Piperazinone derivatives

ES 2 249 043 T3

DESCRIPTION

Piperazinone derivatives.

This invention relates to piperazinone derivatives, to an organic material susceptible to light, heat or oxidation, containing a piperazinone derivative, and to a method for stabilizing such an organic material. This invention further relates to intermediate products.

Various piperazinone derivatives and their use as stabilizers are described in US-A-4,629,752 and US-A-4,480,092.

The present invention relates in particular to a compound of the formula (I)

<img file="ES2249043T3_D0001.tif" />

where at least one group of formula (II) is present

<img file="ES2249043T3_D0002.tif" />

in the repeating unit of formula (I); n is a number from 2 to 100;

Gi, G₂, G₃ and G₄ are independently of each other C alkyl₁-C₄;

radicals R₁ are independently of each other hydrogen, C alkyl₁-C₄, -OH, allyl, C alkoxy₁-C₁₂, cycloalkoxy C₅-C₈, benzyl or acetyl;

R₂ is C alkylene₂-C₁₄ or a -CR group₂'(R₂”) - where R₂'and R₂"Independently hydrogen, C alkyl₁-C₁₈ or C cycloalkyl₅-C_i2;

R₃'and R₃"Are independently hydrogen, C alkyl₁-C₁₈, C alkyl₂-C₁₈ interrupted by oxygen; or C cycloalkyl₅-C_i2;

R₄ is C alkylene₂-C₁₄, C alkylene₄-C₁₄ interrupted by oxygen or sulfur; cycloalkylene C₅-C₇, cycloalkylene C₅-C₇ di (alkylene C₁-C₄), alkylene C₁-C₄ di (cycloalkylene C₅-C₇) or phenylenedi (C₁-C₄);

R₅'and R₅”Are a group of formula (II)

X is -OR₆, -MR₆, -N (R₇) (R₈) or a group of formula (IV);

<img file="ES2249043T3_D0003.tif" />

ES 2 249 043 T3

R₆, R₇ and R₈ are independently hydrogen, C ^ C alkyl₁₈, alkenyl C₃-C₁₈, cycloalkyl C₅-C₁₂ that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄; phenyl that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁C₄ or C alkoxy₁ -C₄; phenylalkyl C₇-C₁₂ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C alkyl₁-C₄; tetrahydrofuryl or C alkyl₂-C₄ which is substituted in position 2, 3 or 4 by C alkoxy₁-C₈, di (C₁-C₄) amino or a group of formula (III);

<img file="ES2249043T3_D0004.tif" />

where E is a direct bond, -O-, -CH₂-, -CH₂CH₂- or&gt; N-CH₃; or -N (R7) (R8) is additionally a group of formula (III);

T is -O- or&gt; NR₉; Y

R₉ is hydrogen, C alkyl₁-C₁₈, hydroxyalkyl C₂-C₁₈, alkenyl C₃-C₁₈, cycloalkyl C₅-C₁₂ that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄; phenylalkyl C₇-C₁₂ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 Ci-C4 alkyl; tetrahydrofurfuryl, a group of formula (II), or C2-C4 alkyl that is substituted in position 2, 3 or 4 by C alkoxy₁-C₈, di (C₁ -C₄) amino or a group of formula (III);

radicals R₁, the radicals R₂, the radicals R₃', the radicals R₃”, The radicals G₁, the radicals G₂, the radicals G₃ or the radicals G₄, have, independently, the same meaning or a different meaning; and in the individual recurring units of formula (I), each of the radicals X, R₄, R₅'and R₅"Has the same meaning or a different meaning;

the terminal group attached to the diamino radical is hydrogen or a group

<img file="ES2249043T3_D0005.tif" />

and the terminal group attached to the triazine radical is Cl or an —N — R group₄—N — H

R, '

R, "

Cl is optionally substituted by a group -X as defined above; the terminal hydrogen of the group —N — R4 — N — H

R, 'R, "is optionally substituted by acyl C₁-C₈, (C alkoxy₁-C₈) carbonyl, (cyclolalkoxy C₅-C₁₂) carbonyl, (C-alkyl₁-C₈) aminocarbonyl, (cycloalkyl C₅-C₁₂) aminocarbonyl, (phenylalkyl C₇-C₉) aminocarbonyl, C alkyl₁-C₉, C cyclo-alkyl₅-C₁₂ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C alkyl₁-C₄; or -CH₂CN.

Examples of alkyl containing no more than 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl,

2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

One of the preferred meanings of R₁ is C alkyl₁-C₄, in particular methyl.

One of the preferred meanings of R₃'and R₃"Are C alkyl₁-C₈, in particular C alkyl₁-C₄, for example methyl.

One of the preferred meanings of R₇, R₈ and R₉ is C alkyl₁-C₈.

An example of C2-Ci8 hydroxyalkyl is 2-hydroxyethyl.

ES 2 249 043 T3

Examples of C alkyl₂-C₁₈ interrupted by oxygen and C alkyl₂-C₄ substituted by Ci-C alkoxy₈, preferably C alkoxy₁ -C₄, in particular methoxy or ethoxy, are 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,

3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.

Examples of C alkyl₂-C₄ substituted by di (C-alkyl₁-C₄) amino, preferably dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl.

The group of the formula (III is preferably / ~ \ I (

Preferred examples of C2-C4 alkyl substituted by a group of the formula (III) are groups of the formula

<img file="ES2249043T3_D0006.tif" />

Y N- (CH-Í The group r ~ \

- (CH,), - is particularly preferred.

Examples of alkenyl containing no more than 18 carbon atoms are allyl, 2-methylallyl, butenyl, hexenyl, undecenyl, and octadecenyl. Alkenyls where the carbon atom at position 1 is saturated are preferred and allyl is particularly preferred.

Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, and dodecyloxy. One of the preferred meanings of R₁ is C alkoxy₆-C₁₂, in particular heptoxy and octoxy.

Examples of acyl (aliphatic, cycloaliphatic, or aromatic) containing no more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, and benzoyl. Alkanoyl C₁ -C₈ and benzoyl are preferred. Acetyl is especially preferred.

Examples of (C alkoxy₁-C₈) carbonyl are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl and octyloxycarbonyl.

Examples of cycloalkyl C₅-C₁₂ that is unsubstituted or substituted by 1, 2 or 3 C alkyl₁-C₄ they are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl. C cycloalkyl is preferred₅-C₈ unsubstituted or substituted, in particular cyclohexyl.

Examples of cycloalkoxy C₅ -C₁₂ They are cyclopentoxy, cyclohexoxy, cycloheeptoxy, cyclooctoxy, cyclodecyloxy, cyclododecyloxy, and methylcyclohexoxy. Cycloalkoxy C is preferred₅-C₈, in particular cyclopentoxy and cyclohexoxy.

Examples of phenyl substituted by 1, 2 or 3 C alkyl₁-C₄ or C alkoxy₁-C₄ they are methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, di-t-butylphenyl, 3,5-di-t-butyl-4-methylphenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl.

Examples of phenylalkyl C₇-C₁₂ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C alkyl₁-C₄ they are benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl, and 2-phenylethyl. Phenylalkyl C is preferred₇-C₉, in particular benzyl.

Examples of alkylene containing no more than 14 carbon atoms are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene. R4 is, for example, C2-C8 alkylene, preferably hexamethylene.

R₂ as a -CR group₂'(R₂") - is preferably methylene.

Examples of C alkylene₄-C₁₄ interrupted by -O- or -S-, for example 1,2 or 3 -O- or -S-, are 3-oxapentan-1,5-diyl,

4-oxaheptan-1,7-diyl, 3,6-dioxaoctan-1,8-diyl, 4,7-dioxadecane-1,10-diyl, 4,9-dioxadodecane-1,12-diyl, 3,6, 9-trioxa4

ES 2 249 043 T3 undecan-1,11-diyl, 4,7,10-trioxatridecan-1,13-diyl, 3-thiapentan-1,5-diyl, 4-thiaheptan-1,7-diyl, 3,6 -dithiaoctan-1,8diyl, 4,7-dithiadecan-1,10-diyl, 4,9-dithiadodecan-1,12-diyl, 3,6,9-trithiaundecan-1,11-diyl and 4,7,10 -trithiatridecan-1,13 diyl.

An example of cycloalkylene C₅-C₇ it is cyclohexylene.

An example of cycloalkylene C₅-C₇ di (alkylene C₁-C₄) is cyclohexylenedimethylene.

Examples of alkylene C₁-C₄ di (cycloalkylene C₅-C₇) are methylenedicyclohexylene and isopropylidenedicyclohexylene.

An example of phenylenedi (C₁-C₄) is phenylene dimethylene.

n is, for example, a number from 3 to 100, 4 to 100, 5 to 100, 6 to 100, 2 to 50, 3 to 50, 4 to 50, 5 to 50, 6 to 50, 2 to 30, 3 to 30.4 to 30, 5 to 30, 6 to 30, 2 to 20, 3 to 20, 4 to 20, 5 to 20 or 6 to 20. n is preferred as a number from 2 to 50, in particular to 7 .

R₃'is preferably hydrogen.

R₂ it is preferably methylene.

X is preferably a group -N (R₇) (R₈), in particular -NH (R₈).

R1 is in particular hydrogen or C1-C4 alkyl such as methyl.

Preferred compounds of formula (I) are those in which

G₁, G₂, G₃ and G₄ are independently C alkyl₁-C₄;

R₂ is C alkylene₂-C₈ or a -CR group₁'(R₂”) - where R₂'and R₂"Independently of each other hydrogen, C alkyl₁-C₈ or C cycloalkyl₅-C₈;

R₃'and R₃"Are independently hydrogen, C alkyl₁ -C₈, C alkyl₂-C₈ interrupted by oxygen; or C cycloalkyl₅-C₈;

R₄ is C alkylene₂-C₁₀, C alkylene₄-C₁₀ interrupted by oxygen or sulfur; cyclohexylene, cyclohexylenedi (C alkylene₁-C₄), alkylene C₁-C₄ di (cyclohexylene) or phenylenedi (C alkylene₁-C₄);

R₅'and R₅"Are a group of formula (II);

R₆, R₇ and R₈ are independently of each other hydrogen, C alkyl₁-C₈, alkenyl C₃-C₁₂, cycloalkyl C₆-C₈ that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄; phenyl that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄ or C alkoxy₁ -C₄; phenylalkyl C₇-C₁₂; tetrahydrofufuryl or C alkyl₂-C₄ which is substituted in position 2, 3 or by C alkoxy₁-C₄, di (C₁ -C₄) amino or a group of formula (III);

or -N (R₇) (R₈ is additionally a group of formula (III); Y

R₉ is hydrogen, C alkyl₁ -C₈, hydroxyalkyl C₂-C₈, alkenyl C₃-C₁₂, cycloalkyl C₅-C₈ that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄; phenylalkyl C₇-C₁₂; tetrahydrofurfuryl, a group of formula (II), or C alkyl₂-C₄ which is substituted in position 2, 3 or 4 by C alkoxy₁-C₄, di (C₁-C₄) amino or a group of formula (III).

Particularly preferred compounds of formula (I) are those in which

G₁, G₂, G₃ and G₄ are independently of each other C alkyl₁-C₄;

R₂ is C alkylene₂-C₄ or a -CR group₂'(R₂”) - where R₂'and R₂"Independently of one another hydrogen or C1-C4 alkyl;

R₃'and R₃"Are independently of each other hydrogen or C-alkyl₁-C₄;

R4 is C2-C10 alkylene;

R₅'and R₅"Are a group of formula (II);

X is -N (R7) (R8) or a group of formula (IV);

R₇ and R₈ are independently of each other hydrogen or C alkyl₁-C₈;

ES 2 249 043 T3 or -N (R₇) (R₈) is further a group of formula (III) where E -O-; and R₉ is hydrogen, Ci-C alkyl₈ or cyclohexyl.

Compounds of formula (I) that are of particular interest are those where n is a number from 2 to 50;

G₁, G₂, G₃ and G₄ are independently of each other C alkyl₁-C₄;

R₁ is hydrogen or C alkyl₁ -C₄;

R2 is methylene;

R₃'is hydrogen and R₃"Is hydrogen or C alkyl₁-C₄;

R4 is C2-C8 alkylene;

R₅'and R₅"Are a group of formula (II); Y

X is -N (R₇) (R₈), where R₇ and R₈ independently of each other hydrogen or C alkyl₁-C₈.

The definition of the terminal groups that saturate the free valences in the compounds of formula (I) depends on the process used for their preparation. The end groups can also be modified after the preparation of these compounds.

Compounds of formula (I) can be prepared, for example, by reacting a compound of formula (Z-OO)

N

Cl

<img file="ES2249043T3_D0007.tif" />

Cl

X (Z-00) with a compound of the formula (ZO)

H — N — R₄—N — H r₅'r₅”(Z-0) where X, R₄, R₅'and R₅”Are as defined above. The compound of the formula (Z-OO) or the compound of the formula (ZO) can be used in an excess of up to 20% by moles, preferably 5% by moles. The molar ratio of the compounds of the formulas (Z-OO) and (ZO) is in particular 1: 1.1. According to a preferred procedure the compound of formula (ZO) is used in an excess of up to 5% by moles.

The reaction is preferably carried out in an inert organic solvent, for example toluene, xylene or benzene, in the presence of an inorganic base at a temperature of 40 ° to 145 ° C, in particular between 60 ° and 140 ° C . Examples of a base are NaOH, KOH, Na₂CO₃ and K₂CO₃.

In this case the terminal group attached to the diamino radical can be hydrogen or a group

<img file="ES2249043T3_D0008.tif" />

Cl

N and the terminal group attached to the triazine radical can be Cl or a group —N — R4 — N — H

R₅'r₅”

X

ES 2 249 043 T3

When the terminal group is Cl it is advantageous to replace it, for example, by a group -X as defined above, in particular -OH, an amino group -N (R7) (R8) or a group of the formula (IV), after completion of the reaction. Examples of suitable substitution groups are pyrrolidin-1-yl, morpholino, -NH₂, -N (C₁-C₈)₂ Y

-NR (C₁ -C₈), R being hydrogen or a group of formula (II).

It is also advantageous to replace the terminal hydrogen of the group —N — R₄—N — H

R5 'R₅"Per acyl C₁-C₈, (C alkoxy₁ -C₈) carbonyl, (cycloalkoxy C₅-C₁₂) carbonyl, (C-alkyl₁-C₈) aminocarbonyl, (C cycloalkyl₅-C₁₂) aminocarbonyl, (phenylalkyl C₇-C₉) aminocarbonyl, C alkyl₁-C₈, cycloalkyl C₅-C₁₂ that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄; alkenyl C₃-C₆, phenylalkyl C₇ -C₈ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4 alkyl; or -CH2CN.

Acyl C is preferred₁-C₈, preferably C alkanoyl₁-C₈, in particular acetyl as shown below in Example 5.

A preferred embodiment of this invention relates to compounds of formula (I) wherein the terminal group attached to the diamino radical is hydrogen, acyl C₁-C₈, (C alkoxy₁ -C₈) carbonyl, (cycloalkoxy C₅-C₁₂) carbonyl, (C-alkyl₁ -C₈) aminocarbonyl, (C cycloalkyl₅-C₁₂) aminocarbonyl, (phenyl-C₇-C₉) aminocarbonyl, C alkyl₁-C₈, cycloalkyl C₅-C₁₂ that is unsubstituted or substituted by 1, 2, or 3 C alkyl₁-C₄; alkenyl C₃-C₆, phenylalkyl C₇-C₉ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C alkyl₁-C₄; or -CH₂CN, and the terminal group attached to the triazine residue is an —N — R4 — N — R group

R₅'R₅"Where R 'is hydrogen, acyl C₁-C₈, (C alkoxy₁-C₈) carbonyl, (cycloalkoxy C₅-C₁₂) carbonyl, (C-alkyl₁-C₈) aminocarbonyl, (C cycloalkyl₅-C₁₂) aminocarbonyl, (phenylalkyl C₇-C₉) aminocarbonyl, C alkyl₁ -C₈ , cycloalkyl C₅ -C₁₂ which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C alkyl₁-C₄; or -CH₂CN.

A particularly preferred embodiment of this invention relates to compounds of formula (I) wherein the terminal group attached to the diamino radical is C alkanoyl.₁-C₈ and the terminal group attached to the triazine residue is an —N — R group₄ —N— (C₁ -C₈ alkanoyl)

R₅'R₅”

Compounds of the formula (ZO) where R₅'is a group of formula (II) corresponds to formula (Z-1)

<img file="ES2249043T3_D0009.tif" />

where G₁, G₂, G₃, G₄, R₁, R₂, R₃,, R₃”, R₄ and R₅"As defined above, and constitute another embodiment of this invention.

ES 2 249 043 T3

When R₃'and / or R₃"Are hydrogen, a compound of the formula (Z-1) can be prepared, for example by reacting - in a stoichiometric ratio, a ketone of the formula (Z-2)

<img file="ES2249043T3_D0010.tif" />

with a diamine of the formula (Z-3)

H — N — R4 — N — H

II

HR₅”(Z-3) where Gi, G₂, G₃, G₄, R_i, R₂, R₃,, R₃”And R₄ are as described before and R₅ is hydrogen, and subsequent hydrogenation.

The reaction which is a reductive amination is conveniently carried out under a hydrogen pressure of 30 to 35 atm in the presence of a hydrogenation catalyst such as platinum on carbon, palladium or Raney nickel, in particular platinum on carbon, neat or in an organic solvent, for example methanol or a mixture of isopropanol and water. The temperature is preferably 40 ° to 100 ° C.

When R3 'and R3 "are different from hydrogen, the compound of the formula (Z-1) can be prepared, for example, by adding an organometallic derivative of the formula R₃'-M, where R₃'C alkyl_i-C_i28, C alkyl₂-C_i8 interrupted by oxygen; or C cycloalkyl₅-C_i2 and M being Li +, MgCl +, Na ', K + or Cu', in particular Li +, to a solution of the corresponding ketimine in an inert organic solvent such as diethyl ether, tetrahydrofuran or xylene at low temperature, for example - 78 ° - 0 ° C. The reaction can be carried out analogously to the procedure described in "Advanced Organic Chemistry, Jerry March, John Wiley &amp; Sons, 4th edition, pages 934-935" or in "The chemistry of the carbon-nitrogen double bond, edited by S. Patai, John Wiley &amp; Sons, 1970, pages 266-272 ".

The ketone of the formula (Z-2) constituting another embodiment of this invention can be prepared, for example, by oxidation of a compound of the formula (Z-4)

<img file="ES2249043T3_D0011.tif" />

where G_i, G₂, G₃, G₄, R_i, R₂ and R₃, are as defined before. The reaction can be carried out analogously to the Swern oxidation (Fieser and Fleser's Reagents for Organic Synthesis, volume 8, John Wiley &amp; Sons, 1980, page 200).

Compounds of formula (Z-4) can be prepared, for example, analogously to the method described in USA-4,167,512.

Compounds of formula (I), as well as intermediates of formulas (Z-1) and (Z-2) are very effective in providing resistance to light, heat and oxidation of organic materials, especially synthetic polymers and copolymers. .

Examples of organic materials that can be stabilized are:

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, for example of cyclopentene or norbor8

ES 2 249 043 T3 ne, polyethylene (which can optionally be cross-linked), for example high-density polyethylene (HDPE), high-density, high-molecular-weight polyethylene (HDPE-HMW), high-density, ultra-high-molecular-weight polyethylene ( HDPEUHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, that is, the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially the following:

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

b) catalytic polymerization using a catalyst that normally contains one or more than one metal from groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls which can be π- or o-coordinated. These metal complexes can be in the free form or fixed on substrates, typically on activated 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 per se in the polymerization or other activators can be used, typically metal alkyls, metal hydrides, methyl alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and / or IIIa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amine, or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene, or single site catalysts (SSC).

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

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene / propylene copolymers, linear low-density polyethylene (LLDPE) and their blends with low-density polyethylene (LDPE), propylene / but-1-ene copolymers , propylene / isobutylene copolymers, ethylene / but-1ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymer and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts ( ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of these copolymers with each other and with polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and their blends with other polymers, for example polyamides.

Four. Hydrocarbon resins (for example C₅-C₉) including their hydrogenated modifications (for example thickeners) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly (alpha-methyl-tyrene).

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

7. Graft copolymers of styrene or alpha-methylstyrene, for example copolymers of styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile, and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and copolymers of acrylonitrile on acrylate / butadiene, as well as their mixtures with the copolymers set out in 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Polymers containing halogen such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of epichlorohydrin, especially polymers of vinyl compounds containing halogen, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

ES 2 249 043 T3

9. Polymers derived from alpha, beta-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylontrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide or acrylonitrile / vinyl halide copolymers or acrylonitrile / vinyl halide copolymers alkyl methacrylate / butadiene.

eleven. Polymers derived from unsaturated alcohols and amines or acyl derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl melate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.

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

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

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

fifteen. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6 / 9.6 / 12.4 / 6.12 / 12, polyamide 11, polyamide 12, aromatic polyamides from m- xylene diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic or / and terephthalic acid and with or without an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefinic copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during the process (RIM polyamide systems).

17. Polyureas, polyimides, polyamideimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as copolyether esters derived from block derivatives; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

twenty. Polysulfones, polyether sulfones, and polyether ketones.

twenty-one. Cross-linked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Drying and non-drying alkyd resins.

2. 3. Unsaturated polyester resins derived from saturated and unsaturated dicarboxylic acid copolyesters with polyhydric alcohols and vinyl compounds as crosslinking agents, and also their low-flammable halogen-containing modifications.

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

25. Alkyd resins, polyester resins and acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example diglycidyl ethers products of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.

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

ES 2 249 043 T3

28. Mixtures of the above-mentioned polymers (polymixtures, 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, thermoplastic POM / PUR, thermoplastic PC / PUR, POM / acrylate, POM / MBS, pPo / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

29. Natural and synthetic organic materials that are pure monomeric compounds or mixtures of these compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (for example phthalates , adipates, phosphates or trimellitates) and also blends of synthetic esters with mineral oils in any weight ratio, typically those used in spinning compositions, as well as aqueous emulsions of these materials.

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

This invention also relates to a composition comprising an organic material susceptible to degradation induced by light, heat or oxidation and at least one compound of formula (I).

The organic material is preferably a synthetic polymer, more particularly one chosen from the groups mentioned above.

Also of interest is a thermoplastic rubber (TPR) as an organic material.

Polyolefins and their copolymers are preferred, for example those indicated above under items 1-3, in particular polyethylene and polypropylene.

Also preferred are polycarbonate such as in item 19 above, and blends, such as in item 28 above, thermoplastic polyurethane (TPU) or polyacetal.

Other materials that can be stabilized with the compounds of formula (I) are recording materials for photographic reproduction and other reprographic techniques as described, for example, in Research Disclosure 1990, 31429 (pages 474-480), GB-A-2,319 .523 or DE-A-19.750.906, page 22, line 15 to page 105, line 32.

Thus, another embodiment of this invention is a recording material, in particular a photographic material, containing at least one compound of formula (I).

Also of particular importance is the stabilization of non-silver reprographic materials, for example those used for pressure-sensitive copying systems, microcapsule photocopying systems, heat-sensitive copying systems, and ink jet printing.

Record materials stabilized with the compounds of formula (I) have an unexpectedly high quality, especially in terms of their light stability.

The registration materials have a structure that is known per se and that corresponds to its usefulness. These consist of a base, for example a paper or plastic film, on which one or more coatings are applied. Depending on the type of material these coatings contain the appropriate components required. In the case of photographic materials the coatings contain, for example, silver halide emulsions, color couplers, colorants and the like. The material intended for inkjet printing has, for example, a conventional base on which a suitable absorption layer is placed. An uncoated paper can also be used for inkjet printing. In the latter case the paper functions simultaneously as a base and has the absorbent for the ink. Materials suitable for inkjet printing are described, inter alia, in US-A-5,073,448, the content of which is considered as part of the present description.

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

The compound of formula (I) can be incorporated into the material even in the course of manufacture; in the manufacture of paper, for example, by adding to the pulp. Another method of use is spraying the material with an aqueous solution of the compound of formula (I), or adding it to the coating.

Coatings for transparent projection recording materials must not contain any light scattering particles such as pigments or fillers.

Color tie coatings can contain other additives, for example antioxidants, light stabilizers (including conventional UV absorbers and / or hindered amine light stabilizers), viscosity improvers, brighteners, biocides and / or antistatics.

The coating is usually prepared as described below. The water soluble components, for example the binder, are dissolved in water and mixed. Solid components, for example fillers and other additives as already described, are dispersed in this aqueous medium. The dispersion is advantageously carried out with the aid

ES 2 249 043 T3 of equipment such as ultrasonic devices, turbine agitators, homogenizers, colloid mills, bead mills, sand mills, high speed agitators and the like. A particular advantage of the compounds of formula (I) is that they can be easily incorporated into the coating.

As indicated above, the registration materials cover a wide field of use. The compounds of formula (I) can be used, for example, in pressure-sensitive copying systems. These can be added to the paper to protect the micro-encapsulated dye precursors from light, or to the binder of the developer layer to protect the dyes formed.

Photocopying systems with highly sensitive microcapsules that are developed by pressure are described, inter alia, in US-A-4,416,966, US-A-4,483,912, US-A-4,352,200, US-A-4,535,050, US-A-4,536,463, US-A-4,551,407, US-A-4,562,137 and US-A-4,608,330 and also in EP-A-139,479, EP-A-162,664, EP-A- 164,931, EP-A-237,024, EPA-237,025 and EP-A-260,129. In all these systems the compounds of formula (I) can be added to the color-accepting layer. Alternatively the compounds of formula (I) can be added to the donor layer to protect the color formers from light.

Compounds of formula (I) can also be used in recording materials based on the principle of photopolymerization, photo-softeners or microcapsule breakage or, in the case of heat-sensitive or photosensitive diazonium salts, leuco dyes are used with oxidizing agent or colored lactones with Lewis acids.

Heat sensitive recording material exploits the color-imparting reaction between a colorless or faintly colored base dye and an organic or inorganic color developer; the recorded image being produced by heat-induced contact of the two materials. This type of heat sensitive recording material is very popular, not only as the recording medium for faxes, computers, etc., but also in many other fields, for example in label printing.

The heat-sensitive recording material according to the present invention consists of a base, a heat-sensitive color-forming recording layer on this base and, optionally, a protective layer on the heat-sensitive color-forming recording layer. . The heat-sensitive color-forming recording layer contains as its main constituent a color imparting compound and a color developing compound, and also a compound of the formula (I). If a protective layer is present, the compound of formula (I) can also be incorporated into the protective layer.

Heat sensitive recording materials are described, for example, in JP-A-Hei 8-267 915.

Other fields of use are recording materials for color diffusion transfer printing, thermal wax transfer printing and dot matrix printing, and for use with electrostatic, electrographic, electrophoretic, magnetographic and electrophotographic laser printers, recorders or plotters. . Of the cited materials preference is given to recording materials for color diffusion transfer printing as described, for example, in EP-A-507,734.

The compounds of formula (I) can also be used in inks (preferably for inkjet printing) for example as described in US-A-5,098,477, the descriptive content of which is considered part of the present description. Accordingly, the invention also preferably relates to an ink comprising at least one compound of the formula (I) as a stabilizer. Ink, especially for ink jet printing, preferably contains water. The inks contain the stabilizer of the formula (I) usually in a concentration of 0.01 to 20% by weight, in particular 0.5 to 10% by weight.

The photographic material according to this invention may be black or white or it may be a colored photographic material. A colored photographic material is preferred.

Examples of color photographic materials are color negative films, color inversion films, color positive films, color photographic paper, color inversion photographic paper, color sensitive materials or for the color diffusion transfer process or the silver bleaching process.

Details of the photographic materials to be stabilized in accordance with this invention and the components that may be used are given, inter alia, in GB-A-2,319,523, DE-A-19,750,906, page 23, line 20 to page 105, line 32, and US-A-5,538,840, column 25, line 60 to column 106, line 31. These parts of US-A-5,538,840 are incorporated herein by reference.

The compounds of this invention can be introduced into any layer of a silver halide photographic material, however, they are preferably incorporated into a chromogenic layer, in particular a layer containing a yellow coupler. They are used, for example, in a ratio of 1% to 200% by weight with the coupler, preferably between 1% and 100%. The compounds of the present invention can be used in combination with other conventional stabilizers that can be incorporated in the same layer or in a different layer. Examples of suitable conventional stabilizers are described in GB-A-2,319,523, DE-A-19,750,906 and US-A-5,538,840 and include in particular phenolic stabilizers, conventional hindered amine stabilizers, UV absorbers, preferably those of the hydroxyphenyl benzotriazole type or of the hydroxyphenyl triazine class and the like.

ES 2 249 043 T3

Examples of yellow couplers are also described in US-A-5,538,840, column 33, line 3 to column 47, line 15.

Thus, other preferred embodiments of this invention are:

(1) A photographic material comprising on a substrate at least one layer containing a compound of the formula (I).

(2) A silver halide color photographic material comprising a support having at least one light sensitive silver halide emulsion layer and optionally one light non-sensitive emulsion layer, characterized in that at least a light sensitive layer contains a compound of formula (I).

(3) A silver halide colored photographic material comprising a support having

a) at least one cyano-forming unit composed of a red-sensitive silver halide emulsion layer containing a cyano dye-forming coupler,

b) at least one magenta-forming unit composed of a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler and

c) at least one yellow-forming unit composed of a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, characterized in that the blue-sensitive layer contains a compound of formula (I).

Another embodiment of this invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating in said organic material at least one compound of formula (I).

The compounds of formula (I) can be used in various proportions depending on the nature of the material to be stabilized, the end use and the presence of other additives.

In general it is appropriate to use, for example, from 0.01 to 5% by weight of the compounds of formula (I), relative to the weight of the material to be stabilized, preferably from 0.05 to 2% in particular of 0.05 to 1%.

The compounds of the formula (I) can be added, for example, to the polymeric materials before, during or after the polymerization or crosslinking of said materials. They can also be incorporated into polymeric materials in pure form or encapsulated in waxes, oils or polymers.

In general, the compounds of formula (I) can be incorporated into the polymeric materials with various processes, such as dry mixing in powder form, or wet mixing in the form of solutions or suspensions or also in the form of a master batch containing the compounds of formula (I) in a concentration of 2.5 to 25% by weight; in these operations the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.

Materials stabilized with the compounds of formula (I) can be used for the production of similar surface coatings, films, tapes, monofilaments, fibers.

If desired, other conventional additives for synthetic polymers can be added to the organic materials containing the compounds of formula (I), such as antioxidants, UV absorbers, nickel stabilizers, pigments, fillers, plasticizers, corrosion inhibitors and metal deactivators. .

Particular examples of said conventional additives are:

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (alphamethyl-cyclohexyl) -4,6-dimethylphenol, 2 , 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols that are linear or branched on the side chains, for example 2,6-di- nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1 '-yl) -phenol, 2,4-di-methyl-6- (1'-methylheptadec-1' -yl) phenol, 2,4-dimethyl -6- (1'-methyltridecl'-yl) phenol and its mixtures.

1.2. Alkylthiomethylphenols, for example 2,4-dioctyl-thiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctyl-thiomethyl-6-ethylphenol, 2,6-di-dodecylthio-methyl-4- nonylphenol.

ES 2 249 043 T3

1.3. Hydroquinones and 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-octade -cycloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and their mixtures (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4thiobis- (6-tert-butyl-3 -methylphenol), 4,4'-thiobis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amyl-phenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl -6- (alpha-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'- methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2 , 2'-methylenebis [6- (alpha-methylbenzyl) -4-non-nylphenol], 2,2'-methylenebis [6- (alpha, alpha-dimethylbenzyl) -4-nonyl-phenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylene-bis (6 -tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl)) butane, 2,6-bis (3-tert-butyl-5-methyl -2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2- methyl-phenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3bis (3'-tert-butyl-4'-hydroxyphenyl) -butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tri-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4 -methyl-phenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2 , 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl-mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2 -methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl -4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithio -terephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso-octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di [4- (1,1,3,3-tetramethylbutyl) phenyl] -2, 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 2,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di- tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -phenol.

1.10. Triazine compounds, for example 2,4-bis (octyl-mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl-mercapto-4, 6-bis (3,5-di-tert-butyl-4-hydroxy-anilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4 -hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4 -hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, l, 3,5-tris- (3,5-di-cyclo-hexyl-4-hydroxybenzyl) isocyanuarate.

1.11. Benzyl phosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid mono-ethyl ester.

1.12. Acylaminophenols, for example 4-hydroxylaurasnilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxy-phenyl) carbamate.

1.13. Esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6 -hexandiol, 1,9-nonandiol, ethylene glycol, 1,2-propandiol, neopentyl glycol, thiodyethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanuarate, N, N'bis (hydroxyethyl) oxamide, 3-thiacanol thiaundeol thiacanol , trimethylhexanediol, tri-methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabi-cyclo- [2.2.2] octane.

1.14. Esters of beta- (5-tert-butyl-4-hydroxy-3-methylphrenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6 -hexandiol, 1,9-nonandiol, ethylene glycol, 1,2-propandiol, neo-pentyl glycol, thiodyethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) -isocyanurate, N, N'-bisalic acid diamide) , 3-thiaundecanol, 3-thia-pentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane; 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] -undecane.

1.15. 3,5-di-tert-butyl-4-hydroxy-phenylacetic acid esters with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodyethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxami14

ES 2 249 043 T3 gives, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] -octane.

1.16. 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid esters with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonandiol, ethylene glycol, 1 , 2-propandiol, neopentyl glycol, thiodyethylene glycol, diethylene glycol, triethylene glycol, penta-erythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadekanol, trimenethylpropane, 4-thiapentadekanol, trimenethylpropane -hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] -octane.

1.17. Beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amides for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, N, N'-bis [2- ( 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) -ethyl] oxamide (Naurgard^RXL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Amino antioxidants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylene-diamine, N, N '-bis- (1,4-dimethylpentyl) - p-phenylenediamine, N, N '-bis (1 -ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N' -bis (1-methylheptyl) -p-phenylene-diamine, N, N'-dicyclohexyl -p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -pphenylene-diamine, N-iso-propyl-N'-phenyl-p-phenylene-diamine, N - (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene-diamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluene-sulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N -allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-diter -octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyl-aminophenol, 4-octadecanoyl-aminophenol, bis (4-methoxy-phenyl) amine, 2,6-di-tert-butyl-4-dimethyl-aminomethylphenol, 2,4'-diaminodiphenylmethanol, 4,4'-diaminodiphenylmethane, N, N, N ', N' -tetramethyl-4,4'-diaminodiphenylmethane, l , 2-bis [(2-methylphenyl) -amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, N -phenyl-1-naphthylamineteroctylated, a mixture of mono- and dialkylated tert-butyl / tertyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of tert-butyl / mono- and dialkylated tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis- (2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetra-methylpiperid-4-yl) -sebacate, 2,2,6,6-tetramethylpiperidin-4-one,

2,2,6,6-tetramethylpiperidin-4-ol.

two. UV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- ( 5'-tert-butyl-2'-hydroxy-phenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethyl-butyl) phenyl) -benzotriazole, 2- (3' , 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzo-triazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) 5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (alpha, alpha-dimethyl-benzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonyl-ethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl-benzotriazole, 2- (3'-tert-butyl -2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonyethyl) phenyl-benzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) - 6-benzotriazol-2-ylphenol]: the trans-esterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [ R-CH₂CH₂-COO-CH₂CH₂]₂- where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (alpha, alpha-dimethyl-benzyl) -5 '- (1,1,2,2-tetra-methylbutyl) -phenyl] -benzotriazole; 2- [2'-hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (alpha, alpha-dimethyl-benzyl) -phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones, for example the derivatives 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'- dimethoxy.

2.3. Substituted and unsubstituted benzoic acid esters, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6- di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example alpha-cyano-beta, beta-diphenyl-ethyl acrylate, alpha-cyano-beta, beta-isooctyl diphenylacrylate, alpha-carbomethoxycyanamate, alpha-cyano-beta-methyl-p-methoxycinnamate, butyl alpha-cyano-betamethyl-p-methoxycinnamate, methyl alpha-carbomethoxy-p-methoxycinnamate and N- (beta-carbomethoxy-beta-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, for example the methyl ester or

ES 2 249 043 T3 ethyl, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl -5-hydroxypyrazole, with or without additional linkages.

2.6. Spherically hindered amines, for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2, 6,6-penta-methyl (4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (1,2,2,6,6-pentamethyl -4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of

1- (2-hydroxyethyl) -2,2,6,6-tetra-methyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N'bis (2,2,6,6-tetramethyl-4- piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) -nitrile-triacetate, tetrakis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, 1,1 '- (1,2etandiyl) -bis- (3,3,5,5-tetra -methylpiperazinone), 4-benzoyl-2,2,6,6-tetra-methylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, bis (1,2,2,6,6-penta-methylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) -malonate, 3-n-octyl7.7.9 .9- tetramethyl-1,3,8-triazaspiro [4.5] -decan-2,4-dione, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) -sebacate, bis (1octyl-oxy- 2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensates of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro -1,3,5-triazine, the condensate of 2-chloro-4,6-bis (4-n-butylamino2.2.6.6- tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-amino-propylamino) ethane, the condensate of 2-chloro-4,6-di- (4n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-amino-propyl- amino) ethane, 8-acetyl-3-dodecyl 7.7.9.9- tetra-methyl-1,3,8-tri-azaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2 , -6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5dione, 3-dodecyl-1- (1,2,2,6,6-penta-methyl-4-piperidyl) -pyrrolidin-2,5- diona, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4 -cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro1,3,5-triazine as well as 4-butylamino -2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]; a condensate of

1,6- hexanediamine and 2,4,6-trichloro-1,3,5-triazine, as well as N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]; N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7, 7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro- [4,5] decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl- 1-oxa-3,8-diaza-4-oxospiro [4.5] decane and epichlorhydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxy-carbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis- (2,2,6,6-tetra-methyl4-piperidyl) hexamethylenediamine, 4-methoxymethylenemalonic acid diester with 1,2,2,6,6-pentamethyl-4-hydroxy-piperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl) ] siloxane, reaction product of anhydride-alpha-olefin-maleic acid copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl oxanilide, 2,2'-didodecyloxy-5,5'-di- tert-butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide,

2- ethoxy-5-tert-butyl-2'-ethyl oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and p-methoxy oxanilides and also of o- and p-ethoxy-di-substituted.

2.8 2- (2-hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- octyloxyphenyl) -4,6-bis- (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy -propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) -phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2 [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis ( 2,4-dimethyl) -1,3,5-triazine, 2- [4- (do-decyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2 , 4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethyl-hexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-saliocyloyl hydrazine, N, N'-bis (salicyloyl) -hydrazine, N, N'-bis (3,5-di-tert-butyl -4-Hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl-hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N '-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) -thiopropionoyl dihydrazide.

Four. Phosphites and phosphonites, eg triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butyl-phenyl) phosphite , diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite , diisode-cyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol diphosphite, bis- (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tris-thearylsorbitol triphosphite, tetrakis (2,4-di-ter -butylphenyl) -4,4'-diphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphokin, bis (2 , 4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4,8,10tetra-tert-butyl-12 -methyl-dibenz [d, g] -1,3,2-dioxa-phosphokin, 2,2 ', 2 "-nitrile- [tri-ethyl-tris (3,3', 5,5'-tetra-tert-butyl-1,1'-diphenyl-2,2'-diyl) -phosphite] , 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-diphenyl-2,2'-di-yl) -phosphite.

5. Hydroxylamines, eg, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilauryl-hydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecyl-hydroxylamine, N, N-dihexadecyl-hydroxylamine, N, N-dioctylhydroxylamine, N, N-dioctylhydroxylamine , N-hexadecyl-N-ctadecylhydroxylamine, N-heptadecyl-N-octa-decylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow fatty amines.

ES 2 249 043 T3

6. Nitrones, for example N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl- nitrone, N-hexa-decyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-ni-trone, N-octadecyl-alpha-pentadecyl-nitrone, N-heptadecyl- alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derivative of N, N-dialkylhydroxylamine derived from hydrogenated tallow fatty amines.

7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide scavengers, for example beta-thiodipropionic acid esters, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, diotadecyl disulfide, tetradecyl -mercapto) pentaerythritol propionate.

9. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts.

10. 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 higher fatty acids, for example calcium stearate, stearate zinc, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

eleven. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol and 1,3: 2,4-di (benzylidene) are especially preferred )sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and powders o fibers from other natural products, synthetic fibers.

13. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents, and blowing agents.

14. Benzofuranones and indolinones, for example those described in US-A-432863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE-A-4316622 , DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5, 7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) -phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [ 2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxy-phenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7di-ter- butyl-benzo-furan-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butyl-benzo-furan-2-one, 3- (2,3-dimethylphenyl) -5, 7-di-tert-butyl-benzo-furan-2-one.

Example 1

A) Preparation of the intermediate of the formula

<img file="ES2249043T3_D0012.tif" />

1) Preparation of 1- (2-nitro-2-methylpropylamino) propan-2-ol.

Following the procedure described below in Example 4A, step 1, 526.3 g (6.66 mol) of 1-amino-2-propanol (95%) are reacted with 561.6 g (6.05 mol) of 2-nitropropane (96%) and 181.7 g (6.05 mol) of paraformaldehyde in 100 ml of isopropanol to give the product to be used in the next reaction without any isolation.

ES 2 249 043 T3

2) Preparation of 1- (2-amino-2-methylpropylamino) propan-2-ol.

Following the procedure described below in Example 4A, step 2, the mixture from step 1 above is hydrogenated using 100 g of Raney Nickel as a catalyst. A white oil is obtained with a boiling point of 116-120 ° C at 13.3 mbar.

3) Preparation of 1- (2-hydroxypropyl) -3,3,5,5-tetramethylpiperazin-2-one.

Following the procedure described below in example 4A, step 3, 250 g (1.71 mol) of 1- (2-amino-2-methylpropylamino) propan-2-ol are reacted with 306.2 g (2, 57 mol) of chloroform and 1509 ml of acetone in the presence of 410.4 g (10.26 mol) of sodium hydroxide in 410 ml of water. A yellow oil is obtained with a boiling point of 137 ° -140 ° C at 1.1 mbar.

4) The intermediate of the above formula is prepared by adding 107 g (0.5 mol) of dimethyl sulfoxide dropwise to a solution of 63.5 g (0.5 mol) of oxalyl chloride in 800 ml of cooled dichloromethane down to -60 ° C. After the addition, a solution of 1- (2-hydroxypropyl) -3,3,5,5-tetramethylpiperazin-2-one in 300 ml of dichloromethane is slowly added, keeping the temperature at -60 ° C. After 20 minutes, 101 g (1 mol) of triethylamine are added. After an additional 30 minutes the temperature is increased to room temperature. The mixture is then filtered and evaporated under vacuum. The crude material is purified by distillation (129 ° C / 1 mm Hg). The product is recovered as a yellow oil. The yield is 80% of theory.

¹NMR: 4.03 (s, 2H); 3.11 (s, 2H); 2.018 (s, 3H); 1.24 (s, 6H); 1.09 (s, 6H)

B) Preparation of the intermediate of the formula

<img file="ES2249043T3_D0013.tif" />

At room temperature, 50 g of Pt (5%) supported on charcoal with 50% of water is added to a mixture of 132.4 g (0.62 mol) of 3,3,5,5-tetramethyl-1- ( 2-oxopropyl) piperazin-21-one and 36.2 g (0.31 mol) of hexamethylenediamine in methanol. The mixture is hydrogenated at 70 ° C and 35 bar for 20 hours. The mixture is then filtered and the organic phase is washed with water, dehydrated over sodium sulfate and evaporated under vacuum. The product is recovered as a yellow resin. The yield is 93% of theory.

¹NMR: 3.37 (dd, 2H); 3.17 (s, 4H); 3.14 (dd, 2H); 2.82 (sext, 2H); 2.61-2.40 (m, 4H); 1.33 (m, 4H); 1.27 (s, 12H); 1.22 (s, 4H); 1.10 (s, 12H); 0.96 (d, 6H)

C) Preparation of the compound of the formula

<img file="ES2249043T3_D0014.tif" />

ES 2 249 043 T3

46.5 g (0.21 mol) of 2-tert-butylamino-4,6-dichlorotriazine in 500 ml of xylene are added to a solution of 125 g (0.23 mol) of the intermediate described under B) in 300 ml of xylene. The solution is heated at 60 ° C for 2 hours, with stirring. Then 25.2 g (0.63 mol) of NaOH in 50 ml of water are added. The mixture is heated to reflux for 5 hours, the water being removed by azeotropic distillation. The mixture is then cooled to 60 ° C and 29 g (0.21 mol) of sodium carbonate in 50 ml of water are added and the mixture is refluxed for a further 24 hours, the water being removed by azeotropic distillation. The mixture is then cooled and filtered. The organic phase is dehydrated over sodium sulfate and evaporated under vacuum. 153.3 g of the product are recovered. The yield is 98% of theory.

Melting point: 96 ° - 99 ° C.

Example 2

Preparation of the compound of the formula

<img file="ES2249043T3_D0015.tif" />

The compound is prepared analogously to the method described in Example 1, using the appropriate starting materials.

Melting point: 130 ° - 140 ° C (yellow powder)

Example 3

Preparation of the compound of the formula

<img file="ES2249043T3_D0016.tif" />

5 g of paraformaldehyde are added to a solution of 36.1 g (0.055 mol) of the compound of Example 1C in tert-amyl alcohol. The mixture is heated to 80 ° C and 7.6 g (0.165 mol) of formic acid dissolved in 10 ml of tert-amyl alcohol are slowly added. The mixture is then stirred for 3 hours at 80 ° C. Then 50 ml of toluene are added, the temperature being cooled to room temperature. A solution of 6.6 g (0.165 mol) of sodium hydroxide in 50 ml of water is then slowly added. After stirring for half an hour, the organic phase is separated, washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated under vacuum (80 ° C / 1.3 mbar).

Melting point: 95 ° - 99 ° C.

ES 2 249 043 T3

Example 4

A) Preparation of the intermediate of the formula

<img file="ES2249043T3_D0017.tif" />

1) Preparation of 2- (2-nitro-2-methyl-propylamino) ethanol.

607.8 g (6.55 mol) of 2-nitropropane and 100 ml of water are added to a solution of 450 g (7.40 mol) of ethanoalmine in 1000 ml of isopropanol. The solution is stirred at room temperature and, while stirring and maintaining the temperature at room temperature, 225.4 g (7.5 mol) of paraformaldehyde and 7 ml of 20% aqueous sodium hydroxide solution ( % weight / volume). The mixture is then heated to 50 ° C, with nitrogen being blown into the mixture to remove excess formaldehyde. The mixture obtained is used for the next reaction without any isolation of the product.

2) Preparation of 2- (2-amino-2-methyl-propylamino) ethanol.

The mixture from 1) is transferred to an autoclave and 100 g of Ni Raney are added. The autoclave is closed and purged with nitrogen. Hydrogen is added up to a pressure of 50 bars. The mixture is kept under a hydrogen pressure of 50 bars at room temperature and under stirring for 8 hours. The mixture is then heated to 50 ° C at the same pressure. The catalyst is then filtered off and the mixture is distilled under vacuum. A white oil is obtained with a boiling point of 100 ° -105 ° C at 13.3 mbar.

3) Preparation of 1- (2-hydroxyethyl) -3,3,5,5-tetramethylpiperazin-2-one.

244.2 g (2.05 mol) of chloroform are added to 180 g (1.36 mol) of 2- (2-amino-2-methyl-propylamino) ethanol in 1204 ml of acetone. The mixture is cooled to 5 ° C under stirring and a solution of 327 g (8.18 mol) of sodium hydroxide in 327 ml of water is slowly added, keeping the temperature of the mixture at 0 ° - 5 ° C during the addition. . The mixture is then stirred at this temperature for a further 2 hours and at room temperature for 15 hours. The pH of the aqueous solution is then corrected to 11 and the mixture is stirred for a further 4 hours. The mixture is then filtered and the residue is washed with acetone. Collect the filtrate and wash acetone and evaporate under vacuum (70 ° C / 24 mbar). Distillation of the residue gives a white oil with a boiling point of 115 ° C at 2.66 mbar. After cooling, a solid product with a melting point of 91 ° - 93 ° C is obtained.

4) Preparation of 1- (2-hydroxyethyl) -3,3,4,5,5-penta-methylpiperazin-2-one.

24.3 g (0.78 mol) of paraformaldehyde are added to a solution of 120 g (0.6 mol) of 1- (2-hydroxyethyl) -3,3,5,5-tetramethylpiperazin-2-one in 300 ml of tert-amyl alcohol. The mixture is then heated to 80 ° C and 35.8 g (0.78 mol) of formic acid dissolved in 30 ml of tert-amyl alcohol are slowly added. The mixture is then kept at 80 ° C for a further 1 hour and cooled to 50 ° C. Then 250 ml of toluene and 100 ml of water are added. The mixture is then stirred and 33 g (0.825 mol) of sodium hydroxide dissolved in 60 ml of water are slowly added. The organic phase is separated, washed with water, dried over anhydrous sodium sulfate, filtered and evaporated under vacuum (60 ° C / 10 mbar). A white solid with a melting point of 77 ° - 80 ° C is obtained.

5) The intermediate of the previous formula is prepared in a similar way to the procedure described in example 1A, step 4, starting from 1- (2-hydroxyethyl) -3,3,4,5,5-pentamethylpiperazin-2-one . A brown oil is obtained.

¹NMR: 9.50 (s, 1H); 4.06 (s, 2H); 3.07 (s, 2H); 2.20 (s, 3H); 1.27 (s, 6H); 1.06 (s, 6H)

ES 2 249 043 T3

B) Preparation of the intermediate of the formula

<img file="ES2249043T3_D0018.tif" />

This intermediate is prepared in a manner analogous to the procedure described in example 1B, starting from the intermediate of step A above.

C) Preparation of the compound of the formula

<img file="ES2249043T3_D0019.tif" />

This compound is prepared analogously to the method described in Example 1C, using the reagent from step B above. The product obtained is a yellow powder.

Melting point: 78 ° - 81 ° C Example 5

Preparation of the compound of the formula

<img file="ES2249043T3_D0020.tif" />

A solution of 15 g of the product from Example 1C, 4 g (0.02 mol) of acetic anhydride and 4 g (0.02 mol) of triethylamine in 150 ml of dichloromethane is refluxed for 5 hours. After cooling, 30 ml of a 40% potassium carbonate solution are added. The organic phase is separated, dried over anhydrous sodium sulfate, filtered and evaporated under vacuum (80 ° C / 1.3 mbar). A white powder is obtained.

Melting point: 103 ° - 107 ° C.

ES 2 249 043 T3

Example 6

Preparation of the compound of the formula

<img file="ES2249043T3_D0021.tif" />

described in Example 5, using the compound of

The compound is prepared analogously to method example 2.

Melting point: 122 ° - 127 ° C (yellow powder)

Example 7

Preparation of the compound of the formula

<img file="ES2249043T3_D0022.tif" />

A solution of 50 g of the compound of Example 2C and 8.9 g (0.024 mol) of 2,4-bis {dibutylamino} -6-chloro- {1,3 is allowed to react for 4 hours at 140 ° C , 5} -triazine in 250 ml of xylene. After cooling to 60 ° C, 0.96 g (0.024 mol) of sodium hydroxide and 4 g of potassium carbonate in 10 ml of water are added. The mixture is heated to reflux and the water of reaction is azeotropically removed. After a further 6 hours the mixture is cooled to 60 ° C, diluted with 50 ml of xylene, filtered and concentrated under vacuum at 140 ° C / 1 mbar. A yellow powder is obtained.

Melting point: 60 ° - 64 ° C

Example I-1

Light stabilizing action on polypropylene tapes

1 g of each of the compounds indicated in Table I-1, 1 g of tris [2,4-ditert-butylphenyl] phosphite, 0.5 g of tetrakis [3- (3,5- pentarithritol di-tert-butyl-4-hydroxyphenyl) propionate] and 1 g of calcium stearate with 1000 g of polypropylene powder (PP ^RMOPLEN S SF) which has a melt index of 3.7 (measured at 230 ° C and 2.16 kg).

The mixtures are extruded at 200-220 ° C to give polymer granules that are subsequently converted into ribbed ribbons 50 µm thick and 2.54 mm wide, using a type of semi-industrial apparatus (^RLeonard-Sumirago (VA) - Italy) and operating under the following conditions:

Extruder temperature 210-230 ° C

Head temperature: 240-260 ° C

Draft ratio: 1: 6

ES 2 249 043 T3

The tapes thus prepared are mounted on a white cardboard and exposed in a Weather-O-Meter 65 WR (ASTM D 2565-85) with a black panel temperature of 63 ° C.

The residual toughness is measured by means of a constant speed tensiometer, on a sample taken after several times of exposure to light; From this, the exposure time (in hours) required to average the initial toughness (T₅₀).

By way of comparison, tapes prepared under the same conditions as indicated above, but without the addition of the stabilizers of the present invention, are set forth.

The results obtained are shown in Table I-1.

TABLE I-1

Stabilizer T₅₀ (hours)

Without stabilizer 520

Compound of Example 1C 2620

Compound of Example 3 2600

The above results show that the compounds of this invention are effective light stabilizers. Example I-2

Light stabilizing action on polypropylene fibers

In a slow mixer, mix 2.5 g of each of the compounds listed in Table I-2, 1 g of tris (2,4-di-t-butylphenyl) phosphite, 1 g of monoethyl 3,5-di -t-butyl-4-hydroxybenzyl-phosphonate of calcium, 1 g of calcium stearate and 2.5 g of titanium dioxide with 1000 g of polypropylene powder (PP ^RMOPLEN FLF 20) which has a melt index: 12.2 g / 10 min (measured at 230 ° C and 2.16 kg).

The mixtures are extruded at 200-230 ° C to obtain polymer granules that are then converted into fibers using a pilot type apparatus (^RLeonard-Sumirago (VA), Italy) and operating under the following conditions:

Extruder temperature 230-245 ° C

Head temperature: 255-260 ° C

Draft ratio: 1: 3.5

Linear density: 11 dtex per filament

The fibers thus prepared are exposed, after mounting on a white cardboard, to a Weather-O-Meter 65 WR (ASTM D 2565-85) with a black panel temperature of 63 ° C.

For samples taken after several times of exposure to light, the residual toughness is measured using a constant speed tensiometer, and then the exposure time in hours required to average the initial toughness (T₅₀).

Fibers prepared under the same conditions as indicated above, but without adding the stabilizers of the present invention, are also exposed for comparative purposes.

The results are shown in Table I-2.

TABLE I-2

Stabilizer T₅₀ (hours)

Without stabilizer 310

Compound of Example 1C 2790

Compound of Example 3 2830

The above results show that the compounds of this invention are effective light stabilizers.

ES 2 249 043 T3

Example II-1

Stabilization of a polycarbonate / acrylonitrile-butadiene-styrene (PC / ABS) mixture pigmented with gray

A commercial PC / ABS mixture is stabilized (^RCycoloy MC 8002) pigmented with 1% by weight of ^RGray 9779 from Uniform Color Company with the addition of 1% by weight of 2- (2'-hydroxy-3 ', 5'-bis (1 ", 1" -dimethylbernzyl) phenyl) benzotriazole and 0.5% by weight of the compound indicated in Table II-1. For comparison, a sample containing only 1% by weight of the benzotriazole stabilizer and an unstabilized sample - both containing 1% by weight of gray pigment serves as a comparison.

Izod bars (2.54 ”L x 0.5” Ax 0.125 ”A were prepared by injection molding on a machine ^RBOY 30, cylinder temperature 246 ° - 268 ° C, die temperature 268 ° C. Accelerated weather wear is carried out using a^RAtlas Ci65A Weather-O-meter (XAW), operating in “Dry XAW” mode (ASTM G26-90, method C). after regular intervals the color change AE is determined in accordance with DIN 6174. The results are reported in Table II-1.

TABLE II-1

<td>Irradiation time: Stabilizer</td><td>249.8 hours AE</td><td>750 hours AE</td>

<td>None</td><td> 3,3</td><td> 9,0</td>

<td>Benzotriazole stabilizer *)</td><td> 1,7</td><td> 6,7</td>

<td>Compound from Example 5</td><td> 0,7</td><td> 4,8</td>

*) 2- (2'-hydroxy-3 ', 5'-bis (1 ", 1" -dimethylbenzyl) phenyl) benzotriazole

The PC / ABS samples stabilized in accordance with this invention show excellent color stability.

Example II-2

Stabilization of a white pigmented polycarbonate / acrylonitrile-butadiene-styrene (PC / ABS) mixture

Samples were prepared from a commercial PC / ABS mixture (^RCycoloy MC 8002) as described in Example II-1 except that TiO2 (^RThiona RCL-4 rutile; ^RSCM chemicals) as a pigment. Weathering and determination is carried out as described in Example II-1. The results are shown in Table II-1.

TABLE II-2

<td>Irradiation time: Stabilizer</td><td>249.6 hours AE</td><td>749.3 hours AE</td><td>999.8 hours AE</td>

<td>None</td><td> 4,6</td><td> 15,4</td><td> 21,8</td>

<td>Benzotriazole stabilizer *)</td><td> 2,8</td><td> 9,5</td><td> 15,7</td>

<td>Compound from Example 5</td><td> 3,4</td><td> 6,4</td><td> 11,3</td>

*) 2- (2'-hydroxy-3 ', 5'-bis (1 ", 1" -dimethylbenzyl) phenyl) benzotriazole

The PC / ABS samples stabilized in accordance with this invention show excellent color stability, particularly at long exposure intervals.

ES 2 249 043 T3

Abbreviations used in Examples III-1 to III-5 below: CoupY1: Compound of the formula

<img file="ES2249043T3_D0023.tif" />

CoupY2: Compound of the formula

<img file="ES2249043T3_D0024.tif" />

Solv1: Compound of the formula o

II

[Ργ ε-ο- (CH,_{) r}-cH,

OR

Ha1: Compound of the formula

<img file="ES2249043T3_D0025.tif" />

Su1: Compound of the formula

<img file="ES2249043T3_D0026.tif" />

ES 2 249 043 T3

Coaddí: Compound of the formula

Coadd2: Compound of the formula

<img file="ES2249043T3_D0027.tif" />

Example III-1

Stabilization of photographic layers

Chromogenic photographic layers were prepared by hand coating a gelatin emulsion containing silver bromide, yellow coupler and an additive of this invention on a polyethylene coated paper.

The composition of the layer is as given in the following Table (amounts in mg / m²)

<td>Component</td><td>Quantity in layer</td>

<td>Jelly</td><td> 5150</td>

<td>AgBr</td><td> 520</td>

<td>CoupY1 Yellow Coupler</td><td> 835</td>

<td>Solv 1 Coupler Solvent</td><td> 278</td>

<td>Additive (Table III-1)</td><td> 250</td>

<td>Hardener Ha1</td><td> 300</td>

<td>Su1 surfactant</td><td> 340</td>

The layers are dried for 7 days in a ventilated cabinet. Dry samples are exposed to white light through a staggered 0.3 logE exposure steps. Developed with the P94 process for color negative paper^RAgfa-Gevaert, following the manufacturer's recommendations.

After exposure and processing, the remission density of the yellow dye in the blue channel is measured. The results are set forth in Table III-1.

TABLE III-1

<td>Additive</td><td>100 x Dmax</td>

<td>None</td><td> 206</td>

<td>Compound from Example 2</td><td> 230</td>

<td>Compound from Example 4C</td><td> 254</td>

These results show that the compounds of the present invention improve maximum dye yield.

ES 2 249 043 T3

Example III-2

Stabilization of photographic layers

Chromogenic photographic layers are prepared by hand coating a gelatin emulsion containing silver bromide, yellow coupler, and an additive of this invention on polyethylene coated paper.

The composition of the layer is as given in the following Table (amounts in mg / m²)

<td>Component</td><td>Quantity in layer</td>

<td>Jelly</td><td> 5150</td>

<td>AgBr</td><td> 520</td>

<td>CoupY2 Yellow Coupler</td><td> 854</td>

<td>Solv 1 Coupler Solvent</td><td> 285</td>

<td>Additive (Table III-2)</td><td> 256</td>

<td>Hardener Ha1</td><td> 300</td>

<td>Su1 surfactant</td><td> 340</td>

The layers are dried for 7 days in a ventilated cabinet. Dry samples are exposed to white light through a staggered 0.3 logE exposure steps. Developed with the P94 process for color negative paper^RAgfa-Gevaert, following the manufacturer's recommendations.

After exposure and processing, the remission density of the yellow dye in the blue channel is measured. The results are set forth in Table III-2.

TABLE III-2

<td>Additive</td><td>100 x Dmax</td>

<td>None</td><td> 176</td>

<td></td><td></td>

<td>Compound from Example 4C</td><td> 214</td>

These results show that the compounds of the present invention improve maximum dye yield. Example III-3

Stabilization of photographic layers

Chromogenic photographic layers are prepared by hand coating a gelatin emulsion containing silver bromide, yellow coupler, and an additive of this invention on polyethylene coated paper.

The composition of the layer is as given in the following Table (amounts in mg / m²)

<td>Component</td><td>Quantity in layer</td>

<td>Jelly</td><td> 5150</td>

<td>AgBr</td><td> 520</td>

<td>CoupY2 Yellow Coupler</td><td> 854</td>

<td>Solv 1 Coupler Solvent</td><td> 278</td>

ES 2 249 043 T3 (Continued)

<td>Component</td><td>Quantity in layer</td>

<td>Additive (Table III-3)</td><td> 250</td>

<td>Hardener Ha1</td><td> 300</td>

<td>Su1 surfactant</td><td> 340</td>

The layers are dried for 7 days in a ventilated cabinet. Dry samples are exposed to white light through a staggered 0.3 logE exposure steps. Developed with the P94 process for color negative paper^RAgfa-Gevaert, following the manufacturer's recommendations.

After exposure and processing, the remission density of the yellow dye in the blue channel is measured. The samples are then exposed in a^RAtlas weather-O-meter so they receive 60kJ / cm² of light energy. The temperature is 43 ° C and the relative humidity is 50%. Density loss (-AD) is determined from a blue density of 1 (OD = 1). The results are set forth in Table III-3.

TABLE III-3

<td>Additive</td><td>-AD (60kJ / cm², from OD = 1)</td>

<td>None</td><td> 55</td>

<td>Compound from Example 2</td><td> 28</td>

<td>Compound of Example 4C</td><td> 35</td>

<td>Compound from Example 1C</td><td> 27</td>

<td>Compound from Example 3</td><td> 33</td>

<td>Compound of Example 5</td><td> 33</td>

These results show that the compounds of the present invention improve the light stability of yellow photographic layers.

Example III-4

Stabilization of photographic layers

Chromogenic photographic layers are prepared by hand coating a gelatin emulsion containing silver bromide, yellow coupler, and an additive of this invention on polyethylene coated paper.

The composition of the layer is as given in the following Table (amounts in mg / m²)

<td>Component</td><td>Quantity in layer</td>

<td>Gelatin a</td><td> 5150</td>

<td>AgBr</td><td> 520</td>

<td>CoupY2 Yellow Coupler</td><td> 854</td>

<td>Solv 1 Coupler Solvent</td><td> 285</td>

<td>Additive (Table III-4)</td><td> 256</td>

<td>Hardener Ha1</td><td> 300</td>

<td>Su1 surfactant</td><td> 340</td>

ES 2 249 043 T3

The layers are dried for 7 days in a ventilated cabinet. Dry samples are exposed to white light through a staggered 0.3 logE exposure steps. Developed with the P94 process for color negative paper^RAgfa-Gevaert, following the manufacturer's recommendations.

After exposure and processing, the remission density of the yellow dye in the blue channel is measured. The samples are then exposed in a^RAtlas weather-O-meter so they receive 60kJ / cm² of light energy. The temperature is 43 ° C and the relative humidity is 50%. Density loss (-AD) is determined from a blue density of 1 (OD = 1). The results are set forth in Table III-4.

TABLE III-4

<td>Additive</td><td>-AD (60kJ / cm², from OD = 1)</td>

<td>None</td><td> 47</td>

<td>Compound from Example 2</td><td> 26</td>

<td>Compound of Example 4C</td><td> 24</td>

<td>Compound from Example 1C</td><td> 20</td>

<td>Compound from Example 3</td><td> 22</td>

<td>Compound of Example 5</td><td> 22</td>

These results show that the compounds of the present invention improve the light stability of yellow photographic layers.

Example III-5

Stabilization of photographic layers

Chromogenic photographic layers are prepared by hand coating a gelatin emulsion containing silver bromide, yellow coupler, and an additive of this invention in combination with a co-stabilizer on polyethylene coated paper.

The composition of the layer is as given in the following Table (amounts in mg / m²)

<td>Component</td><td>Quantity in layer</td>

<td>Jelly</td><td> 5150</td>

<td>AgBr</td><td> 520</td>

<td>CoupY1 Yellow Coupler</td><td> 835</td>

<td>Solv 1 Coupler Solvent</td><td> 278</td>

<td>Additive of this invention</td><td>according to Table III-5</td>

<td>Co-stabilizer</td><td>according to Table III-5</td>

<td>Hardener Ha1</td><td> 300</td>

<td>Su1 surfactant</td><td> 340</td>

The layers are dried for 7 days in a ventilated cabinet. Dry samples are exposed to white light through a staggered 0.3 logE exposure steps. Developed with the P94 process for color negative paper^RAgfa-Gevaert, following the manufacturer's recommendations.

After exposure and processing, the remission density of the yellow dye in the blue channel is measured. The samples are then exposed in a^RAtlas weather-O-meter so they receive 60kJ / cm² of light energy. The temperature is 43 ° C and the relative humidity is 50%. Density loss (-AD) is determined from a blue density of 1 (OD = 1). The results are set forth in Table III-5.

ES 2 249 043 T3

TABLE III-5

<td>Additive of this invention</td><td>mg / m²</td><td>co-stabilizer</td><td>mg / m²</td><td>-D (60kJ / cm², from OD = 1)</td>

<td>None</td><td></td><td>none</td><td></td><td> 55</td>

<td> -</td><td></td><td>Coadd1</td><td> 250</td><td> 42</td>

<td>Comp. from Ex. 1C</td><td> 250</td><td> -</td><td> -</td><td> 40</td>

<td>Comp. from Ex. 1C</td><td> 125</td><td>Coadd1</td><td> 125</td><td> 37</td>

<td> -</td><td> -</td><td>Coadd2</td><td> 250</td><td> 48</td>

<td>Comp. from Ex. 1C</td><td> 125</td><td>Coadd2</td><td> 125</td><td> 35</td>

These results show that the compounds of the present invention improve the efficiency of the classical stabilizers used in yellow photographic layers.