloro-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole, each alkyl independently ₄ , C ₈ , C ₁₂  And C ₁₆ Preparation of the mixture of

A mixture of 65.4 g of 5-chloro-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole, 45 mL dodecene and 13 mL methane sulfonic acid was heated to 170 ° C. under nitrogen. Additionally 135 mL of dodecene was added for 4.5 hours. The reaction mixture was cooled to 100 ° C., quenched with 400 g of crushed ice, and then extracted three times with ethyl acetate. The organic phases were combined, washed with water, aqueous sodium carbonate, water and brine again, dried over anhydrous magnesium sulfate and concentrated. The polyvalent residue was removed by bulb to bulb distillation under vacuum at 0.2 mm and below 210 ° C. Unreacted starting material was removed by distillation (0.01 mm, 160 ° C.) to give 45 g of the title mixture as a yellow oil.

Example 12

5-phenylthio-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole, each alkyl independently being C ₄ , C ₈ , C ₁₂  And C ₁₆ Preparation of the mixture of

The title compound was prepared according to the method 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

5-benzenesulfonyl-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole (alkyl each independently is C ₄ , C ₈ , C ₁₂  And C ₁₆ Preparation of the mixture of

The crude product of Example 12, a mixture of 350 mL of isopropanol, 14.7 mL of formic acid and 1.8 mL of concentrated sulfuric acid was heated to reflux and 30 mL of 50% hydrogen peroxide was added dropwise over 2 hours. After refluxing for another 3 hours, the reaction mixture was cooled and 10% aqueous sodium sulfate and aqueous sodium carbonate were added. Isopropanol was evaporated and the residue was extracted with methylene chloride. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated to give 45 g of crude product as viscous french oil. 30 g of this crude product were purified by chromatography on silica gel (heptane: ethyl acetate, 4: 1) to give 28.9 g of the title mixture as a yellow oil.

Example 14

5-diphenylphosphinyl-2- (2-hydroxy-3,5-tert-butylphenyl) -2H-benzotriazole

In a flame dried 500 mL three-bottomed flask equipped with a cooler, magnetic 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 Inserted through 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 was added all at once to the red mixture. The resulting brown solution was stirred at 135 ° C. for 3.5 h and cooled to room temperature. The mixture was quenched with a portion of saturated ammonium chloride solution and ethyl acetate was added. The organic layer was separated, washed three times with water, washed once with brine and dried over anhydrous magnesium sulfate. When exothermic, 50% hydrogen peroxide was added to the solution. The mixture was left for 30 minutes, washed once with 10% sodium metabisulfite solution, three times with saturated sodium carbonate, once with brine, and finally dried over anhydrous magnesium sulfate. The mixture was filtered through a plug of silica gel and the solvent was removed under reduced pressure to yield 8.0 g of a crude yellow solid. The crude product was chromatographed with heptane: ethyl acetate 1: 1 at medium pressure to give 4.2 g (yield 27%) of the title compound as a yellow solid at a melting point of 98-100 ° C.

Example 15

5-diphenylphosphinyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

According to the method of Example 14, when 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole was used as the benzotriazole intermediate starting material The title compound was prepared.

Example 16-26

According to the general method of Example 1, additional 2H-benzotriazole of formula (5a) was prepared.

Example 27

Preparation of 5-octylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

The title compound was prepared using the method of Example 6 with 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and octyl mercaptan .

Example 28

Preparation of 5-octylsulfonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

5-octylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in Example 27 was prepared using the general method of Example 7. Oxidized with sulfone without purification of the intermediate.

Example 29

Preparation of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole

In the general manner of a) and b) of Example 1, the monoazo intermediate of the title compound was prepared from 17.3 g of 4-chloro-2-nitroaniline to give 34.7 g of a dark red monoazo addition product wet cake.

Reduction of monoazo adducts

A mixture of 20 g sodium hydroxide, 500 mL water and 26.3 g of the monoazo adduct wet cake prepared above was heated to 30 ° C. Zinc powder (33.0 g) was added for 2 hours. After the addition, 180 g of 40% aqueous sodium hydroxide solution was added dropwise for 1 hour. The mixture was stirred at rt for 96 h. The zinc residue was filtered off. The aqueous solution was neutralized to pH5-6 and the resulting slurry was filtered. The resulting filtrate was washed well with water and dried to afford 22.5 g of crude product. The crude product was purified by Soxhlet extractor with acetone to give 9.6 g of the title compound.

Example 30

Preparation of 5-chloro-2- (2-hydroxy-4-octyloxyphenyl) -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 anhydrous potassium carbonate and 100 mL of acetone was refluxed for 24 hours. About 100 mL of water and acetone were added to the resulting mixture to isolate 10.6 g of crude product. Column chromatography with petroleum ether gave 0.9 g of the title compound, whose structure was confirmed by H nmr and mass spectrometry.

Example 31

Preparation of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole

In the general manner of Example 29, the title compound was prepared from 10.3 g of 4-amino-3-nitrobenzotrifluoride to give 6.4 g of the title compound whose structure was confirmed by H nmr.

Example 32

Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole

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

Example 33

Preparation of 5-trifluoromethyl-2- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -2 H-benzotriazole

Of 2.3 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 1.3 mL of butyl glycidyl ether and 100 mg of ethyl triphenylphosphonium bromide prepared in Example 31 The mixture was poured into 50 mL of xylene and heated to reflux for 14 hours under nitrogen. Water (25 mL) and 25 mL of ethyl acetate were added to isolate 3 g of crude product. Recrystallization from heptane yielded 2.1 g of the title compound, whose structure was confirmed by nmr.

Example 34

Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2H-benzotriazole

The title compound was prepared by the general method of Examples 1 and 29 with 4-amino-3-nitrobenzotrifluoride and 3-aminophenol as starting materials. The structure of the product was confirmed as nmr.

Example 35

5-trifluoromethyl-2- [2-hydroxy-4- (2-ethylhexanoylamino) phenyl]-

Preparation of 2H-benzotriazole

To a mixture of 4 g of lifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2H-benzotriazole and 1.4 g of triethylamine in 75 mL of toluene was added dropwise a hexahexanoyl chloride mixture in 125 mL of toluene. The resulting mixture was treated with 100 mL of water and the crude product formed was purified by chromatography to give 1.9 g of the title compound at melting point of 179-181 ° C. The structure was confirmed by nmr.

Example 36

5-Carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-

Preparation of 2H-benzotriazole

a) esterification of 4-amino-3-nitrobenzoic acid

To a 2 L three-necked flask with a mechanical stirrer was added 700 mL of methanol, 20 g of xylene, 14 g of concentrated sulfuric acid and 100 g of 4-amino-3-nitrobenzoic acid. The solution was heated to reflux for 33 hours. The mixture was cooled to 35 ° C. and the pH was neutralized to 7.8. Water (1 L) was added, the solids were collected, washed with 500 mL, and dried overnight to yield 100.9 g of methyl 4-amino-3-nitrobenzoate.

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

To a 1 L three-necked flask with a mechanical stirrer was added 177 g of 96% sulfuric acid and slowly 11 g of sodium nitrite for 90 minutes. The mixture was warmed to 30 ° C. to initiate the reaction. The temperature was kept below 70 ° C. The mixture was then cooled to 15 ° C. and 30 g of methyl 4-amino-3-nitrobenzoate was added for 2 hours while maintaining the temperature at 15-20 ° C. The mixture was cooled to 0 ° C. and 200 g of ice were added to prepare a solution suitable for the coupling reaction to form a monoazo compound.

c) monoazo adducts

To a 2 L three-necked flask with a mechanical stirrer and an addition funnel, 52 g of 2-a-cumyl-4-tert-octyl phenol, 20 g of water, 315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide were added. The mixture was cooled to −5 ° C., and the diazonium salt solution prepared in b) was added for 2 hours while cooling the temperature to keep it below 3 ° C. After adding the diazonium salt solution, the pH was adjusted to 6.5-7.0. This mixture was added to 500 mL of xylene and washed three times with 500 mL of water at 60 ° C. Xylene was distilled off to give 186 g of monoazo adduct containing xylene residue.

d) reduction of the monoazo adduct

To a 500 mL flask equipped with a mechanical stirrer, 186 g of monoazo adduct prepared in c), 125 g of 2-butanol and 1.7 g of 2,3-dichloro-1,4-naphthoquinone were added. This mixture was heated to 90 ° C. and the resulting solution was charged to an addition funnel on a separate flask. 175 g of 2-butanol and 18.6 g of sodium hydroxide were added to the second flask. The flask was heated to 95 ° C. and monoazo solution was added for 2 hours while methyl ethyl ketone and 2-butanol were distilled off. 2-butanol (100 g) was added and the azeotrope was distilled off. The mixture was then cooled and 300 g of xylene and 200 mL of water were added. The pH was adjusted to 7-7.5 with 20% sulfuric acid. The aqueous phase was separated at 60 ° C. and the organic phase was washed twice with 200 mL water. Xylene was distilled off and the formed residue was crystallized from methanol to give 8.8 g of the title compound having a melting point of 141-143 ° C.

Example 37

5- [N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-α-cumyl-5-tert-octyl) phenyl]-

Preparation of 2H-benzotriazole

a) Saponification of 5-carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole

1.8 g potassium hydroxide and 40 mL methanol were added to a 250 mL three-necked flask equipped with a mechanical stirrer, thermometer, cooler and nitrogen inlet. The mixture was warmed to 40 ° C. to dissolve potassium hydroxide. To this solution was added 2.7 g of 5-carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole in 40 mL of methanol prepared in Example 36. did. The reaction mixture was refluxed for 6 hours. The mixture was cooled and acidified with hydrochloric acid. Ether and ethyl acetate were added and the organic layer was separated and dried over anhydrous sodium sulfate. After complete removal of solvent in vacuo, 2.5 g of 5-carboxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole was isolated.

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

In a 250 mL flask with stirrer, thermometer, reflux condenser, Dean-Stark trap and nitrogen inlet, 5-carboxy-2- (2-hydroxy-3-α-cumyl-5- as prepared in a). 2.5 g of tert-octylphenyl) -2H-benzotriazole was added. Toluene (100 mL) was added and the mixture was refluxed to remove traces of water. The mixture was cooled and 0.76 g of oxalyl chloride in 15 mL of toluene was added. The reaction mixture was slowly heated to 60 ° C. and left at 60-65 ° C. for 8 hours until all hydrogen chloride was removed to give the acid chloride title compound.

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

To a 500 mL flask equipped with a mechanical stirrer, a drying tube, a thermometer, and a dropping funnel, 0.8 g of di-n-butylamine, 6 mL of pyridine and 25 mL of toluene were added. The mixture was cooled to 0 ° C., and the acid chloride solution prepared in b) was charged into a dropping funnel and added to the reaction mixture at −5 ° C. to 10 ° C. over 30 minutes. The reaction mixture was stirred at the same temperature for 1.5 hours and left overnight at room temperature. After the mixture was filtered, the vacuum was removed to give 3.0 g of an unpurified solid. The solid product was purified by chromatography to give 1.2 g of the title compound as a tan solid at melting point 131-133 ° C. The structure was confirmed by nmr and mass spectrometer m / z 596.

Example 38

5-trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole

The title compound was prepared from the diazo compound of 4-amino-3-nitrobenzotrifluoride and 4-tert-octylphenol according to the general method of Example 1, and purified by chromatography on silica gel. The product was recrystallized from heptane or methanol to give the title compound as an almost white solid at melting point 80-81 ° C.

Use Example 39

The following experiments were carried out to determine the effect of various 2H-benzotriazole UV absorbers substituted by various electron removal and electron donor groups on the thermal durability and loss rate from high solids thermosetting acrylic paints.

The solid solid thermosetting acrylic transparent paint was prepared by mixing an experimental acrylic polyol resin and hexamethoxymethylmelamine (Resimene ^R 747, Monsanto) at a solid content ratio of 60/40. Dodecylbenzene sulfonic acid catalyst (Nacure ^R 5225; King Industries) was added at 0.70 wt%. Flow aid Modaflow ^R (Monsanto) was added at 0.25% by weight to form a model acrylic melamine resin system.

The model clear paint was reduced to xylene to a viscosity of 26-27 seconds using a Zahn # 2 cup and 50 psi (3.5) by conventional air spraying on a 1 ″ × 3 ″ (2.54 cm × 7.62 cm) quartz slide. Kg / cm ² ). The slides were cured by hot heat at 260 ° F. (127 ° C.) for 30 minutes. Transparent paints sterically hindered amine light stabilizer, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (TINUVIN ^R 123, Ciba-Geigy) 1 weight Stabilized in%. Various test benzotriazole UV absorbers were incorporated into the clear paint at 5 mmol by weight. Film thicknesses on quartz slides range from 1.15 to 1.41 mils (0.029 to 0.036 mm).

The film on the quartz slide was exposed to the outside under Xenon Arc Weather-Ometer under the following conditions by controlling the irradiation to 6500 W using an inner quartz and an outer borosilicate S-shape filter. The irradiation cycle is as follows: 40 minutes of direct irradiation without water spray, followed by 20 minutes of light and front spray followed by 60 minutes of light irradiation, and finally 60 minutes of fast rear spray (concentration). 0.55 W / M ² , 340 nm, and 1.98 kJ / hour were set. In the light cycle, the temperature of the black panel was adjusted to 70 ± 2 ° C. In the light cycle, the relative humidity is 50-55%, in the dark cycle 100%. The absorbance of the longwave UV bands as a function of xenon discharge outdoor exposure time is reported in the table below.

To follow the loss of the UV absorber from the clear paint, the UV spectrum was measured after outdoor exposure at initial and constant time intervals. The UV spectrophotometer measured the absorption of a straight line below 5.5 absorbance using a reference beam attenuation technique.

Decomposition products from the UV absorbers are unlikely to affect the UV spectrum. This was tested according to the absorption of the band of about 300 nm and the band of about 340 nm. The ratio did not change even when the sample was exposed outdoors. This indicates that the UV spectrum of an outdoor exposed film corresponds to the amount of UV absorber remaining in the film in a very small amount if there is any influence on the spectrum by the photolysate.

The data in the table below is based on the structure of formula (1) after 1211 hours of exposure of the clear coating containing the test benzotriazole UV absorber.

Examining these data provides clear conclusions about the photostability of the 2H-benzotriazole UV absorbers and the propensity of substitution to affect the photostability.

An increase in photostability occurs when R ₁ is α-cumyl or phenyl and G ₂ is an electron remover such as phenyl-sulfonyl or cyano.

The characteristics of the R ₂ group have a lesser effect on the photostability of the benzotriazole UV absorbers.

From these observations the ideal benzotriazole UV absorber could theoretically be devised as a G ₂ valent electron remover, R ₁ being an effectively bulky group and R ₂ being a heat stable component. Such an ideal compound may be benzotriazole wherein G ₂ is phenyl-sulfonyl, R ₁ is α-cumyl and R ₂ is tert-octyl. This benzotriazole is generally claimed in US Pat. No. 5,280,124. The data given in Example 40 below confirm that this expected and “ideal” compound actually exhibits a much lower loss rate than the state of the art.

Example 40

According to the general method of Example 39, a number of additional benzotriazole test compounds were incorporated into a high solids thermosetting acrylic melamine resin at a concentration between 1.93 and 3% by weight, so that the same molar concentration of the test benzotriazole at the same film thickness Was obtained, and the starting absorbance of about 2.0 absorbance was sufficiently shown.

The experimental disks were exposed to X180 cycles (0.45 watts / M ² ) on a Xenon Arc Weather-Ometer. Initial UV absorbance was measured at approximately 250 hour intervals for the first 2000 hours and at 500 hour intervals thereafter. Each transparent paint contained 1 weight% of sterically hindered amine light stabilizers and bis- (1-octyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) sebacate.

The data in the table below is based on the compound of formula (1) after 1253 hours exposure of the clear paint containing the test benzotriazole UV absorber.

The data in the table below is based on the compound of formula (1) after 1489 hours of exposure of the clear paint containing the test benzotriazole UV absorber.

The data in the table below is based on the compound of formula (1) after 2521 hours exposure of a clear paint containing the test benzotriazole UV absorber.

It has been found from the above three tables that S and in particular T compounds having electron-removing groups at the 5-position of the benzo ring are more durable than benzotriazoles having no such component in the benzo ring.

The data in the table below is based on the compound of formula (1) after 1264 hours of exposure of the clear paint containing the test benzotriazole UV absorber.

The data in the table below is based on the compound of formula (1) after 1518 hours exposure of the clear paint containing the test benzotriazole UV absorber.

The data in the table clearly show that the benzotriazoles substituted by electron eliminators on the benzo ring, in particular groups such as trifluoromethyl or phenyl sulfonyl, are particularly durable, as measured by low absorption loss after exposure to actinic radiation. Indicates. Compounds S, U, V and W are particularly durable and fit the tables presented above. In fact, the prediction that Compound U is particularly durable is demonstrated by the data. Examining the data of compounds T and U shows that having an effective bulky group such as α-cumyl at the R ₁ position shows a beneficial effect compared to having an alkyl component such as tert-butyl at that position.

The benzotriazole UV absorbers according to the invention, wherein the 5-position of the benzo ring is substituted by the electron removal component, have enhanced durability and show very low loss rates when incorporated into automotive paints.

Claims (8)

(a) a group consisting of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin having a carbamate pendant group crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing a carbamate group Resin selected from, and (b) 0.01 to 5% by weight of benzotriazole represented by the following formula (1), (2), (3), or (4) based on the solid of the resin, Enhanced durability and low incorporation in paints, indicating an absorbance loss of less than 0.22 after 1200 hours exposure, or an absorbance loss of less than 0.27 after 1500 hours exposure, or an absorbance loss of less than 0.40 after 2500 hours exposure in the Xenon-Arc Weather-Ometer. Coating composition stabilized with benzotriazole having a loss rate:

(One)

(2)

(3)

(4) In the above formula G _1, G ₂ or T is an electron removing radical, G ₁ is hydrogen or halogen, G ₂ is halogen, nitro, cyano, R ₃ SO-, R ₃ SO _2- , -COOG ₃ , CF _3- , -P (O) (C ₆ H ₅ ) ₂ , -CO-G ₃ , -CO -NH-G ₃ , -CO-N (G ₃ ) ₂ , -N (G ₃ ) -CO-G ₃ ,

or

ego, G ₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, Phenyl or said phenyl or phenylalkyl substituted by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring, R ₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, Phenyl or said phenyl or phenylalkyl substituted by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring, R ₂ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, Or said phenyl or said phenylalkyl substituted by 1 to 3 alkyl having 1 to 4 carbon atoms on the phenyl ring; Or R ₂ is hydroxy or -OR ₄ , R ₄ is straight or branched chain alkyl of 1 to 24 carbon atoms; Or said alkyl substituted by one or more -OH, -OCO-R ₁₁ , -OR ₄ , -NCO or -NH ₂ groups or mixtures thereof; Or in the middle comprising one or more —O—, —NH—, or —NR ₄ groups or mixtures thereof, and unsubstituted or by one or more —OH, —OR ₄ , or —NH ₂ groups or mixtures thereof The alkyl or the alkenyl which may be substituted; Or R ₂ is —SR ₃ , -NHR ₃ or —N (R ₃ ) ₂ ; Or R ₂ is-(CH ₂ ) _m -CO-X- (Z) _p -YR ₁₅ , X is -O- or -N (R ₁₆ )-, Y is -O- or -N (R ₁₇ )- Z is C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkylene comprising 1 to 3 nitrogen atoms, oxygen atoms or mixtures thereof in between, or C ₃ -C each substituted by a hydroxy group ₁₂ -alkylene, butenylene, butynylene, cyclohexylene or phenylene, m is 0, 1 or 2, p is 1 or p is 0 when X and Y are -N (R ₁₆ )-, and -N (R ₁₇ )-, respectively, R ₁₅ is —CO—C (R ₁₈ ) ═C (H) R ₁₉ groups or, when Y is —N (R ₁₇ ) —, together with R ₁₇ forms a —CO—CH═CH—CO group, R ₁₈ is hydrogen or methyl and R ₁₉ is hydrogen, methyl or CO-XR ₂₀ and R ₂₀ is hydrogen, C ₁ -C ₁₂ -alkyl or a formula

Is the flag of, R ₁₆ and R ₁₇ are independently of each other hydrogen, C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -alkyl containing 1 to 3 oxygen atoms in between, or cyclohexyl or C ₇ -C ₁₅ -aral K ₁ and R ₁₆ together with R ₁₇ form ethylene when Z is ethylene, n is 1 or 2, when n is 1, R ₅ is Cl, OR ₆ or NR ₇ R ₈ , or R ₅ is —PO (OR ₁₂ ) ₂ , -OSi (R ₁₁ ) ₃ or -OCO-R ₁₁ , or contains -O-, -S- or -NR ₁₁ in the middle and is unsubstituted or -OH or Straight or branched C ₁ -C ₂₄ -alkyl, unsubstituted or substituted by C ₅ -C ₁₂ cycloalkyl, unsubstituted or substituted by -OH, which may be substituted by -OCO-R ₁₁ or Side chain C ₂ -C ₁₈ alkenyl, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-R ₁₃ or glycidyl, R ₆ is hydrogen, unsubstituted or straight or branched C ₁ -C ₂₄ alkyl substituted by one or more OH, OR ₄ , or NH ₂ groups, or —OR ₆ is — (OCH ₂ CH ₂ ) _w OH or — ( OCH ₂ CH ₂ ) _w OR ₂₁ , w is 1 to 12, and R ₂₁ is alkyl of 1 to 12 carbon atoms, R ₇ and R ₈ independently of one another are hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched C ₃ -C ₁₈ alkyl, C _5- , comprising -O-, -S- or -NR ₁₁ -in the middle; C ₁₂ cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxyalkyl, or R ₇ and R ₈ , taken together with the N atom, are a pyrrolidine, piperidine, piperazine or morpholine ring, when n is 2, R ₅ is one of the divalent radicals -OR ₉ -O- or N (R ₁₁ ) -R ₁₀ -N (R ₁₁ )-, R ₉ is C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, in between -O- or -CH ₂ -CHOH-CH ₂ -OR ₁₄ -O-CH ₂ Straight or branched C ₄ -C ₁₀ alkylene comprising -CHOH-CH _2- ; R ₁₀ is —O—, cyclohexylene, or

or

Straight chain or branched C ₂ -C ₁₂ alkylene, or R ₁₀ and R ₁₁ may combine with two nitrogen atoms to form a piperazine ring, R ₁₄ is straight or branched C ₂ -C ₈ alkylene, in the middle -O-, cycloalkylene, arylene or

or

Straight or branched C ₄ -C ₁₀ alkylene comprising a, R ₇ and R ₈ are independently of each other hydrogen, alkyl of 1 to 18 carbon atoms or R ₇ and R ₈ together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopenta Methylene or 3-methyliminopentamethylene, R ₁₁ is hydrogen, straight or branched C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched C ₃ -C ₁₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl, R ₁₂ is straight or branched C ₁ -C ₁₈ alkyl, straight or branched C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₅ aralkyl, R ₁₃ is H, straight or branched C ₁ -C ₁₈ alkyl substituted by -PO (OR ₁₂ ) ₂ , unsubstituted or phenyl substituted by OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OR ₁₂ , R ₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, of 7 to 15 carbon atoms 1,1,2 wherein the aryl or perfluoroalkyl moiety substituted by phenylalkyl, aryl of 6 to 10 carbon atoms or one or two alkyl having 1 to 4 carbon atoms is 6 to 16 carbon atoms , 2-tetrahydroperfluoroalkyl, L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and T is -SO-, -SO _2- , -SO-E-SO-, -SO ₂ -E-SO _2- , -CO-, -CO-E-CO-, -COO-E-OCO-,- CO-, NG ₃ -E-NG ₃ -CO- or -NG ₃ -CO-E-CO-NG ₃ E is alkylene having 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or cyclohexylene having 8 to 12 carbon atoms in the middle or at the end. The composition of claim 1 wherein component (b) is a compound represented by formula (1a):

(1a) In the above formula G ₂ is fluoro, chloro, cyano, R ₃ SO _2- , CF _3- , -CO-G ₃ , -COO-G ₃ or -CO-N (G ₃ ) ₂ , G ₃ is alkyl of 1 to 12 carbon atoms, R ₁ is phenyl or phenyl substituted on the phenyl ring by hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or 1 to 2 alkyl groups having 1 to 4 carbon atoms Alkyl, R ₂ is substituted by alkyl of 1 to 12 carbon atoms, phenyl, phenyl alkyl of 7 to 15 carbon atoms or CH ₂ CH ₂ COOG ₄ , wherein G ₄ is hydrogen, alkyl of 1 to 24 carbon atoms or OH; , Said alkyl comprising 1 to 6 -O- atoms in the middle or substituted with OH and containing 1 to 6 -O- atoms in the middle, and R ₃ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted with one or two alkyls having 1 to 4 carbon atoms. The compound of claim 2, wherein the compound is represented by formula (1a) G ₂ is fluoro, chloro, cyano, R ₃ SO _2- , CF _3- , -COO-G ₃ or -CO-N (G ₃ ) ₂ , G ₃ is alkyl of 1 to 8 carbon atoms, R ₁ is hydrogen, phenyl or α-cumyl, R ₂ is alkyl or phenyl of 4 to 12 carbon atoms, and R ₃ is phenyl or alkyl of 8 to 12 carbon atoms. The method of claim 3, wherein G ₂ is phenyl-SO _2- , octyl-SO _2- , fluoro or CF _3- , R ₁ is α-cumyl or phenyl, and R ₂ is tert-butyl or tertiary octyl. The composition of claim 1 wherein component (a) is a thermosetting acrylic melamine resin or an acrylic urethane resin. A compound represented by the following formula (5), (6), (7) or (8):

(5)

(6)

(7)

(8) In the above formula G ₁ is hydrogen or halogen, G ₂ is cyano, E ₃ SO-, E ₃ SO _2- , -COOG ₃ , CF _3- , -P (O) (C ₆ H ₅ ) ₂ , -CO-G ₃ , -CO-NHG ₃ or -CO-N (G ₃ ) ₂ , G ₃ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl or Said phenyl or phenylalkyl substituted by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring, E ₁ is hydrogen, phenylalkyl of 7 to 15 carbon atoms, phenyl or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl having 1 to 4 carbon atoms on the phenyl ring, E ₂ is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl or Said phenyl or phenylalkyl substituted by 1 to 3 alkyl having 1 to 4 carbon atoms on the phenyl ring; Or E ₂ is hydroxy or —OE ₄ , wherein E ₄ is straight or branched alkyl of 1 to 24 carbon atoms; Or said alkyl substituted by one or more -OH, -OCO-E ₁₁ , -OE ₄ , NCO or -NH ₂ groups or mixtures thereof; Or in the middle may comprise one or more —O—, —NH— or —NE ₄ — groups or mixtures thereof and may be unsubstituted or substituted by one or more —OH, —OE ₄ or NH ₂ groups or mixtures thereof. The alkyl or the alkenyl; Or E ₂ is -SE ₃ , -NHE ₃ or -N (E ₃ ) ₂ ; Or E ₂ is- (CH ₂ ) _m -CO-X- (Z) _p -YE ₁₅ , At this time, X is -O- or -N (R ₁₆ )- Y is -O- or -N (R ₁₇ )-, Z is C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkylene comprising 1 to 3 nitrogen atoms, oxygen atoms or mixtures thereof in between, or C ₃ -C each substituted by a hydroxy group ₁₂ -alkylene, butenylene, butynylene, cyclohexylene or phenylene, m is 0, 1 or 2, p is 1, or p is 0 when X and Y are -N (R ₁₆ )-and -N (R ₁₇ )-, respectively, E ₁₅ is —CO—C (E ₁₈ ) = C (H) E ₁₉ , or when Y is —N (E ₁₇ ) —, together with E ₁₇ form a —CO—CH═CH—CO group, E ₁₈ is hydrogen and methyl, E ₁₉ is hydrogen, methyl or CO-XE ₂₀ , E ₂₀ is hydrogen, C ₁ -C ₁₂ -alkyl or a formula

Is the flag of, E ₁₆ and E ₁₇ independently of one another are hydrogen, C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -alkyl containing 1 to 3 oxygen atoms in between, or cyclohexyl or C ₇ -C ₁₅ -aralkyl And when Z is ethylene, E ₁₆ forms ethylene with E ₁₇ , n is 1 or 2, when n is 1, E ₅ is Cl, OE ₆ or NE ₇ E ₈ , or E ₅ is -PO (OE ₁₂ ) ₂ , -OSi (E ₁₁ ) ₃ or -OCO-E ₁₁ , or contains -O-, -S- or -NE ₁₁ in the middle and is unsubstituted or -OH, Straight or branched chain C ₁ -C ₂₄ alkyl which may be substituted by —OCO—E ₁₁ C ₅ -C ₁₂ cycloalkyl substituted by unsubstituted or —OH, straight or branched chain C which may be substituted by -OH ₂ -C ₁₈ alkenyl, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-E ₁₃ or glycidyl, E ₆ is hydrogen, unsubstituted or straight or branched C ₁ -C ₂₄ alkyl substituted by one or more OH, OE ₄ or NH ₂ groups, or —OE ₆ is — (OCH ₂ CH ₂ ) _w OH or — (OCH ₂ CH ₂ ) _w OE ₂₁ , w is 1 to 12, E ₂₁ is alkyl of 1 to 12 carbon atoms, E ₇ and E ₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched C ₃ -C ₁₈ alkyl comprising -O-, -S- or -NE ₁₁ in the middle, C ₅ -C ₁₂ Cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxyalkyl, or E ₇ and E ₈ combine with the N atom to form a pyrrolidine, piperidine, piperazine or morpholine ring, when n is 2, E ₅ is one of the divalent radicals -OE ₉ -O- or -N (R ₁₁ ) -E ₁₀ -N (E ₁₁ )-, E ₉ is C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, in between -O- or -CH ₂ -CHOH-CH ₂ -OE ₁₄ -O-CH ₂ Straight or branched C ₄ -C ₁₀ alkylene comprising -CHOH-CH _2- , E ₁₀ is -O-, cyclohexyl or

or

Straight chain or branched C ₂ -C ₁₂ alkylene, or E ₁₀ and E ₁₁ may be combined with two nitrogen atoms to form a piperazine ring, E ₁₄ is straight or branched C ₂ -C ₁₂ alkylene, in the middle -O-, cyclohexyl, arylene or

or

Straight or branched C ₄ -C ₁₀ alkylene comprising a, E ₇ and E ₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or E ₇ and E ₈ together are alkylene, 3-oxapentamethylene, 3-iminopentamethylene or 4 to 6 carbon atoms or 3-methyliminopentamethylene, E ₁₁ is hydrogen, straight or branched C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched C ₃ -C ₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl, E ₁₂ is straight or branched C ₁ -C ₁₈ alkyl, straight or branched C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl, E ₁₃ is straight chain or branched C ₁ -C ₁₈ alkyl substituted by H, —PO (OR ₁₂ ) ₂ , unsubstituted or phenyl substituted by OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OE ₁₂ , E ₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, of 7 to 15 carbon atoms 1,1,2 wherein the aryl or perfluoroalkyl moiety substituted by phenylalkyl, aryl of 6 to 10 carbon atoms or one or two alkyl having 1 to 4 carbon atoms is 6 to 16 carbon atoms , 2-tetrahydroperfluoroalkyl, L is alkylene of 1 to 12 carbon atoms, alkylidene, benzylidene, p-xylylene or cycloalkylidene of 2 to 12 carbon atoms, and T is -SO-, -SO _2- , -SO-E-SO-, -SO ₂ -E-SO _2- , -CO-, -CO-E-CO-, -COO-E-OCO-, or -CO-NG ₅ -E-NG ₅ -CO-, E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene comprising cyclohexylene of 8 to 12 carbon atoms in the middle or terminal; G ₅ is G ₃ or hydrogen, and With the proviso that when G ₂ is E ₃ SO- or E ₃ SO _2- , E ₁ is not phenylalkyl. 7. Compounds according to claim 6, represented by formula (5a).

(5a) In the above formula, G ₂ is cyano, E ₃ SO _2- , CF _3- , -COO-G ₃ , -CO-NHG ₃ or -CO-N (G ₃ ) ₂ , G ₃ is alkyl of 1 to 12 carbon atoms, E ₁ is hydrogen, phenyl, phenylalkyl of 7 to 15 carbon atoms or the phenyl or the phenylalkyl substituted by 1 to 2 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, E ₂ is alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or CH ₂ CH ₂ COOG ₄ , G ₄ is substituted by hydrogen, alkyl of 1 to 24 carbon atoms or OH Or an alkyl comprising one to six -O- atoms in the middle, or substituted by OH and one to six -O- atoms in the middle, E ₃ is alkyl of 8 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted with one or two alkyls having 1 to 4 carbon atoms, provided that G ₂ is E ₃ SO- or When E ₃ SO _2- , E ₁ is not phenylalkyl. (a) organic materials of natural, semisynthetic or synthetic polymers, and (b) thermal, oxidation or light induced decomposition furnaces, consisting of 0.01 to 5% by weight of the compounds represented by the formulas (5), (6), (7) or (8) according to Stabilized composition.