BE1011537A3 - Coating composition containing a compound stabilizer said compound and its use. - Google Patents

Abstract

The invention relates to a coating composition comprising a stabilizing compound which is a UV absorber belonging to the class of benzotriazoles. The benzotriazoles incorporated into the coating composition according to the invention are characterized in that they are substituted at position 5 of the benzo ring by an electron accepting group. Some of these compounds are new and are included in the invention. The invention also relates to a composition of organic material, such as a natural, semi-synthetic or synthetic polymer or a recording material, stabilized by these new compounds against degradation caused by heat, light or oxidation, as well as the use of said benzotriazoles for the stabilization of a coating composition.

Description

       

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   "Coating composition comprising a stabilizing compound, said compound and its use"
Benzotriazole UV absorbers which are substituted on the benzo nucleus by electron accepting groups show increased durability and lower rate of loss when incorporated into automotive coatings.



   Benzotriazoles have long been an important class of UV absorbers and have gained great commercial importance and wide acceptance in many industrial applications. However, as the requirements become more stringent and restrictive, research continues to find even more stable and durable benzotriazoles. Factors that make this research more urgent are the phasing out of solvents that are hazardous air pollutants (HAPS), such as xylene, because of the environmental problems they cause, and their replacement by non-solvent HAPS, such as esters, ethers or ketones, and the highest durability requirements placed on automotive coatings.

   In fact, the automobile industry is most concerned by the loss of UV absorbers by paints and coatings for automobiles, as observed in the publication by J. L. Gerlock et al., Proc. 36th Annual Tech. Sym. (Cleveland Coating Society), May 18, 1993.



   Vysokomol Soedin, Ser. A 18 (3), 553 (1976) describes the linear dependence between the hydrogen bonding strength and the light stability in benzotriazoles.



   J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995), describe the photodegradation of benzotriazole-type UV absorbers in poly (methyl methacrylate) films. Structural variation generally resulted in only slight differences in degradation rates, unless the substitution broke the intramolecular hydrogen bonds which are critical for stability. Pickett et al. have not reviewed any benzotriazole

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 containing both electron acceptor and electron donor groups, such as those of the present invention.



   The prior art concludes that strengthening hydrogen bonds leads to a more stable benzotriazole, but does not teach how it can be done. The present invention discloses benzotriazoles which exhibit increased durability, but, surprisingly, this increased durability is not always associated with greater hydrogen bonding strength. In fact, compounds with better durability often have weaker, rather than stronger, hydrogen bonds.



   US patents? 4,226,763.4 278,589, 4,315,848.4 275,004.4 347 180.5 554,760.5 563,242, 5,574,166 and 5,607,987 describe certain benzotriazoles substituted with an a-cumyl group at position 3 hydroxyphenyl nucleus, which show very good durability in automotive coatings. These benzotriazoles represent the current state of the art. The present invention proposes to prepare benzotriazoles which show an even better durability and lower rates of loss compared to those of the benzotriazoles of the prior art.



   U.S. patents 5,278,314.5 280,124, 5,436,349 and 5,516,914 describe red shifted benzotriazoles. These benzotriazoles are substituted at position 5 of the benzo ring by thioether, alkylsulfonyl or phenylsulfonyl groups. The red shift of the benzotriazoles is advantageous for spectral reasons. A group at position 5 which also has the property of attracting electrons provides the additional advantages of low rates of loss and durability as obtained in the present invention.



   The present invention relates to UV absorbers of the benzotriazole type having increased stability and durability and offering a low rate of loss when incorporated into coatings for automobiles.

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 EMI3.1
 



  More particularly, the present invention relates to a coating composition stabilized by a benzotriazole, which benzotriazole exhibits increased durability and a low rate of loss when incorporated into said coating, said composition comprising (a) a resin chosen from the group formed by a thermosetting acrylic melamine resin, an acrylic urethane resin, a carboxylated epoxy resin, a silane modified acrylic melamine resin, an acrylic resin having lateral carbamate groups crosslinked by melamine or a crosslinked acrylic polyol resin by melamine containing carbamate groups, and (b) 0.01 to 5% by weight, relative to the weight of the dry matter of resin, of a benzotriazole of formula A, B,

   C or D
 EMI3.2
 

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 EMI4.1
 
 EMI4.2
 where G., G or T is an electron acceptor radical, G1 is hydrogen or a halogen,
G2 is a halo, nitro, cyano, R3S0-, R3SO2-, -COOG3, CF3-, -P (O) (C6H5) 2, -CO-G3, -CO-NH-G3, -CO-N (G3) radical ) 2, -N (G3) -CO-G3,
 EMI4.3
 
G3 is hydrogen, a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, a phenyl group, or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms,

     R1 is hydrogen, a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, a phenyl group, or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms,
R2 is a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 with 15 carbon atoms, a phenyl group,

   

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 or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 3 alkyl groups of 1 to 4 atoms
 EMI5.1
 of carbon ; or R2 is a hydroxyl group or -OR. where R4 is a straight or branched chain alkyl group of 1 to 24 carbon atoms; or said alkyl group substituted by one or more -OH, -OCO-R11, -OR4, -NCO or -NH2 or a combination of them; or said alkyl or alkenyl group
 EMI5.2
 interrupted by one or more-O -, - NH-or-NR. or a combination of them, and which may be unsubstituted or substituted by one or more -OH, -OR4 or -NH2 or a combination of them; or R2 is -SR3, -NHR3 or -N (R3) 2;

   or R2 is
 EMI5.3
 or
X is -O- or -N (R16) -,
Y is -O- u -N (R17) -,
Z is a C2-C12 alkylene group, a C4-C12 alkylene group interrupted by one to three nitrogen atoms, oxygen atoms or a combination of them,
 EMI5.4
 or is a CC alkylene group, butenylene, 12, but'nylene, butynylene, cyclohexylene or phenylene, each being substituted by a hydroxyl group, m is 0.1 or 2, p is 1, or else p can also be 0 when X and Y are
 EMI5.5
 respectively-N (R. e) - and-N (R. y) -, R, E is a group-CO-C (R. g) = C (H) Rq or, when Y is - N (R. y) -, forms with R17 a group -CO-CH = CH-CO-, where R18 is hydrogen or a methyl group and R.

   q is hydrogen, a methyl group or -CO-X-RQ where R-, is hydrogen, a C1-C12 alkyl group or a group of formula
 EMI5.6
 

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 where the symbols R1, R3, X, Z, m and p are as defined above, and R16 and R17 are each, independently of the other,
 EMI6.1
 hydrogen, a C1-C2 alkyl group, a C1-C6 alkyl group. interrupted by 1 to 3 oxygen atoms, a cyclohexyl group or an aralkyl group at Cy-Ce, and, in the case where Z is an ethylene group, R16 with R ene, R.

   y can also form an ethylene group, n is 1 or 2, - when n is 1, Re is Cl, OR6 or NRyRg, or Re is-PO (OR), -OSi (R) or-OCO-R, or a straight or branched chain C1-C24 alkyl group which is interrupted by -O-, -S- or -NR11- and which may be unsubstituted or substituted by -OH or -OCO-R11, a Ce-C12 cycloalkyl group which is unsubstituted or substituted
 EMI6.2
 2 -C18 straight chain by-OH, a C2-C1S alkenyl group with straight or branched chain which is unsubstituted or substituted by-OH, an aralkyl group in Cy-C.

   e, -CH-CHOH-R or a glycidyl group, R6 is hydrogen, a C1-C24 alkyl group with 6 1 24 straight or branched chain which is unsubstituted or substituted by one or more OH, OR4 or NH2, or -OR6 is
 EMI6.3
 - (OCHCH) OH or- (OCHCHOR where w is 1 to 12 and R21 is an alkyl group of 1 to 12 carbon atoms,
R7 and Po are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkyl group
 EMI6.4
 in C3-C18 with straight or branched chain which is interrupted by - O -, - S-or-NR l-, a cycloalkyl group in Ce-C12, an aryl group in Cl-cl or a hydroxyalkyl group in Cl-c3, or R7 and Rg form with the atom N a cycle of pyrrolidine, piperidine, piperazine or morpholine, - when n is 2, Re is one of the divalent radicals -O-R9-O- and -N (R11)

  -R10-N (R11) -,
Rg is a C2-C8 alkylene group, an alkenylene group
 EMI6.5
 C4-CS'C4 alkynylene'cyclohexylene or C4-Cl0 4 8 alkylene, C4 alkynylene, straight or branched chain which is interrupted by -O- or by -CH2-CHOH-CH2-O-R14-O -CH2-CHOH-CH2-,

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 EMI7.1
 R10 is a straight-chained or branched C-C alkylene group which can be interrupted by -O-, a cyclohexylene group or
 EMI7.2
 
 EMI7.3
 or R10 and R11, with the two nitrogen atoms, form a piperazine ring, R14 is a C-Co alkylene group with a straight or branched chain, a C alkylene group

   o straight or branched chain which is interrupted by-0-, a cycloalkylene group, an arylene group or
 EMI7.4
 where R7 and Rg are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, or else R7 and R8 together form an alkylene group of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3- methyliminopentamethylene,

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R11 is hydrogen, a C1-C18 straight or branched chain alkyl, C5-C12 cycloalkyl, C3-C8 straight or branched alkenyl, Ce-C aryl or C7-C15 aralkyl,
 EMI8.1
 R12 is a straight-chain or branched C1-Cl8 alkyl group C-3-8 straight chain or branched C-alkenyl, C-C cycloalkyl, Cg-C aryl or C-C aralkyl, R13 is H,

   a C1-C8 straight or branched chain alkyl group which is substituted by-PO (OR12) 2, a phenyl group which is unsubstituted or substituted by OH, a Cy-C aralkyl group <e or-CHOR,
R3 is an alkyl group of 1 to 20 carbon atoms, a hydroxyalkyl group of 2 to 20 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, an aryl group of 6 to 10 carbon atoms or said aryl group substituted by one or two alkyl groups of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl of which the perfluoroalkyl moiety counts 6 to 16 carbon atoms,
L is an alkylene group of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
T is -SO-, -SO2-, -SO-E-SO-,

   -SO2-E-SO2-, -CO-,
 EMI8.2
 - CO-E-CO -, - COO-E-OCO -, - CO-NG-E-NG-CO-ou-NG-CO-E-CONu3-, where E is an alkylene group of 2 to 12 atoms of carbon, a cycloalkylene group of 5 to 12 carbon atoms or an alkylene group interrupted or terminated by a cyclohexylene group of 8 to 12 carbon atoms, which benzotriazole exhibits increased durability and low rates of loss when the coating is exposed to a actinic radiation, as denoted by a loss less than 0.22 absorbance unit after 1200 hours of exposure, or less than 0.27 absorbance unit after 1500 hours of exposure or less than 0.40 absorbance unit after 2500 hours of exposure in a Weather-O-Meter xenon arc device.

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 EMI9.1
 



  Preferably, component (b) is a compound of formula A '
 EMI9.2
 
 EMI9.3
 or G2 is a fluoro, chloro, cyano, RSO-, CF -, - CO-G, -COO-G or-CO-N (G) radical,
G3 is an alkyl group of 1 to 12 carbon atoms,
R1 is hydrogen, an alkyl group of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups of 1 to 4 atoms carbon,
R2 is an alkyl group of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or
 EMI9.4
 - CHCHCOOG.

   where G <is hydrogen, an alkyl group of 1 to 24 carbon atoms or the said alkyl group substituted by OH, interrupted by 1 to 6 atoms of -O- or both substituted by OH and interrupted by 1 to 6 atoms of- O-, and R3 is an alkyl group of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl group substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms.



   Most preferably, in the compound of formula A ':
G2 is a fluoro, chloro, cyano, R3SO2-, CF3-, -COO-G3 or -CO-N (G3) 2 radical,
G3 is an alkyl group of 1 to 8 carbon atoms, R. is hydrogen, a phenyl or a-cumyl group,
R2 is an alkyl group of 4 to 12 carbon atoms or phenyl, and
R3 is a phenyl or alkyl group of 8 to 12 carbon atoms.

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   Particularly preferred compounds are the compounds of formula A ′ where G2 is a phenyl-SO 2 -, octyl-SO 3, fluoro or CF radical. <is an a-cumyl or phenyl group and R2 is a tert-butyl or tert-octyl group.



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



   Examples of these various groups or radicals are as follows:
When any of the radicals R1 to R21 are alkyl groups, they are for example methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl groups , tert-octyl, lauryl, tert-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; when any of said radicals are alkenyl groups, they are, for example, allyl or oleyl groups; when any of said radicals are cycloalkyl groups, they are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl groups; when any of said radicals are phenylalkyl groups, they are, for example, benzyl, phenethyl, a-methylbenzyl and a, a-dimethylbenzyl groups;

   and when any of said radicals are aryl groups, they are, for example, phenyl, naphthyl, or, if they are substituted by one or more alkyl groups, they are, for example, tolyl and xylyl groups. When R6 is an alkyl group
 EMI10.1
 interrupted by one or more -0- and / or substituted by one or more-OH, the fragment -OR6 can be, for example, - (OCHCH) OH or- (OCHCH) OR, where w is 1 to 12 and R21 is an alkyl group of 1 to 12 carbon atoms.



   When E is an alkylene group, it is for example an ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene group; when E is a cycloalkylene group, it is for example a cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene or cyclododecylene group;

  <Desc / Clms Page number 11>

 and when E is an alkylene group interrupted or terminated by a cyclohexylene group, it is for example the saturated diyl radical derived from limonene, called here the dihydrolimonenediyl group.



   Another preferred embodiment of the invention is a compound of formula III where R1 is a tert-butyl group, n is 1, R3 is a phenyl group and Rc is - OR6 where R6 is a straight chain or substituted octyl group .



  Another preferred embodiment of the present invention is a compound of formula C where n is 2, R1 is
 EMI11.1
 a tert-butyl group, R3 is a phenyl group and Rc is -O-Rg-O-where Rg is a C2-C24 alkylene group interrupted by -0- or by -CH2-CHOH-CH2-0-R14-0 -CH2-CHOH-CH2-.



   When the present compounds contain a free carboxyl group in the case where R2 is -CH2CH2COOR6 where R6 is hydrogen, the alkali metal or amine salts of these acids are also considered to be included in the present invention, and make it possible to use these UV absorbers in aqueous systems due to the greater solubility in water offered by the present compounds of this type.



   R6'R7 and Rg can be the following C3-C18 alkyl groups, which are interrupted by-O -, - S-or-NR <.- and may be substituted by OH: methoxymethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl,
 EMI11.2
 CHOCHCHOCHCH-, CHCHOCHCHOCHCH-, CHgOCHCHOCHCH-, ethylthiopropyle, octylthiopropyle, dodecyloxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, -CH2CH2-NH-C4H9, -CH2CH2CH2CH2CH2CH2H2CH2CH2CH2H2CH2CH2CH2H2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2H2 -CHCH (C) CHg.



  Rc, Ry, Ro, R and R may be the following C 6 -C cycloalkyl groups: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl. In the case of R6 'this group can also be substituted by-OH.



     Ru, reg and R11 can be the following alkenyl groups: allyl, methallyl, 2-n-hexenyl and 4-n-octenyl.

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   When R6 is an alkenyl group, it can be an alkenyl group as defined for Ry, Rg or R11, but it can also be -CH = CH2, an n-undec-10-enyl group or n-octadec-9-enyl , and the radical R6 may also be substituted by-OH.



   R7 and Rg may be the following Cy-Ce aralkyl groups: benzyl, α-phenethyl, 2-phenethyl and 4-tert-butylbenzyl.
 EMI12.1
 



  When R < <, R or R are aralkyl groups, they can be defined each, independently of the others, as for R7 or Ro.



  Ry, Rg and R11 may each be, independently of the others, one of the following C6-C14 aryl groups: phenyl, ta-naphthyl and ss-naphthyl.



  When R7 or Rg is a C1-C6 hydroxyalkyl group, it may be one of the following groups: hydroxy-methyl, 2-hydroxyethyl and 2-hydroxypropyl.



   The C2-C8 alkylene groups represented by Rg and
 EMI12.2
 R e ene, R14 can be the following groups: ethylene, propylene, butylene, hexylene and octylene.



   The alkylene groups represented by Rio can be the same groups, but, in addition, they can also be higher molecular weight groups such as decylene and dodecylene.



   When Rg is a C 4 -C alkenylene group, an example of an appropriate group is as follows: butenylene.



   In the case of Rg and R14, alkylene groups
 EMI12.3
 in suitable straight or branched chain C4-C10 which are in C ee approp interrupted by -0- are the following groups: -CHCHOCH2CH2 -'- CH (CH3) -CH2-0-CH2-CH (CH3) -CH2CH20CH2CH20CH2CH2et-CHCHOCHCHOCHCHOCHCH -.



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



   When R14 is an arylene group, it can be, in particular, the following groups: 1, 3-phenylene and 1,4-phenylene.

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



   When Z is a C4-C12 alkylene group which is
 EMI13.1
 interrupted by oxygen, it is for example: -CH-CHO-CH2-CH2 -'- CH2-CH2-0-CH2-CH2-CH2 -'- CH2-CH2-0-CH2-CH2- 0-CH- CH-ou-CH-CH-0-CH-CH-O-CH-CH-O-CH-CH-, and, when the alkylene group is interrupted by nitrogen, i.e. by a group -N (R) - where R is as defined above, it is, for example, -CH-CHNH-CH-CH-CH-CH -, - CH-CH-CH-NH- (CH) g- or -CH-CH-CHN (CH) -CH-CH (CH) (CH) -.



  As a C3-C12 alkylene group substituted by a hydroxyl group, Z is a 2-hydroxytetramethylene, 2-hydroxyhexamethylene or, in particular, 2-hydroxytrimethylene group.



   As the cyclohexylene group, Z is for example a 1,4-cyclohexylene group or, in particular, 1,2-cyclohexylene.



   As the phenylene group, Z is for example an m-phenylene or p-phenylene group. m can be 0.1 or 2, but preferably 2. p is preferably 1, but it can also be 0 if X and Y are both linked via nitrogen.



   As a C1-C8 alkyl group, R1 is for example one of the groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl. The tert-octyl group is preferred.



   As C 1 -C 4 alkyl groups <, Ricy Rn and R20 can have the same definition as that given previously for Ru. and may further be the straight or branched chain nonyl, decyl, undecyl or dodecyl groups.

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   When R16 or R17 is an alkyl group interrupted by oxygen atoms, the examples which apply are the same as those described above for Z.



   Examples of aralkyl groups for R16 and R17 are the groups: benzyl, a-methylbenzyl, 1-phenylethyl, ex, a-dimethylbenzyl and 1-phenylpropyl.



   If Z is an ethylene group, R16 and Ry can also form an ethylene group, which is equivalent to bridging using a piperazine group.



   When Y is a group -N (R) -, R and R17 together form a group -CO-CH = CH-CO-, and thus form the
 EMI14.1
 
The preferred meaning of R15 is, however, -CO-C (R18) = CHR14, and R18 and R19 are each preferably a methyl group and in particular hydrogen.



   R2 is -CH2-CH2-CO-O-C (G) = CH2 and G is hydrogen or a methyl group.



   The present invention also relates to new benzotriazoles of formulas I, II, III and IV
 EMI14.2
 

  <Desc / Clms Page number 15>

 
 EMI15.1
   G. is hydrogen or halogen,
G2 is a cyano radical, E3SO-, E3SO2-, -COOG3, CF3-, - P (0) (C6H5) 2, -CO-G3, -CO-NH-G3, -CO-N (G3),
G3 is a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 with 15 carbon atoms, a phenyl group, or the said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms,
E1 is hydrogen, a phenylalkyl group of 7 to 15 carbon atoms or phenyl,

   or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms,
E2 is a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, a phenyl group, or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 3 alkyl groups of 1 to 4 atoms

  <Desc / Clms Page number 16>

 
 EMI16.1
 carbon; or E2 is a hydroxyl group or-OE. where E4 is a straight or branched chain alkyl group of 1 to 24 carbon atoms; or said alkyl group substituted by one or more -OH, -OCO-E11, -OE4, -NCO or -NH2 or a combination of them;

   or said alkyl or alkenyl group
 EMI16.2
 interrupted by one or more -O-, - NH-or-NE.-or a combination of them, and which may be unsubstituted or substituted by one or more -OH, -OE4 or -NH2 or a combination of between them ; or E2 is -SE3, -NHE3 or -N (E3) 2; or E2 is
 EMI16.3
 or
 EMI16.4
 X is -0- or -N (E16) - 'Y is-0-or-N (E) -, Z is a C 2 -C 12 alkylene group, a C alkylene group <C interrupted by one to three nitrogen atoms, oxygen atoms or a combination of them, or is a C-C alkylene group <, butenylene, butynylene, cyclohexylene or phenylene, each being substituted by a hydroxyl group, m is 0.1 or 2, p is 1, or else p can also be 0 when X and Y are respectively -N (E16) - and -N (E17) -, E15 is a group -CO-C (Eg) = C (H)

     E19 or, when Y is -N (E17) -, forms with E17 a group -CO-CH = CH-CO-, where
 EMI16.5
 E18 is hydrogen or a methyl group and E19 is hydrogen, a methyl group or -CO-X-EQ where EQ is hydrogen, a C1-C12 alkyl group or a group of formula
 EMI16.6
 where the symbols E1, G2, X, Z, m and p are as defined above, and

  <Desc / Clms Page number 17>

 
 EMI17.1
 E16 and E. y are each, independently of the other, hydrogen, a C1-C6 alkyl group <, a C 1 -C alkyl group.

   interrupted by 1 to 3 oxygen atoms, a cyclohexyl group or a C7-C15 aralkyl group, and, in the case where Z is an ethylene group, E16 with E17 may also form an ethylene group, n is 1 or 2,
 EMI17.2
 - when n is 1, Ec is Cl, OE6 or NEyEg, or ES is -PO (OE), -OSi (E) or -OCO-E, or a C1-C24 straight or branched chain alkyl group which is interrupted par-O -, - S-ou-NE ..- and which may be unsubstituted or substituted by-OH or-OCO-El., a C-cl2 cycloalkyl group which is unsubstituted or substituted by-OH, a straight chain C2-C18 alkenyl group
 EMI17.3
 or branched which is unsubstituted or substituted by-OH, a C-Ce aralkyl group, -CHL-CHOH-E.

   or a glycidyl group,
E6 is hydrogen, a straight or branched chain C1-C24 alkyl group which is unsubstituted or substituted by one or more OH, OE4 or NH2, or else OE6 is
 EMI17.4
 - (OCHCH) OH or- (OCHCHOE where w is 1 to 12 and E21 is an alkyl group of 1 to 12 carbon atoms,
E7 and Eg are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, a straight or branched chain C3-C18 alkyl group which is interrupted
 EMI17.5
 by-O -, - S-or-NE.

    <-, a Ce-C cycloalkyl group <, a C6-C14 aryl group or a Ca-C3 hydroxyalkyl group, or else E7 and Eg form with the N atom a cycle of pyrrolidine, piperidine, piperazine or morpholine, - when n is 2, Ee is the one of the divalent radicals -O-E9-O- and -N (E11) -E10-N (E11) -,
Eg is a C-Cg alkylene, C-alkenylene, C alkynylene, cyclohexylene or C4-C10 straight or branched chain alkylene group which is interrupted by -O- or by-CH2-CHOH-CH2-0 -E14-O-CH2-CHOH-CH2-,

  <Desc / Clms Page number 18>

 
 EMI18.1
 E10 is a straight or branched chain C2-C12 alkylene group which may be interrupted by-0-, a cyclohexylene group or
 EMI18.2
 or E10 and En,

   with the two nitrogen atoms, form a piperazine ring,
E14 is a straight chain C2-C8 alkylene group
 EMI18.3
 or branched, a C 1 -C alkylene group. o straight or branched chain which is interrupted by-0-, a cycloalkylene group, an arylene group or
 EMI18.4
 where E7 and Eg are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, or else E7 and Eg together form an alkylene group of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3- methyliminopentamethylene,
 EMI18.5
 E11 is hydrogen, C1-C18 to 11-18 straight or branched chain, C1-C cycloalkyl, alkenyl

  <Desc / Clms Page number 19>

 in C3-C8 with straight or branched chain, aryl in C6-C14 or aralkyl in Cy-C.

   e,
E12 is a C1-C8 straight chain alkyl group
 EMI19.1
 or branched, straight-chain or branched C3-C18 alkenyl, C1-C6 cycloalkyl. Q, C6-C16 aryl or C-C aralkyl. vs,
E13 is H, a straight or branched chain Ci-Ci alkyl group which is substituted by -PO (OE12) 2, a phenyl group which is unsubstituted or substituted by OH, a Cy-C aralkyl group or -CH2OE12 ,
E3 is an alkyl group of 1 to 20 carbon atoms, a hydroxyalkyl group of 2 to 20 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, an aryl group of 6 to 10 carbon atoms or said aryl group substituted by one or two alkyl groups of 1 to 4 carbon atoms or 1.1, 2,

  2-tetrahydroperfluoroalkyle in which the perfluoroalkyl fragment has 6 to 16 carbon atoms,
L is an alkylene group of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
T is -SO-, -SO2-, -SO-E-SO, -SO2-E-SO2-, -CO-, -CO-E-CO-, -COO-E-OCO-, -CO-NG5- E-NG5-CO-, where E is an alkylene group of 2 to 12 carbon atoms, a cycloalkylene group of 5 to 12 carbon atoms or an alkylene group interrupted or terminated by a cyclohexylene group of 8 to 12 carbon atoms, and Ge is G3 or hydrogen, and provided that E1 is not a phenylalkyl group when G2 is E3SO- or E3SO2-.



   Preferably, the new benzotriazole is a compound of formula I '
 EMI19.2
 

  <Desc / Clms Page number 20>

 
 EMI20.1
 or
G2 is a cyano radical, E3SO2-, CF3-, -COO-G3, -CO-NHG3 or -CO-N (G3) 2,
G3 is an alkyl group of 1 to 12 carbon atoms, E1 is hydrogen, a phenyl, phenylalkyl group of 7 to 15 carbon atoms or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups of 1 with 4 carbon atoms,
E2 is an alkyl group of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or -CH2CH2COOG4 where G4 is hydrogen, an alkyl group of 1 to 24 carbon atoms or said alkyl group substituted by OH , interrupted by 1 to 6 atoms of -O-or both substituted by OH and interrupted by 1 to 6 atoms of -O-,

   and
E3 is an alkyl group of 8 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl group substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms, and provided that E1 is not a phenylalkyl group when G2 is E3SO- or E3SO2-.



   Most preferably, in the compound of formula I ':
G2 is a cyano radical, ESO-, CF -, - CO-G or -CO-N (G3) 2,
G3 is an alkyl group of 1 to 8 carbon atoms, E. is hydrogen, a phenyl or a-cumyl group,
E2 is an alkyl group of 4 to 12 carbon atoms, and
 EMI20.2
 E3 is a phenyl or octyl group, and provided that E1 is not an a-cumyl group when G2 is ESO-.



  Particularly preferred compounds are the compounds of formula where G2 is CF-, E. is an α-cumyl group and E2 is a tert-butyl or tert-octyl group.



   The present invention also relates to a composition stabilized against degradation caused by heat, oxidation or light, which comprises:

  <Desc / Clms Page number 21>

 (a) an organic material subject to degradation caused by heat, oxidation or light, and (b) an amount with stabilizing effect of a compound of formula I, II, III or IV.



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



   Most preferably, the polymer is a polyolefin or a polycarbonate, in particular polyethylene or polypropylene, very particularly polypropylene.



   In another preferred embodiment of the present invention, the organic material is a resin selected from a thermosetting acrylic melamine resin, an acrylic urethane resin, a carboxylated epoxy resin, a silane modified acrylic melamine resin, an acrylic resin having lateral carbamate groups crosslinked by melamine or an acrylic polyol resin crosslinked by melamine containing carbamate groups.



   The most preferred resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.



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



   The recording materials according to the invention are suitable for pressure-sensitive duplicating systems, photocopying systems using microcapsules, heat-sensitive duplicating systems, photographic materials and inkjet printing.



   The recording materials according to the invention are distinguished by an unexpected improvement in quality, in particular as regards the fastness to light.



   The recording materials according to the invention have the structure known for their particular use. They consist of a usual support, for example paper or a plastic film, which has been coated with one or more

  <Desc / Clms Page number 22>

 several layers. These layers contain the necessary constituents depending on the type of material. For example, in the case of photographic materials, they contain silver halide emulsions, color developers, dyes, etc. Materials which are particularly suitable for inkjet printing have a layer which is particularly absorbent for ink on a conventional support. Uncoated paper can also be used for inkjet printing. In this case, the paper serves as both a support and an ink absorbing layer.

   A suitable material for inkjet printing is, for example, described in the U.S. Patent.



    NO 5,073,448 (included here by reference).



   The recording material can also be transparent as, for example, in the case of films for projection.



   The compounds of formulas I, II, III and IV can be incorporated into the mill material as soon as it is produced, for example in the production of paper, by being added to the pulp. A second application method consists in spraying an aqueous solution
 EMI22.1
 of the compound of formula I, II, III or IV on the mill material or to add the compound of formula I, II, III or IV to the coating composition.



   Coating compositions for transparent recording materials suitable for projection cannot contain light dispersing particles such as pigments and fillers.



   The coating composition which binds a dye may contain a number of other additives, for example antioxidants, light stabilizers (including UV absorbers which do not belong to the class of UV absorbers according to the invention), viscosity improving agents, fluorescent brightening agents, biocides and / or antielectrostatic agents.

  <Desc / Clms Page number 23>

 



   The coating composition is usually prepared as follows: The water-soluble components, for example the binder, are dissolved in water and stirred together. The solid components, for example the fillers and other additives already described, are dispersed in this aqueous medium. The dispersion is advantageously crushed by means of devices such as ultrasonic dispersers, turbine agitators, homogenizers, colloidogenic mills, ball mills, sand mills, high speed agitators, etc. The compounds of formulas I, II, III and IV can be easily incorporated into the coating composition.



   The recording material according to the present invention preferably contains 1 to 5000 mg / m2, in particular 50 to 1200 mg / m2, of a compound of formula I.



   As indicated previously, the recording materials according to the invention cover a wide field. The compounds of formulas I, II, III and IV can, for example, be used in pressure sensitive duplicating systems. They can be introduced either into the paper in order to protect against light the microencapsulated dye precursors present therein, or in the binder of the developing layer in order to protect the dyes which are formed therein.



   Photocopying systems using photosensitive microcapsules which are developed by application of pressure are described in U.S. patents.



  NO 4,416,966.4 483,912.4 352,200.4 535,050.4 5,365,463, 4,551,407, 4,562,137 and 4,608,330, and also in documents EP-A-139,479, EP-A-162 664, EP-A-164 931, EP-A-237 024, EP-A-237 025 and EP-A-260 129. In all these systems, the compounds can be introduced into the dye-receiving layer. The compounds can however also be introduced into the donor layer in order to protect the chromogenic agents against light.



   Photographic materials which can be stabilized are dyes and photographic layers

  <Desc / Clms Page number 24>

 containing these dyes or their precursors, for example paper and photographic film. Suitable materials are described, for example, in U.S. Patent No. 5,364,749 (included here by reference). The compounds of formulas I, II, III and IV act here as an anti-UV filter against electrostatic lightning. In color photography materials, color developers and colorants are also protected against photochemical decomposition.



   The present compounds can be used for all types of color photography materials.



  For example, they can be used for color paper, color invert paper, direct color positive material, color negative film, color positive film, color invert film, etc. They are preferably used, among other things, for a color photographic material which contains an invertible substrate or which forms positives.



   Color photographic recording materials usually contain, on a support, layers of silver halide emulsion sensitive to blue and / or sensitive to green and / or sensitive to red and, if desired, a protective layer, the compounds preferably being either in the green-sensitive layer or the red-sensitive layer, or in a layer situated between the green-sensitive layer and the red-sensitive layer, or in a layer placed above silver halide emulsion layers.



   The compounds of formulas I, II, III and IV can also be used in recording materials based on principles of photopolymerization, photoplasticization or rupture of microcapsules, and also in cases where diazonium salts sensitive to light, leucobases of dyes containing an oxidizing agent or lactones of dyes containing a Lewis acid.

  <Desc / Clms Page number 25>

 



   In addition, they can be used in recording materials to be used for dye diffusion transfer printing, thermal wax transfer printing and dot matrix printing, and for use in printers and electrostatic, electrographic, electrophoretic, magnetographic and electrophotographic laser plotters. Among the above, preferred are recording materials for dye diffusion transfer printing, for example as described in document EP-A-507 734.



   They can also be used in inks, preferably for inkjet printing, for example as described in more detail in the U.S. Patent.



    ? 5,098,477 (included here by reference).



   The compounds of the present invention exhibit superior stability to hydrolysis, superior stability to processing and storage, as well as good resistance to extraction when they are present in a stabilized composition.



   The methodology used to prepare the present compounds is described in the prior art. The intermediate compounds required to prepare the present compounds are mostly commercial products.



   The preferred compounds are those in which one of X and Y is-0-, and in particular those in which X and Y are both-0-.



   In general, the polymers which can be stabilized include the following:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins such as cyclopentene or norbornene, polyethylene (which can optionally be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LDPE), branched low density polyethylene (LDPE).

  <Desc / Clms Page number 26>

 



   The polyolefins, that is to say the polymers of monoolefins illustrated by examples in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various processes, and in particular those which follow: a) radical polymerization (normally under high pressure and at high temperature). b) Catalytic polymerization using a catalyst which normally contains one or more metals from Groups IVb, Vb, VIb or VIII of the Periodic Table.

   These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups which may be coordinated by n or o bonds. These metal complexes can be in the free form or be fixed on substrates, typically on an activated form of magnesium chloride, titanium-III chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium.

   The catalysts can be used in isolation in the polymerization or else other activators, typically metal alkyls, metal hydrides, metal halides, metal metal oxides or metal alkyloxanes, can be used. being elements of Groups la, lia and / or IIIa of the Periodic Table. The activators can be suitably modified with additional ester, ether, amine or silyl group. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (Du Pont), metallocenes or monosite catalysts (SSC).

  <Desc / Clms Page number 27>

 



   2. Mixtures of the polymers mentioned in 1), for example mixtures of polypropylene and polyisobutylene, polypropylene and polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).



   3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LDPE) and its mixtures with low density polyethylene (LDPE), propylene copolymers / but-1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene copolymers / butadiene, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers,

   ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as ethylene terpolymers with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and the blends of these copolymers with each other and with the polymers mentioned in 1) above, for example blends of polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate (EVA) copolymers, LDPE / ethylene-acrylic acid copolymers (EAA), PEBDL / EVA and PEBDL / EAA, and alternating or random polyalkylene / carbon monoxide copolymers and their mixtures with other polymers, for example polyamides.



   4. Hydrocarbon resins (eg Cc-Cq), including their hydrogenated modification products (eg tackifiers), and mixtures of polyalkylenes and starch.



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

  <Desc / Clms Page number 28>

 
 EMI28.1
 



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



  7. Grafted copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers;

   styrene and acrylonitrile on alkyl polyacrylates or alkyl polymethacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as their mixtures with the copolymers listed in 6), for example mixtures of copolymers known as ABS polymers, MBS, ASA or AES.



  8. Halogenated polymers such as polychloroprene, chlorinated rubbers, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo and copolymers of epichlorohydrin, in particular polymers of halogenated vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride,

  <Desc / Clms Page number 29>

 as well as their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.



   9. Polymers which are derived from unsaturated acids in a, P and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles modified with butyl acrylate to improve impact resistance.



   10. Copolymers of the monomers mentioned in 9) with one another or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or the acrylonitrile / alkyl methacrylate / butadiene terpolymers.



   11. Polymers which are derived from unsaturated alcohols and amines, or their acylated derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers formed with the olefins mentioned in 1) above.



   12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, poly (ethylene oxide), poly (propylene oxide) or their copolymers formed with bisglycidyl ethers.



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



   14. Phenylene polyoxides and polysulphides and mixtures of phenylene polyoxides with styrenic polymers or polyamides.



   15. Polyurethanes which are derived, on the one hand, from polyethers, polyesters or polybutadienes having terminal hydroxyl groups, and, on the other hand, from aliphatic or aromatic polyisocyanates, as well as their precursors.

  <Desc / Clms Page number 30>

 



   16. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or amino carboxylic acids or corresponding lactams, for example polyamide 4, polyamide 6, polyamides 6-6,6-10, 6 -9, 6-12,4-6, 12-12, polyamide 11, polyamide 12, aromatic polyamides prepared from m-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene-terephthalamide or poly-m-phenylene-isophthalamide;

   and also block copolymers of the above-mentioned polyamides with polyolefins, olefinic copolymers, ionomers or elastomers chemically linked or grafted, or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified by EPDM or ABS; and polyamides condensed during processing (R.I.M systems for polyamides).



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



   18. Polyesters which are derived from dicarboxylic acids and diols and / or hydroxy carboxylic acids or corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyetheresters derived from polyethers having terminal hydroxyl groups; and also polyesters modified with polycarbonates or MBS.



   19. Polycarbonates and polyestercarbonates.



   20. Polysulfones, polyethersulfones and polyetherketones.



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

  <Desc / Clms Page number 31>

 



   22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyalcohols and vinyl compounds as crosslinking agents, and also their halogenated modification products with low flammability.



   24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy-acrylates, urethane-acrylates or polyester-acrylates.



   25. Alkyd resins, polyester resins and acrylic resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.



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



   27. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, for example cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose; as well as rosins and their derivatives.



   28. Blends of the above polymers, 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 / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6-6 and copolymers, PA / PEHD, PA / PP, PA / PPO.



   29. Natural and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, 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 trimellates) and also mixtures of synthetic esters with mineral oils in all weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.

  <Desc / Clms Page number 32>

 



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



   32. Polyketimines in combination with unsaturated acrylic polyacetylacetate resins or with unsaturated acrylic resins. Unsaturated acrylic resins include urethane acrylates, polyetheracrylates, vinyl or acrylic copolymers having side unsaturated groups and acrylated melamines.



  Polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.



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



   34. Epoxy-melamine resins such as light-stable epoxy resins crosslinked with a co-etherified melamine resin with high dry matter epoxy functionality such as LSE-4103 (Monsanto).



   In general, the compounds of the present invention are used in an amount of from about 0.01 to about 5% by weight of the stabilized composition, although this rate may vary with the particular substrate and use. An advantageous range is from about 0.05 to about 3%, and in particular from 0.05 to about 1%.



   The stabilizers of the present invention can be readily incorporated into organic polymers by conventional techniques at any convenient stage prior to their transformation into shaped articles. For example, the stabilizer can be mixed with the polymer as a dry powder, or a suspension or emulsion of the stabilizer can be mixed with a solution, suspension or emulsion of the polymer. The resulting stabilized polymer compositions of the invention may optionally also contain about 0.01 to about 5%, preferably about 0.025 to about 2% and especially about 0.1 to about 1% by weight of various conventional additives, such as the substances listed below, or mixtures of them.

  <Desc / Clms Page number 33>

 



  1. Antioxidants 1.1. Alkylated monophenols, for example:
 EMI33.1
 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-isobutylphenol
2,6-dicyclopentyl-4-methylphenol 2- (a-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 diphenyl thioethers, 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:
 EMI33.2
 2, 2'-methylene-bis (6-tert-butyl-4-methylphenol) 2, 2'-methylene-bis (6-tert-butyl-4-ethylphenol) 2, 2'-methylene-bis [4-methyl -6- (a-methylcyclohexyl) - phenol] 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol) 2,2'-methylene-bis (6-nonyl-4-methylphenol)
 EMI33.3
 2, 2'-methylene-bis [6- (a-methylbenzyl) -4-nonylphenol] 2, 2'-methylene-bis [6- (a, a-dimethylbenzyl) -4-nonylphenol] 2, 2'-methylene -bis (4,6-di-tert-butylphenol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol) 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol ) 4,4'-methylene-bis (2,6-di-tert-butylphenol) 4,4'-methylene-bis (6-tert-butyl-2-methylphenol)

  <Desc / Clms Page number 34>

 
 EMI34.1
 1, 1-bis (S-tert-butyl-4-hydroxy-2-methylphenyl) butane 2, 6-bis (3-tert-butyl-S-methyl-2-hydroxybenzyl)

   - 4-methylphenol 1, 1, 3-tris (S-tert-butyl-4-hydroxy-2-methylphenyl) - butane 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) - 3 -n-dodecylmercaptobutane bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate] ethylene glycol di (3-tert-butyl-4-hydroxy-S-methylphenyl) dicyclopentadiene
 EMI34.2
 bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.



  1. 5. Benzylated compounds, for example:
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6- trimethylbenzene bis sulfide (3,5-di-tert-butyl-4-hydroxybenzyl) ester d 3,5-di-tert-butyl-4-hydroxy-benzylthioglycolic acid isooctyl
 EMI34.3
 bis (4-tert-butyl-3-hydroxy-) dithioterephthalate
2,6,5-dimethylbenzyl) isocyanurate of 1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) isocyanurate of 1, 3, 5-tris (4-tert-butyl-3-hydroxy-
2,6-dimethylbenzyl) dioctadecyl ester of 3,5-di-tert-butyl acid
4-hydroxybenzylphosphoric calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphoric monoethyl ester.



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

  <Desc / Clms Page number 35>

 



  1.7. Esters of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono or polyalcohols, for example with the following alcohols: methanol diethylene glycol octadecanol triethylene glycol
1,6-hexanediol pentaerythritol neopentyl glycol tris (hydroxyethyl) isocyanurate thiodiethylene glycol dihydroxyethyloxamide triethanolamine triisopropanolamine 1.8. Esters of ss- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono or polyalcohols, for example with the following alcohols: methanol diethylene glycol octadecanol triethylene glycol
1,6-hexanediol pentaerythritol neopentyl glycol tris (hydroxyethyl) isocyanurate thiodiethylene glycol dihydroxyethyloxamide triethanolamine triisopropanolamine 1.9.

   Amides of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example: N, N'-di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-di (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazine.

  <Desc / Clms Page number 36>

 
 EMI36.1
 1. 10.

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



  2. UV light absorbents and light stabilizers 2.1. 2- (2'-hydroxyphenyl) benzotriazoles, for example the derivatives bearing substituents 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5'- (1, 1,3 , 3-tetramethylbutyl),
 EMI36.2
 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 (a, a-dimethylbenzyl), 3'-tert- butyl-5'- (2- (w-hydroxyocta (ethylene-oxy) carbonylethyl), 3'-dodecyl-5'-methyl and 3'-tert-butyl-5'- (2-octyloxycarbonyl) ethyl and 5'-methylated dodecyl derivatives.



  2.2. 2-hydroxybenzophenones, for example derivatives carrying substituents 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxyet2'-hydroxy- 4, 4'-dimethoxy.



  2.3. Optionally substituted benzoic acid esters, for example: phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylrésorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylrésorcinol, ester of 2, 4-di- 3,5-di-tert-butyl-4-hydroxybenzoic acid tert-butylphenyl acid and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.



  2.4. Acrylates, for example: ethyl ester or isooctyl ester of a-cyano-P acid, ss-diphenylacrylic, methyl ester of a-carbomethoxycinnamic acid, methyl ester or butyl ester of a-cyano acid -ss-methyl-p-methoxy-
 EMI36.3
 cinnamic acid, methyl ester of α-carbomethoxyp-methoxycinnamic acid and N- (ss-carbomethoxy-p-cyanovinyl) - 2-methylindoline.



  2.5. Nickel compounds, for example: complexes of nickel with 2, 2'-thio-bis [4- (1, 1,3, 3-tetramethylbutyl) phenol]

  <Desc / Clms Page number 37>

 such as the 1: 1 or 1: 2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4- acid 3, 5-di-tert-butylbenzylphosphonic hydroxy such as methyl, ethyl or butyl ester, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.



  2.6. Sterically hindered amines, for example: bis (2,2, 6, 6-tetramethylpiperidyl) sebacate, bis- (1,2, 2,6, 6-pentamethylpiperidyl) sebacate, bis (1,2, 2 ester) , 6, 6pentamethylpiperidyl) of n-butyl-3,5,5-di-tert-butyl-4-hydroxybenzylmalonic acid, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N, N'bis (2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and
 EMI37.1
 4-tert-octylamino-2, 6-dichloro-s-triazine, tris nitrilotriacetate (2, 2, 6, 6-tetramethylpiperidyl), butane- 1, 2, 3, 4-tetrakis tetracarboxylate (2, 2 , 6, 6-tetramethyl- 4-piperidyl), 1, 1'- (1, 2-ethanediyD-bis (3,3, 5, 5-tetramethylpiperazinone), bis (1-octyloxy-2, 2.6) sebacate , 6tetramethylpiperidine-4-yl).



  2.7. Diamides of oxalic acid, for example: 4,4'-dioctyloxyoxanilide, 2, 2'-dioctyloxy-5, 5'-di-tert-butyloxanilide, 2, 2'-didodécyloxy-5, 5'-di-erù -butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) - oxamide, 2-ethoxy-S- tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2 '-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho-and para-methoxy-oxan iles as well as o- and p-ethoxy-oxanilides.
 EMI37.2
 



  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-triazine, 2, 4-bis (2, 4-dihydroxyphenyl) -6- (4chlorophenyl) -s-triazine, 2, 4-bis [2- hydroxy-4- (2-hydroxy-

  <Desc / Clms Page number 38>

 
 EMI38.1
 ethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine, 2,4-bis- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (2,4-dimethylphenyl) -s- triazine, 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-bromophenyl) -s-triazine, 2,4-bis [2-hydroxy- 4- (2-acetoxyethoxy ) phenyl] -6- (4-chlorophenyl) - triazine, 2,4-bis (2,4-dihydroxyphenyl) -6- (2,4-dimethylphenyl) - s-triazine.



  3. Metal deactivators, for example: N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis- (salicyloyl) hydrazine, N, N'-bis (3, 5-di- tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2, 4-triazole, bisbenzylidene-dihydrazide of oxalic acid.



  4. Phosphites and phosphonites, for example: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites, tris- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl-pentaerythritol diphosphite, bis (2,4, 6-tri-) diphosphite
 EMI38.2
 tert-butylphenyl) -pentaerythritol, bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol, bis (2,4-di-tert-butylphenyl) -pentaerythritol, tristearyl-sorbitol triphosphite , 4'-diphenylene-diphosphonite of tetrakis (2,4-di-tert-butylphenyl).



  5. Compounds which destroy peroxides, for example: esters of ss-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioetrakis disulfide, (ss-dodecylmercapto) pentaerythritol propionate.



  6. Hydroxylamines, for example: N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditétradécylhydroxylamine, N, N-dihexadécylhydroxylamine, Nécylamine -hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

  <Desc / Clms Page number 39>

 



  6. Nitrones, for example: N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl -alpha-pentadecylnitrone, N-octadecylalpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecylalpha-heptadecylnitrone, N-octadecyl-nitrone-hexadecone hydrogenated tallow amine.



  8. Stabilizers for polyamides, for example: copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts.



  9. Basic co-stabilizers, for example: melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of acids higher fats such as Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.



  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, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.



  12. Other additives, for example: plasticizers, lubricants, emulsifying agents, pigments, optical brightening agents, flame retardants, anti-electrostatic agents, swelling agents and sulphurous synergism agents such as dilauryl thiodipropionate or distearyl thiodipropionate.



  13. Benzofurannones and indolinones, for example: compounds proposed in documents US-A-4,325,863, US-A-4,338,244
 EMI39.1
 and US-A-5,175,312, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-ditert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2- stearoyloxyethoxy) phenyl] benzofuran-2-one, 3, 3'-bis [5, 7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one],

  <Desc / Clms Page number 40>

 
 EMI40.1
 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2-one , 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.



   The co-stabilizers, with the exception of the benzofurannones mentioned in 13 in the list, are added for example at concentrations of 0.01 to 10% relative to the total weight of the material to be stabilized.



   Other preferred compositions include, in addition to components (a) and (b), other additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.



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



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



   A particularly advantageous phenolic antioxidant is chosen from n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentane-tetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate di-n-octadecyl, 1,3,5-tris isocyanurate (3,5-di-tert-butyl-4-hydroxybenzyl), bis ( 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) of thiodiethylene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene lebis (3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis-
 EMI40.2
 (4, 6-di-tert-butylphenol),

   1,3,5-tris- (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,3,3-tris- (2-methyl-4-hydroxy-5- tert-butylphenyl) butane, 1,3 / 5-tris isocyanurate [2- (3, S-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl], 3,5-di (3, S- di-tert-butyl-4-hydroxybenzyl) -

  <Desc / Clms Page number 41>

 mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3, S-di-tert-butyl-4-hydroxyanilino) - 3,5-di (octylthio) -s-triazine, N, N'-hexamethylene-bis-
 EMI41.1
 (3, S-di-tert-butyl-4-hydroxyhydrocinnamamide), the calcium salt of bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonate), bis [3, 3-di ( 3-tert-butyl-4-hydroxyphenyl) - ethylene butyrate, 3,

   Octyl 5-di-tert-butyl-4-hydroxybenzylthioglycolate, bis (3, 5-di-tert-butyl-4-hydroxy-
 EMI41.2
 hydrocinnamoyl) hydrazide and N, N'-bis [2- (3, S-di-tertbutyl-4-hydroxyhydrocinnamoyloxy) ethyl] oxamide.



   The most popular phenolic antioxidant is neopentane-tetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydro-cinnamate , 1,3,5-trimethyl-2,4,6-tris-
 EMI41.3
 (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).



   A particularly advantageous sterically hindered amine is chosen from bis sebacate (2, 2, 6, 6tetramethylpiperidine-4-yle), bis sebacate (1,2, 2,6, 6pentamethylpiperidine-4-yle), ( 3,5-di-tert-butyl-4-hydroxybenzyl) di (1,2,2,6,6-pentamethylpiperidine-4-yl) butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1, 3, 8-triazaspiro [4. 5] decane-2,4-dione, tris nitrilotriacetate (2,2,6,6tetramethylpiperidine-4-yl), 1,2-bis (2,2,6,6-tetramethyl-3-oxopiperazine-4 -yl) ethane, 2,2,4,4-tetramethyl-7-oxa- 3, 20-diaza-21-oxodispiro [5. 1.11.

   2] heneicosan, the polycondensation product of 2,4-dichloro-6-tert-octylaminos-triazine and 4,4'-hexamethylene-bis (2,2,2,6,6tetramethylpiperidine), the polycondensation product 1- (2-hydroxyethyl) -2, 2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 4,4'-hexamethylene-bis (2,2-amino , 6,6tetramethylpiperidine) and 1,2-dibromoethane, butane-

  <Desc / Clms Page number 42>

 1,2,4,4-tetrakis tetracarboxylate (2,2,6,6-tetramethylpiperidine-4-yl), butane-1,2,3,4-tetrakis tetracarboxylate (1,2, 2,6, 6-pentamethylpiperidine-4-yl), the polycondensation product of 2,4-dichloro-6-morpholinos-triazine and 4,4'-hexamethylene-bis (2,2,2,6,6tetramethylpiperidine), N, N ', N ", N'" - tetrakis [4, 6bis (butyl- (1,

   2,2,6,6-pentamethylpiperidine-4-yl) amino) - s-triazine-2-yl] -1,10-diamino-4,7-diazadecane, butane-1,2,3,4-tetracarboxylate mixed of [2, 2,6, 6-tetramethyl-
 EMI42.1
 piperidine-4-yl / (3, P, P ', P'-tetramethyl-3, 9- (2, 4, 8, 10- tetraoxaspiro [5.5] undecane) diethyl], butane-1,2, [1,2,2,6,6,6-pentamethylpiperidine-4-yl / P, ss, ss', ss'-tetramethyl-3, 9- (2,4,8,10-tetraoxaspiro- [3,4,4] mixed tetracarboxylate 5.

     5] undecane) diethyl], octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4'-ethylenebis (2,2, 6,6-tetramethylpiperazine-3-one) , N-2,2,6,6tetramethylpiperidine-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidine-4-yl-n-dodecylsuccinimide, N-1-acetyl-2 , 2, 6,6-tetramethylpiperidine-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.

   5] decane-2, 4-dione, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl) sebacate, bis (1-cyclohexyloxy-2, 2,6, 6) succinate -tetramethylpiperidine-4-yl), 1-octyloxy-2,2,6,6-tetramethyl-
 EMI42.2
 4-hydroxypiperidine, lepoly {[6-tert-octylamino-s-triazine- 2, 4-diyl] [2- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine- 4-yl) imino-hexamethylene- [ 4- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine-4-yl) imino] and 2, 4, 6-tris [N- (1-cyclo-hexyloxy-2, 2.6, 6- tetramethylpiperidine-4-yl) -n-butylamino] s-triazine.



   A highly preferred sterically hindered amine is bis (2,2,6,6-tetramethylpiperidine-4-yl) sebacate, bis (1,2, 2,6, 6-pentamethylpiperidine-4-yl) sebacate, bis (1,2,5,6-pentamethylpiperidine-4-yl) (3,5,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, the polycondensation product of 1- (2-hydroxyethyl) - 2, 2,6, 6-tetramethyl- 4-hydroxypiperidine and succinic acid, the product

  <Desc / Clms Page number 43>

 polycondensation of 2,4-dichloro-6-tert-octylamino-s-triazine and of 4,4'-hexamethylene-bis (2,2,2,6,6tetramethylpiperidine), N, N ', N' ', N '' '- tetrakis [4, 6-bis- (butyl (1,2, 2,6, 6-pentamethylpiperidine-4-yl) amino) -
 EMI43.1
 s-triazine-2-yl] -1, 10-diamino-4, 7-diazadecane, sebacate debis (1-octyloxy-2, 2, 6,

   6-tetramethylpiperidine-4-yl), bis succinate (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine-4-yl), 1-octyloxy-2, 2, 6, 6-tetramethyl-4hydroxypiperidine, poly {[6-tert-octylamino-s-triazine- 2, 4-diyl] [2- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine-4-yl) imino-hexamethylene- [4- ( 1-cyclohexyloxy-2, 2, 6, 6tetramethylpiperidine-4-yl) imino] or 2, 4, 6-tris [N- (1- cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl) - n-butylamino] -s-triazine.



   The present composition may contain, in addition, another UV absorber chosen from s-triazines, oxanilides, hydroxybenzophenones, benzoates and α-cyanoacrylates.



   In particular, the present composition may contain, in addition, a stabilizing amount of at least one other 2-hydroxyphenyl-2H-benzotriazole, another tris-aryl-s-triazine or a sterically hindered amine, or a mixture of them.



   Preferably, 2-hydroxyphenyl-2H-benzotriazole
 EMI43.2
 is selected from 2- (2-hydroxy-3, 5-di-tert-amylphenyl) - 2H-benzotriazole, le2- [2-hydroxy-3, 5-di (a, a-dimethylbenzyl) phenyl] -2H- benzotriazole, 2- [2-hydroxy-3- (a, a-dimethyl-benzyl) -5-octylphenyl] -2H-benzotriazole, 2- {2-hydroxy- 3-tert-butyl-5- [2- (w-hydroxy-octa (ethylene-oxy) carbonyl) - ethyl] phenyl} -2H-benzotriazole and 2- {2-hydroxy-3-tert-butyl-5- [2- (octyloxy) carbonyl) ethyl] phenyl } -2H-benzotriazole.



   Preferably, the other tris-aryl-s-triazine is
 EMI43.3
 chosen from 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy- 4-octyloxyphenyl) -s-triazine, la2, 4-diphenyl-6- (2-hydroxy- 4-hexyloxyphenyl) - s-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-di / tridecyloxy-2-hydroxypropoxy) -

  <Desc / Clms Page number 44>

 
 EMI44.1
 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 varnishes which can be stabilized against the action of light and humidity according to the present invention are the conventional oven varnishes which are used, in particular, for automobile coatings (topcoats automotive), for example varnishes based on alkyd / melamine resins and alkyd / acrylic / melamine resins (see: H. Wagner and HF Sarx, "Lackkunstharze" (1977), pages 99-123).



  Other crosslinking agents include glycoluril resins, blocked isocyanates or epoxy resins.



   The stabilized varnishes according to the invention can be used both for metallized finishing coatings and for solid-color finishes, in particular in the case of finishing touch-ups, as well as for various applications of continuous strip coating.



  The stabilized varnishes according to the invention are preferably applied in the conventional manner by two methods, either the single-layer method or the two-layer method. In the latter method, the base layer containing the pigment is applied first, then a covering layer of colorless varnish is applied thereto.



   It should also be noted that the compounds of the present invention can be used in non-acid catalyzed thermosetting resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. The epoxy and epoxy polyester resins are crosslinked by conventional crosslinking agents such as acids, acid anhydrides, amines, etc. Likewise, the epoxide can be used as a crosslinking agent for various acrylic resin systems or polyesters which have been modified by the presence of reactive groups on the structure of the skeleton.

  <Desc / Clms Page number 45>

 



   When used in two-layer topcoats, the compounds of the present invention can be incorporated into the colorless layer or simultaneously with the colorless layer and the pigmented base layer.



   When it is desired to obtain a water-soluble, water-miscible or water-dispersible coating product, the ammonium salts of the acid groups present in the resin are formed. A powder coating composition can be prepared by reacting the glycidyl methacrylate with selected alcohols.



   The present benzotriazoles are prepared by conventional methods for the preparation of compounds of this type. The usual method involves the diazotization of a substituted o-nitraniline, then the coupling of the resulting diazonium salt with a substituted phenol and the reduction of the intermediate azobenzene to the corresponding corresponding benzotriazole. The starting materials suitable for preparing these benzotriazoles are for the most part commercial products or can be prepared by normal methods of organic synthesis.



   Although the present benzotriazoles are particularly suitable for applications in automotive coatings due to their increased durability, it is believed that they should also be particularly useful in other applications where better durability is required, such as in solar films , etc.



   The following examples are presented for illustrative purposes only.



   Example 1
 EMI45.1
 Preparation of 5-trifluoromethyl-2- (2-hydroxy-3-a-cumyl-5tert-octylphenyl) -2H-benzotriazole a) Diazotization of 4-amino-3-nitro- (trifluoromethyl) benzene
A 500 ml three-necked flask equipped with a mechanical stirrer is loaded with 41.2 g of 4-amino-3-nitro- (trifluoromethyl) benzene, 52 ml of concentrated hydrochloric acid and 100 ml of distilled water. The stirred solution is cooled

  <Desc / Clms Page number 46>

 at 5 ° C. and 17.3 g of sodium nitrite dissolved in 50 ml of water are added.

   The solution is stirred between 0 and 5 C for 2 hours, then filtered and stored at -10 C. b) Monoazo adduct
A 1000 ml flask equipped with a mechanical stirrer is loaded with 40 g of sodium hydroxide dissolved in 200 ml of methanol and 32.4 g of 2-a-cumyl-4-tert-octylphenol dissolved in 50 ml of xylene . The solution is cooled to 5 ° C. and the solution of the diazo derivative of 4-amino-3-nitro- (trifluoromethyl) benzene prepared in part a) is
 EMI46.1
 added between 0 and 5 C in a 2 hour period. Then, 100 ml of xylene are added and the organic phase is washed with water, aqueous hydrochloric acid, water, an aqueous solution of sodium bicarbonate and finally water.

   The solvent is removed under reduced pressure and the residue is purified by chromatography (silica gel, heptane: ethyl acetate 95: 5) to give 42.1 g of the adduct in the form of a dark red paste. c) Reduction of the monoazo adduct
A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 ml of water, 42.1 g of the monoazo adduct prepared in part b) and 400 ml of ethanol.
 EMI46.2
 The mixture is heated to 80 ° C. and 27 g of formamidine-sulfinic acid are added in portions with stirring. After 1.5 hours, the solution is cooled to room temperature and 100 ml of water are added. The pH is adjusted to pH 7 with concentrated hydrochloric acid. The ethanol is removed in vacuo and the aqueous phase is extracted with methylene chloride.

   The solvent is then evaporated under vacuum and the residue is purified by chromatography (silica gel, heptane: toluene at 9: 1) and crystallized from ethanol.



  The title compound is obtained in an amount of 5.6 g in the form of a pale yellow solid melting at 119-121 C.



   Example 2 Preparation of 5-fluoro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared according to the general procedure of Example 1 using 31.2 g of

  <Desc / Clms Page number 47>

 4-fluoro-2-nitraniline. In part c) of the operating sequence, an additional 9 g of formamidinesulfinic acid is necessary to complete the reduction.



  Purification of the crude product on silica gel (heptane: toluene 1: 1) gives 4.5 g of the title compound as an off-white solid. Further purification by recrystallization from an acetonitrile: toluene mixture gives 1.1 g of the title compound melting at 93-96 C.



   Example 3 Preparation of 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tertoctylphenyl) -2H-benzotriazole
The general procedure of Example 1, parts a) and b), is followed to prepare the intermediate monoazo compound for the preparation of the title compound from 339.3 g of 4-chloro-2-nitraniline. The crude product is purified by recrystallization from methanol to give 70.9 g of dark red monoazo adduct. c) Reduction of the monoazo adduct
A mixture of 11.8 g of sodium hydroxide and 138 g of 2-butanol is heated to 95 C. A solution of 60.1 g of the above monoazo adduct and 1.3 g of 2.3 -dichloro-1,4-naphthoquinone in 90 g of 2-butanol is added over a period of 90 minutes with stirring.

   The reaction mixture is heated to remove the 2-butanone formed as a by-product, additional 2-butanol being added to replace the distillate. The reaction mixture is cooled to 85 ° C., washed with 2.5N sulfuric acid and brine, then concentrated. The residue is recrystallized from a methanol: xylene mixture to give 45.6 g of the title compound in the form of a pale yellow solid melting at 104-105 C.



   Example 4 Preparation of 5-phenylthio-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole
 EMI47.1
 To a stirred mixture of 75 g of 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 105 g of

  <Desc / Clms Page number 48>

 N-methylpyrrolidone heated to 90 ° C., 44.3 g of a 45% aqueous solution of potassium hydroxide are first added in a period of 15 minutes, then 20.4 g of thiophenol in another period of 15 minutes. The reaction mixture is then heated between 170 and 175 C for 4 hours while removing the water by distillation. After cooling to 100 ° C., xylene and water are added and the resulting mixture is acidified with a 15% aqueous solution of hydrogen chloride.

   The organic phase is separated and washed with water, then concentrated. The crude product residue is recrystallized from methanol to give 82 g of the title compound as a pale yellow solid melting at 124-125 C.



   Example 5
 EMI48.1
 Preparation of 5-benzenesulfonyl-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole
A 1000 ml flask is loaded with 75.2 g of 5-phenylthio-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) - 2H-benzotriazole, prepared in Example 4,102 g of xylene , 0.9 g sodium tungstate dihydrate and 18.4 g formic acid. The mixture is heated to 50 C. To this stirred mixture, 36.3 g of 50% hydrogen peroxide are added slowly so that the temperature does not exceed 85 C. An additional xylene and water are then added . The organic phase is separated, washed with an aqueous solution of sodium sulfite, then twice with water and concentrated.

   The crude product residue is recrystallized from methanol to give 75.2 g of the title compound in the form of a light yellow solid melting at 170-171 C.



   Example 6 Preparation of 5-nonylthio-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared by following the procedure of Example 4 with 30 g of 5-chloro 2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 17, 6 g of nonylmercaptan.

  <Desc / Clms Page number 49>

 



   Example 7 Preparation of 5-nonylsulfonyl-2- (2-hydroxy-3-a-cumyl-
 EMI49.1
 5-tert-octylphenyl) -2H-benzotriazole 5-nonylthio-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole, prepared in Example 6, is oxidized to the sulfone without purification of the intermediate sulfide using 8.7 g of formic acid, 0.7 g of sodium tungstate dihydrate and 17.6 g of 50% hydrogen peroxide to give the title compound as a yellow resin with a molecular ion of m / e 631.



   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 followed, to prepare the intermediate monoazo compound for the preparation of the title compound from 4-chloro-2-nitraniline and 2-phenyl-4- tert-octylphenol. The crude product is purified by recrystallization from ethanol to give a dark red monoazo adduct.



   The title compound is prepared according to the reduction procedure of Example 3 from 65 g of the monoazo adduct prepared above, 19.9 g of sodium hydroxide and 2.4 g of 2.3 -dichloro-1,4-naphthoquinone. The crude product is purified by chromatography on silica gel (hexane: ethyl acetate 5: 1), giving a fraction which consists mainly of the title compound having a molecular ion of m / e 433.



   Example 9 Preparation of 5-phenyl thio-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared according to the procedure of Example 4 from 20 g of the compound of Example 8.20, 4 g of a 45% aqueous solution of potassium hydroxide, 10.3 g of thiophenol and 100 g of N-methylpyrrolidone. The title compound is an oil purified by chromatography on silica gel using toluene as eluent.

  <Desc / Clms Page number 50>

 
 EMI50.1
 



  Example 10 Preparation of 5-benzenesulfonyl-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared according to the procedure of Example 5 from 20 g of the sulphide of Example 9.6, 4 g of formic acid, 15.0 g of 50% hydrogen peroxide and 0.6 g of sodium tungstate dihydrate. Recrystallization of 2.5 g of raw material from a xylene / methanol mixture gives 2.0 g of the purified title compound in the form of a light yellow powder melting at 204-206 C.



   Example 11 Preparation of a mixture of 5-chloro-2- (2-hydroxy-3, 5-di-
 EMI50.2
 alkylphenyl) -2H-benzotriazoles (the alkyl groups being independently C <, Çgj; C-, and C c A mixture of 65.4 g of 5-chloro-2- (2-hydroxy-3, 5dialkylphenyl) -2H-benzotriazoles, 45 ml of dodecene and 13 ml of methanesulfonic acid is heated to 170 C under nitrogen. An additional 135 ml of dodecene is added over a 4.5 hour period. The reaction mixture is allowed to cool to 100 ° C., then quenched with 400 g of crushed ice and extracted three times with ethyl acetate. The organic phases are combined, washed with water, an aqueous solution of sodium bicarbonate, more water and brine, dehydrated over anhydrous magnesium sulfate and finally concentrated.

   The polymer residue is removed by distillation in a ball tube under a vacuum of 26.7 Pa and up to
 EMI50.3
 210 C. The unreacted starting material is then removed by distillation (at 1.3 Pa, 160 C) to give 45 g of the title mixture in the form of a yellow oil.



   Example 12
 EMI50.4
 Preparation of a mixture of 5-phenylthio-2- (2-hydroxy- 3, 5-dialkylphenyl) -2H-benzotriazoles (the alkyl groups being independently C, Cg, C. and C The mixture of the title is prepared according to the procedure of Example 4 using 40 g of the mixture of Example 11, 11, 2 g of potassium hydroxide and 12.3 ml of thiophenol.

  <Desc / Clms Page number 51>

 



   Example 13 Preparation of a mixture of 5-benzenesulfonyl-2- (2-hydroxy-3, 5-dialkylphenyl) -2H-benzotriazoles (the alkyl groups being independently C4, C8, Cl2 and C16
A mixture of the crude product of Example 12.350 ml of isopropanol, 14.7 ml of formic acid and 1.8 ml of concentrated sulfuric acid is heated to reflux and 30 ml of peroxide are added dropwise. hydrogen at 50% in a 2 hour period. After an additional 3 hours at reflux, the reaction mixture is cooled and a 10% aqueous sodium sulfite solution and an aqueous sodium bicarbonate solution are added. The isopropanol is evaporated and the residue is extracted with methylene chloride. The organic phase is washed with water, then dried over anhydrous magnesium sulfate.

   The solution is concentrated to leave 45 g of crude product in the form of a viscous orange oil. A portion of about 30 g of this crude product is purified by chromatography on silica gel (heptane: ethyl acetate 4: 1) to give 28.9 g of the title mixture in the form of a yellow oil.



   Example 14 5-diphenylphosphinyl-2- (2-hydroxy-3, 5-tert-butylphenyl) - 2H-benzotriazole
A 500 ml three-necked round bottom flask, flame dried, equipped with a condenser, a magnetic stirrer and a thermometer, is loaded with 100 ml of dimethyl sulfoxide, 7.41 g (0.066 mol) of ter- potassium butylate and 11.17 g (0.060 mol) of diphenylphosphine using a syringe. A suspension of 10.56 g (0.030 mol) of 5-chloro 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -2H-benzotriazole in 50 ml of dimethyl sulfoxide is added all at once to the mixture red. The resulting brown solution is stirred at 135 ° C for 3.5 hours, then cooled to room temperature.

   The mixture is quenched with a portion of a saturated ammonium chloride solution and then ethyl acetate is added. The organic phase is separated and washed three times with water, once with brine,

  <Desc / Clms Page number 52>

 then dehydrated over anhydrous magnesium sulfate. 50% hydrogen peroxide is added to the solution, which produces heat. The mixture is left to stand for 30 minutes, then washed once with a 10% solution of sodium metabisulfite, three times with saturated sodium bicarbonate solution, once with brine and finally dehydrated over anhydrous magnesium sulfate . The mixture is filtered with a plug of silica gel and the solvent is removed under reduced pressure to leave 8.0 g of a crude yellow solid.

   The crude product is treated by medium pressure chromatography using heptane: ethyl acetate at 1: 1 to give 4.2 g (27% yield) of the title compound in the form of a yellow solid melting at 98-100 C.



   Example 15 5-diphenylphosphinyl-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole
Following the procedure of Example 14, the title compound is prepared using 5-chloro 2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole as the intermediate benzotriazole of departure.



   Example 16 to 26
Following the general procedure of Example 1, the following other 2H-benzotriazoles of formula I 'are prepared.
 EMI52.1
 
 <tb>
 <tb>



  Example <SEP> G2 <SEP> E1 <SEP> E2
 <tb> 16 <SEP> CF3 <SEP> phenyl <SEP> tert-octyl
 <tb> 17 <SEP> CF3 <SEP> a-cumyle <SEP> tert-butyl
 <tb> 18 <SEP> CN <SEP> a-cumyle <SEP> tert-octyl
 <tb> 19 <SEP> CN <SEP> a-cumyle <SEP> nonyle
 <tb> 20 <SEP> CN <SEP> a-cumyle <SEP> tert-butyl
 <tb> 21 <SEP> COOCH <SEP> a-cumyle <SEP> dodecyl
 <tb> 22 <SEP> F <SEP> phenyl <SEP> ert-octyle
 <tb>
 

  <Desc / Clms Page number 53>

 
 EMI53.1
 
 <tb>
 <tb> 23 <SEP> CF3 <SEP> a-cumyle <SEP> nonyle
 <tb> 24 <SEP> CF ..

    <SEP> a-cumyle <SEP> dodecyl
 <tb> 25 <SEP> CON <SEP> (Bu) <SEP> 2 <SEP> a-cumyle <SEP> tert-octyl
 <tb> 26 <SEP> COOCH3 <SEP> phenyl <SEP> tert-octyl
 <tb>
 
 EMI53.2
 Example 27 Preparation of 5-octylthio-2- (2-hydroxy-3-a-cumyl-5-tertoctylphenyl) -2H-benzotriazole The title compound is prepared by following the procedure of Example 6 with 5-chloro -2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and octylmercaptan.



  Example 28 Preparation of 5-octylsulfonyl-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole 5-octylthio-2- (2-hydroxy-3-a-cumyl-5 -tert-octylphenyl) -2H-benzotriazole, prepared in Example 27, is oxidized to the sulfone without purification of the intermediate sulfide using the general method of Example 7.



  Example 29 Preparation of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole Following the general procedure of Example 1, parts a) and b), the monoazo compound intermediate of the title compound is prepared from 17.3 g of 4-chloro-2-nitraniline to give 34.7 g of a wet cake of the dark red monoazo adduct.



  Reduction of the monoazo adduct A mixture of 20 g of sodium hydroxide, 500 ml of water and 26.3 g of the wet cake of the monoazo adduct prepared above is warmed to 30 C. Add 33 , 0 g of zinc powder in successive portions in 2 hours. At the end of this addition, 180 g of a 40% aqueous sodium hydroxide solution are added dropwise over 1 hour. The mixture is stirred at temperature

  <Desc / Clms Page number 54>

 room for 96 hours. The zinc residue is removed by filtration. The aqueous solution is neutralized to pH 5-6 and the resulting suspension is filtered. The resulting filter cake is washed well with water and dried to give 22.5 g of crude product. The crude product is purified by extraction with a Soxhlet apparatus with acetone to give 9.6 g of the title compound.



   Example 30 Preparation of 5-chloro-2- (2-hydroxy-4-octyloxyphenyl) - 2H-benzotriazole
A mixture of 6.5 g of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 7.1 g of 1-bromooctane, 5.2 g of anhydrous potassium carbonate and 100 ml of acetone is heated at reflux for 24 hours. To the resulting mixture, about 100 ml of water and ethyl acetate are added and 10.6 g of crude product are isolated. Column chromatography using petroleum ether gives 0.9 g of the title compound, the structure of which is confirmed by proton 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 is prepared from 10.3 g of 4-amino-3-nitro- (trifluoromethyl) benzene to give 6.4 g of the title compound whose structure is confirmed by proton NMR.



   Example 32 Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole
The title compound is prepared according to the general procedure of Example 30 from 5.6 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole. The crude product is purified by column chromatography to give 1.1 g of the title compound in the form of a white solid melting at 79-81 C. The structure is confirmed by proton NMR and mass spectrometry.

  <Desc / Clms Page number 55>

 
 EMI55.1
 



  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 dihydroxyphenyl) -2H-benzotriazole prepared in Example 31, 1.3 ml of butyl ether and glycidyl ether and 100 mg of ethyl bromide triphenylphosphonium in 50 ml of xylene is heated at reflux under nitrogen for 14 hours. 25 ml of water and 25 ml of ethyl acetate are added and 3 g of the crude product are isolated. Recrystallization from heptane gives 2.1 g of the title compound, the structure of which is confirmed by NMR.



   Example 34 Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2H-benzotriazole
The title compound is prepared according to the general procedures of Examples 1 and 29 starting from 4-amino-3-nitro- (trifluoromethyl) benzene and 3-aminophenol. The structure of the product is confirmed by NMR.



   Example 35 Preparation of 5-trifluoromethyl-2- [2-hydroxy-4- (2-ethyl-hexanoylamino) phenyl] -2H-benzotriazole
To a mixture of 4 g of 5-trifluoromethyl-2- (2hydroxy-4-aminophenyl) -2H-benzotriazole and 1.4 g of triethylamine in 75 ml of toluene, a mixture of 2-ethylhexanoyl chloride is added dropwise in 125 ml of toluene. The resulting mixture is treated with 100 ml of water and the crude product formed is purified by column chromatography to give 1.9 g of the title compound melting at 179-181 C. The structure is confirmed by NMR.



   Example 36
 EMI55.2
 Preparation of 5-carbomethoxy-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole a) Esterification of 4-amino-3-nitrobenzoic acid
700 ml of methanol, 20 g of xylene, 14 g of concentrated sulfuric acid and 100 g of acid are added to a 2-liter three-necked flask equipped with a mechanical stirrer.

  <Desc / Clms Page number 56>

 
 EMI56.1
 4-amino-3-nitrobenzoic acid. The solution is heated at reflux for 33 hours. The mixture is cooled to 350C and neutralized to pH 7.8. 1 liter of water is added.

   The solid is collected and washed with 500 ml to give, after drying overnight, 100.9 g of methyl 4-amino-3-nitrobenzoate. b) Diazotization of methyl 4-amino-3-nitrobenzoate
A three-liter three-necked flask equipped with a mechanical stirrer is loaded with 177 g of 96% sulfuric acid, then 11 g of sodium nitrite are added slowly over a period of 90 minutes. The mixture is warmed to 300C to initiate the reaction.

   The temperature is kept below 70 C. The mixture is then cooled to 150 ° C. and 30 g of methyl 4-amino-3-nitrobenzoate are added over a period of 2 hours while maintaining the temperature between 15 and 20 ° C. The mixture is cooled to 00C and 200 g of ice are added so that the solution is suitable for the coupling reaction to form a monoazo compound. c) Monoazo adduct
52 g of 2-a-cumyl-4-tert-octylphenol, 20 g of water, 315 g of methanol, 7 g are added to a 2-liter three-necked flask equipped with a mechanical stirrer and a dropping funnel. g of xylene and 150 g of sodium hydroxide.

   The mixture is cooled to -5 ° C. and the diazonium salt solution prepared in step b) is added over a period of 2 hours, under cooling to keep the temperature below 3 ° C. After adding the salt solution of diazonium, the pH is adjusted to 6.5-7.0. The mixture is poured into 500 ml of xylene and washed three times with 500 ml of water at 60 C. The xylene is removed by distillation to leave 186 g of monoazo adduct containing residual xylene. d) Reduction of the monoazo adduct
186 g of the monoazo adduct prepared in step c), 125 g of 2-butanol and 1.7 g of 2,3-dichloro-1 are added to a 500 ml flask equipped with a mechanical stirrer , 4-naphthoquinone.

   The mixture is heated to 90 ° C.

  <Desc / Clms Page number 57>

 and the resulting solution is then placed in the dropping funnel of a separate flask. In this other flask, 175 g of 2-butanol and 18.6 g of sodium hydroxide are added. The flask is heated to 950C and the monoazo compound solution is added over two hours while distilling off the methyl ethyl ketone and 2-butanol. 100 g of 2-butanol are added and an azeotropic mixture is distilled off. The mixture is then cooled and 300 g of xylene and 200 ml of water are added. The pH is adjusted to 7-7.5 with 20% sulfuric acid. At 60 ° C., the aqueous phase is separated and the organic phase is washed twice with 200 ml of water.

   The xylene is removed by distillation and the residue formed is crystallized from methanol to give 8.8 g of the title compound melting at 141-143 C.



  * Example 37 Preparation of 5- [N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-a-cumyl-5-tert-octyl) phenyl] -2H-benzotriazole a) Saponification of 5-carboxy -2- (2-hydroxy-3-a-cumyl- 5-tert-octylphenyl) -2H-benzotriazole
1.8 g of potassium hydroxide and 40 ml of methanol are added to a 250 ml three-necked flask equipped with a mechanical stirrer, a thermometer, a condenser and a nitrogen inlet. The mixture is warmed to 400C to dissolve the potassium hydroxide. To this solution is added 2.7 g
 EMI57.1
 of 5-carbomethoxy-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole, prepared in Example 36, and 40 ml of methanol. The reaction mixture is heated at reflux for six hours. The mixture is then cooled and acidified with hydrochloric acid.

   Ether and ethyl acetate are added, and the organic phase is separated and dried over anhydrous sodium sulfate. After removing the solvent under vacuum, 2.5 g of 5-carboxy-
 EMI57.2
 2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole. b) 5-chlorocarbonyl-2- (2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl) -2H-benzotriazole
The 2.5 g of 5-carboxy-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in step a)

  <Desc / Clms Page number 58>

 are placed in a 250 ml flask equipped with a stirrer, a thermometer, a reflux condenser, a Dean-Stark separator and a nitrogen inlet. 100 ml of toluene are added and the mixture is heated to reflux to remove all traces of water.

   The mixture is then cooled and 0.76 g of oxalyl chloride in 15 ml of toluene is added.
 EMI58.1
 The reaction mixture is slowly heated to 60 ° C and kept between 60 and 65 ° C for 8 hours until all of the hydrogen chloride has been removed to give the title acid chloride. c) 5- [N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-a-cumyl-5-tert-octyl) phenyl] -2H-benzotriazole
0.8 g of di-n-butylamine, 6 ml of pyridine and 25 ml are added to a 500 ml flask equipped with a mechanical stirrer, a drying tube, a thermometer and a dropping funnel. ml of toluene.

   The mixture is cooled to 0 ° C. and the acid chloride solution prepared in step b) is placed in the dropping funnel and added to the mixture
 EMI58.2
 reaction over a period of 30 minutes at -5 ° C. to -10 ° C. The reaction mixture is stirred at this temperature for 1.5 hours, then stored at room temperature overnight. The mixture is filtered, then concentrated in vacuo to leave 3.0 g of crude solid. The solid product is chromatographed to give 1.2 g of the title compound in the form of a tan solid, melting at 131-133 C.



  The structure is confirmed by NMR and mass spectrometry, m / z 596.



   Example 38 5-trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared according to the general procedure of Example 1 from the diazo derivative of 4-amino-3-nitro- (trifluoromethyl) benzene and 4-tert-octylphenyl, and purified by chromatography on silica gel . Recrystallization of the product from heptane or methanol gives the title compound as an almost white solid melting at 80-81 C.

  <Desc / Clms Page number 59>

 



   Example 39: Use
The following tests were carried out to determine the effects of various UV absorbers of the 2H-benzotriazole type substituted by various donor and electron acceptor groups on the thermal durability and the rate of loss by a high solids thermosetting acrylic varnish.



   The colorless high-solids thermosetting acrylic varnish is prepared by mixing an experimental acrylic polyol resin and hexamethoxymethylmelamine (Resimene 747, Monsanto) in a 60/40 dry matter ratio. Dodecylbenzenesulfonic acid (Nacure 5225, King Industries) is added as a catalyst at a concentration of 0.70% by weight. A flow aid, Modaflow (Monsanto), is added in a concentration of 0.25% by weight to form a model system of acrylic melamine resin.



   The model colorless varnish is diluted with xylene to a viscosity of 26-27 seconds using a Zahn cut? 2 and applied by a conventional air sprayer at 345 kPa on a quartz blade measuring 2.54 cm x 7.62 cm. Curing is carried out by baking the slide for 30 minutes at 127 C. The colorless varnish is stabilized with 1% by weight of a sterically hindered amine type light stabilizer, bis- (1-octyloxy-) sebacate. 2,2,6,6-tetramethylpiperidine-4-yl) (TINUVINO 123, Ciba-Geigy). The various UV absorbers of the experimental benzotriazole type are incorporated into the colorless varnish in a concentration of 5 mmol% by weight. The layer thickness on the quartz plates varies from 0.029 to 0.036 mm.



   The layers on the quartz slides are subjected to an accelerated aging test under the following conditions in a Weather-O-Meter apparatus with xenon arc with an irradiance adjusted to 6500 W, using an internal quartz filter and external borosilicate filter. type S. The irradiation cycle is as follows: 40 minutes of direct irradiation without spraying water, then 20 minutes

  <Desc / Clms Page number 60>

 
 EMI60.1
 of light with front spraying, then 60 minutes of light irradiation and about 60 minutes of darkness with rear spraying (condensation). The settings are fixed at 0.55 w / m2 at 340 nm, 1.98 kJ / h. In the light period, the temperature of the black panel is set to 702 C.



  The relative humidity is 50 to 55% in the light period and 100% in the dark period. The table below gives the absorbance of the long-wavelength UV band as a function of the number of hours of aging accelerated by the xenon arc.



  To monitor the loss of UV absorbers by the colorless layers, the UV spectra are measured initially and after accelerated aging at regular time intervals. The UV spectrophotometer measures absorbance linearly up to 5.5 absorbance units using a reference beam attenuation technique.



  It is assumed that the degradation products of the UV absorber do not affect the UV spectrum. This hypothesis is checked by following the ratio of the absorbances of the band at approximately 300 nm and of the band at approximately 340 nm. The ratio does not change during the aging of the sample. This suggests that the UV spectrum of aged layers corresponds to the amount of UV absorber remaining in the layer, the degradation products by light having very little, if any, influence on the spectrum.



  The results presented in the table below are based on the structural formula A after 1211 hours of exposure of the colorless layers containing the UV absorbers of the benzotriazole type under test.
 EMI60.2
 
 <tb>
 <tb>



  COMPOUND <SEP> LOSS <SEP> OF UNITS <SEP> G2 <SEP> Rl <SEP> R2
 <tb> COMPOSED <SEP> OF ABSORBANCE <SEP> G2 <SEP> R1 <SEP> R2
 <tb> A <SEP> 1, <SEP> 7982 <SEP> hydrogen <SEP> -PO <SEP> (OEt) <SEP> 2 <SEP> tert-octyl
 <tb> B <SEP> 1.6300 <SEP> hydrogen <SEP> nitro <SEP> tert-octyl
 <tb> C <SEP> 1, <SEP> 4863 <SEP> phenyl-S- <SEP> tert-butyl <SEP> -CH2-CH2COOC8H17
 <tb> D <SEP> 1, <SEP> 4002 <SEP> hydrogen <SEP> hydrogen-CH-CHCOOCH
 <tb>
 

  <Desc / Clms Page number 61>

 
 EMI61.1
 
 <tb>
 <tb> E <SEP> 1, <SEP> 1872 <SEP> methoxy <SEP> tert-butyl <SEP> methyl
 <tb> F <SEP> 0, <SEP> 5259 <SEP> hydrogen <SEP> tert-butyl <SEP> -CH2-CH2COOCH3
 <tb> G <SEP> 0.4527 <SEP> hydrogen <SEP> hydrogen <SEP> a-cumyle
 <tb> H <SEP> 0.4420 <SEP> hydrogen <SEP> tert-butyl <SEP> -CH2-CH2COOC8H17
 <tb> 0, <SEP> 4299 <SEP> hydrogen <SEP> tert-octyl <SEP> a-cumyle
 <tb> J <SEP> 0,

    <SEP> 4134 <SEP> hydrogen <SEP> hydrogen <SEP> tert-octyl
 <tb> K <SEP> 0, <SEP> 3777 <SEP> hydrogen <SEP> tert-octyl <SEP> tert-octyl
 <tb> L <SEP> 0.3712 <SEP> hydrogen <SEP> er-butyle-CHCHCHOH
 <tb> M <SEP> 0, <SEP> 3433 <SEP> hydrogen <SEP> a-cumyle-CH-CHCOOCHg
 <tb> N <SEP> 0.3098 <SEP> cyano <SEP> tert-butyl <SEP> tert-butyl
 <tb> 0 <SEP> 0.2689 <SEP> phenyl-SO2- <SEP> tert-butyl <SEP> -CH2-CH2COOC8H17
 <tb> p <SEP> 0.2576 <SEP> hydrogen <SEP> a-cumyle <SEP> a-cumyle
 <tb> Q <SEP> 0.2492 <SEP> hydrogen <SEP> a-cumyle <SEP> tert-octyl
 <tb>
 
The examination of these results leads to some clear conclusions concerning the light stability of UV absorbers of the 2H-benzotriazole type and concerning the nature of the substitution which influences this light stability.



   Greater light stability occurs when R1 is an α-cumyl or phenyl group and when G2 is an electron acceptor group such as phenylsulfonyl or cyano.



   The nature of the group R2 has less influence on the light stability of UV absorbers of the benzotriazole type.



   From these observations, it is theoretically possible to design an idealized benzotriazole UV absorber in which G2 is an electron accepting group, R. is an efficient bulky group and R2 is a heat stable fragment. One such idealized compound can be a benzotriazole in which G2 is the phenylsulfonyl group, R1 is the α-cumyl group and R2 is the tert-octyl group.

  <Desc / Clms Page number 62>

 



  This benzotriazole is claimed in a generic context in the US patent? 5,280,124. The results given in Example 40 below confirm this prediction and this "idealized" compound effectively exhibits a very low rate of loss, much lower than that which exists in the current state of the art.



   Example 40
Following the general procedure of Example 39, a number of other experimental compounds of the benzotriazole type are incorporated into a thermosetting acrylic melamine resin with a high dry extract at concentrations of between 1.93 and 3% by weight, suitable to give equal molar concentrations of benzotriazoles in the same layer thickness, and sufficient to give an initial absorbance of about 2.0 absorbance units.



   The test discs are exposed in a Weather-O-Meter xenon arc apparatus at X180 cycles (0.45 watt / m2). The initial UV absorbance is measured, and then measurements are made at intervals of about 250 hours for the first 2,000 hours, and every 500 hours thereafter. Each colorless varnish also contains 1% by weight of a sterically hindered amine type light stabilizer, bis (1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate.



   The results provided in the table below are based on compounds of formula A after 1253 hours of exposure of the colorless layers containing the UV absorbers of the benzotriazole type under test.
 EMI62.1
 
 <tb>
 <tb>



  COMPOUND <SEP> LOSS <SEP> OF UNITS
 <tb> OF ABSORBENT
 <tb> R <SEP> 0.2424 <SEP> hydrogen <SEP> phenyl <SEP> a-cumyle
 <tb> Q <SEP> 0.2351 <SEP> hydrogen <SEP> a-cumyle <SEP> tert-octyl
 <tb> S <SEP> 0, <SEP> 1271 <SEP> CF3 <SEP> a-cumyle <SEP> tert-octyl
 <tb> T <SEP> 0, <SEP> 1827 <SEP> phenyl-SO2- <SEP> tert-butyl <SEP> tert-butyl
 <tb>
 

  <Desc / Clms Page number 63>

 
The results provided in the table below are based on compounds of formula A after 1489 hours of exposure of the colorless layers containing the UV absorbers of the benzotriazole type under test.
 EMI63.1
 
 <tb>
 <tb>



  COMPOUND <SEP> LOSS <SEP> OF UNITS <SEP>
 <tb> COMPOUND <SEP> OF ABSORBANCE <SEP> G2 <SEP> R1 <SEP> R2
 <tb> R <SEP> 0, <SEP> 3724 <SEP> hydrogen <SEP> phenyl <SEP> a-cumyle
 <tb> Q <SEP> 0.287 <SEP> hydrogen <SEP> a-cumyle <SEP> tert-octyl
 <tb> S <SEP> 0.1547 <SEP> CF3 <SEP> a-cumyle <SEP> tert-octyl
 <tb> T <SEP> 0, <SEP> 2654 <SEP> phenyl-SO2- <SEP> tert-butyl <SEP> tert-butyl
 <tb>
 
The results given in the table below are based on compounds of formula A after 2521 hours of exposure of the colorless layers containing the UV absorbers of the benzotriazole type under test.
 EMI63.2
 
 <tb>
 <tb>



  COMPOUND <SEP> LOSS <SEP> OF UNITS
 <tb> OF ABSORBANCE <SEP> G2 <SEP> R1 <SEP> R2
 <tb> R <SEP> 0, <SEP> 4854 <SEP> hydrogen <SEP> phenyl <SEP> a-cumyle
 <tb> Q <SEP> 0.4054 <SEP> hydrogen <SEP> a-cumyle <SEP> tert-octyl
 <tb> S <SEP> 0.2192 <SEP> CF3 <SEP> <x-cumyl <SEP> tert-octyl
 <tb> T <SEP> 0.3570 <SEP> phenyl-SO-tert-butyl <SEP> ert-butyl
 <tb>
 
It is clear from the three tables above that Compounds S and in particular T, which have an electron acceptor group at position 5 of the benzo nucleus are notably more durable than benzotriazoles which do not have such a group on the nucleus benzo.



   The results given in the table below are based on compounds of formula A after 1264 hours of exposure of the colorless layers containing the UV absorbers of the benzotriazole type under test.
 EMI63.3
 
 <tb>
 <tb>



  COMPOUND <SEP> LOSS <SEP> OF UNITS <SEP> G2 <SEP> R, <SEP> R2
 <tb> COMPOUND <SEP> OF ABSORBANCE <SEP> G2 <SEP> R1 <SEP> R2
 <tb> Q <SEP> 0.2293 <SEP> hydrogen <SEP> a-cumyle <SEP> tert-octyl
 <tb> S <SEP> 0.0921 <SEP> CF3 <SEP> a-cumyle <SEP> tert-octyl
 <tb> T <SEP> 0, <SEP> 1965 <SEP> phenyl-SO-ter-butyl <SEP> tert-butyl
 <tb>
 

  <Desc / Clms Page number 64>

 
 EMI64.1
 
 <tb>
 <tb> U <SEP> 0, <SEP> 0944 <SEP> phenyl-SO2-a-cumyl <SEP> tert-octyl
 <tb> V <SEP> 0, <SEP> 1719 <SEP> chloro <SEP> a-cumyle <SEP> tert-octyl
 <tb> W <SEP> 0.1655 <SEP> fluoro <SEP> a-cumyle <SEP> tert-octyl
 <tb> X <SEP> 0, <SEP> 1796 <SEP> hydrogen <SEP> phenyl <SEP> tert-octyl
 <tb>
 
The results provided in the table below are based on compounds of formula A after 1518 hours of exposure of the colorless layers containing the UV absorbers of the benzotriazole type under test.

   
 EMI64.2
 
 <tb>
 <tb>



  COMPOUND <SEP> LOSS <SEP> OF UNITS <SEP> G2 <SEP> R, <SEP> R2
 <tb> COMPOUND <SEP> OF ABSORBANCE <SEP> G2 <SEP> R1 <SEP> R2
 <tb> Q <SEP> 0.2662 <SEP> hydrogen <SEP> a-cumyle <SEP> tert-octyl
 <tb> S <SEP> 0.1166 <SEP> CF3 <SEP> a-cumyle <SEP> tert-octyl
 <tb> T <SEP> 0, <SEP> 2423 <SEP> phenyl-SO-er-butyl <SEP> tert-butyl
 <tb> U <SEP> 0.1144 <SEP> phenyl <SEP> -SO2- <SEP> &alpha;

  -cumyle <SEP> tert-octyl
 <tb> V <SEP> 0, <SEP> 1955 <SEP> chloro <SEP> a-cumyle <SEP> tert-octyl
 <tb> W <SEP> 0, <SEP> 1668 <SEP> fluoro <SEP> a-cumyle <SEP> tert-octyl
 <tb> X <SEP> 0, <SEP> 2220 <SEP> hydrogen <SEP> phenyl <SEP> tert-octyl
 <tb>
 
The results appearing in these tables clearly show that the benzotriazoles substituted by an electron acceptor group on the benzo nucleus, in particular a group such as trifluoromethyl or phenylsulfonyl, are particularly durable, as evidenced by low values of rate of loss of absorbance after exposure to actinic radiation. Compounds S, U, V and W are particularly durable and correspond to the profile proposed above. Indeed, the above results confirm the prediction that Compound U must be particularly durable.

   Examination of the results for Compounds T and U highlights the additional advantageous effect which an effective large group such as the a-cumyl group brings to the position of R. instead of a simple alkyl fragment such as the group tert-butyl at this position.


    

Claims (25)

 CLAIMS 1. A coating composition stabilized by a benzotriazole, which benzotriazole exhibits increased durability and a low rate of loss when incorporated into said coating, characterized in that it comprises (a) a resin chosen from the group formed by a resin of thermosetting acrylic melamine, acrylic urethane resin, carboxylated epoxy resin, silane modified acrylic melamine resin, acrylic resin having melamine crosslinked carbamate groups or melamine crosslinked polyol acrylic resin containing carbamate groups , and (b) 0.01 to 5% by weight, relative to the weight of the dry matter of resin, of a benzotriazole of formula A, B, C or D  EMI65.1    <Desc / Clms Page number 66>    EMI66.1    EMI66.2  where G.,  G or T is an electron acceptor radical, G1 is hydrogen or halogen, G2 is a halo, nitro, cyano, R3S0-, R3SO2 -, - COOG3, CF3 -, - P (O) (C6H5) 2, -CO-G3, -CO-NH-G, -CO-N (G3) radical ) 2, -N (G3) -CO-G3,  EMI66.3   G3 is hydrogen, a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, a phenyl group, or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms, R1 is hydrogen, a straight or branched chain alkyl group of 1 to 24 carbon atoms,  a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, a phenyl group, or said phenyl or phenylalkyl group substituted on the phenyl ring with 1 to 4 alkyl groups of 1 to 4 carbon atoms, R2 is a straight or branched chain alkyl group of 1 to 24 carbon atoms, a straight or branched chain alkenyl group of 2 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 with 15 carbon atoms, a phenyl group,  <Desc / Clms Page number 67>  or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 3 alkyl groups of 1 to 4 atoms  EMI67.1  of carbon ;  or R2 is a hydroxyl group or -OR. where R4 is a straight or branched chain alkyl group of 1 to 24 carbon atoms; or said alkyl group substituted by one or more -OH, -OCO-R11, -OR4, -NCO or -NH2 or a combination of them; or said alkyl or alkenyl group  EMI67.2  interrupted by one or more -O -, - NH-or-NR.-or a combination of them, and which may be unsubstituted or substituted by one or more -OH, -OR4 or -NH2 or a  EMI67.3  association of them; or R2 is-SR, -NHR-. or - N (R-.);  or R2 is  EMI67.4    EMI67.5  or X is -O-or-N (Rg) -, Y is -O- or -N (R17) -, Z is a C2-C12 alkylene group, an alkylene group  EMI67.6  in C interrupted by a in C4-C12 interrupted by one to three nitrogen atoms, oxygen atoms or a combination of them, or is a C3-C12 alkylene group, butenylene, butynylene, cyclohexylene or phenylene, each being substituted by a hydroxyl group, m is 0.1 or 2, p is 1, or else p can also be 0 when X and Y are  EMI67.7  respectively-N (R. g) - and-N (R. y) -, R15 is a group -CO-C (R. o) = C (H) R19 or, when Y is - N (R) -, forms with R17 a group-CO-CH = CH-CO-, where R18 is hydrogen or a methyl group and R19 is hydrogen, a methyl group or-CO-X-Ro where R.  is hydrogen, a C1-C12 alkyl group or a group of formula  EMI67.8    <Desc / Clms Page number 68>  where the symbols R1, R3, X, Z, m and p are as defined above, and R16 and R17 are each, independently of the other,  EMI68.1  hydrogen, a C1-C2 alkyl group, a C3-C12 alkyl group interrupted by 1 to 3 oxygen atoms, a cyclohexyl group or a Cy-Cc aralkyl group, and, in the case where Z is a ethylene group, R16 with R17 can also form an ethylene group, n is 1 or 2,  EMI68.2  - when n is 1, Re is Cl, OR6 or NRyRg, or Rg is-PO (OR), -OSi (R) or-OCO-R, or a straight chain or branched C1-C24 alkyl group an alkyl group in C ee which is interrupted by-O-, -S-or-NR <.- and which may be unsubstituted or substituted by -OH or -OCO-R11 'a C 1-6 cycloalkyl group which is unsubstituted or substituted C e cycloalkyl by-OH, an alkenyl group C2-C18 straight or branched chain which is unsubstituted or substituted by-OH, an aralkyl group in Cy-C <e, -CH-CHOH-R.  or a glycidyl group, R6 is hydrogen, a C1-C24 straight or branched chain alkyl group which is unsubstituted or substituted by one or more OH, OR4 or NH2, or -OR6 is  EMI68.3  - (OCHCH) OH or- (OCHCHOR where w is 1 to 12 and R21 is an alkyl group of 1 to 12 carbon atoms, R7 and R8 are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, a group  EMI68.4  straight or branched chain C3-C18 alkyl which is interrupted by-O -, - S-ou-NR <.-, a cycloalkyl group in Ce-C, an aryl group in Cc-C <.  or a C1-C3 hydroxyalkyl group, or else R7 and R8 form with the N atom a ring of pyrrolidine, piperidine, piperazine or morpholine, - when n is 2, R5 is one of the divalent radicals  EMI68.5  - O-R -0- and -N (R) -R -N (R) Rg is a C-Cg alkylene, C-Cg alkenylene, C alkynylene, cyclohexylene or C <-C alkylene. straight or branched chain which is interrupted by -0- or by-CH-CHOH-CH-0-R-O-CH-CHOH-CH-,  <Desc / Clms Page number 69>    EMI69.1  R10 is a C2-C12 straight or branched chain alkylene group which may be interrupted by-0-, a cyclohexylene group or  EMI69.2  or R10 and R11 'with the two nitrogen atoms, form a piperazine ring, R14 is a straight chain C2-C8 alkylene group  EMI69.3  or branched, a C 1 -C alkylene group.  o straight or branched chain which is interrupted by-0-, a cycloalkylene group, an arylene group or  EMI69.4  WHERE R7 and Ro are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, or else R7 and Rg together form an alkylene group of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3- methyliminopentamethylene,  EMI69.5  R11 is hydrogen, C1-C8 straight or branched chain alkyl, C6 -C cycloalkyl, alkenyl  <Desc / Clms Page number 70>  in C3-C8 with straight or branched chain, aryl in C6-C14 or aralkyl in Cy-C. e, R12 is a straight chain alkyl group  EMI70.1  or branched, C-C alkenyl.  o straight or branched chain, C 6 -C 6 cycloalkyl o C 6 -C 16 aryl or C 6 -C aralkyl, R13 is H, a straight chain C1-C8 alkyl group 13 ic, 8 straight chain or branched which is substituted by-PO (OR 12) 21 a phenyl group which is unsubstituted or substituted by OH, a C7-C15 aralkyl group or -CH2OR12, R3 is an alkyl group of 1 to 20 carbon atoms, a hydroxyalkyl group of 2 to 20 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, an aryl group of 6 to 10 carbon atoms or said aryl group substituted by one or two alkyl groups of 1 to 4 carbon atoms or 1, 1, 2, 2-tetrahydroperfluoroalkyl including the perfluoro- fragment alkyl has 6 to 16 carbon atoms, L is an alkylene group of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and T is -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CO-,  EMI70.2  - CO-E-CO -, - COO-E-OCO -, - CO-NG-E-NG-CO-ou-NG-CO-E-CONu3-, where E is an alkylene group of 2 to 12 atoms of carbon, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by a cyclohexylene group of 8 to 12 carbon atoms, which benzotriazole exhibits increased durability and low rates of loss when the coating is exposed to actinic radiation, such as denoted by a loss less than 0.22 absorbance unit after 1200 hours of exposure, or less than 0.27 absorbance unit after 1500 hours of exposure or less than 0, 40 absorbance unit after 2500 hours of exposure in a Xenon Arc Weather-O-Meter.  2] henicosane, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (2,2,2,6,6-tetramethylpiperidine), the product polycondensation of 1- (2-hydroxyethyl) -2, 2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 4,4'-hexamethylenebis (2,2-amino , 6,6-tetramethylpiperidine) and 1,2-dibromoethane, butane-1,2, 3,4-tetrakis- (2,2,6,6-tetramethylpiperidine-4-yl) tetracarboxylate, butane -1,2, 3,4- tetrakis tetracarboxylate (1,2,2,6,6-pentamethylpiperidine-4-yl), the polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylene-bis- (2,2,2,6,6-tetramethylpiperidine), N, N ', N ",    Nlfl- tetrakis [4,6-bis (butyl- (1,2,2,6,6-pentamethylpiperidine-  EMI73.2  4-yl) amino) -s-triazine-2-yl] -1, 10-diamino-4, 7-diazadecane, butane-1, 2, 3, 4-tetracarboxylate mixed from [2, 2, 6, 6 -tetra-  <Desc / Clms Page number 74>    EMI74.1  methylpiperidine-4-yl / ss, ss, P ', ss'-tetramethyl-3, 9- (2, 4, 8, 10tetraoxaspiro [5. 5] undecane) diethyl], butane-1, 2, 3, 4tetracarboxylate mixed of [1, 2, 2, 6, 6-pentamethylpiperidine-4-yl / P, ss, P ', ss'-tetramethyl-3, 9- (2, 4, 8, 10-tetraoxaspiro- [5.  2. Composition according to claim 1, characterized in that component (b) is a compound of formula A '  <Desc / Clms Page number 71>    EMI71.1    EMI71.2  where G2 is fluoro, chloro, cyano, R3S02- 'CFg -, - CO-G, -COO-G or-CO-N (Gg), G3 is an alkyl group of 1 to 12 carbon atoms, Ri is hydrogen, an alkyl group of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or said phenyl or phenylalkyl group substituted on the phenyl ring with 1 or 2 alkyl groups of 1 to 4 carbon atoms, R2 is an alkyl group of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or - CH2CH2COOG4 where G4 is hydrogen, an alkyl group of 1 to 24 carbon atoms or said alkyl group substituted by OH ,  interrupted by 1 to 6 atoms of -O- or both substituted by OH and interrupted by 1 to 6 atoms of -O-, and R3 is an alkyl group of 1 to 18 carbon atoms, aryl of 6 to 10 atoms of carbon or said aryl group substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms.    3-trisC2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris isocyanurate [2- (3,5-ditert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl], 3 , 5-di- (3, 5-di-tert-butyl-4-hydroxybenzyl) mesitol, bis (3, 5-di-  EMI72.4  tert-butyl-4-hydroxyhydrocinnamate) of hexamethylene, 1- (3,5-di-ert-butyl-4-hydroxyanilino) -3,5-di (octylthio) s-triazine, N, N'-hexamethylene -bisC3, S-di-tert-butyl- 4-hydroxyhydrocinnamamide), the calcium salt of ethyl bis (3,5-ditert-butyl-4-hydroxybenzylphosphonate), bis [3, 3diC3-tert-butyl- Ethylene 4-hydroxyphenyl) butyrate], octyl-3-S-di-tert-butyl-4-hydroxybenzylthioglycolated bisC3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N'-bis [2-C3, S-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] oxamide.    <Desc / Clms Page number 73>   3. Composition according to claim 2, characterized in that, in the compound of formula A ', G2 is a fluoro, chloro, cyano, R3S02-' CF -, - COO-G or-CO-N (G) radical, G3 is an alkyl group of 1 to 8 carbon atoms, R1 is hydrogen, a phenyl or a-cumyl group, R2 is an alkyl group of 4 to 12 carbon atoms or phenyl, and R3 is a phenyl or alkyl group from 8 to 12 carbon atoms. 4. Composition according to claim 3, characterized in that  <Desc / Clms Page number 72>    EMI72.1  G2 is a phenyl-SO-, octyl-SO-, fluoro or Caf3- radical, R1 is an a-cumyl or phenyl group, and R2 is a tert-butyl or tert-octyl group.  5] decane-2, 4-dione, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl) sebacate, bis (1-cyclohexyloxy-2, 2,6, 6) succinate -tetramethylpiperidine-4-yl), 1-octyloxy-2, 2,6, 6-tetramethyl- 4-hydroxypiperidine, lepoly {[6-tert-octylamino-s-triazine-  EMI74.2  2, 4-diyl] [2- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine- 4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine- 4-yl) imino] and 2, 4, 6-tris [N- (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl) -n-butylamino] - s-triazine.    5] undecane) diethyl], octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4'-ethylenebis (2,2, 6,6-tetramethylpiperazine-3-one) , N-2,2,6,6tetramethylpiperidine-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidine-4-yl-n-dodecylsuccinimide, N-1-acetyl-2 , 2, 6,6-tetramethylpiperidine-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.  5. Composition according to claim 1, characterized in that the component (a) is a resin which is a thermosetting acrylic melamine resin or an acrylic urethane resin.  6. Composition according to claim 1, characterized in that it additionally contains an amount with a stabilizing effect of a phenolic antioxidant chosen from  EMI72.2  3,5-di-tert-butyl-4-hydroxyhydrocinnamate of n-octadecyl, tetrakisC3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) of neopentane-tetrayl, 3,5-di-tert-butyl-4 - di-n-octadecyl hydroxybenzylphosphonate, 1,3, 5- isocyanurate  EMI72.3  trisC3, 5-di-tert-butyl-4-hydroxybenzyl), bis (3, 5-ditert-butyl-4-hydroxyhydrocinnamate) of thiodiethylene, 1, 3, 5-trimethyl-2, 4, 6-trisC3, 5-di-tert-butyl-4-hydroxy benzyl) benzene, bisC3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate) of 3, 6-dioxaoctamethylene, 2, 6-di-tert-butylp-cresol, 2, 2'-ethylidene-bisC4, 6-di-tert-butylphenol), isocyanurate of 1, 3, 5-trisC2, 6-dimethyl-4-tert-butyl-3-hydroxybenzyl), 1, 1 ,  7. Composition according to Claim 6, characterized in that the phenolic antioxidant is neopentane- tetrakis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)  EMI73.1  tetrayl, n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6,6-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-butylp-cresol or 2,2 ' -ethylidene-bis (4,6-di-tert-butylphenol).  8. Composition according to claim 1, characterized in that it contains, in addition, an amount with stabilizing effect of a sterically hindered amine chosen from bis (2,2,6,6-tetramethylpiperidine-4- sebacate) yl), bis (1,2, 2,6, 6-pentamethylpiperidine-4-yl) sebacate, di (1,2, 2 (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate , 6, 6-pentamethylpiperidine-4-yl), 4-benzoyl-2,2, 6,6-tetramethylpiperidine, 4-stearyloxy-2,2, 6,6tetramethylpiperidine, 3-n-octyl-7,7 , 9,9-tetramethyl-1,3, 8-triazaspiro [4. 5] decane-2,4-dione, tris nitrilotriacetate (2,2,6,6-tetramethylpiperidine-4-yl), 1,2-bis- (2,2,6,6-tetramethyl-3- oxopiperazine-4-yl) ethane, 2, 2,4, 4tetramethyl-7-oxa-3, 20-diaza-21-oxodispiro [5. 1.11.  9. Composition according to claim 8, characterized in that the sterically hindered amine is bis (2,2,6,6-tetramethylpiperidine-4-yl) sebacate, bis (1,2, 2, sebacate) 6, 6-pentamethylpiperidine-4-yl), (3,5,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate  EMI74.3  bis (1, 2, 2, 6, 6-pentamethylpiperidine-4-yl), 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-octylaminos-triazine and 4,4'-hexamethylene-bis (2,2,2,6,6tetramethylpiperidine), N, N ', N '', N '' '- tetrakis [4, 6-bis- (butyl (1,2, 2,6, 6-pentamethylpiperidine-4-yl) amino) - s-triazine-2-ylJ-1, 10- diamino-4,7-diazadecane, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl) sebacate,  bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-  <Desc / Clms Page number 75>    EMI75.1  4-hydroxypiperidine, poly {[6-tert-octylamino-s-triazine- 2, 4-diyl] [2- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidine-4-yl) imino] or 2,4, 6-tris [N- (1-cyclohexyloxy-2, 2,6 , 6-tetramethylpiperidine-4-yl) -n-butylamino] - s-triazine.  10. Composition according to claim 1, characterized in that it contains, in addition, another UV absorber chosen from s-triazines, oxanilides, hydroxybenzophenones, benzoates and a-cyanoacrylates.  11. Composition according to claim 10, characterized in that it also contains an s-triazine which is 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxy-  EMI75.2  phenyl) -s-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2hydroxy-4 - (3-di / tridecyloxy-2-hydroxypropoxy) phenyl] s-triazine or 2- (2-hydroxyethylamino) -4,6-bis [N-butyl- N- (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl) amino] -s-triazine.  12. Compound characterized in that it corresponds to formula I, II, III or IV  EMI75.3    <Desc / Clms Page number 76>    EMI76.1    EMI76.2  where G1 is hydrogen or halogen, G2 is a cyano radical, E3SO-, ESO -, - COOG-, CF ..-, - P (O) (C6HS) 2 '-CO-G3'-CO-NH -G3'-CO-N (G3) 2 'G3 is a straight or branched chain alkyl group of 1 to 24 carbon atoms, straight or branched chain alkenyl group of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 atoms of carbon, phenylalkyl of 7 to 15 carbon atoms or phenyl, or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms, E1 is hydrogen, a phenylalkyl group of 7 with 15 carbon atoms or phenyl,  or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms, E2 is a straight chain or branched alkyl group of 1 to 24 carbon atoms, straight or branched alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl, or the said phenyl or phenylalkyl group substituted on the phenyl ring by 1 to 3 alkyl groups of 1 to 4 atoms carbon; or E2 is a hydroxyl group or-OE. where E <is a straight or branched chain alkyl group of 1 to 24 carbon atoms; or said group  <Desc / Clms Page number 77>  alkyl substituted by one or more -OH, -OCO-E11, -OE4, -NCO or -NH2 or a combination of them;  or said alkyl or alkenyl group interrupted by one or more -O-, -NH- or -NE4- or a combination of them, and which may be unsubstituted or substituted by one or more  EMI77.1  - OH, -OE <or-NH or a combination of them; or E2 is -SE, -NHE or -N (E); or E2 is  EMI77.2    EMI77.3  where X is -O- or -N (E16) -, Y is -O- or -N (E17) -,  EMI77.4  Z is a CC alkylene group, a C4-C12 alkylene group interrupted by one to three nitrogen atoms, oxygen atoms or a combination of them, or is a C3-C12 alkylene group, butenylene, butynylene , cyclohexylene or phenylene, each being substituted by a hydroxyl group, m is 0.1 or 2, p is 1, or else p can also be 0 when X and Y are respectively -N (E16) - and -N (E17) -, E15 is a group -CO-C (E18)    = C (H) E19 or, when Y is - N (E17) -, forms with E17 a group -CO-CH = CH-CO-, where  EMI77.5  E18 is hydrogen or a methyl group and E19 is hydrogen, a methyl group or -CO-X-EQ where E is hydrogen, a C1-C12 alkyl group or a group of formula  EMI77.6  where the symbols E., G, X, Z, m and p are as defined above, and E16 and E. v are each, independently of the other,  EMI77.7  hydrogen, a C <-C alkyl group, a C3-C12 alkyl group interrupted by 1 to 3 oxygen atoms,  <Desc / Clms Page number 78>  a cyclohexyl group or a C7-C15 aralkyl group, and, in the case where Z is an ethylene group, E16 with E17 may also form an ethylene group, n is 1 or 2,  EMI78.1  - when n is 1, Ec is Cl, OE6 or NEyEg, or Ec is-PO (OE), -OSi (E).  or-OCO-E, or a straight or branched chain C1-C24 alkyl group which is interrupted by-O -, - S-or-NE ...- and which may be unsubstituted or substituted by-OH or- OCO-E <<, a Ce-C12 cycloalkyl group which is unsubstituted or substituted by-OH, a straight chain C2-C18 alkenyl group  EMI78.2  or branched which is unsubstituted or substituted by-OH, a C-C aralkyl group.  e, -CH-CHOH-E or a glycidyl group, Eg is hydrogen, a straight or branched chain C1-C24 alkyl group which is unsubstituted or substituted by one or more OH, OE4 or NH2, or -OE6 is - (OCH2CH2) wOH or - (OCH2CH2) wOE21 where w is 1 to 12 and E21 is an alkyl group of 1 to 12 carbon atoms, Ey and Eg are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, a chain C3-C18 alkyl group straight or branched which is interrupted by-O -, - S-or-NE.-, a C5-C12 cycloalkyl group, a C6-C14 aryl group or a C1-C3 hydroxyalkyl group, or E7 and Eo form with the atom N a cycle of pyrrolidine, piperidine, piperazine or morpholine, - when n is 2, Ee is one of the divalent radicals -O-E9-O- and -N (E11) -E10-N (E11) -,  EMI78.3  Eg is a C-Co alkylene, C-C8 alkenylene, C alkynylene, cyclohexylene or C <-C alkylene. Q with straight or branched chain which is interrupted by -0- or by -CH2-CHOH-CH2-0-E14-0-CH2-CHOH-CH2- ' E10 is a straight or branched chain C2-C12 alkylene group which may be interrupted by -O-, a cyclohexylene group or  <Desc / Clms Page number 79>    EMI79.1  or E10 and E11, with the two nitrogen atoms, form a piperazine ring, E14 is a C2-C8 straight or branched chain alkylene group, a C.sub.1 alkylene group  o straight or branched chain which is interrupted by -O-, a cycloalkylene group, an arylene group or  EMI79.2    EMI79.3  WHERE E7 and Eg are each independently hydrogen, an alkyl group of 1 to 18 carbon atoms, or else E7 and Eo together form an alkylene group of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3- methyliminopentamethylene, E11 is hydrogen, a Ci-Ci, straight or branched chain, Cc-C <cycloalkyl, C - Cr alkenyl, straight or branched chain, C6-C14 aryl or aralkyl in Cy-C,  <Desc / Clms Page number 80>    EMI80.1  E12 is a C1-C18 straight or branched chain alkyl, C3-C18 straight or branched chain alkenyl, C1-C6 cycloalkyl, C1-C6 aryl or Cy-C aralkyl, E13 is H,  a straight or branched chain C1-C18 alkyl group which is substituted by -PO (OE), a phenyl group which is unsubstituted or substituted by OH, a C7-C15 aralkyl group or -CH2OE12, E3 is an alkyl group of 1 to 20 carbon atoms, a hydroxyalkyl group of 2 to 20 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, a phenylalkyl group of 7 to 15 carbon atoms, an aryl group of 6 to 10 carbon atoms or said aryl group substituted by one or two alkyl groups of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl of which the perfluoroalkyl moiety counts 6 to 16 carbon atoms, L is an alkylene group of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene,  and  EMI80.2  T is SO -, - SO? -, - SO-E-SO -, - SO-E-SO -, - CO-, - CO-E-CO -, - COO-E-OCO-ou-CO- NG-E-NG-CO-, where E is an alkylene group of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by a cyclohexylene group of 8 to 12 carbon atoms, and G is G3 or hydrogen, and provided that E1 is not a phenylalkyl group  EMI80.3  when G2 is E .. SO- or ESO-.  13. Compound according to claim 12, characterized in that it corresponds to formula I '  EMI80.4    <Desc / Clms Page number 81>    EMI81.1  or G2 is a cyano radical, ESO-, CF -, - COO-G-., -CO-NHG3 or -CO-N (G3) 2, G3 is an alkyl group of 1 to 12 carbon atoms, E. is hydrogen, a phenyl, phenylalkyl group of 7 to 15 carbon atoms or said phenyl or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups of 1 to 4 carbon atoms, E2 is an alkyl group of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or -CH2CH2COOG4 where G4 is hydrogen, an alkyl group of 1 to 24 carbon atoms or said alkyl group substituted by OH ,  interrupted by 1 to 6 atoms of -O-or both substituted by OH and interrupted by 1 to 6 atoms of -O-, and E3 is an alkyl group of 8 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl group substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms, and provided that En is not a phenylalkyl group when G2 is E3SO- or E3SO2-.  14. Compound according to claim 13, characterized in that G2 is a cyano radical, E3SO2-, CF3-, -CO-G3 or -CO-N (G3) 2, G3 is an alkyl group of 1 to 8 carbon atoms, E. is hydrogen, a phenyl or a-cumyl group, E2 is an alkyl group of 4 to 12 carbon atoms, and E3 is a phenyl or octyl group, and  EMI81.2  provided that El is not an a-cumyl group when G2 is E3SO2-.  15. Compound according to claim 14, characterized in that G2estCF3-, E. is an a-cumyl group, and E2 is a tert-butyl or tert-octyl group.  <Desc / Clms Page number 82>    16. Composition stabilized against degradation caused by heat, oxidation or light, characterized in that it comprises (a) an organic material subject to degradation caused by heat, oxidation or light, and ( b) an amount with stabilizing effect of a compound of formula I, II, III or IV according to claim 12.  17. Composition according to claim 16, characterized in that the organic material is a natural, semi-synthetic or synthetic polymer.  18. Composition according to claim 17, characterized in that the polymer is a thermoplastic polymer.  19. Composition according to claim 18, characterized in that the polymer is a polyolefin or a polycarbonate.  20. Composition according to claim 19, characterized in that the polymer is a polyethylene or a polypropylene.  21. Composition according to claim 20, characterized in that the polymer is a polypropylene.  22. Composition according to claim 16, characterized in that the organic material is a resin chosen from a thermosetting acrylic melamine resin, an acrylic urethane resin, a carboxylated epoxy resin, an acrylic melamine resin modified with a silane, an acrylic resin having lateral carbamate groups crosslinked by melamine or an acrylic polyol resin crosslinked by melamine containing carbamate groups.  23. Composition according to claim 22, characterized in that the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.  24. Composition according to claim 16, characterized in that the organic material b) is a recording material.  25. Use of a benzotriazole of formula A, B, C or D as defined in claim 1, in an amount of 0.01 to 5% by weight relative to the weight of  <Desc / Clms Page number 83>  resin dry matter, for stabilizing a coating composition which comprises a resin chosen from a thermosetting acrylic melamine resin, an acrylic urethane resin, a carboxylated epoxy resin, a silane modified acrylic melamine resin, a resin acrylic having melamine crosslinked side carbamate groups or a melamine crosslinked acrylic polyol resin containing carbamate groups.