DE19748658A1 - Benzotriazole UV absorbent with increased durability - Google Patents

Abstract

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings. Some of the benzotriazoles are new and may be incorporated into any organic material, as stabilizers. The coating compositions are based on thermoset acrylic melamine resins, acrylic urethane resins, epoxy carboxy resins, silane modified acrylic melamine resins, acrylic resins with carbamate pendant groups crosslinked with melamine or acrylic polyol resins crosslinked with melamine containing carbamate groups.

Description

Benzotriazole UV absorbent that is on the benzo ring are substituted with electron-withdrawing radicals, he shows increased durability and low loss rates when in Motor vehicle coatings are incorporated.

The benzotriazoles have long been an important one Class of UV absorbers (UVA) and have wide com commercial importance and acceptance in many industrial Applications acquired. There is a lot in the prior art number of publications dealing with their manufacture and Deal application. However, since the requirements are constant will increase, the search for even more stable and durable Benzotriazoles continued. The gradual exclusion of HAPS solvents, such as xylene, due to environmental concerns and replacing them with non-HAPS solvents such as esters, Ethers or ketones, and the higher shelf life requirements on automotive coatings make this search more urgent. In fact, the automotive industry is over UVA losses from automotive paints and coatings, as in the publication of J.L. Gerlock et al., Proc. 36. Annual Tech. Sym. (Cleveland Coating Society), May 18, 1993, spelled out, very concerned.

Vysokomol Soedin, Ser. A. 18 (3), 553 (1976), be writes the linear dependence on hydrogen bonding starch and photostability in benzotriazoles.

J.E. Pickett et al., Angew. Macromol. Chem. 232, 229 (1995) describe the degradation of benzotriazole UV absorpti agents in poly (methyl methacrylate) films by light. A structural change generally caused little Differences in degradation rates unless the substitution the intramolecular hydrogen bonds required for the stabilization are critical, broke up. Pickett et al. examined no benzotriazoles which, as in the present invention,  both electron-withdrawing and electron-withdrawing groups have pen.

The state of the art leads to the conclusion conclusion that an increase in hydrogen leads to a more stable benzotriazole, but experiences not how this can be done. The present Er invention discloses benzotriazoles which show increased shelf life gene, however, this increased durability is surprisingly not always with a greater hydrogen bond strength bound. In fact, compounds have increased durability often weaker, not stronger hydrogen bonds on.

U.S.-A-4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 write selected, in the 3-position of the hydroxyphenyl benzotriazoles substituted with an α-cumyl group, the very good durability in automotive coatings gen. These benzotriazoles give the current status of Technology again. The present invention is based on position directed by benzotriazoles, which provide even better hold availability and lower loss rates than the benzotriazoles of Show state of the art.

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

The present invention relates to benzotriazole UV Absorbent with increased stability and durability and a low loss rate when used in automotive applications layers are incorporated.

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

• (a) a resin selected from the group consisting of made of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modifier acrylic melamine, an acrylic resin cross-linked with melamine Carbamate side groups or one containing carbamate groups melamine crosslinked acrylic polyol resin and
• (b) 0.01 to 5 weight percent, based on the resin solids, of a benzotriazole of the formula A, B, C or D.
  wherein
  G ₁ , G ₂ or T represents an electron-withdrawing radical,
  G _{1 represents} hydrogen or halogen,
  G ₂ 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 ,
  represents
  G _{3 is} hydrogen, straight or branched chain alkyl having 1 to 24 carbon atoms, straight or branched chain alkenyl having 2 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group on the phenyl ring having 1 to 4 alkyl having 1 to 4 carbon atoms,
  R _{1 is} hydrogen, straight or branched chain alkyl having 1 to 24 carbon atoms, straight or branched chain alkenyl having 2 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group on the phenyl ring having 1 to 4 alkyl having 1 to 4 carbon atoms,
  R ₂ straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on Phenyl ring having 1 to 3 alkyl having 1 to 4 carbon atoms; or R _{2 is} hydroxyl or -OR ₄ , wherein R _{4 is} straight or branched chain alkyl having 1 to 24 carbon atoms; or this alkyl group substituted with one or more groups -OH, -OCO-R ₁₁ , -OR ₄ , -NCO or -NH ₂ or mixtures thereof; or this alkyl or alkenyl group, interrupted by one or more groups -O-, -NH- or -NR ₄ - or mixtures thereof, and which are unsubstituted or with one or more groups -OH, -OR ₄ or -NH ₂ or Gemi may be substituted thereof; or R _{2 represents} -SR ₃ , -NHR ₃ or -N (R ₃ ) ₂ ;
  wherein R ₃ alkyl with 1 to 20 carbon atoms, hydroxyalkyl with 2 to 20 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, aryl with 6 to 10 carbon atoms or this aryl group with one or two alkyls with 1 to 4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, in which the perfluoroalkyl radical has 6 to 16 carbon atoms,
  or R ₂
  - (CH ₂ ) _m -CO-X- (Z) _p -YR ₁₅
  represents
  wherein
  X represents -O- or -N (R ₁₆ ) -,
  Y represents -O- or -N (R ₁₇ ) -,
  ZC ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene, interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C ₃ -C ₁₂ alkylene, butenylene, butylene, cyclohexylene or phenylene, each substituted with a hydroxyl group,
  R ₁₆ and R ₁₇ independently of one another represent hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkyl, interrupted by 1 to 3 oxygen atoms, or represent cyclohexyl or C ₇ -C ₁₅ aralkyl and R ₁₆ together with R ₁₇ also forms ethylene when Z is ethylene,
  m is zero, 1 or 2,
  p is 1 or p is also zero if X and Y represent -N (R ₁₆ ) - and -N (R ₁₇ ) -,
  R _{15 represents} a group -CO-C (R ₁₈ ) = C (H) R ₁₉ or, if Y represents -N (R ₁₇ ) - together with R _{17 represents} a group -CO-CH = CH-CO-, wherein R _{18 represents} hydrogen or methyl and R _{19 represents} hydrogen, methyl or -CO-XR ₂₀ , wherein R _{20 is} hydrogen, C ₁ -C ₁₂ alkyl or a group of the formula
  represents
  wherein the symbols G ₁ , G ₂ , R ₁ , X, Z, m and p have the meanings defined before
  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 straight or branched chain C ₁ -C ₂₄ alkyl which is interrupted by -O-, -S- or -NR ₁₁ and which is unsubstituted or substituted by -OH or -OCO-R ₁₁ , C ₅ -C ₁₂ cycloalkyl which is unsubstituted or is substituted with -OH represents straight-chain or branched-chain C ₂ -C ₁₈ alkenyl which is unsubstituted or substituted with -OH, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-R ₁₃ or glycidyl,
  R _{6 represents} hydrogen, straight-chain or branched-chain C ₁ -C ₂₄ alkyl which is unsubstituted or substituted by one or more groups OH, OR ₄ or NH ₂ , or -OR ₆ - (OCH ₂ CH ₂ ) _w OH or - (OCH ₂ CH ₂ ) _w OR ₂₁ , in which w is 1 to 12 and R _{21 represents} alkyl having 1 to 12 carbon atoms,
  R ₇ and R _{8 are} independently hydrogen, alkyl having 1 to 18 carbon atoms, straight or branched chain C ₃ -C ₁₈ alkyl which is interrupted by -O-, -S- or -NR ₁₁ -, C ₅ -C ₁₂ Represent cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxylalkyl, or R ₇ and R ₈ together with the N atom represent a pyrrolidine, piperidine, piperazine or morpholine ring,
  when n is 2, R _{5 represents} one of the divalent radicals -OR ₉ -O- or -N (R ₁₁ ) -R ₁₀ -N (R ₁₁ ) -,
  R ₉ C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, straight or branched chain C ₄ -C ₁₀ alkylene, which by -O- or by -CH ₂ -CHOH -CH ₂ -OR ₁₄ -O-CH ₂ -CHOH-CH ₂ - is interrupted,
  R _{10 represents} straight-chain or branched-chain C ₂ -C ₁₂ alkylene which is substituted by -O-, cyclohexylene or
  may be interrupted, or R ₁₀ and R ₁₁ form a piperazine ring with the two nitrogen atoms,
  R ₁₄ straight or branched chain C ₂ -C ₈ alkylene, ge wheel or branched chain C ₄ -C ₁₀ alkylene through -O-, cycloalkylene, arylene or
  may be interrupted, in which R ₇ and R ₈ independently represent hydrogen, alkyl having 1 to 18 carbon atoms, or R ₇ and R ₈ together represent alkylene having 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene ,
  R _{11 is} hydrogen, straight or branched chain C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched chain C ₃ -C ₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ Aralkyl represents
  R ₁₂ straight or branched chain C ₁ -C ₁₈ alkyl, straight or branched chain C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₅ - Aralkyl,
  R ₁₃ H, straight or branched chain C ₁ -C ₁₈ alkyl which is substituted with -PO (OR ₁₂ ) ₂ , phenyl which is unsubstituted or substituted with OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OR ₁₂ ,
  L represents alkylene having 1 to 12 carbon atoms, alkylidene having 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
  T -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 -
  wherein E represents alkylene with 2 to 12 carbon atoms, cycloalkylene with 5 to 12 carbon atoms or alkylene, interrupted by or terminated with cyclohexylene with 8 to 12 carbon atoms,
  the benzotriazole showing increased durability and low loss rates when the coating is exposed to actinic radiation, confirmed by a loss of less than 0.22 absorbance units after exposure for 1200 hours, or less than 0.27 absorbance units after 1500 hours Exposure, or less than 0.40 absorbance units after 2500 hours of exposure in a Xenon Arc Weather-O-meter.

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

wherein
G _{2 represents} fluorine, chlorine, cyano, R ₃ SO ₂ -, CF ₃ -, -CO-G ₃ , -COO-G ₃ or -CO-N (G ₃ ) ₂ ,
G _{3 represents} alkyl having 1 to 12 carbon atoms,
R _{1 represents} hydrogen, alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or this phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups having 1 to 4 carbon atoms,
R ₂ alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or -CH ₂ CH ₂ COOG ₄ , in which G _{4 is} hydrogen, alkyl having 1 to 24 carbon atoms or this alkyl group, substituted by OH, interrupted by represents one to six atoms -O- or both substituted with OH and interrupted by one to six atoms -O-, and
R _{3 represents} alkyl having 1 to 18 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms.

More preferred is in the compound of formula A '
G ₂ fluorine, chlorine, cyano, R ₃ SO ₂ -, CF ₃ -, -COO-G ₃ or -CO-N (G ₃ ) ₂ ,
G ₃ alkyl having 1 to 8 carbon atoms,
R _{1 is} hydrogen, phenyl or α-cumyl,
R _{2 is} alkyl of 4 to 12 carbon atoms or phenyl and
R _{3 is} phenyl or alkyl of 8 to 12 carbon atoms.

In particular, compounds of the formula A 'are those in which G _{2 is} phenyl-SO ₂ -, octyl-SO ₂ -, fluorine or CF ₃ -, R _{1 is} α-cumyl or phenyl and R _{2 is} tert-butyl or tert-octyl , prefers.

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

Examples of these various residues are as follows:
If one of the radicals R ₁ to R _{21 is} alkyl, such groups are, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, tert-octyl, Lauryl, tert-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; if one of the radicals is alkenyl, such groups are, for example, allyl or oleyl; if one of the radicals is cycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; if one of the radicals is phenylalkyl, such groups are, for example, benzyl, phenethyl, α-methylbenzyl and α, α-dimethylbenzyl; and when one of the radicals is aryl they are, for example, phenyl, naphthyl or, when substituted with alkyl, they are, for example, tolyl and xylyl. If R _{6 is} alkyl substituted with one or more groups -O- and / or substituted with one or more groups -OH, the radical -OR _{6 can,} for example, be (OCH ₂ CH ₂ ) _w OH or - (OCH ₂ CH ₂ ) represent _w OR ₂₁ , wherein w is 1 to 12 and R _{21 represents} alkyl having 1 to 12 carbon atoms.

For example, when E is alkylene, it is ethyl len, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, Octamethylene, decamethylene and dodecamethylene; if E Cyclo represents alkylene, it is for example cyclopentylene, Cy clohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E is alkylene interrupted by or terminated with Cy clohexylene, it is, for example, the saturated Diyl radical derived from limonene, herein dihydrolimony diyl called.

A further preferred embodiment of the invention is a compound of the formula III, in which R _{1 is} tert-butyl, n is 1, R _{3 is} phenyl and R _{5 is} -OR ₆ , in which R _{6 is} a straight-chain or substituted octyl group. A further preferred embodiment of the present invention is also a compound of the formula C, in which n is 2, R _{1 is} tert-butyl, R _{3 is} phenyl and R _{5 is} -OR ₉ -O-, in which R _{9 is} C ₂ - C ₂₄ alkylene, interrupted by -O- or by -CH ₂ -CHOH-CH ₂ -OR ₁₄ -O-CH ₂ -CHOH-CH ₂ -.

If the present compounds contain a free carboxy radical in which R _{2 represents} -CH ₂ CH ₂ COOR ₆ , in which R _{6 represents} hydrogen, the alkali metal or amine salts of the acids are also conceivable as part of this invention, such UV absorbers due to the Increased water solubility of the present compounds can be used in aqueous systems.

R ₆ , R ₇ and R ₈ can be the following C ₃ -C ₁₈ -alkyl radicals which are interrupted by -O-, -S- or -NR ₁₁ - and can be substituted by OH: methoxyethyl, 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, dode cyloxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybu tyl, 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 can be the following C ₅ -C ₁₂ cycloalkyl radicals: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In the case of R ₆ , the radical can also be substituted with -OH.

R ₇ , R ₈ and R ₁₁ may be the following alkenyl groups: allyl, methallyl, 2-n-hexenyl or 4-n-octenyl.

When R _{6 is} alkenyl, it can have the same meaning as R ₇ , R ₈ and R ₁₁ as alkenyl radicals, but it can also be -CH = CH ₂ , n-undec-10-enyl or n-octadec-9-enyl be and it is also possible that the radical R _{6 is} substituted with -OH.

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

If R ₁₁ , R ₁₃ or R _{12 are} aralkyl, they can independently of one another have the same meanings as for R ₇ or R ₈ .

Independently of one another, R ₇ , R ₈ and R _{11 can 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-hydroxyethyl 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 can mean the following radicals, but can also additionally represent groups of relatively high molecular weight, such as decylene or dodecylene.

When R _{9 is} C ₄ -C ₈ alkenylene, the following is an example of a suitable group: butenylene.

In the case of R ₉ and R ₁₄ , suitable straight or branched chain C ₄ -C ₁₀ alkylene groups which are interrupted by -O- 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 represents} a cycloalkylene group, the following groups are included: 1,3-cyclohexylene and 1,4-cyclo hexylene.

If R _{14 represents} arylene, this can in particular be the following groups: 1,3-phenylene or 1,4-phenylene.

As C ₂ -C ₁₂ alkylene, Z is a straight or branched chain. It is for example: ethylene, propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene, 2,2-amylidene or 2-ethylhexamethylene. C ₂ -C ₆ alkylene groups are preferred.

If ZC ₄ -C ₁₂ alkylene is interrupted by oxygen, it 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 when alkylene is interrupted by nitrogen, this means a group -N (R ₁₆ ) -, wherein R _{16 is} as defined above, 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 -.

As C ₃ -C ₁₂ alkylene, substituted with a hydroxyl group, Z is 2-hydroxytetramethylene, 2-hydroxyhexame and especially 2-hydroxytrimethylene.

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

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

m can be zero, 1 or 2, but it is preferred wise 2.

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

As C ₁ -C ₈ alkyl, R _{1 is,} for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-hexyl, n- Heptyl, n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.

As C ₁ -C ₁₂ alkyl, R ₁₆ , R ₁₇ and R _{20 can have} the same meaning as those given above for R ₁ , and can also be a straight or branched chain nonyl, decyl, undecyl or represent dodecyl group.

When R ₁₆ and R _{17 are} alkyl interrupted by oxygen atoms, the examples in question are the same as those described for Z above.

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

When Z represents ethylene, R ₁₆ and R ₁₇ together can also form ethylene, which is equivalent to bridging by a piperazine group.

If Y represents a group -N (R ₁₇ ) -, R ₁₅ and R ₁₇ together form a group -CO-CH = CH-CO- and thus form the substituent

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

However, the preferred meaning for R ₁₅ is -CO-C (R ₁₈ ) = CHR ₁₄ , where R ₁₈ and R _{19 are} preferably methyl and in particular hydrogen.

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

The present invention also relates to new benzotriazoles of the formulas I, II, III or IV

wherein
G _{1 represents} hydrogen or halogen,
G ₂ 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 represents
G ₃ straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on Phenyl ring having 1 to 4 alkyl having 1 to 4 carbon atoms,
E _{1 represents} hydrogen, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on the phenyl ring with 1 to 4 alkyl with 1 to 4 carbon atoms,
E ₂ straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on Phenyl ring having 1 to 3 alkyl having 1 to 4 carbon atoms; or E ₂ hydroxyl or -OE ₄ , wherein E _{4 is} straight or branched chain alkyl having 1 to 24 carbon atoms; or this alkyl group substituted with one or more groups -OH, -OCO-E ₁₁ , -OE ₄ , -NCO or -NH ₂ or mixtures thereof; or this alkyl or alkenyl group, interrupted by one or more groups -O-, -NH- or -NE ₄ - or mixtures thereof, which are unsubstituted or with one or more groups -OH, -OE ₄ or -NH ₂ or mixtures there of which may be substituted; or E _{2 represents} -SE ₃ , -NHE ₃ or -N (E ₃ ) ₂ ; or E ₂
- (CH ₂ ) _m -CO-X- (Z) _p -YE ₁₅
represents
wherein
X represents -O- or -N (E ₁₆ ) -,
Y represents -O- or -N (E ₁₇ ) -,
ZC ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene, interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C ₃ -C ₁₂ alkylene, butenylene, butylene, cyclohexylene or phenylene, each substituted with a hydroxyl group,
m is zero, 1 or 2,
p is 1 or p is also zero if X and Y represent -N (E ₁₆ ) - and -N (E ₁₇ ) -,
E _{15 represents} a group -CO-C (E ₁₈ ) = C (H) E ₁₉ or, if Y represents -N (E ₁₇ ) - together with E _{17 represents} a group -CO-CH = CH-CO-, wherein E _{18 represents} hydrogen or methyl and E _{19 represents} hydrogen, methyl or -CO-XE ₂₀ , wherein E _{20 is} hydrogen, C ₁ -C ₁₂ alkyl or a group of the formula

represents
wherein the symbols G ₁ , G ₂ , X, Z, m and p have the meanings defined above and E ₁₆ and E ₁₇ independently of one another are hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkyl, interrupted by 1 to 3 oxygen atoms, or represent cyclohexyl or C ₇ -C ₁₅ aralkyl and E ₁₆ together with E ₁₇ in the case where Z represents ethylene also form ethylene,
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 straight or branched chain C ₁ -C ₂₄ alkyl which is interrupted by -O-, -S- or -NE ₁₁ and which is unsubstituted or substituted by -OH or -OCO-E ₁₁ , C ₅ -C ₁₂ cycloalkyl which is unsubstituted or is substituted with -OH, represents straight-chain or branched-chain C ₂ -C ₁₈ alkenyl which is unsubstituted or substituted with -OH, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-E ₁₃ or glycidyl,
E _{6 is} hydrogen, straight or branched chain C ₁ -C ₂₄ alkyl which is unsubstituted or substituted by one or more groups OH, OE ₄ or NH ₂ , or -OE ₆ - (OCH ₂ CH ₂ ) _w OH or - (OCH ₂ CH ₂ ) _{w represents} OE ₂₁ , in which w is 1 to 12 and E _{21 represents} alkyl having 1 to 12 carbon atoms,
E ₇ and E _{8 are} independently hydrogen, alkyl having 1 to 18 carbon atoms, straight or branched chain C ₃ -C ₁₈ alkyl which is interrupted by -O-, -S- or -NE ₁₁ -, C ₅ -C ₁₂ Represent cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxylalkyl, or E ₇ and E ₈ together with the N atom represent a pyrrolidine, piperidine, piperazine or morpholine ring,
when n is 2, E _{5 represents} one of the divalent radicals -OE ₉ -O- or -N (E ₁₁ ) -E ₁₀ -N (E ₁₁ ) -,
E ₉ C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, straight or branched chain C ₄ -C ₁₀ alkylene, which is by -O- or by -CH ₂ -CHOH -CH ₂ -OE ₁₄ -O-CH ₂ -CHOH-CH ₂ - is interrupted,
E _{10 represents} straight-chain or branched-chain C ₂ -C ₁₂ alkylene which is substituted by -O-, cyclohexylene or

may be interrupted, or E ₁₀ and E ₁₁ form a piperazine ring with the two nitrogen atoms,
E ₁₄ straight or branched chain C ₂ -C ₈ alkylene, ge wheel or branched chain C ₄ -C ₁₀ alkylene through -O-, cycloalkylene, arylene or

may be interrupted, in which E ₇ and E ₈ independently represent hydrogen, alkyl having 1 to 18 carbon atoms, or E ₇ and E ₈ together represent alkylene having 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene ,
E _{11 is} hydrogen, straight or branched chain C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched chain C ₃ -C ₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ Aralkyl represents
E ₁₂ straight or branched chain C ₁ -C ₁₈ alkyl, straight or branched chain C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₅ - Aralkyl,
E ₁₃ H, straight or branched chain C ₁ -C ₁₈ alkyl which is substituted with -PO (OE ₁₂ ) ₂ , phenyl which is unsubstituted or substituted with OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OE ₁₂ ,
E ₃ alkyl having 1 to 20 carbon atoms, hydroxyalkyl having 2 to 20 carbon atoms, alkenyl having 3 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group with one or two alkyls with 1 to 4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, in which the perfluoroalkyl radical has 6 to 16 carbon atoms,
L represents alkylene having 1 to 12 carbon atoms, alkylidene having 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
T -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-,
wherein E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene, interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms;
G _{5 represents} G ₃ or hydrogen and with the proviso that E ₁ does not represent phenylalkyl if G _{2 represents} E ₃ SO or E ₃ SO ₂ .

The new benzotriazole is preferably a compound of the formula I '

wherein
G _{2 is} cyano, E ₃ SO ₂ -, CF ₃ -, -COO-G ₃ , -CO-NHG ₃ or -CO-N (G ₃ ) 2,
G _{3 represents} alkyl having 1 to 12 carbon atoms,
E _{1 represents} hydrogen, phenyl, phenylalkyl with 7 to 15 carbon atoms or this phenyl or phenylalkyl group, substituted on the phenyl ring with 1 or 2 alkyl groups with 1 to 4 carbon atoms,
E ₂ alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or -CH ₂ CH ₂ COOG ₄ , in which G _{4 is} hydrogen, alkyl having 1 to 24 carbon atoms or this alkyl group, substituted by OH, with interruptions by represents one to six atoms -O-, or both substituted with OH and interrupted by one to six atoms -O-,
E _{3 represents} alkyl having 8 to 18 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group, substituted by one or two alkyl having 1 to 4 carbon atoms, and
with the proviso that E _{1 is} not phenylalkyl when G _{2 is} E ₃ SO- or E ₃ SO ₂ -.

More preferred is in the compound of formula I '
G ₂ cyano, E ₃ SO ₂ -, CF ₃ -, -CO-G ₃ or -CO-N (G ₃ ) ₂ ,
G ₃ alkyl having 1 to 8 carbon atoms,
E _{1 is} hydrogen, phenyl or α-cumyl,
E ₂ alkyl of 4 to 12 carbon atoms and
E ₃ phenyl or octyl and
with the proviso that E _{1 is} not α-cumyl when G _{2 is} E ₃ SO ₂ -.

Compounds of the formula I 'in which G _{2 is} CF ₃ -, E _{1 is} α-cumyl and E _{2 is} tert-butyl or tert-octyl are particularly preferred.

The present invention also relates to a composition comprising stabilized against thermal, oxidative or light-induced degradation

• (a) an organic material that is thermal, is subject to oxidative or light-induced degradation, and
• (b) an effectively stabilizing amount of a verb extension of formula I, II, III or IV.

The organic material is preferably a natural one ches, semi-synthetic or synthetic polymer, in particular another a thermoplastic polymer.

Most preferably the polymer is a polyolefin or polycarbonate, especially polyethylene or polypropy len, especially polypropylene.

In a further preferred embodiment of the In the present invention, the organic material is a resin selected from the group consisting of a thermosetting Acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, one with Mela min cross-linked acrylic resin with carbamate side groups or one Acrylpo crosslinked with melamine containing carbamate groups lyol resin.

Most preferably the resin is a thermosetting Acrylic melamine resin or an acrylic urethane resin.

In a further preferred embodiment of the In the present invention, the organic material is an on drawing material.

The recording materials according to the invention are for pressure-sensitive copying systems, photocopying systems under Use of microcapsules, heat-sensitive copying systems, suitable for photographic materials and inkjet printing.

The recording materials according to the invention are characterized by an unexpected improvement in quality activity, especially with regard to light fastness.

The recording materials according to the invention have the structure known for the special use. she  consist of a common carrier, for example paper or plastic film with one or more layers was coated. Depending on the material type these layers keep the appropriate compo required in the case of photographic materials, for example Silver halide emulsions, dye couplers, dyes and the like. Material that is special for inkjet printing is suitable, has a layer on a conventional carrier which is particularly absorbent for printing ink. Unbe layered paper can also be used for inkjet printing be applied. In this case, the paper works simultaneously as a carrier material and as an ink absorption layer. Ge suitable material for inkjet printing is for example in US-A-5 073 448 (incorporated by reference in this specification taken) described.

The recording material can also be transparent as in the case of projection foils.

The compounds of formula I, II, III or IV can already in the paper production in the carrier material the manufacture of the latter are incorporated, at the play by adding them to paper pulp. A white Another method of application is spraying the carrier materials with an aqueous solution of the compounds of the Formula I, II, III or IV or the addition of the compounds the coating composition.

Coating compositions for transparent recording materials suitable for projection seen, must not contain particles that contain light scatter, for example pigments and fillers.

The dye-binding coating composition can be a variety of other additives, such as antioxidants dantien, light stabilizers (including also UV absorber agents that do not belong to the UV absorbers of Er invention), viscosity improvers, fluorescence enhancers solvents, biocides and / or antistatic agents ten.

The coating composition is usually like manufactured below: the water-soluble components,  for example the binder, are dissolved in water and with stirred up each other. The solid components, for example Fillers and other additives that have already been described are dispersed in this aqueous medium. The Tues version is preferably with devices, for example Ultrasonic probes, turbine stirrers, homogenizers, colloid mills, ball mills, sand mills, high speed stirrers and the like. The compounds of the formulas I, II, III and IV can easily be incorporated into the coating composition be incorporated.

The recording material according to the invention preferably contains 1 to 5000 mg / m ² , in particular 50-1200 mg / m ² , of a compound of the formula I.

As already mentioned, the invention comprises Recording materials a wide area. The connections of the formula I, II, III or IV can, for example, in print sensitive copier systems can be used. You can either incorporated into the paper to make the microein to protect encapsulated dye precursors from light, or in the binder of the developer layer around the ones formed there Protect dyes.

Photocopying systems using photosensitivity microcapsules, which are developed by pressure, are in US-A-4,416,966, 4,483,912, 4,352,200, 4,535,050, 4 536 463, 4 551 407, 4 562 137 and 4 608 330, also in 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 of these Systems can receive the compounds in the dye layer can be used. The connections can, however can also be used in the donor layer to the color image to protect from light.

Photographic materials that are stabilized can be photographic dyes and layers that sol che dyes or precursors thereof, e.g. B. fotogra fish paper and photographic transparencies. Suitable materia lines are described, for example, in US-A-5 364 749 (by reference included in the description). The connection gene of formula I, II, III or IV act here as a UV filter  against electrostatic lightning. In color photographic materia lien become couplers and dyes also against photoche Mix decomposition protected.

The present compounds can be used for all types color photographic materials are used. Example you can use it for color proof paper, color reversal paper, di rect-positive color paper, color negative film, color positive film, Color reversal film, etc. can be used. You will prefer among other things for color photographic materials that an order contain sweeping substrate, or for the production of positives used.

Color photographic materials included usually a carrier, a blue sensitive and / or green sensitive and / or red sensitive silver halide emulsions onsschicht and, if desired, a protective layer, wherein the compounds preferably either in the green sensitive chen or in the red-sensitive or in a layer between green sensitive and red sensitive layer or in a layer on top of the silver halide emulsion layers lie.

The compounds of formulas I, II, III or IV can in recording materials based on the principles pien of photopolymerization, photoplastification or Auf tearing of microcapsules or in cases where heat sensitive and light-sensitive diazonium salts, leuco color substances with an oxidizing agent or dye lactones used with Lewis acids.

They can also be used in recording materials for Dye diffusion transfer printing, thermal wax transfer printing and non-matrix printing or for use with electrostatics , electrographic, electrophoretic, magnetographic phical and laser electrophotographic printers and Pen plotters can be used. From the above drawing materials for dye diffusion transfer printing are, for example, those described in EP-A-507 734 before moves.

You can also print inks, for example for Inkjet printing such as B. additionally in US-A-5 098 477  (incorporated into the revelation by this reference) wrote, used.

The compounds of the invention show excellent nete hydrolytic stability, handling and storage stability quality as well as good resistance to extractability, if they are in a stabilized composition.

The procedure for making the present Connections are described in the prior art. Which he required intermediates for the preparation of the present the connections are mostly objects of trade.

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

Generally, polymers that can be stabilized include:

• 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and also poly mers of cycloolefins, for example cyclopentene or nor boron, polyethylene (which, if appropriate can be networked), e.g. B. high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
  Polyolefins, ie polymers of monoolefins, which were exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be produced by different processes, in particular by the following processes:
• a) Radical polymerization (usually under High pressure and at elevated temperature).
• b) catalytic polymerization using a Catalyst, which is usually one or more than one metal of groups IVb, Vb, VIb or VIII of the periodic table of the Contains items. These metals usually have one or more than one ligand, generally oxides, halides, Alcoholates, esters, ethers, amines, alkyls, alkenyls and / or Aryls, which can be either π or σ coordinated. This Metal complexes can be in free form or fixed to substra ten are present, generally on activated magnesium chlo  rid, titanium (III) chloride, aluminum oxide or silicon dioxide. These catalysts can dissolve in the polymerization medium be insoluble or insoluble. The catalysts can be used as such used in the polymerization or additional Ak tivators can be used, generally Metallal kyle, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of the groups Ia, IIa and / or IIIa of the Periodic Table of the Elements. The activators can expediently with additional Modified ester, ether, amine or silyl ether groups be. These catalyst systems are usually Phillips, Standard Oil Indiana-, Ziegler (-Natta) -, TNZ (DuPont) -, Me called tallocen or single site catalysts (SSC).
• 2. Mixtures of polymers listed under 1) for example mixtures of polypropylene with Polyisobu tylen, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for Example LDPE / HDPE).
• 3. Copolymers of monoolefins and diolefins other or with other vinyl monomers, for example ethylene / Linear Low Density Polyethylene (LLDPE) Propylene Copolymers and its mixtures with low-density polyethylene (LDPE), Propylene / but-1-ene copolymers, propylene / isobutylene copolyme right, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, Ethylene / methylpentene copolymers, ethylene / heptene copolymers, Ethylene / octene copolymers, propylene / butadiene copolymers, iso butylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, Ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate co polymers and their copolymers with carbon monoxide or ethyl len / acrylic acid copolymers and their salts (ionomers) and Terpolymers of ethylene with propylene and a diene such as He xadiene, dicyclopentadiene or ethylidene norbornene and Ge mixing such copolymers with one another and with polymers, which were mentioned in 1) above, for example Polypro pylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate Copolymers (EVA), LDPE / ethylene acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or statistical Po  lyalkylene / carbon monoxide copolymers and mixtures thereof whose polymers, e.g. B. polyamides.
• 4. Hydrocarbon resins (for example C ₅ -C ₉ ) including hydrogenated modifications thereof (for example tackifiers) and mixtures of polyalkylenes and starch.
• 5. Polystyrene, poly- (p-methylstyrene), poly- (α-methyl styrene).
• 6. Copolymers of styrene or α-methylstyrene with Di or acrylic derivatives, such as styrene / butadiene, Styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / Alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / male acid anhydride, styrene / acrylonitrile / methyl acrylate; Mixtures high impact resistance from styrene copolymers and others Polymer, for example polyacrylate, a diene polymer or a Ethylene / propylene / diene terpolymer; and block copolymers from Sty rol, for example styrene / butadiene / styrene, styrene / isoprene / sty rol, styrene / ethylene / butylene / styrene or styrene / ethylene / propy len / styrene.
• 7. graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadi en-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Sty rol, acrylonitrile and methyl methacrylate on polybutadiene; Sty rol and maleic anhydride on polybutadiene; Styrene, acrylic nitrile and maleic anhydride or maleimide on poly butadiene; Styrene and maleimide on polybutadiene; Styrene and Alkyl acrylates or methacrylates on polybutadiene, styrene and Acrylonitrile on ethylene / propylene / diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl meth acrylates, styrene and acrylonitrile on acrylate / butadiene copo lymeren and mixtures thereof with those listed under 6) Copolymers, for example the copolymer blends known as ABS, MBS, ASA or AES polymers.
• 8. Halogen-containing polymers, such as polychloroprene, chlo rated rubbers, chlorinated or sulfochlorinated poly ethylene, copolymers of ethylene and chlorinated ethylene, epi chlorohydrin homopolymers and copolymers, especially polymers halogen-containing vinyl compounds, for example polyvinyl  chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinyli denfluoride and copolymers thereof, such as vinyl chloride / vinyl lidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride rid / vinyl acetate copolymers.
• 9. Polymers derived from α, β-unsaturated made acids and derivatives thereof, such as polyacrylates and Po lymethacrylates, polymethyl methacrylates, polyacrylamides and Polyacrylonitrile, impact modified with butyl acrylate.
• 10. Copolymers of monomers listed under 9) with each other or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / Al kylacrylate copolymers, acrylonitrile / alkoxyalkylacrylate or Acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.
• 11. Polymers made by unsaturated alcohols and Amines are derived, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stea rat, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, Po lyallyl phthalate or polyallyl melamine and their copolymers with olefins mentioned under 1) above.
• 12. Homopolymers and copolymers of cyclic Ethers such as polyalkylene glycols, polyethylene oxide, polypropy lenoxid or copolymers thereof with bisglycidyl ethers.
• 13. Polyacetals such as polyoxymethylene and those poly oxymethylenes containing ethylene oxide as a comonomer, poly acetals, modified with thermoplastic polyurethanes, Acrylates or MBS.
• 14. Polyphenylene oxides and sulfides and mixtures of Polyphenylene oxides with styrene polymers or polyamides.
• 15. Polyurethanes, on the one hand from polyethers, Po lyesters or polybutadienes with terminal hydroxyl groups pen and on the other hand of aliphatic or aromatic Po lyisocyanates and precursors are derived from them.
• 16. Polyamides and copolyamides that are derived of diamines and dicarboxylic acids and / or of aminocarbon acids or the corresponding lactams, such as polyamide 4, Po lyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides, starting from m-Xy  loldiamine and adipic acid; Polyamides made from hexa methylenediamine and isophthalic acid and / or terephthalic acid and optionally with an elastomer as a modifier tel, for example poly-2,4,4-trimethylhexamethylene terephthalate amide or poly-m-phenylene isophthalamide; and also block copo polymers of the above-mentioned polyamides with polyolefins, Olefin copolymers, ionomers or chemically bound or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetrame ethylene glycol; as well as polyamides or copolyamides with EPDM or ABS, and polyamides used during manufacture be condensed (RIM polyamide systems).
• 17. Polyureas, polyimides, polyamide imides, and Polybenzimidazoles.
• 18. Polyesters derived from dicarboxylic acids and diols and / or of hydroxycarboxylic acids or the equivalent lactones such as polyethylene terephthalate, polybutylene rephthalate, poly-1,4-dimethylolcyclohexane terephthalate and Po lyhydroxybenzoate and block copolyether esters of polyethers with hydroxyl end groups and also polyester, mo differs with polycarbonates or MBS.
• 19. Polycarbonates and polyester carbonates.
• 20. Polysulfones, polyether sulfones and polyetherke tone.
• 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines of others on the one hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
• 22. Drying and non-drying alkyd resins.
• 23. Unsaturated polyester resins derived from Copo with saturated and unsaturated dicarboxylic acids polyhydric alcohols and vinyl compounds as Vernet agents and also halogen-containing modifications thereof lower flammability.
• 24. Crosslinkable acrylic resins derived from substit ated acrylates, such as epoxy acrylates, urethane acrylates or Polyester acrylates.  
• 25. alkyd resins, polyester resins and acrylate resins, ver wets with melamine resins, urea resins, polyisocyanates or epoxy resins.
• 26. Crosslinked epoxy resins derived from Polyep oxides, for example of bisglycidyl ethers or of cycloali phatic diepoxides.
• 27. Natural polymers, such as cellulose, rubber, Gelatin and chemically modified homologous derivatives thereof, such as cellulose acetates, cellulose propionates and cellulose butes rate or the cellulose ethers, such as methyl cellulose; such as Natural resins and their derivatives.
• 28. Mixtures of polymers mentioned above (polymer blends), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.
• 29. Naturally occurring and synthetic organic Materials that are purely monomeric compounds or mixtures such compounds are, for example, mineral oils, animal and vegetable fats, oils and waxes or oils, fats and Waxes based on synthetic esters (for example Phthalates, adipates, phosphates or trimellitates) and also Mixtures of synthetic esters with mineral oils in belie other weight ratios, generally those that are considered Spin agents are used, as well as aqueous emulsions sol materials.
• 30. Aqueous emulsions natural or synthetic rubber, for example natural latex or latices of carboxylated styrene / butadiene copolymers.
• 31. Polysiloxanes, such as the soft hydrophilic poly siloxanes, which are described, for example, in US Pat. No. 4,259,467 and the hard polyorgano siloxanes, which are described, for example, in US Pat. No. 4,355,147.
• 32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated Acrylic resins. The unsaturated acrylic resins close the ure  thanacrylates, polyether acrylates, vinyl or acrylic copolymers with unsaturated side groups and the acrylated melamine a. The polyketimines are made from polyamines and ketones in Presence of an acid catalyst produced.
• 33. Radiation-curable compositions containing ethylenic unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.
• 34. epoxy melamine resins, such as light-stable epoxy resins, crosslinked with an epoxy-functional melamine resin with a high solids content, such as LSE 4103 (Monsanto).

In general, the compounds will be present the invention in an amount of from about 0.01 to about 5% by weight the stabilized mass applied, although this with the particular substrate and application will fluctuate. A advantageous range is about 0.05 to about 3%, ins particularly 0.05 to about 1%.

The stabilizers of the present invention can easily into organic polymers by common techniques in any suitable stage prior to making the mold levels of it can be entered. For example, the stabilizer be mixed with the polymer in dry powder form or a suspension or emulsion of the stabilizer can with a solution, suspension or emulsion of the polymer mixed will. The stabilized polymer masses obtained from the Er if necessary, about 0.01 to about 5%, preferably about 0.025 to about 2%, especially about 0.1 up to about 1% by weight, contain various customary additives, such as the materials or mixtures listed below from that.

1. Antioxidants

1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol
2-tert-butyl-4,6-dimethylphenol
2,6-di-tert-butyl-4-ethylphenol
2,6-di-tert-butyl-4-n-butylphenol
2,6-di-tert-butyl-4-iso-butylphenol
2,6-dicyclopentyl-4-methylphenol
2- (α-methylcyclohexyl) -4,6-dimethylphenol
2,6-dioctadecyl-4-methylphenol
2,4,6-tricyclohexylphenol
2,6-di-tert-butyl-4-methoxymethylphenol.

1.2. Alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol
2,5-di-tert-butylhydroquinone
2,5-di-tert.amylhydroquinone
2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis (6-tert.butyl-4-methylphenol)
2,2'-thiobis (4-octylphenol)
4,4'-thiobis (6-tert.butyl-3-methylphenol)
4,4'-thiobis (6-tert-butyl-2-methylphenol).

1.4. Alkylidene bisphenols, for example
2,2'-methylenebis (6-tert-butyl-4-methylphenol)
2,2'-methylenebis (6-tert-butyl-4-ethylphenol)
2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol]
2,2'-methylenebis (4-methyl-6-cyclohexylphenol)
2,2'-methylenebis (6-nonyl-4-methylphenol)
2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol]
2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol]
2,2'-methylenebis (4,6-di-tert-butylphenol)
2,2'-ethylidenebis (4,6-di-tert-butylphenol)
2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol)
4,4'-methylenebis (2,6-di-tert.butylphenol)
4,4'-methylenebis (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) buty rat]
Di (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene
Di [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.

1.5. Benzyl compounds, for example
1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene
Di (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester
Bis (4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolated phthalate
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) iso cyanurate
3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid dioctadecyl ester
Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphorsäu remonoethylester.

1.6. Acylaminophenols, for example
Lauric acid 4-hydroxyanilide
Stearic acid 4-hydroxyanilide
2,4-bis (octylmercapto) -6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine
Octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. B. with
Methanol
Octadecanol
1,6-hexanediol
Neopentyl glycol
Thiodiethylene glycol
Triethanolamine
Diethylene glycol
Triethylene glycol
Pentaerythritol
Tris (hydroxyethyl) isocyanurate
Dihydroxyethyl oxalic acid diamide
Triisopropanolamine.

1.8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) per pionic acid with mono- or polyhydric alcohols, e.g. B. with
Methanol
Octadecanol
1,6-hexanediol
Neopentyl glycol
Thiodiethylene glycol
Triethanolamine
Diethylene glycol
Triethylene glycol
Pentaerythritol
Tris (hydroxyethyl) isocyanurate
Dihydroxyethyl oxalic acid diamide
Triisopropanolamine.

1.9. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g. B.
N, N'-Di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine
N, N'-Di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine
N, N'-Di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

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

2. UV absorbers and light stabilizers

2.1. 2- (2, -hydroxyphenyl) benzotriazoles, for example the 5'- Methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3- Tetramethylbutyl) -, 5-chloro-3 ', 5'-di-tert.butyl-, 5-chloro-3'- tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl-, 4'- Octoxy-, 3 ', 5'-di-tert.amyl-, 3', 5'-bis (α, α-dimethylbenzyl), 3'-tert-butyl-5 '- (2- (ω-hydroxyocta- (ethyleneoxy) carbonyl) ethyl) -, 3'-dodecyl-5'-methyl-, 3'-tert-butyl-5 '- (2-octyloxy carbonyl) ethyl and dodecylated 5'-methyl derivatives.

2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyl  oxy-, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy deri vate.

2.3. Esters of optionally substituted benzoic acids, for example phenyl salicylate, 4-tert-butylphenyl salicylate, Octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert.butylben zoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxy 2,4-di-tert-butylphenyl benzoate and 3,5-di-tert. butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4. Acrylates, for example α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxycinnamic acid 50878 00070 552 001000280000000200012000285915076700040 0002019748658 00004 50759uremethyl ester, N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, for example nickel complexes from 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol] as the 1: 1 or 1: 2 complex, optionally with additional Li such as n-butylamine, triethanolamine or N-cyclohexyldi ethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4- Hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, e.g. B. the methyl, ethyl or butyl ester, nickel complexes of Ketoximes, e.g. B. of 2-hydroxy-4-methylphenylundecylketoxim, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, ge optionally with additional ligands.

2.6. Sterically disabled amines, for example bis- (2,2,6,6- tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpi peridyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxy piperidine and succinic acid, the condensation product of N, N '(2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and 4- tert-octylamino-2,6-dichloro-s-triazine, tris- (2,2,6,6-tetrame thylpiperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetrame thyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '- (1,2-  Ethanediyl) bis- (3,3,5,5-tetramethylpiperazinone), bis (1-octyl oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyl oxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-bu tyl-2'-ethyloxanilide and their mixture with 2-ethoxy-2'-ethyl 5,4'-di-tert.butyloxanilide and mixtures of ortho- and para methoxy as well as o- and p-ethoxy disubstituted oxanili the.

2.8. Hydroxyphenyl-s-triazines, for example 2,6-bis- (2,4- dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-tri azine; 2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-tri azine; 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4- chlorphenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydroxyeth oxy) phenyl] -6- (2,4-dimethylphenyl) -s-triazine; 2,4-bis [2-hy doxy-4- (2-hydroxyethoxy) phenyl] -6- (4-bromophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-acetoxyethoxy) phenyl] -6- (4-chlorophe nyl) -s-triazine; 2,4-bis (2,4-dihydroxyphenyl) -6- (2,4-dimethyl phenyl) -s-triazine.

3. Metal deactivators, for example N, N'-diphenyloxal acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis- (sa licyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphe nylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis- (benzylidene) oxalic acid dihydrazide.

4. phosphites and phosphonites, for example triphenyl phosphite, Diphenylalkylphosphites, phenyldialkylphosphites, tri (nonylphe nyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diste arylpentaerythritol diphosphite, tris (2,4-di-tert.butylphenyl) phosphite, Diisodecylpentaerythritol 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'-dipheny lylene diphosphonite.

5. Compounds that remove peroxide, for example esters of β-thiodipropionic acid, for example lauryl, stearyl, Myristyl or tridecyl ester, mercaptobenzimidazole or that Zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarb amate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate.

6. hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N- Diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilauryl hydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecyl hydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N- octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Nitrones, for example N-benzyl-α-phenylnitrone, N-ethyl-α- methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecylni tron, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-penta decylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α- heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-Hepta decyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, Ni tron derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in a combination nation with iodides and / or phosphorus compounds and salts of divalent manganese.

9. Basic costabilizers, for example melamine, polyvi nylpyrrolidone, dicyandiamide, triallyl cyanurate, urea deri vate, hydrazine derivatives, amines, polyamides, polyurethanes, alka lime metal salts and alkaline earth metal salts of higher fatty acid ren, for example Ca stearate, Zn stearate, Mg stearate, Na-Ri cinoleate and K-palmitate, antimony pyrocatecholate or zinc pyro catecholate.  

10. Nucleating agents, for example 4-tert-butylbenzoic acid, Adipic acid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, glim mer, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example plasticizers, lubricants, Emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents and propellants and thiosynergists, such as Dilauryl thiodipropionate or distearyl thiodipropionate.

13. Benzofuranones and indolinones, for example those disclosed in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2- on, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] ben zofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxy ethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-eth oxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) - 5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivalo yloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.

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

Other preferred compositions include additional Lich additives to components (a) and (b), in particular phenolic antioxidants, light stabilizers or Processing stabilizers.

Particularly preferred additives are phenolic anti oxidants (item 1. of the list), sterically hindered amines (Point 2.6. Of the list), phosphites and phosphonites (point 4. the list) and peroxide-destroying compounds (point 5. the List).

Other additives (stabilizers), which are also be are particularly preferred are Benzofuran-2-ones, such as as in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312 described.  

The phenolic antioxidant of particular interest is selected from the group consisting of 3,5-di-tert-bu tyl-4-hydroxyhydrocinnamic acid n-octadecyl ester, tetrakis (3,5- di-tert-butyl-4-hydroxyhydrocinnamic acid) neopentane tray ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid di-n-octade cylester, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocy anurate, thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocin namate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydro xybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert- butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 1,3,5-tris (2,6- dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] isocyanurate, 3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl) mesi tol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinna mat), 1- (3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di (octyl thio) -s-triazine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-4- hydroxyhydrocinnamamide), calcium bis (ethyl-3,5-di-tert-butyl- 4-hydroxybenzylphosphonate), ethylene bis [3,3-di (3-tert-butyl-4- hydroxyphenyl) butyrate], 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetic acid octyl ester, bis (3,5-di-tert-butyl-4-hydro xyhydrocinnamoyl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl- 4-hydroxyhydrocinnamoyloxy) ethyl] oxamide.

A most preferred phenolic antioxidant is tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) neo pentantetraylester, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid re-n-octadecyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene bis (4,6-di-tert-butylphenol).

The hindered amine compound of particular interest se is selected from the group consisting of bis- (2,2,6,6- tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethyl piperidin-4-yl) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4- yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzo yl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetra methylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza  spiro [4.5] decane-2,4-dione, tris (2,2,6,6-tetramethylpiperidine- 4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxopipe razin-4-yl) ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21- oxodispiro [5.1.11.2] heneicosan, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethy lenbis (amino-2,2,6,6-tetramethylpiperidine), polycondensate product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hy droxypiperidine and succinic acid, polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidine-4- yl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-penta methylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, polycon Densation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6-bis (butyl-1,2,2,6,6-pentamethyl piperidin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-di azadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl / β, β, β ', β'-tet ramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] hour can) 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] undecane) diethyl] -1,2,3,4-bu tantetracarboxylate, octamethylene bis (2,2,6,6-tetramethyl pipe ridine-4-carboxylate), 4,4'-ethylene bis (2,2,6,6-tetramethylpi perazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecyl succinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecyl succinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n- dodecyl succinimide, 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-tetramethylpiperidin-4-yl) succinate, 1-octyloxy 2,2,6,6-tetramethyl-4-hydroxypiperidine, poly - {[6-tert-octyl amino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetrame thylpiperidin-4-yl) iminohexamethylene- [4- (1-cyclohexyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) imino] and 2,4,6-tris [N- (1- cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylami no] -s-triazine.

A most preferred hindered amine compound is bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate,  Bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di (1,2,2,6,6- pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybene zyl) butylmalonate, the polycondensation product of 1- (2-Hy droxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and Bern succinic acid, the polycondensation product of 2,4-dichloro-6- tert-octylamino-s-triazine and 4,4'-hexamethylene bis (amino 2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6- bis (butyl- (1,2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-tri azin-2-yl] -1,10-diamino-4,7-diazadecane, di- (1-octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyl oxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy 2,2,6,6-tetramethyl-4-hydroxypiperidine, poly- [6-tert-octyl amino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetrame thylpiperidin-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-butyl amino] -s-triazine.

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

In particular, the present composition can additionally an effective stabilizing amount of at least another 2-hydroxyphenyl-2H-benzotriazole; a wide one ren tris-aryl-s-triazine; or hindered amine or mixtures of which included.

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

The other tris-aryl-s-triazine is preferably from selected from the group consisting of 2,4-bis (2,4-dimethyl phenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,4-diphe nyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine; 2,4-bis (2,4-di  methylphenyl) -6- [2-hydroxy-4- (3-do- / tri-decyloxy-2-hydroxy propoxy) phenyl] -s-triazine; and 2- (2-hydroxyethylamino) -4,6- bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine- 4-yl) amino] -s-triazine.

The alkyd resin paints that are resistant to the action of Light and moisture stabili according to the present invention Can be siert, are common stove enamels, esp are particularly suitable for coating motor vehicles (Car topcoats), for example paints based on Alkyd / Me laminate resins and alkyd / acrylic / melamine resins (see H. Wagner and H.F. Sarx, "Lackkunstharze" (1977), pages 99-123). On their crosslinking agents are glycouril resins, blocked iso cyanates or epoxy resins.

The varnishes stabilized according to the invention are both for metal top coats as well as solid shading decks paints, especially in the case of touch-up paints and for various coil coating applications suitable. The invent Varnishes stabilized in accordance with the invention are preferably used in standard by two methods, either by the one layer process or the two-layer process applied. In the latter process, the pigment-containing base coat is used first and then a top coat of clear lacquer over it carried.

It must also be noted that the invention Compounds for use in non-acid catalyzed thermosetting resins are applicable, e.g. B. in epoxy, Ep oxide polyesters, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicone, isocyanates or isocyanurates. The epoxy and epoxy polyester resins are mixed with conventional crosslinking agents, such as acids, acid anhydrides, Amines and the like crosslinked. Consequently, the epoxies as a crosslinking agent for various acrylic or poly ester resin systems are used by the presence was modified by reactive groups on the scaffold structure the.

When used in two-coat top coats, can the compounds of the invention in the clear coat or so  probably in the clear coat as well as in the pigmented primer be incorporated.

If water-soluble, water-miscible or water-di Aspectable coatings are desired, ammonium salts of acid groups present in the resin. The powder coating composition can be reacted of glycidyl methacrylate with selected alcohol components getting produced.

The present benzotriazoles are replaced by conventional ones Methods of making such connections. The Ordinary procedures involve the diazotization of a sub substituted o-nitraniline, followed by coupling of the obtained Diazonium salt with a substituted phenol and reduction of the azobenzene intermediate to the corresponding desired ten benzotriazole. The raw materials for this benzo Most of the triazoles are commercially available or can be normal processes of organic synthesis will.

Although the present benzotriazoles with their he increased durability especially for automotive coating applications are suitable, it is conceivable that they also in other applications in which their increased durability is required, like sun foils and the like, especially are usable.

The examples below are for illustrative purposes only Purposes.

example 1 Preparation of 5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5- tert-octylphenyl) -2H-benzotriazole a) Diazotization 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-nitrobenzotri fluoride, 52 ml concentrated hydrochloric acid and 100 ml distillate water. The stirred solution is abge to 5 ° C. cools and 17.3 g sodium nitrite, dissolved in 50 ml water, who that admitted. The solution is ge at 0 to 5 ° C for two hours stirred, then filtered and stored at -10 ° C.  

b) Monoazo adduct

To a 1000 ml flask equipped with a mecha African stirrer, 40 g of sodium hydroxide, dissolved in 200 ml Methanol, and 32.4 g of 2-α-cumyl-4-tert-octylphenol in 50 ml Given xylene. The solution is cooled to 5 ° C and the Di azo solution of 4-amino-nitro-benzotrifluoride, made in Part a, is at 0 to 5 ° C over a period of two hours that admitted. Then 100 ml of xylene are added and the organic layer with water, aqueous hydrochloric acid, water, aqueous sodium bicarbonate solution and finally water to wash. The solvent is removed under reduced pressure distant and the residue by chromatography (silica gel, Heptane: ethyl acetate 95: 5) purified to give it 42.1 g of the adduct product as a dark red paste.

c) Reduction of the monoazo adduct

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

Example 2 Preparation of 5-fluoro-2- (2-hydroxy-3-α-cumyl-5-tert-octyl phenyl) -2H-benzotriazole

The title compound is according to the general Ver drive from Example 1 using 31.2 g of 4-fluoro-2- nitraniline manufactured. Part c of the procedure includes others 9 g formamidine sulfinic acid required to reduce the  to complete. Purification of the crude product on silica gel (Heptane: toluene 1: 1) gives 4.5 g of the title compound as whitish solid. Further purification by recrystallization tion from acetonitrile: toluene provides 1.1 g of the title compound, which melts at 93-96 ° C, ready.

Example 3 Preparation of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octyl phenyl) -2H-benzotriazole

Following the general procedure of Example 1, parts a and b, becomes the monoazo intermediate of the title compound made from 339.3 g of 4-chloro-2-nitraniline. The raw product is purified by recrystallization from methanol under Ge 70.9 g of deep red monoazo adduct.

c) Reduction of the monoazo adduct

A mixture of 11.8 g sodium hydroxide and 138 g 2-butanol is heated to 95 ° C. A solution of 60.1 g of the the above monoazo adduct and 1.3 g of 2,3-dichloro-1,4-naph quinone in 90 g of 2-butanol is stirred over a 90 minutes added. The reaction mixture is heated to remove the 2-butanone by-product, wherein further 2-butanol is added to replace the distillate Zen. The reaction mixture is cooled to 85 ° C. with 2.5 N Washed sulfuric acid and brine and then concentrated. The residue is extracted from methanol: xylene installs to obtain 45.6 g of the title compound as a light yellow solid that melts at 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-hy droxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 105 g N-methylpyrrolidone, heated to 90 ° C., is initially 44.3 g 45% aqueous potassium hydroxide solution over a period of time 15 minutes, then 20.4 g of thiophenol within a further Given 15 minutes. The reaction mixture then becomes four  Heated to 170-175 ° C, the water through distill lation is removed. After cooling to 100 ° C, xylene and water are added and the resulting mixture is mixed with Acidified 15% aqueous hydrochloric acid solution. The organic Layer is separated, washed with water and then concentrated concentrated. The raw product residue is made from metha nol recrystallized to obtain 82 g of the title pro Duct as a pale yellow solid at 124-125 ° C melts.

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

A 1000 ml flask is filled with 75.2 g of 5-phenylthio-2- (2- hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole, herge in Example 4, 102 g of xylene, 0.9 g of sodium tungstate di hydrate and 18.4 g of formic acid. The mixture will heated to 50 ° C. Add to the stirred mixture slowly 36.3 g of 50% hydrogen peroxide, so that the tempe temperature does not exceed 85 ° C. More xylene and water are added afterwards. The organic layer is removed separates, with aqueous sodium sulfite, then twice with Was washed and concentrated. The raw product residue is recrystallized from methanol to obtain 75.2 g the title compound as a pale yellow solid, which at 170-171 ° C melts.

Example 6 Preparation of 5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert- octylphenyl) -2H-benzotriazole

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

Example 7 Preparation of 5-nonylsulfonyl-2- (2-hydroxy-3-α-cumyl-5- tert-octylphenyl) -2H-benzotriazole

5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphe nyl) -2H-benzotriazole, prepared in Example 6, becomes Sulfone without purification of the thio intermediate using of 8.7 g of formic acid, 0.7 g of sodium tungstate dihydrate and 17.6 g of 50% hydrogen peroxide oxidized to gain tion of the title compound as a yellow resin, which is a molecular ion from m / e 631 shows.

Example 8 Preparation of 5-chloro-2- (2-hydroxy-3-phenyl-5-tert-octyl phenyl) -2H-benzotriazole

The general procedure of Example 1, Parts a and b, is used to title the monoazo intermediate compound of 4-chloro-2-nitraniline and 2-phenyl-4-tert-oc to produce tylphenol. The raw product is made by umkristal lization from methanol cleaned to obtain a deep red monoazo adduct.

The title compound is processed according to the reduction procedure Ren of Example 3 from 65 g of the Mo prepared above noazoadducts, 19.9 g sodium hydroxide and 2.4 g 2,3-dichloro- 1,4-naphthoquinone. The raw product is through Chromatography on silica gel (hexane: ethyl acetate 5: 1) cleaned to obtain a fraction that is predominantly the Title compound which has a molecular ion of m / e 433 shows.

Example 9 Preparation of 5-phenylthio-2- (2-hydroxy-3-phenyl-5-tert- octylphenyl) -2H-benzotriazole

The title compound is processed according to the procedure of Bei game 4 from 20 g of the compound of Example 8, 20.4 g 45% aqueous potassium hydroxide, 10.3 g thiophenol and 100 g of N-methylpyrrolidone. The title link is a Oil, purified by chromatography on silica gel with Ver use of toluene as eluent.  

Example 10 Preparation of 5-benzenesulfonyl-2- (2-hydroxy-3-phenyl-5- tert-octylphenyl) -2H-benzotriazole

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

Example 11 Preparation of a mixture of 5-chloro-2- (2-hydroxy-3,5-di alkylphenyl) -2H-benzotriazole (alkyl is independently C ₄ , C ₈ , C ₁₂ and C ₁₆ )

A mixture of 65.4 g of 5-chloro-2- (2-hydroxy-3,5-dial kylphenyl) -2H-benzotriazole, 45 ml dodecene and 13 ml methane sulfonic acid is heated to 170 ° C. under nitrogen. Further 135 ml of dodecene are used within a period of 4.5 hours that admitted. The reaction mixture will cool to 100 ° C leave and then stop with 400 g of crushed ice and extracted three times with ethyl acetate. The organic Layers are combined, with water, aqueous sodium bi carbonate solution, washed again with water and brine, over dried anhydrous magnesium sulfate and finally on concentrated. The polymeric residue is Flask distillation under vacuum at 0.2 mm and up to 210 ° C away. Unreacted starting material is then through Distillation (at 0.01 mm, 160 ° C) removed, with 45 g of Title mixture can be obtained as a yellow oil.

Example 12 Preparation of a mixture of 5-phenylthio-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole (alkyl is independently C ₄ , C ₈ , C ₁₂ and C ₁₆ )

The title mix is made according to the procedure of Bei game 4 using 40 g of the mixture of example 11, 11.2 g of potassium hydroxide and 12.3 ml of thiophenol.  

Example 13 Preparation of a mixture of 5-benzenesulfonyl-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole (alkyl is independent, C ₄ , C ₈ , C ₁₂ and C ₁₆ )

A mixture of the crude product of Example 12, 350 ml Isopropanol, 14.7 ml formic acid and 1.8 ml concentrated Sulfuric acid are heated under reflux and 30 ml of 50% Hydrogen peroxide is added dropwise over a period of time of two hours added. After another three hours under The reaction mixture is cooled under reflux and 10% water aqueous sodium sulfite and aqueous sodium bicarbonate solution are admitted. The isopropanol is evaporated and the Extract the residue with methylene chloride. The organic Layer is washed with water and then over what dried magnesium sulfate. The solution is below Leave behind 45 g of crude product as a viscous orange oil concentrated. About 30 g of the crude product are separated by chroma topography on silica gel (heptane: ethyl acetate 4: 1) ge cleans as 28.9 g of the title mixture yellow oil.

Example 14 5-diphenylphosphinyl-2- (2-hydroxy-3,5-tert-butylphenyl) -2H- benzotriazole

To a flame-dried 500 ml three-necked round bottom flask ben, equipped with a cooler, magnetic stirrer and thermome ter, 100 ml of dimethyl sulfoxide, 7.41 g (0.066 mol) of Ka lium-tert-butoxide and 11.17 g (0.060 mol) of diphenylphosphine given over a syringe. A 10.56 g slurry (0.030 mol) 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H- benzotriazole in 50 ml of dimethyl sulfoxide becomes the given red mixture. The brown solution obtained is at 135 ° C stirred for 3.5 hours and then to room temperature cooled down.

The mixture becomes saturated with one part Ammonium chloride solution stopped and then acetic acid added ethyl ester. The organic layer is separated and washed three times with water, once with saline and  then dried over anhydrous magnesium sulfate. To the Solution is countered with exothermic 50% hydrogen peroxide ben. The mixture is allowed to settle for 30 minutes, then once with 10% sodium metabisulfite solution, three times with saturated ter sodium bicarbonate solution, washed once with brine and finally dried over anhydrous magnesium sulfate. The mixture is filtered through a layer of silica gel and the Solvent removed under reduced pressure under Ge recovery of 8.0 g of a dirty yellow solid. The Crude product is used with medium pressure chromatography formation of heptane: ethyl acetate, 1: 1, treated under Provision of 4.2 g (27% yield) of the title compound as a yellow solid that melts at 98-100 ° C.

Example 15 5-Diphenylphosphinyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphe nyl) -2H-benzotriazole

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

Examples 16-26

According to the general procedure of Example 1 the following further 2H-benzotriazoles of the formula I ' produced.  

Example 27 Preparation of 5-octylthio-2- (2-hydroxy-3-α-cumyl-5-tert- octylphenyl) -2H-benzotriazole

Using the procedure of Example 6 with 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H- benzotriazole and octyl mercaptan the title compound here poses.

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-octylphe nyl) -2H-benzotriazole, prepared in Example 27, becomes Sulfone without purification of the thio intermediate using tion of the general procedure of Example 7 oxidized.

Example 29 Preparation of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotri azole

Following the general procedure of Example 1, parts a & b, becomes the monoazo intermediate of the title compound  made from 17.3 g of 4-chloro-2-nitraniline with recovery 34.7 g of a deep red, moist cake from the monoazoad ducts.

Reduction of the monoazo adduct

A mixture of 20 g sodium hydroxide, 500 ml water and 26.3 g of Mo's previously made moist cake noazoaddukts is heated to 30 ° C. Zinc powder (33.0 g) added in portions within two hours. In the end the This addition, dropwise 180 g of 40% aqueous sodium Umhydroxidlösung added over an hour. The mixture will stirred at ambient temperature for 96 hours. The zinc residue is removed by filtration. The aqueous solution is on pH 5-6 neutralized and the slurry obtained fil trated. The filter cake obtained is washed well with water and dried to 22.5 g of raw product. The raw product is purified by Soxhlet extraction with acetone under Ge recovery of 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-dihydroxyphe nyl) -2H-benzotriazole, 7.1 g 1-bromooctane, 5.2 g aqueous Ka lium carbonate and 100 ml of acetone is refluxed for 24 hours heated. About 100 ml of water are added to the mixture obtained and ethyl acetate and 10.6 g of crude product isolated. Column chromatography using Pe trol ether gives 0.9 g of the title compound, its structure is confirmed by H-NMR and mass spectrometry.

Example 31 Preparation of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H- benzotriazole

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

Example 32 Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-octyloxyphe nyl) -2H-benzotriazole

The title compound is according to the general Ver drive from Example 30 from 5.6 g of 5-trifluoromethyl-2- (2,4-di hydroxyphenyl) -2H-benzotriazole. The raw product is purified by column chromatography to obtain of 1.1 g of the title compound as a white solid, which at 79-81 ° C melts. The structure is determined by H-NMR and masses spectrometry confirmed.

Example 33 Preparation of 5-trifluoromethyl-2- [2-hydroxy-4- (3-butoxy-2- hydroxypropoxy) phenyl] -2H-benzotriazole

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

Example 34 Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) - 2H-benzotriazole

The title compound is according to the general ver proceed from example 1 and example 29, starting from 4-amino 3-nitrobenzotrifluoride and 3-aminophenol. The Structure of the product is confirmed by NMR.

Example 35 Preparation of 5-trifluoromethyl-2- [2-hydroxy-4- (2-ethylhexa noylamino) phenyl] -2H-benzotriazole

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

Example 36 Preparation of 5-carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert- octylphenyl) -2H-benzotriazole a) Esterification of 4-amino-3-nitrobenzoic acid

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

b) Diazotization of 4-amino-3-nitrobenzoic acids thylester

To a 1 liter three-necked flask equipped with a mechanical stirrer, 177 g of 96% sulfuric acid and then slowly countered 11 g of sodium nitrite within 90 minutes ben. The mixture is at 30 ° C to start the reaction warms, the temperature is kept below 70 ° C. The Ge Mix is then cooled to 15 ° C and 30 g of 4-amino-3-ni Trobenzoic acid methyl ester are under within two hours Keep the temperature between 15 and 20 ° C added. The Ge the mixture is cooled to 0 ° C. and 200 g of ice are added, to the solution for the coupling reaction, to form a To make monoazo compound suitable.

c) Monoazo adduct

To a 2 l three-necked flask equipped with one mechanical stirrer and an addition funnel, 52 g 2-α-cumyl-4-tert-octylphenol, 20 g water, 315 g methanol, 7 g of xylene and 150 g of sodium hydroxide. The mixture will  cooled to -5 ° C and the Di prepared in step b Azonium salt solution is used over a two hour period while cooling to keep the temperature below 3 ° C ben. After the diazonium salt solution is added, the pH adjusted to 6.5-7.0. The mixture is poured into 500 ml Poured xylene and washed three times with 500 ml of water at 60 ° C . The xylene is removed by distillation under Ge recovery of 186 g of the monoazo adduct, the remaining xylene contains.

d) Reduction of the monoazo adduct

To a 500 ml flask equipped with a mecha African stirrer, 186 g of monoadduct are manufactured in Step c, 125 g 2-butanol and 1.7 g 2,3-dichloro-1,4-naphtho given quinone. The mixture is heated to 90 ° C and he held solution is then to the addition funnel at egg given a separate piston. Be in the second piston 175 g of 2-butanol and 18.6 g of sodium hydroxide were added. The col ben is heated to 95 ° C and the monoazo solution becomes internal added half an hour while distilling off Me ethyl ethyl ketone and 2-butanol. 2-Butanol (100 g) is added ben and distilled off an azeotrope. The mixture is then cooled and 300 g of xylene and 200 ml of water are added. The pH is adjusted to 7-7.5 with 20% sulfuric acid poses. The aqueous phase is separated off at 60 ° C. and the organic phase washed twice with 200 ml of water. The Xy lol is removed by distillation and the back formed was crystallized from methanol to obtain 8.8 g the title compound, which melts at 141-143 ° C.

Example 37 Preparation of 5- [N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-α- cumyl-5-tert-octyl) phenyl] -2H-benzotriazole a) Saponification of 5-carbomethoxy-2- (2-hydroxy-3-α-cu myl-5-tert-octylphenyl) -2H-benzotriazole

To a 250 ml three-necked flask equipped with one mechanical stirrer, thermometer, cooler and nitrogen 1.8 g of potassium hydroxide and 40 ml of methanol are added.  

The mixture is used to dissolve the potassium hydroxide at 40 ° C warmed up. 2.7 g of 5-carbomethoxy-2- (2-hy droxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole, herge in Example 36, placed in 40 ml of methanol. The Reacti on mixture is heated under reflux for six hours. The Ge the mixture is then cooled and acidified with hydrochloric acid. Ether and ethyl acetate are added and the orga African layer is separated and over anhydrous sodium dried sulfate. After vacuum stripping of the solvent 2.5 g of 5-carboxy-2- (2-hydroxy-3-α-cumyl-5-tert-octyl phenyl) -2H-benzotriazole isolated.

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

The 2.5 g of 5-carboxy-2- (2-hydroxy-3-α-cumyl-5-tert- octylphenyl) -2H-benzotriazole, prepared in step a, who into a 250 ml flask equipped with a stirrer, Thermometer, reflux condenser, Dean-Stark trap and nitrogen admission, given. Toluene (100 ml) is added and the Ge heated to reflux to remove traces of water. The mixture is then cooled and 0.76 g of oxalyl chloride in 15 ml of toluene are added. The reaction mixture is there after slowly warmed to 60 ° C and at 60-65 ° C for eight hours held until the hydrogen chloride gas is expelled, un ter obtaining 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 mecha African stirrer, drying tube, thermometer and dropping funnel, 0.8 g of di-n-butylamine, 6 ml of pyridine and 25 ml of toluene given. The mixture is cooled to 0 ° C and the acid chloride solution, prepared in step b, is in the Added dropping funnel and to the reaction mixture via a Period of 30 minutes at -5 ° C to -10 ° C added. The Re action mixture is stirred at the temperature for 1.5 hours and then kept at ambient temperature overnight. The Mixture is filtered and then vacuum stripped under Ge  recovery of 3.0 g raw solids. The raw product becomes chro matographed, providing 1.2 g of the title compound dung as a brown solid that melts at 131-133 ° C. The Structure is determined by NMR and mass spectrometry, m / z 596, be confirms.

Example 38 5-trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzo triazole

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

Example of use 39

To the effect of thermal durability and the Loss rate from a thermosetting acrylic coating with high solids content of various 2H-benzotriazole UV Absorbents that pull with a variety of electronics the and electron donor groups are substituted the following tests were performed.

A clear coat based on thermosetting acrylic Resin with a high solids content is obtained by mixing one experimental acrylic polyol resin and hexamethoxymethylmela min (Resimene® 747, Monsanto) at a solids ratio made by 60/40. The dodecylbenzenesulfonic acid catalyst tor (Nacure® 5225; King Industries) weighs 0.70 percent added. A flow aid Modaflow® (Monsanto) is with 0.25 weight percent added to produce a Acrylic melamine resin model system.

The model clearcoat is treated with xylene to a viscosity of 26-27 seconds using an outlet vessel of type no. 2 (tooth cup # 2) and with a conventional air spray device at 50 psi (3.5 kg / cm ² ) over a Quartz disc measuring 1 '' × 3 '' (2.54 cm × 7.62 cm) applied.

Hardening is accomplished by baking the disc for 30 minutes 260 ° F (127 ° C) reached. The clear coat is with 1 weight pro cent of a hindered amine light stabilizer, bis- (1-octyl oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123, Ciba-Geigy) stabilized. The various test Benzotri Azole UV absorbers are in with 5 mmol weight percent incorporated the clear coat. The film thickness of the quartz disks ranges from 1.15 to 1.41 mils (0.029 to 0.036 mm).

The films on the quartz disks are weathered in accordance with the following conditions in a xenon arc weather-o-meter with a controlled irradiation of 6500 W using a filter of the type (quartz inside and borosilicate glass outside). The exposure cycle is as follows: 40 minutes of direct exposure to water without spraying, followed by 20 minutes of light plus spraying from the front, followed by 60 minutes of light exposure and finally 60 minutes of dark plus spraying from the rear (condensation). Curing takes place at 0.55 W / m ² at 340 nm, 1.98 kJ / hour. In the light cycle, the black panel temperature is set at 70 ± 2 ° C. The relative humidity in the light cycle is in the range of 50-55% and 100% in the dark cycle. The absorbance of the long-wave UV band as a function of the xenon arc exposure time in hours is recorded in the table below.

To the loss of UV absorber from the clear to track paints, UV spectra are initially and then measured at regular intervals after weathering. The UV spectrophotometer measures the absorbance linearly up to 5.5 absorbance units using the reference beam Damping method.

It is believed that the degradation products from the UV Absorbents do not contribute to the UV spectrum. This by tracking the extinction ratio of the gang tested at about 300 nm and the band at about 340 nm. The Ratio does not change after weathering the sample. This shows that the UV spectrum of the weathered films shows the amount Corresponds to UV absorber that remained in the film, taking it very little, if any, to the spectrum Photo degradation products contributes.  

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

The review of this data leads to a fairly clear conclusion about the photostability of 2H-Benzo triazole UV absorbers and the nature of the Substitution that affects photostability.  

Increased photostability occurs when R _{1 is} α-cumyl or phenyl and when G _{2 is} an electron-withdrawing group such as phenyl-sulfonyl or cyano.

The nature of group R ₂ has less influence on the photostability of the benzotriazole UV absorber.

From these observations, an idealized benzotriazole UV absorber could theoretically be designed, in which G _{2 is} an electron-withdrawing group, R _{1 is} an effective bulky group and R _{2 is} a thermally stable group. Such an idealized compound could be a benzotriazole, wherein G _{2 is} phenylsulfonyl, R _{1 is} α-cumyl and R _{2 is} tert-octyl. This benzotriazole is claimed generically in US-A-5,280,124. The data in Example 40 below confirm this prediction and this "idealized" connection actually shows a very low loss rate, well below the current state of the art.

Example 40

Following the general procedure of Example 39 a variety of additional benzotriazole test compounds in a thermosetting acrylic melamine resin with high strength proportion of substance in concentrations between 1.93 and 3 weight percent at equal molar concentrations of testbenzo triazole incorporated at the same film thickness and sufficient, thus an initial absorbance of approximately 2.0 extinction units ten is obtained.

The test panes are exposed in a xenon arc weatherometer at X180 cycle (0.45 watt / m ² ). The initial UV absorbance is measured, followed by measurement at approximately 250 hour intervals for the first 2000 hours and 500 hours after each. Each clearcoat also contains 1% by weight of a hindered amine light stabilizer, namely bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) seba cat.

The data in the table below are based on Ver Binding of Formula A after 1253 hours exposure of the clear  paints that ent the test benzotriazole UV absorbers stopped.

The data in the table below are based on Compounds of Formula A after 1489 hours of exposure Clear varnishes that test the benzotriazole UV absorber contained.

The data in the table below are based on Compounds of formula A after 2521 hours of exposure Clear varnishes that test the benzotriazole UV absorber contained.

It is clear from the three tables above that Connections S and in particular T, which is an electron have the group in the 5-position of the benzo ring, si are significantly more durable than non-benzotriazoles Show group at the benzoring.

The data in the table below are based on Compounds of Formula A after 1264 hours of exposure Clear varnishes that test the benzotriazole UV absorber contained.

The data in the table below are based on Compounds of Formula A after 1518 hours of exposure Clear varnishes that test the benzotriazole UV absorber contained.

The data in these tables clearly show that benzotriazoles substituted by an electron-withdrawing group on the benzo ring, especially a group such as trifluoromethyl or phenylsulfonyl, are particularly durable as measured by low loss rate absorbance values after exposure to actinic radiation. Connections S, U, V and W are particularly durable and fit into the profile proposed above. The stipulation that compound U would be particularly durable can actually be gathered from the above data. Examination of the data for the compounds T and U shows the additional advantageous effect of the presence of an effective space-filling group, such as α-cumyl, in the R ₁ position compared to an ordinary alkyl radical, such as tert-butyl, at that point .

Claims (25)

1. Coating composition stabilized with a benzotriazole, the benzotriazole having increased durability and a low loss rate when incorporated into the coating, the composition comprising

• (a) a resin selected from the group consisting of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin crosslinked with melamine having carbamate side groups or an acrylic polyol resin crosslinked with melamine containing carbamate groups, and
• (b) 0.01 to 5 weight percent, based on the resin solids, of a benzotriazole of the formula A, B, C or D.
  wherein
  G ₁ , G ₂ or T represents an electron-withdrawing radical,
  G _{1 represents} hydrogen or halogen,
  G ₂ 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 ,
  represents
  G _{3 is} hydrogen, straight or branched chain alkyl having 1 to 24 carbon atoms, straight or branched chain alkenyl having 2 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group on the phenyl ring having 1 to 4 alkyl having 1 to 4 carbon atoms,
  R _{1 is} hydrogen, straight or branched chain alkyl having 1 to 24 carbon atoms, straight or branched chain alkenyl having 2 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group on the phenyl ring having 1 to 4 alkyl having 1 to 4 carbon atoms,
  R ₂ straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on Phenyl ring having 1 to 3 alkyl having 1 to 4 carbon atoms; or R _{2 is} hydroxyl or -OR ₄ , wherein R _{4 is} straight or branched chain alkyl having 1 to 24 carbon atoms; or this alkyl group substituted with one or more groups -OH, -OCO-R ₁₁ , -OR ₄ , -NCO or -NH ₂ or mixtures thereof; or this alkyl or alkenyl group, interrupted by one or more groups -O-, -NH- or -NR ₄ - or mixtures thereof, and which are unsubstituted or with one or more groups -OH, -OR ₄ or -NH ₂ or Gemi may be substituted thereof; or R _{2 represents} -SR ₃ , -NHR ₃ or -N (R ₃ ) ₂ ;
  wherein R ₃ alkyl with 1 to 20 carbon atoms, hydroxyalkyl with 2 to 20 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, aryl with 6 to 10 carbon atoms or this aryl group with one or two alkyls with 1 to 4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, in which the perfluoroalkyl radical has 6 to 16 carbon atoms,
  or R ₂
  - (CH ₂ ) _m -CO-X- (Z) _p -YR ₁₅
  represents
  wherein
  X represents -O- or -N (R ₁₆ ) -,
  Y represents -O- or -N (R ₁₇ ) -,
  ZC ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene, interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C ₃ -C ₁₂ alkylene, butenylene, butylene, cyclohexylene or phenylene, each substituted with a hydroxyl group,
  R ₁₆ and R ₁₇ independently of one another represent hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkyl, interrupted by 1 to 3 oxygen atoms, or represent cyclohexyl or C ₇ -C ₁₅ aralkyl and R ₁₆ together with R ₁₇ also forms ethylene when Z is ethylene,
  m is zero, 1 or 2,
  p is 1 or p is also zero if X and Y represent -N (R ₁₆ ) - and -N (R ₁₇ ) -,
  R _{15 represents} a group -CO-C (R ₁₈ ) = C (H) R ₁₉ or, if Y represents -N (R ₁₇ ) - together with R _{17 represents} a group -CO-CH = CH-CO-, wherein R _{18 represents} hydrogen or methyl and R _{19 represents} hydrogen, methyl or -CO-XR ₂₀ , wherein R _{20 is} hydrogen, C ₁ -C ₁₂ alkyl or a group of the formula
  represents
  wherein the symbols G ₁ , G ₂ , R ₁ , X, Z, m and p have the meanings defined before
  n is 1 or 2,
  when n is 1, R _{5 is} Cl, OR ₆ or NR ₇ R ₈ or
  R _{5 represents} -PO (OR ₁₂ ) ₂ , -OSi (R ₁₁ ) ₃ or -OCO-R ₁₁ ,
  or straight or branched chain C ₁ -C ₂₄ alkyl which is interrupted by -O-, -S- or -NR ₁₁ and which is unsubstituted or substituted by -OH or -OCO-R ₁₁ , C ₅ -C _12- cycloalkyl which is unsubstituted or substituted with -OH, straight-chain or branched-chain C ₂ -C ₁₈ alkenyl which is unsubstituted or substituted with -OH, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-R ₁₃ or glycidyl,
  R _{6 represents} hydrogen, straight-chain or branched-chain C ₁ -C ₂₄ alkyl which is unsubstituted or substituted by one or more groups OH, OR ₄ or NH ₂ , or -OR ₆ - (OCH ₂ CH ₂ ) _w OH or - (OCH ₂ CH ₂ ) _w OR ₂₁ , in which w is 1 to 12 and R _{21 represents} alkyl having 1 to 12 carbon atoms,
  R ₇ and R _{8 are} independently hydrogen, alkyl having 1 to 18 carbon atoms, straight or branched chain C ₃ -C ₁₈ alkyl which is interrupted by -O-, -S- or -NR ₁₁ -, C ₅ -C ₁₂ Represent cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxylalkyl, or R ₇ and R ₈ together with the N atom represent a pyrrolidine, piperidine, piperazine or morpholine ring,
  when n is 2, R _{5 represents} one of the divalent radicals -OR ₉ -O- or -N (R ₁₁ ) -R ₁₀ -N (R ₁₁ ) -,
  R ₉ C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, straight or branched chain C ₄ -C ₁₀ alkylene, which by -O- or by -CH ₂ -CHOH -CH ₂ -OR ₁₄ -O-CH ₂ -CHOH-CH ₂ - is interrupted,
  R _{10 represents} straight-chain or branched-chain C ₂ -C ₁₂ alkylene which is substituted by -O-, cyclohexylene or
  may be interrupted, or R ₁₀ and R ₁₁ form a piperazine ring with the two nitrogen atoms,
  R ₁₄ straight or branched chain C ₂ -C ₈ alkylene, ge wheel or branched chain C ₄ -C ₁₀ alkylene through -O-, cycloalkylene, arylene or
  may be interrupted, in which R ₇ and R ₈ independently represent hydrogen, alkyl having 1 to 18 carbon atoms, or R ₇ and R ₈ together represent alkylene having 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene ,
  R _{11 is} hydrogen, straight or branched chain C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched chain C ₃ -C ₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ Aralkyl represents
  R ₁₂ straight or branched chain C ₁ -C ₁₈ alkyl, straight or branched chain C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₅ - Aralkyl,
  R ₁₃ H, straight or branched chain C ₁ -C ₁₈ alkyl which is substituted by -PO (OR ₁₂ ) ₂ , phenyl which is unsubstituted or substituted by OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OR ₁₂ ,
  L represents alkylene having 1 to 12 carbon atoms, alkylidene having 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
  T -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 -
  wherein E represents alkylene with 2 to 12 carbon atoms, cycloalkylene with 5 to 12 carbon atoms or alkylene, interrupted by or terminated with cyclohexylene with 8 to 12 carbon atoms, the benzotriazole showing increased durability and low loss rate values when coating actinic radiation confirmed by loss of less than 0.22 absorbance units after 1200 hours exposure, or less than 0.27 absorbance units after 1500 hours exposure, or less than 0.40 absorbance units after 2500 hours exposure in a Xenon Arc Weather O meter.

2. The composition of claim 1, wherein component (b) is a compound of formula A '
represents what
G _{2 represents} fluorine, chlorine, cyano, R ₃ SO ₂ -, CF ₃ -, -CO-G ₃ , -COO-G ₃ or -CO-N (G ₃ ) ₂ ,
G _{3 represents} alkyl having 1 to 12 carbon atoms,
R _{1 represents} hydrogen, alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or this phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups having 1 to 4 carbon atoms,
R ₂ alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or -CH ₂ CH ₂ COOG ₄ , in which G _{4 is} hydrogen, alkyl having 1 to 24 carbon atoms or this alkyl group, substituted by OH, interrupted by represents one to six atoms -O- or both substituted with OH and interrupted by one to six atoms -O-, and
R _{3 represents} alkyl having 1 to 18 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms. 3. A composition according to claim 2, wherein in the compound of the formula A '
G _{2 represents} fluorine, chlorine, cyano, R ₃ SO ₂ -, CF ₃ -, -COO-G ₃ or -CO-N (G ₃ ) ₂ ,
G _{3 represents} alkyl with 1 to 8 carbon atoms,
R _{1 represents} hydrogen, phenyl or α-cumyl,
R _{2 represents} alkyl of 4 to 12 carbon atoms or phenyl and
R _{3 represents} phenyl or alkyl of 8 to 12 carbon atoms. 4. The composition according to claim 3, wherein G _{2 is} phenyl-SO ₂ -, octyl-SO ₂ -, fluorine or CF ₃ -,
R _{1 represents} α-cumyl or phenyl and
R _{2 represents} tert-butyl or tert-octyl. 5. The composition of claim 1, wherein component (a) a thermosetting acrylic melamine resin or an acrylic represents urethane resin.   6. The composition of claim 1, which additionally a stabilizing amount of a phenolic antioxidant, selected from the group consisting of 3,5-di-tert-butyl-4- n-octadecyl hydroxyhydrocinnamate, tetrakis (3,5-di-tert- butyl-4-hydroxyhydrocinnamic acid) neopentane tray ester, 3,5-di- tert-butyl-4-hydroxybenzylphosphonic acid di-n-octadecyl ester, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, Thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybene cyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert-butyl- 4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'- Ethylidene bis (4,6-di-tert-butylphenol), 1,3,5-tris (2,6-dime thyl-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] isocyan urate, 3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, He xamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di (octylthio) -s-tri azine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydro cinnamamide), calcium bis (ethyl-3,5-di-tert-butyl-4-hydroxyben zylphosphonate), ethylene bis [3,3-di (3-tert-butyl-4-hydroxyphe nyl) butyrate], 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid acid octyl ester, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamo yl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhy drocinnamoyloxy) ethyl] -oxamide, contains. 7. The composition of claim 6, wherein the pheno antioxidant tetrakis (3,5-di-tert-butyl-4-hydroxyhydro cinnamic acid) neopentanetetraylester, 3,5-di-tert-butyl-4-hydroxy n-octadecyl hydrocinnamate, 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) represents. 8. The composition of claim 1, which additionally an effectively stabilizing amount of a hindered amine, selected from the group consisting of bis (2,2,6,6-tetrame  thylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperi din-4-yl) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) - (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzoyl- 2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetrame thylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza spiro [4.5] decane-2,4-dione, tris (2,2,6,6-tetramethylpiperidine- 4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxopipe razin-4-yl) ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21- oxodispiro [5.1.11.2] heneicosan, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethy lenbis (amino-2,2,6,6-tetramethylpiperidine), polycondensate product of 1- (2-hydroxyethyl) -2,2,6,6, -tetramethyl-4- hydroxypiperidine and succinic acid, polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidine-4- yl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentame thylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, polycondenses tion product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6-bis (butyl-1,2,2,6,6-pentamethyl piperidin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diaza decane, mixed [2,2,6,6-tetramethylpiperidin-4-yl / β, β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] hours can) 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] undecane) diethyl] 1,2,3,4-bu tantetracarboxylate, octamethylene bis (2,2,6,6-tetramethyl pipe ridine-4-carboxylate), 4,4'-ethylenebis (2,2,6,6-tetramethylpipe razin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecyl succinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecyl succinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n- dodecyl succinimide, 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-tetramethylpiperidin-4-yl) succinate, 1-octyloxy 2,2,6,6-tetramethyl-4-hydroxypiperidine, poly - {[6-tert-octyl amino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetrame thylpiperidin-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-  2,2,6,6-tetramethylpiperidin-4-yl) imino] and 2,4,6-tris [N- (1- cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylami no] -s-triazine. 9. The composition of claim 8, wherein the go moderate amine bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, Bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di- (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hy droxybenzyl) butylmalonate, the polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and Succinic acid, the polycondensation product of 2,4-dichloro- 6-tert-octylamino-s-triazine and 4,4'-hexamethylene bis (amino 2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6- bis (butyl- (1,2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-tri azin-2-yl] -1,10-diamino-4,7-diazadecane, di- (1-octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyl oxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy 2,2,6,6-tetramethyl-4-hydroxypiperidine, poly - {[6-tert-octyl amino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetra methylpiperidin-4-yl) iminohexamethylene [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-butyl represents amino] -s-triazine. 10. The composition of claim 1, further comprising a further UV absorber, selected from the group, be standing from the s-triazines, the oxanilides, the hydroxyben zophenones, benzoates and the α-cyanoacrylates. 11. The composition of claim 10, wherein the Zu composition additionally contains an s-triazine which contains 2,4- Bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-tri azine; 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine; 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-do- / tri-decyl oxy-2-hydroxypropoxy) phenyl] -s-triazine; or 2- (2-hydroxy ethylamino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetra represents methylpiperidin-4-yl) amino] -s-triazine.   12. Compound of formula I, II, III or IV
wherein
G _{1 represents} hydrogen or halogen,
G ₂ 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 represents
G ₃ straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on Phenyl ring having 1 to 4 alkyl having 1 to 4 carbon atoms,
E _{1 represents} hydrogen, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on the phenyl ring with 1 to 4 alkyl with 1 to 4 carbon atoms,
E ₂ straight or branched chain alkyl with 1 to 24 carbon atoms, straight or branched chain alkenyl with 2 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 7 to 15 carbon atoms, phenyl or this phenyl or phenylalkyl group, substituted on Phenyl ring having 1 to 3 alkyl having 1 to 4 carbon atoms; or E ₂ hydroxyl or -OE ₄ , wherein E _{4 is} straight or branched chain alkyl having 1 to 24 carbon atoms; or this alkyl group substituted with one or more groups -OH, -OCO-E ₁₁ , -OE ₄ , -NCO or -NH ₂ or mixtures thereof; or this alkyl or alkenyl group, interrupted by one or more groups -O-, -NH- or -NE ₄ - or mixtures thereof, which are unsubstituted or with one or more groups -OH, -OE ₄ or -NH ₂ or mixtures there of which may be substituted; or E _{2 represents} -SE ₃ , -NHE ₃ or -N (E ₃ ) ₂ ; or E ₂
- (CH ₂ ) _m -CO-X- (Z) _p -YE ₁₅
represents
wherein
X represents -O- or -N (E ₁₆ ) -,
Y represents -O- or -N (E ₁₇ ) -,
ZC ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene, interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C ₃ -C ₁₂ alkylene, butenylene, butylene, cyclohexylene or phenylene, each substituted with a hydroxyl group,
m is zero, 1 or 2,
p is 1 or p is also zero if X and Y represent -N (E ₁₆ ) - and -N (E ₁₇ ) -,
E _{15 represents} a group -CO-C (E ₁₈ ) = C (H) E ₁₉ or, if Y represents -N (E ₁₇ ) - together with E _{17 represents} a group -CO-CH = CH-CO-, wherein E _{18 represents} hydrogen or methyl and E _{19 represents} hydrogen, methyl or -CO-XE ₂₀ , wherein E _{20 is} hydrogen, C ₁ -C ₁₂ alkyl or a group of the formula
represents
wherein the symbols G ₁ , G ₂ , X, Z, m and p have the meanings defined above and E ₁₆ and E ₁₇ independently of one another are hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkyl, interrupted by 1 to 3 oxygen atoms or represent cyclohexyl or C ₇ -C ₅ aralkyl and E ₁₆ together with E ₁₇ in the case where Z represents ethylene also form ethylene,
n is 1 or 2,
if n is 1, E _{5 represents} Cl, OE ₆ or NE ₇ E ₈ or
E _{5 represents} -PO (OE ₁₂ ) ₂ , -OSi (E ₁₁ ) ₃ or -OCO-E ₁₁ ,
or straight or branched chain C ₁ -C ₂₄ alkyl which is interrupted by -O-, -S- or -NE ₁₁ and which is unsubstituted or substituted by -OH or -OCO-E ₁₁ , C ₅ -C _12- cycloalkyl which is unsubstituted or substituted with -OH, straight-chain or branched-chain C ₂ -C ₁₈ alkenyl which is unsubstituted or substituted with -OH, C ₇ -C ₁₅ aralkyl, -CH ₂ -CHOH-E ₁₃ or glycidyl,
E _{6 is} hydrogen, straight or branched chain C ₁ -C ₂₄ alkyl which is unsubstituted or substituted by one or more groups OH, OE ₄ or NH ₂ , or -OE ₆ - (OCH ₂ CH ₂ ) _w OH or - (OCH ₂ CH ₂ ) _{w represents} OE ₂₁ , in which w is 1 to 12 and E _{21 represents} alkyl having 1 to 12 carbon atoms,
E ₇ and E _{8 are} independently hydrogen, alkyl having 1 to 18 carbon atoms, straight or branched chain C ₃ -C ₁₈ alkyl which is interrupted by -O-, -S- or -NE ₁₁ -, C ₅ -C ₁₂ Represent cycloalkyl, C ₆ -C ₁₄ aryl or C ₁ -C ₃ hydroxylalkyl, or E ₇ and E ₈ together with the N atom represent a pyrrolidine, piperidine, piperazine or morpholine ring,
when n is 2, E _{5 represents} one of the divalent radicals -OE ₉ -O- or -N (E ₁₁ ) -E ₁₀ -N (E ₁₁ ) -,
E ₉ C ₂ -C ₈ alkylene, C ₄ -C ₈ alkenylene, C ₄ alkynylene, cyclohexylene, straight or branched chain C ₄ -C ₁₀ alkylene, which is by -O- or by -CH ₂ -CHOH -CH ₂ -OE ₁₄ -O-CH ₂ -CHOH-CH ₂ - is interrupted,
E _{10 represents} straight-chain or branched-chain C ₂ -C ₁₂ alkylene which is substituted by -O-, cyclohexylene or
may be interrupted, or E ₁₀ and E ₁₁ form a piperazine ring with the two nitrogen atoms,
E ₁₄ straight or branched chain C ₂ -C ₈ alkylene, ge wheel or branched chain C ₄ -C ₁₀ alkylene through -O-, cycloalkylene, arylene or
may be interrupted, in which E ₇ and E ₈ independently represent hydrogen, alkyl having 1 to 18 carbon atoms, or E ₇ and E ₈ together represent alkylene having 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene ,
E _{11 is} hydrogen, straight or branched chain C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, straight or branched chain C ₃ -C ₈ alkenyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ Aralkyl represents
E ₁₂ straight or branched chain C ₁ -C ₁₈ alkyl, straight or branched chain C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₆ aryl or C ₇ -C ₁₅ - Aralkyl,
E ₁₃ H, straight or branched chain C ₁ -C ₁₈ alkyl which is substituted with -PO (OE ₁₂ ) ₂ , phenyl which is unsubstituted or substituted with OH, C ₇ -C ₁₅ aralkyl or -CH ₂ OE ₁₂ ,
E ₃ alkyl having 1 to 20 carbon atoms, hydroxyalkyl having 2 to 20 carbon atoms, alkenyl having 3 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, phenylalkyl having 7 to 15 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group with one or two alkyls with 1 to 4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, in which the perfluoroalkyl radical has 6 to 16 carbon atoms,
L represents alkylene having 1 to 12 carbon atoms, alkylidene having 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
T -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-,
wherein E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene, interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms;
G _{5 represents} G ₃ or hydrogen, and with the proviso that E ₁ does not represent phenylalkyl if G _{2 represents} E ₃ SO- or E ₃ SO ₂ -. 13. A compound according to claim 12 which is a compound of formula I '
represents what
G _{2 is} cyano, E ₃ SO ₂ -, CF ₃ -, -COO-G ₃ , -CO-NHG ₃ or -CO-N (G ₃ ) ₂ ,
G _{3 represents} alkyl having 1 to 12 carbon atoms,
E _{1 represents} hydrogen, phenyl, phenylalkyl with 7 to 15 carbon atoms or this phenyl or phenylalkyl group, substituted on the phenyl ring with 1 or 2 alkyl groups with 1 to 4 carbon atoms,
E ₂ alkyl having 1 to 12 carbon atoms, phenyl, phenylalkyl having 7 to 15 carbon atoms or -CH ₂ CH ₂ COOG ₄ , in which G _{4 is} hydrogen, alkyl having 1 to 24 carbon atoms or this alkyl group, substituted by OH, with interruptions by represents one to six atoms -O-, or both substituted with OH and interrupted by one to six atoms -O-,
E _{3 represents} alkyl having 8 to 18 carbon atoms, aryl having 6 to 10 carbon atoms or this aryl group, substituted by one or two alkyl having 1 to 4 carbon atoms, and
with the proviso that E _{1 is} not phenylalkyl when G _{2 is} E ₃ SO- or E ₃ SO ₂ -. 14. The compound of claim 13, wherein
G _{2 represents} cyano, E ₃ SO ₂ -, CF ₃ -, -CO-G ₃ or -CO-N (G ₃ ) ₂ ,
G _{3 represents} alkyl with 1 to 8 carbon atoms,
E _{1 represents} hydrogen, phenyl or α-cumyl,
E _{2 represents} alkyl having 4 to 12 carbon atoms and
E _{3 is} phenyl or octyl and with the proviso that E _{1 is} not α-cumyl when G _{2 is} E ₃ SO ₂ -. 15. The compound of claim 14, wherein
G ₂ CF ₃ - represents
E _{1 represents} α-cumyl and
E _{2 represents} tert-butyl or tert-octyl. 16. A composition stabilized against thermal, oxidative or light induced degradation, comprising

• (a) an organic material which is subject to thermal, oxidative or light-induced degradation, and
• (b) an effectively stabilizing amount of a compound of formula I, II, III or IV according to claim 12.

17. The composition of claim 16, wherein the orga African material a natural, semi-synthetic or syn represents synthetic polymer. 18. The composition of claim 17, wherein the poly mer is a thermoplastic polymer. 19. The composition of claim 18, wherein the poly mer is a polyolefin or polycarbonate. 20. The composition of claim 19, wherein the poly mer represents polyethylene or polypropylene. 21. The composition of claim 20, wherein the poly Mer represents polypropylene. 22. The composition of claim 16, wherein the orga niche material a resin, selected from the group, best made of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modifier acrylic melamine, an acrylic resin cross-linked with melamine Carbamate side groups or one containing carbamate groups Crosslinked melamine represents acrylic polyol resin.   23. The composition of claim 22, wherein the resin a thermosetting acrylic melamine resin or an acrylic urethane resin represents. 24. The composition of claim 16, wherein the orga African material b) represents a recording material. 25. Use of a benzotriazole compound of For mel A, B, C or D according to claim 1 in an amount of 0.01 up to 5 percent by weight based on the resin solids Stabilizing a coating composition, the Composition a resin selected from the group, best made of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modifier acrylic melamine, an acrylic resin cross-linked with melamine Carbamate side groups or one containing carbamate groups Crosslinked melamine represents acrylic polyol resin.