JPH11315067A - Production of sterically hindered amine ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively derive the corresponding 1-allyloxy-substitution product and produce the subject compound by oxidizing a 1-allyl-substituted sterically hindered amine. SOLUTION: A compound represented by formula I (R1 to R4 are each a 1-8C alkyl, a 1-5C hydroxyalkyl or the like; R5 to R9 are each H, a 1-8C alkyl, a 2-6C alkenyl or the like; R contains 2-500 carbon atoms and is an organic cross-linking group forming a 5- to a 7-membered ring cyclic structure together with the carbon atoms and nitrogen atom to which the group is directly bound) is oxidized to thereby produce the objective compound represented by formula II. Oxygen, a peroxide, a nitrate, a permanganate, a chlorate, etc., are cited as an oxidizing agent used in the oxidizing reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a new process for the preparation of sterically hindered amine ethers, new compounds of this kind, and as stabilizers for organic materials against decomposition by light, oxygen and / or heat. The use as well as the corresponding compounds.

[0002]

BACKGROUND OF THE INVENTION Numerous publications have described the stabilization of organic materials using specific sterically hindered amine (HALS) compounds as stabilizers. A useful class of sterically hindered amines are compounds in which the nitrogen atom is part of a heterocyclic ring and the nitrogen atom has additional organic substituents attached beyond the oxygen atom (NOR-Hals; Kurmada J. Polym. Sci, Poly. Chem. 22nd edition, 27th edition
7-81 (1984); U.S. Pat. No. 5,204,473); etherification of free oxyl- or hydroxylamine using appropriate reagents induces oxygen-linked substituents on these compounds. Is done.

[0003]

Some N-allyl nitroxides rearrange to amine ethers under certain conditions (Meisenheimer rearrangement; Chem. Ber. 52, 1667 (191).
9); Chem. Ber. 55, 513 (1922)). Nitroxide splitting (Cope elimination) with the formation of alkenes and hydroxylamines is a competitive reaction, the rate of which increases with increasing steric hindrance (J. March, Adva
nced Organic Chemistry, IV Edition, Wiley, 1992).

[0004]

SUMMARY OF THE INVENTION It is now surprising that
Oxidation of the allyl-substituted sterically hindered amine results in the corresponding 1
-An allyloxy-substituted product was found to be effectively induced. Therefore, the present invention provides the following formula I (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a C 1-8 alkyl group or a C 1
Represents 5 to 5 hydroxyalkyl groups;
₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ are the same as the carbon atom to which the group is attached. R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are independently a hydrogen atom, a C 1 -C 8 alkyl group, An alkenyl group having 2 to 8 atoms, an aryl group having 5 to 12 carbon atoms, and 1 to 4 carbon atoms
A haloalkyl group or an electron withdrawing group; or an aryl group having 6 to 12 carbon atoms substituted by a residue selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Represents a group; and R ₇ and R ₈ may together form a chemical bond; and R contains 2 to 500 carbon atoms and the group is directly bonded Represents an organic bridging group which together with the carbon and nitrogen atoms forms a substituted 5, 6 or 7 membered cyclic structure; R is preferably a nitrogen, oxygen, phosphorus, sulfur, It is a hydrocarbon group having 2 to 500 carbon atoms which optionally contains 1 to 200 heteroatoms selected from a silicon atom and a halogen atom. A process for the preparation of a compound of the formula Wherein all residues R and R ₁ to R ₉ are as defined in formula I. R ₇ and R ₈ together form an allene double bond in Formula I and a triple bond in Formula II as a chemical bond.

[0005]

DETAILED DESCRIPTION OF THE INVENTION Compounds of Formula I and Formula II
In products as well as further products, R₁, R _Two, R_ThreeYou
And R_FourIs independently preferably a methyl group or ethyl
Represents a group, in particular a methyl group. R as electron withdrawing group_Five, R
₆, R₇, R₈And R₉Represents -CN, nitro group, halo
Gen atom or -COOR_Ten(Where R_TenIs the number of carbon atoms
1 to 12 alkyl groups, 5 to 12 carbon atoms
Cycloalkyl groups, phenylenes having 7 to 9 carbon atoms
Represents a alkyl group or a phenyl group. )including. Electronic offer
Preferably the group is -CN or -COOR_Ten(Where
An alkyl group having 1 to 12 carbon atoms, 5 carbon atoms
Represents 12 cycloalkyl groups or phenyl groups,
Especially R_TenIs an alkyl group having 1 to 12 carbon atoms or
Represents a cyclohexyl group. ). Preferably,
R_Five, R₆, R₇, R₈And R₉Is independently a hydrogen atom
Or a methyl group, especially a hydrogen atom. Also, R_FiveAnd
And R₆Is independently a hydrogen atom or a methyl group, especially a hydrogen atom
Represents a child, R₇, R₈And R₉But independently haloalk
Group, phenyl group, vinyl group, nitro group, CN, COO
R_TenOr R₇And R₈Become together
Compounds that form a chemical bond are also preferred.

More preferred with respect to the bridging group R are mainly as described below for compounds of the formulas III, IV and V.

Formula II wherein R ₁ , R ₂ , R ₃ and R
₄ represents, independently of one another, an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms, or R ₁ and R ₂ together with the carbon atom to which the group is attached And R ₃ and R ₄ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group; _5, R _6,
R ₇ , R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 8 carbon atoms.
An alkenyl group, an aryl group having 5 to 12 carbon atoms and an electron withdrawing group; or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 6 carbon atoms substituted by a halogen atom Represents 12 to 12 aryl groups; and R optionally comprises 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, and contains 2 carbon and nitrogen atoms Represents a hydrocarbon group having 3 to 500 carbon atoms which forms a substituted 6-membered cyclic structure together with Of particular interest is a process for preparing compounds of formula I by oxidizing compounds of formula (I).

The aryl group represents a group complying with the Debye-Hückel rule; the aryl group having 6 to 12 carbon atoms is preferably a phenyl group and a naphthyl group. An alkyl group is a branched or unbranched group and within the definition given, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. Butyl group, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, n-hexyl group, 1-methylhexyl group,
n-heptyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1,3-trimethyl Hexyl group, 1,1,3
3-tetramethylpentyl group, nonyl group, decyl group, undecyl group, 1-methylundecyl group, dodecyl group,
1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.

An alkanoyl group is an alkyl group bonded beyond a carbonyl bond; thus, alkanoyl groups having 2 to 20 carbon atoms include acetyl, propionyl, butyryl, hexanoyl and stearolyl. A haloalkyl group is a halogen atom, for example 1 or 2
Alkyl group substituted by two halogen atoms.
Halogen is preferably chlorine or bromine, especially bromine. A cycloalkyl group is a saturated monovalent monocyclic hydrocarbon residue, for example a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl group; preferably a cyclohexyl group.

Organic residues or hydrocarbon groups containing heteroatoms, for example alkyl or alkylene groups interrupted by hetero groups such as oxygen or NH, are usually oxo, oxa, hydroxy, carboxy, carboxy, ester Group, amino group, amide group, nitro group, nitrile group, isocyanato group, fluoro group, chloro group, bromo group, phosphate group, phosphonate group, phosphite group, silyl group, thio group, sulfide group, sulfinyl group, sulfo group A pyrrolyl group, an indyl group, a carbazolyl group, a furyl group, a benzofuryl group, a thiophenyl group, a benzothiophenyl group, a pyridyl group, a sinolyl group, an isosinolyl group,
Pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazolyl group, benzotriazolyl group, triazinyl group,
Pyrazolyl, imidazolyl, thiazolyl, oxazolyl and corresponding saturated and / or unsaturated groups,
These heteroatoms are included as representative functional groups such as heterocyclic groups such as, for example, piperidyl, piperazinyl, and morpholinyl groups. They may be interrupted by one or more of these groups; in any order, usually OO, ON (excluding nitro, cyanato, isocyanato, nitroso groups), It does not include types of bridges such as NN (except in heterocyclic ring structures), NP or PP.

Preferably, in an organic residue or hydrocarbon group containing a heteroatom such as R, there is no one or more heteroatoms linked by a single bond to the same carbon atom. Usually, a spacer consisting of one or more heteroatoms is embedded in a carbon chain or ring, or
Inserted during hydrogen bonding.

The compounds of the formula I can be monomers or polymers. They have the formula I ' When the compound represented by the formula I ′ is a polymer, the compound represented by the formula I ′ is contained in the repeating structural unit.

The starting compounds of the formula II are known in the art and can be obtained analogously to known compounds. The process of the invention can either start from the isolated compounds of the formula II or use solutions of these starting compounds as obtained directly after the synthesis.

In the process according to the invention, known oxidizing agents such as oxygen, peroxide or other oxidizing agents such as nitrates, permanganates, chlorates; preferably systems based on peroxides such as hydrogen peroxide, especially peroxides It is possible to carry out the oxidation reaction using an acid such as perbenzoic acid or peracetic acid. The oxidizing agent is conveniently used in stoichiometric or excess amounts, for example by using 1 to 2 moles of active oxygen atoms for each group of formula I 'in the desired product. Is done.

Suitable solvents, for example aromatic or aliphatic hydrocarbons, alcohols, esters, amides, ethers or halogenated hydrocarbons; for example benzene, toluene, xylene, mesitylene, methanol, ethanol, propanol, butanol, dimethylformamide, dimethyl It is possible to carry out the reaction in the presence of sulphoxide, methylene chloride; preferably C1 -C4 alcohols, benzene, toluene, xylene or chlorinated C1 -C6 hydrocarbons.

The temperature and pressure are not critical,
Mainly dependent on the oxidant system used; preferably the temperature is maintained in the range between -20 ° C and + 40 ° C during the reaction. Conveniently the pressure is maintained near atmospheric pressure, for example between 0.5 and 1.5 bar; if the oxidation is carried out with gaseous oxygen, the pressure of oxygen or oxygen / inert gas may be above atmospheric pressure .

In the process of the invention, further processing steps known in the art, with or without prior isolation of the product of formula I, such as hydrogenation of ethylenic double bonds, ethylene It is possible to continue the halogenation of the system double bond, for example bromination and / or polymerization.

The ethylenic double bonds (carbon-carbon double bonds) in the compounds of formula I can be prepared by methods known in the art, for example by using gaseous hydrogen under catalytic conditions or by using a hydrogenating agent. Hydrogenation of the bond). Preferred is catalytic hydrogenation; eg Pt, Pt, Pd, Ni, R on a support such as carbon.
u, Rh or without support, Raney-Ni
A known catalyst such as can be used.

The hydrogenation of the allene double bond in the compounds of the formula I in which R ₇ and R ₈ together represent a chemical bond proceeds in two steps. The first step derives a partial hydrogenation product, which can be isolated or subjected to further derivation, which has the formula IV Wherein R, R ₁ to R ₆ and R ₉ are as defined above.

By complete hydrogenation, the following formula III Wherein R, R ₁ to R ₆ and R ₉ are as defined above for Formula I, and R ₇ and R ₈ are hydrogen, C _1-8 alkyl, C 3 An alkenyl group of from 8 to 8 carbon atoms of 5 to 12
Substituted with an aryl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an electron-withdrawing group; or a residue selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Number of carbon atoms 6
To 12 aryl groups. Is obtained.

Halogenation is a second follow-up reaction, for example, J. March, Advanced Organic Chemistry: Reaction
mechanisms and Structure, 4th edition, Wiley, 1992, 81st
As summarized on page 2, it is possible to carry out the process according to the invention mainly using the appropriate reactants according to methods known in the art. Thus, a halogen atom is added to the carbon-carbon double bond of the compound of formula I or IV to give an α, β-dihalogenated product. The halogen reagent X ₂ (X represents F, Cl, Br, I or preferably Cl or Br, especially Br) is used in gaseous, liquid or solid state, in pure state or in solution. It is possible. It is also possible to release the halogen during the reaction in approximate amounts, using a suitable carrier carrier or source.

It is also possible to carry out the reaction by methods known in the art using hydrogen pressures in the general range, preferably between 0.5 and about 200 bar, in particular between 1 and 100 bar. (1 bar = 10 ⁵ Pa). The reaction can be carried out using a suitable solvent, for example water, a hydrocarbon such as hexane, a gasoline cut, toluene, xylene, ester, ether, halogenated hydrocarbon or an alcohol such as methanol or ethanol. It is also possible to carry out the reaction without a solvent. The temperature is not critical and is mainly at −10 ° C. and about 15 ° C.
It is in the range between 0 ° C., for example between 0 ° C. and the boiling point of the solvent, for example in the range from 0 to 100 ° C. or 20 to 80 ° C.

Therefore, the present invention relates to the formula V (Wherein, R, R ₁ , R ₂ , R ₃ and R ₄ , R ₅ , R ₆
And R ₉ is as defined for formula I, R ₇
And R ₈ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 5 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, An electron withdrawing group; or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms substituted by a residue selected from a halogen atom; And both R ₂₀ and R ₂₁ represent either a hydrogen atom or a halogen atom. A process for the preparation of a compound of the formula (II), characterized by oxidizing the compound of the formula (II) and hydrogenating and / or halogenating the intermediate of the formula (I) obtained. Also about the method.

Processes for deriving the intermediates of the formula I before hydrogenation and / or halogenation into further structures of the formula I, for example processes of esterification, dimerization, trimerization or polymerization Or it is also possible to carry out the process described above in a manner in which the intermediate of the formula I is first hydrogenated and further derivatized, for example by esterification, dimerization, trimerization or polymerization. .

Formula V wherein R contains from 2 to 500 carbon atoms and, together with the carbon and nitrogen atoms to which the group is directly attached, the substituted 5,6
Or an organic bridging group forming a 7-membered cyclic structure;
₁ , R ₂ , R ₃ and R ₄ independently represent an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms, or R ₁ and R
₂ represents, together with the carbon atom to which the group is attached, a cycloalkyl group having 5 to 12 carbon atoms, or R ₃ and R ₄ together with the carbon atom to which the group is attached. Represents a cycloalkyl group having 5 to 12 carbon atoms; R ₅ , R ₆ and R ₉ independently of one another are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
An alkenyl group having 8 to 8 carbon atoms, an aryl group having 5 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an electron withdrawing group; or an alkyl group having 1 to 4 carbon atoms;
Represents an alkoxy group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms substituted by a residue selected from a halogen atom; R ₇ and R ₈ are a hydrogen atom,
An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 5 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, an electron withdrawing group; having 1 to atom 4 alkyl group, an alkoxy group having 1 to 4 carbon atoms, C 6 carbon atoms substituted by residues selected from halogen atoms or an aryl group of 12; and the R ₂₀ and R ₂₁ Both represent a hydrogen atom or a halogen atom. ) Is preferred. The most preferred products of the process of the invention are those of the formula III described further below.
c, IVa and Va.

In general, all products of the process according to the invention can be used as stabilizers for organic materials against the detrimental effects of light, oxygen and heat. Formula I,
Compounds represented by Ia, III, IV and V are particularly useful. The best results are of the formula III wherein R, R ₁ , R
₂ , R ₃ and R ₄ are as defined for formula I, and R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms. C 2 -C 8 alkenyl, C 5 -C 12 aryl, CN, COOR ₁₀ (R ₁₀ is as defined for formula I), or C 1 -C 8 And represents an aryl group having 6 to 12 carbon atoms substituted by a residue selected from an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Is achieved by the compound represented by the formula: The organic materials most effectively stabilized by the compounds of the present invention are the following organic polymeric materials, such as coatings and thermoplastic bulk polymers, films or fibers. The polymer is a pesticide such as sulfur atoms and / or
Or when in contact with pesticides containing halogen atoms,
The products of the process of the present invention achieve both stabilization against the harmful effects of light and pesticides. This is especially important for polymers used in agricultural applications, such as films, tapes or fibers, mainly for polyolefins such as PE or PP or polyolefin copolymers. Preferred compounds for this use are of the formula I
II, in particular those of the formula IIIc below.

An important utility for all of the products of the process of the present invention is the stabilization of paper and pulp, especially paper or pulp still containing lignin, against yellowing. It is possible to use the products of the invention as described, for example, in WO 98/04381 and the corresponding U.S. Ser. No. 09 / 119,567 and the publications cited therein. it can. Formula II
A monomer compound represented by I, for example, wherein R is an alkylene group having 3 to 12 carbon atoms or O, NH,
Represents a C 4 -C 12 alkylene group interrupted by OCO or NHCO, R ₁ to R ₄ represent a methyl or ethyl group, especially a methyl group, and R ₅
It is most preferred for this application that R to R ₉ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, especially a hydrogen atom; for example 1-propyloxy-2,2,6,6 6-Tetramethylpiperidine, 1-propyloxy-2,2,6,6-tetramethylpiperidin-4-one or the product of Example 4a of the invention (see below).

Furthermore, the products of the process according to the invention can be used effectively as flame retardants for organic polymers.
Thus, by using the products of the present invention, the organic polymer is stabilized against the detrimental effects of light, oxygen and heat, while the flammability of the polymer is effectively reduced.
The products of the present invention are described, for example, in WO 98/134.
No. 69 and corresponding U.S. Pat.
No. 104718 and the publications cited therein and EP 792911 or US Pat.
It can be used as described in 393812. Most preferably for this use, compounds of formula III or V, in particular R ₅ , R ₆ , R ₇ , R ₈ ,
The use of a compound represented by the following formula IIIc or V in which at least one of R ₉ , R ₂₀ or R ₂₁ is a halogen atom, particularly a bromine atom. The compound of the present invention alone or, for example, halogenated, phosphorus, bromine,
Silicon and antimony compounds, metal hydroxides,
It can be used as a flame retardant in combination with known flame retardants such as flame retardant compounds selected from metal hydrates and metal oxides or mixtures thereof.

Some of the compounds of formula III are
It has further been found that they are particularly well suited as stabilizers for organic materials against the detrimental effects of light, oxygen and heat.

Accordingly, the present invention provides:
Brittle organic polymers, and B) Formulas IIIa, IVa or Va[Wherein each of R ′ and R isE represents an organic crosslinking group represented by_TwoIs -CO- or-
(CH_Two)_p-(Wherein P is 0, 1 or 2)
E;₁Is the two residues R_{twenty four}And R_{twenty five}Carbon with
Represents an atom, or> NR _{twenty five}Represents or
Represents an oxygen atom, and R_{twenty four}And R_{twenty five}Is a hydrogen atom or
Represents an organic residue, and the crosslinking group R has a total of 2 to 500
Carbon atoms that contain carbon atoms and are directly
5, 6 or 7 substituted together with
R is characterized by forming a membered cyclic structure;₁, R_Two,
R_ThreeAnd R_FourAre independently of each other C 1 -C 8
An alkyl group or hydroxy having 1 to 5 carbon atoms
Represents an alkyl group, or R₁And R_TwoIs the group
5 carbon atoms with the carbon atoms attached
Represents 12 cycloalkyl groups or R_ThreeAnd
And R_FourTogether with the carbon atom to which the group is attached
Represents a cycloalkyl group having 5 to 12 atoms;
R_Five, R₆, R₇, R₈And R₉Is water independently of each other
An element atom, an alkyl group having 1 to 8 carbon atoms, a carbon atom
An alkenyl group having 2 to 8 carbon atoms, 5 to 12 carbon atoms
Aryl group, haloalkyl having 1 to 4 carbon atoms
A group, an electron withdrawing group; or an alkyl having 1 to 4 carbon atoms
Group, C1 -C4 alkoxy group, halogen
6 carbon atoms replaced by residues selected from atoms
From 12 to 12 aryl groups;₂₀And R_{twenty one}Is halo
Gen atom; and R_{twenty two}And R_{twenty three}Represents a hydrogen atom
Or together represent a chemical bond. ]
Also provided is a composition comprising at least one compound of the formula:

Usually, R ′ in the formula IIIa is a bridging group Wherein R ₂₄ and R ₂₅ together represent ＯO,
Or R ₂₄ represents a hydrogen atom, and R ₂₅ represents a hydrogen atom or a hydroxy group. ). R ′ contains 1 to 200 heteroatoms selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and a halogen atom;
Represents a C 7 -C 500 hydrocarbon group which, together with two of the carbon atoms and the nitrogen atom, forms a substituted 5- or 6-membered cyclic structure; and R ₁ , R ₂ , R
₃ and R ₄ are as defined above, of the formula IIIa
Is preferred.

The present invention further provides for the use of a compound of formula IIIa for stabilizing an organic polymer against decomposition by oxidation, heat or actinic radiation.
The invention likewise comprises a method for stabilizing an organic polymer against decomposition by heat, oxidation and / or actinic radiation, comprising adding at least one compound of the formula IIIa to the polymer.

The following categories (a ') to (i')
A more detailed example of a hindered amine is described. (A ') The following equation (1a)(Where n₁Is a number from 1 to 4, G and G₁Is
Each independently represents a hydrogen atom or a methyl group;₁₁Is
n-propoxy group, O-CH = C = CH_Two, O-CH =
CH-CH_ThreeOr halogenated n-propoxy groups, especially
represents an n-propoxy group or a bromide n-propoxy group,
And n₁If is 1, G₁₂Is one of a hydrogen atom and an oxygen atom
Not interrupted or interrupted by one or more
C 1 -C 18 alkyl, cyano
Tyl group, benzoyl group, glycidyl group; aliphatic, alicyclic
Aromatic, aromatic aliphatic, unsaturated or aromatic carboxylic acids,
Monovalent radicals or monovalent radicals of rubamic or phosphorus-containing acids
Ryl groups, preferably having 2 to 18 carbon atoms
Aliphatic carboxylic acid radicals having 7 to 15 carbon atoms
Alicyclic carboxylic acid groups, or 3 to 5 carbon atoms
Groups of α, β-unsaturated carboxylic acids having atoms, 7 to
Table showing aromatic carboxylic acid groups having 15 carbon atoms
And each carboxylic acid is -COOZ ₁₂One of the groups
Substituted with an aliphatic, alicyclic or aromatic moiety by 3
Where Z₁₂Is hydrogen atom, carbon atom number 1
To 20 alkyl groups, 3 to 12 carbon atoms
Lucenyl group, cycloalkyl having 5 to 7 carbon atoms
Group, phenyl group or benzyl group, n₁Place of 2
If G₁₂Is an alkenyl group having 2 to 12 carbon atoms,
Alkenylene group having 4 to 12 atoms, xylylene
Group; aliphatic, cycloaliphatic, aromatic aliphatic or aromatic dical
Divalent radicals of boric acid, dicarbamic acid or phosphorus-containing acids
Or a divalent silyl group, preferably 2 to 36 carbon atoms
Aliphatic dicarboxylic acid radicals having 8 to 14 atoms
Of an alicyclic or aromatic dicarboxylic acid having
Groups or aliphatic, aliphatic having 8 to 14 carbon atoms
Represents a group of a cyclic or aromatic dicarbamic acid,
Dicarboxylic acid is -COOZ₁₂By one or two of the radicals
Can be substituted with an aliphatic, alicyclic or aromatic moiety
Come, n₁Is 3, if G₁₂Is -COOZ₁₂Fat by group
Can be substituted with an aromatic, cycloaliphatic or aromatic moiety
Trivalent aliphatic, cycloaliphatic or aromatic tricarboxylic acids
Group, trivalent group of aromatic tricarbamic acid or phosphorus-containing
Represents a trivalent or trivalent silyl group of an acid;₁
If is 4, G₁₂Is an aliphatic, alicyclic or aromatic tetra
Represents a tetravalent group of carboxylic acid. ).

The above-mentioned carboxylic acid radicals in each case mean a radical of the formula (—CO) _x R, where x is as defined above and R has the meaning given by the definition given. Occurs. Alkyl groups with up to 20 carbon atoms are, for example, methyl, ethyl, n-propyl, n-
Butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- It is a tridecyl group, n-tetradecyl group, n-hexadecyl group or n-octadecyl group.

Examples of some groups of G ₁₂ are shown below. G
_{When 12} is a monovalent group of a carboxylic acid, it is, for example, an acetyl group, a caproyl group, a stearoyl group, an acryloyl group, a methacryloyl group, a benzoyl group or a β- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyl group. When G ₁₂ is a monovalent silyl group, it is represented, for example, by the formula — (C _j H _2j ) —Si (Z ′) ₂ Z ″, wherein j is an integer in the range of 2 to 5, and Z ′ And Z ″ independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)

When G ₁₂ is a divalent group of a dicarboxylic acid, it may be, for example, a malonyl group, a succinyl group, a glutaryl group, an adipoyl group, a suberoyl group, a sebacoil group, a maleoyl group, an itaconyl group, a phthaloyl group, a dibutylmalonyl group, Dibenzylmalonyl group, butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonyl group or bicycloheptenedicarbonyl group or the following formula Is a group represented by When G ₁₂ is a trivalent group of a tricarboxylic acid, it is, for example, a trimerlytoyl group, a citrile group or a nitrilotriacetyl group.

If G ₁₂ is a tetravalent radical of a tetracarboxylic acid, it is, for example, a tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or pyromerlitic acid. G ₁₂
When is a divalent group of dicarbamic acid, it is, for example, a hexamethylenedicarbamoyl group or a 2,4-toluylenedicarbamoyl group. G and G ₁ represent a hydrogen atom, G ₁₁ represents a hydrogen atom or a methyl group, n ₁ is 2, and G ₁₂ is a diacyl group of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms. Formula (Ia)
The compound represented by is preferred.

(B ') The following equation (1b)(Where G and G₁Are independently a hydrogen atom or
Represents a methyl group;₁₁Represents an n-propoxy group;₁₃
Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
Hydroxyalkyl group having 2 to 5 carbon atoms, carbon atom
A cycloalkyl group having 5 to 7 carbon atoms, 7 to 7 carbon atoms
8 aralkyl groups, C 1 -C 18 alka
A noyl group, an alkenoyl group having 3 to 5 carbon atoms,
Nzoyl group or the following formula (1b-1)Represented by the group represented by_TwoIs the number 1, 2 or 3
And n_TwoIf is 1, then G₁₄Is a hydrogen atom, carbon
C 1 -C 18 alkyl, C 3 -C 3
8 alkenyl groups, cycloalkyl having 5 to 7 carbon atoms
Kill group: hydrogen atom, cyano group, alkoxycarbonyl group
Or 1 carbon atom substituted by a carbamide group
4 alkyl group; glycidyl group, formula —CH_Two-CH
(OH) -Z or a group represented by the formula -CONH-Z
Wherein Z represents a hydrogen atom, a methyl group or a phenyl group.
And n_TwoIf is 2, then G₁₄Is 2 to 1 carbon atoms
2 alkylene groups, arylene having 6 to 12 carbon atoms
Group, xylylene group, -CH_Two-CH (OH) -CH _Two
Or a group of -CH_Two-CH (OH) -CH_Two-OD-
O represents a group of the formula: wherein D is an aralkyl having 2 to 10 carbon atoms.
A alkylene group, an arylene group having 6 to 15 carbon atoms,
Represents a cycloalkylene group having 6 to 12 carbon atoms,
Where G₁₃Is an alkanoyl group, an alkenoyl group or a ben
If it is not a zoyl group, G₁₄Is 1-oxo instead
-An alkylene group having 2 to 12 carbon atoms, aliphatic or fatty
Cyclic or aromatic dicarboxylic acids or dicarbamic acids
Or alternatively represents a -CO- group
Represents n_TwoIf is 3, then G₁₄IsRepresents a group represented by_TwoWhere is 1
If G₁₃And G₁₄Together are aliphatic, alicyclic or
Is a divalent aromatic 1,2- or 1,3-dicarboxylic acid
Can represent a group. ).

Some examples for the groups G ₁₃ , G ₁₄ and D are given below. All alkyl substituents are as defined for (a '). Any cycloalkyl substituent having 5 to 7 carbon atoms especially represents a cyclohexyl group. G ₁₃ as C 7 -C 8 aralkyl represents in particular phenylethyl or especially benzyl. G ₁₃ as C 2 -C 5 hydroxyalkyl is in particular 2-hydroxyethyl or 2
-A hydroxypropyl group.

G ₁₃ as alkanoyl having 1 to 18 carbon atoms is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, preferably an acetyl group, G ₁₃ as alkenoyl groups 3 to 5 carbon atoms atoms are especially acryloyl. G ₁₄ as an alkenyl group having 2 to 8 carbon atoms is, for example, an allyl group, a methallyl group, a 2-butenyl group, a 2-pentenyl group, a 2-hexenyl group or a 2-octenyl group.

G ₁₄ as hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted C 1 -C 4 alkyl is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonyl It may be a methyl group, a 2-ethoxycarbonylethyl group, a 2-aminocarbonylpropyl group or a 2- (dimethylaminocarbonyl) ethyl group. All of the alkylene groups having 2 to 12 carbon atoms are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene. All C 6 -C 15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4′-diphenylene.

C 6 -C 12 cycloalkylene is in particular cyclohexylene. G ₁₄ as 1-oxo-C 2 -C 12 alkylene is
Preferably the following formula Is a group represented by Preferred is a compound represented by the formula (1b), wherein n ₂ is 1 or 2, G and G ₁ represent a hydrogen atom, G ₁₃ represents a hydrogen atom, and has 1 carbon atom.
To 12 alkyl groups or the following formula: When n ₂ is 1, G ₁₄ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and when n ₂ is 2, G ₁₄ represents an alkylene group having 2 to 8 carbon atoms or 1-oxo- represents an alkylene group having 2 to 8 carbon atoms.

(C ') The following equation (1c) (Wherein n ₃ is the number 1 or 2, G, G ₁ and G
₁₁ is as defined in (b '), and n
_{When 3} is 1, G ₁₅ represents an alkylene group having 2 to 8 carbon atoms, a hydroxyalkylene group having 2 to 8 carbon atoms or an acyloxyalkylene group having 4 to 22 carbon atoms, and n ₃ represents 2 In this case, G ₁₅ is (—CH ₂ )
₂ C (CH ₂ -) represents a _second group. ).
G ₁₅ as a C 2-8 alkylene group or a C 2-8 hydroxyalkylene group is
For example, an ethylene group, a 1-methylethylene group, a propylene group, a 2-ethylpropylene group or a 2-ethyl-2-hydroxymethylpropylene group. G ₁₅ as an acyloxyalkylene group having 4 to 22 carbon atoms is, for example, a 2-ethyl-2-acetoxymethylpropylene group.

(D ') The following equations (1d-1) and (1d-2)
Or (1d-3) (Wherein n ₄ is the number 1 or 2, G, G ₁ and G
₁₁ is as defined in (b ′), and G ₁₆ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, a benzyl group, a glycidyl group or an alkoxyalkyl group having 2 to 6 carbon atoms. And n ₄ is 1
G ₁₇ is a hydrogen atom, a C 1 -C 12
An alkyl group, an alkenyl group having 3 to 5 carbon atoms,
C 7 -C 9 aralkyl, C 5
To 7 cycloalkyl group, a hydroxyalkyl group having 2 -C 4 alkoxyalkyl group 2 -C 6, an aryl group of 6 to 10 carbon atoms, a glycidyl group or the formula - (CH ₂₎ p- COO-Q
Or formula represents - (CH ₂₎ p-O-CO-Q, a group represented by, p in the formula is 1 or 2, Q is C 1 -C
And when n ₄ is 2, G ₁₇ represents 2 to 1 carbon atoms.
An alkylene group having 2 carbon atoms, an alkenylene group having 4 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, -C
_{H 2 -CH (OH) -CH 2} -O-D'-O-CH 2 -
CH (OH) —CH ₂ — (wherein D ′ represents an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, and a cycloalkylene group having 6 to 12 carbon atoms). Group or —CH ₂ CH (O
D ″) CH ₂ — (OCH ₂ —CH (OD ″) C
H ₂ ) ₂ — (wherein D ″ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an allyl group, a benzyl group, an alkanoyl group having 2 to 12 carbon atoms or a benzoyl group). T ₁ and T ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an unsubstituted or halogen or a carbon atom having 1 carbon atom;
To represent a C 6 alkyl substituted carbon atoms 4 to 10 an aryl group or an aralkyl group having 7 to 9 carbon atoms, alternatively T ₁ and T ₂ together with the carbon atoms to which they are attached carbon Forming a cycloalkane ring having 5 to 14 atoms; ). The compound represented by the formula (1d-3) is preferable.

Equations (1d-1), (1d-2) and (1d-1)
Some modifications of d-3) are shown below. All of the alkyl substituents having 1 to 12 carbon atoms are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl. , 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl. All C 1 -C 18 alkyl substituents are represented, for example, by the radicals mentioned above and in addition also represent, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. .

All C2 -C6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl. Tert-butoxyethyl, isopropoxyethyl or propoxypropyl. G ₁₇ as an alkenyl group having 3 to 5 carbon atoms is, for example, 1
-A propenyl group, an allyl group, a methallyl group, a 2-butenyl group or a 2-pentenyl group. G ₁₇ , T ₁ and T ₂ as C 7 -C 9 aralkyl are in particular phenethyl or especially benzyl. If T ₁ and T ₂ together at a carbon atom form a cycloalkane ring, it can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

G ₁₇ as C 2 -C 4 hydroxyalkyl is, for example, 2-hydroxyethyl,
A 2-hydroxypropyl group, a 2-hydroxybutyl group or a 4-hydroxybutyl group. G ₁₇ , T ₁ and T ₂ as an aryl group having 6 to 10 carbon atoms are:
Especially unsubstituted or halogen atom or carbon atom 1
Or a phenyl group or an α- or β-naphthyl group substituted by 4 alkyl groups. G ₁₇ as an alkylene group having 2 to 12 carbon atoms is, for example, an ethylene group, a propylene group, a 2,2-dimethylpropylene group,
It is a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group or a dodecamethylene group. G ₁₇ as an alkenylene group having 4 to 12 carbon atoms is
In particular, a 2-butenylene group, a 2-pentenylene group or 3-
It is a hexenylene group.

G ₁₇ as C 6 -C 12 arylene is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4′-diphenylene. D ″ as an alkanoyl group having 2 to 12 carbon atoms is, for example, a propionyl group, a butyryl group, an octanoyl group, a dodecanoyl group, and an acetyl group is preferable. D ′ as an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms or a cycloalkylene group having 6 to 12 carbon atoms
Has, for example, one of the definitions given for D in (b ′).

(E ') The following equation (1e) Wherein n ₅ is the number 1 or 2, and G ₁₈ is Or (Wherein G and G ₁₁ are as defined in (b ′), G ₁ and G ₂ represent a hydrogen atom, a methyl group or together a substituent 、 O, and E is —O— or — N
D '''- represents, A is an alkylene group of 6 to 2 -C - (CH _{2) 3} -O- and represents, X ₁ is the number 0
Or 1 and D ′ ″ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 5 carbon atoms, or a cycloalkyl group having 5 to 7 carbon atoms. Wherein G ₁₉ is the same as G ₁₈ , or —N (G ₂₁ ) (G ₂₂ ), —OG
_{23, -N (H) (CH} 2 OG 23) or -N (CH ₂ O
G ₂₃ ) represents one of the groups ( ₂ ), and when n is 1, G ₂₀ is G ₁₈
Or the same as G _19, and when n is 2, G ₂₀ is -E-D ^IV -E- (alkylene or -N of from D ^IV is 2 -C formula 8 (G ₂₁₎ - of G ₂₁ represents an alkylene group having 2 to 8 carbon atoms in which the chain is interrupted by one or two of the groups; and G ₂₁ represents an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group. A benzyl group or a hydroxyalkyl group having 1 to 4 carbon atoms or the following formula: Or G ₂₂ represents an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a benzyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, and G ₂₃ represents a hydrogen atom, a carbon atom Represents 1 to 12 alkyl or phenyl groups, or G ₂₁ and G ₂₂
Are taken together to form a C 4 -C 5 alkylene group or a C 4 -C 5 oxaalkylene group, for example —CH ₂ CH ₂ OCH ₂ CH ₂ — or of the formula —CH ₂ C
H ₂ N (G ₁₁ ) CH ₂ CH ₂ — represents a group. ] The compound represented by these.

Some variations on formula (Ie) are shown below. All C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n
-Butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl . All hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl. All C 5 -C 7 cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl groups are preferred. A as an alkylene group having 2 to 6 carbon atoms is, for example, an ethylene group, a propylene group, a 2,2-dimethylpropylene group, a tetramethylene group or a hexamethylene group. When G ₂₁ and G ₂₂ together are an alkylene or oxaalkylene group having 4 to 5 carbon atoms, for example, a tetramethylene group, a pentamethylene group or a 3-oxapentamethylene group.

Examples of polyalkylpiperidine compounds of this type are those represented by the following formula:

(F ') The following equation (1f) (Wherein G ₁₁ is as defined in (b ′)).

(G ′) oligomers or polymer compounds having a repeating structural unit containing a 2,2,6,6-tetraalkylpiperidine group, particularly polyesters, polyethers, polyamides, polyamines, polyurethanes,
Polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and copolymers thereof containing such groups. Examples of 2,2,6,6-polyalkylpiperidine compounds from this class are compounds of the formula: wherein m ₁ to m ₁₄ are numbers from 2 to about 200, preferably 2 To 100, for example 2 to 50, 2 to 40 or 3 to 40 or 4 to 10. Definitions of free valence saturated end groups in oligomeric or polymeric compounds are given below, depending on the method used to prepare the compounds. It is also possible to modify the terminal groups after the synthesis of the compound.

For example, the following equation (1g-1) Wherein the index n ranges from 1 to 15, especially 3
From 9 to 9; R ₁₂ has 2 to 1 carbon atoms
2 alkylene groups, alkenylene groups having 4 to 12 carbon atoms, cycloalkylene groups having 5 to 7 carbon atoms,
C5-C7 cycloalkylenedi (C1-C4alkylene) groups, C1-C4
An alkylenedi (cycloalkylene having 5 to 7 carbon atoms) group, a phenylene (alkylene having 1 to 4 carbon atoms) group, a 1,4-piperazinediyl group, -O
— Or> N—X _{1 wherein} X ₁ represents an acyl group having 1 to 12 carbon atoms or an (carbonyl having 1 to 12 carbon atoms) carbonyl group, or is given below except for a hydrogen atom Represents an alkylene group having 4 to 12 carbon atoms interrupted by one of the definitions of R ₁₄ ), or R ₁₂ has the formula (Ib ′) or (I
c ') Wherein m is 2 or 3, and X ₂ is a carbon atom having 1 to 18 carbon atoms, an unsubstituted or substituted by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms. An unsubstituted or substituted phenyl group substituted by one, two or three of an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; an unsubstituted or carbon atom Represents a phenylalkyl group having 7 to 9 carbon atoms which is substituted on the phenyl group by 1, 2 or 3 of the alkyl groups having 1 to 4 groups; and the radicals X ₃ independently of one another have 2 to 12 carbon atoms. of a group represented by) represents an alkylene group;. group B independently of one another are Cl, -OR _13,
—N (R ₁₄ ) (R ₁₅ ) or the following formula (IIId) R ₁₃ , R ₁₄ and R ₁₅ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; one of an unsubstituted or an alkyl group having 1 to 4 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms substituted by 2 or 3 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; an unsubstituted or an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms A phenyl group substituted by 1, 2 or 3 alkoxy groups; unsubstituted or 7 to 9 carbon atoms substituted on the phenyl group by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms A phenylalkyl group; a tetrahydrofurfuryl group, or —O at the 2, 3 or 4 position
H, an alkoxy group having 1 to 8 carbon atoms, a di (alkyl having 1 to 4 carbon atoms) amino group or the following formula (I
e ') (Wherein Y represents —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ), and represents an alkyl group having 2 to 4 carbon atoms substituted by a group represented by the formula: Or —N (R ₁₄ ) (R ₁₅ ) additionally represents a group of formula (Ie ′); X represents —O— or> N—R ₁₆ ;
₁₆ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
An alkenyl group having 3 to 18 carbon atoms, an unsubstituted or an alkyl group having 1 to 4 carbon atoms, 1, 2 or 3
C 5 -C 12 cycloalkyl substituted by C; C 7 -C 9 cycloalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 of C 1 -C 4 alkyl; Phenylalkyl group; tetrahydrofurfuryl group, the following formula (IIIf) Or -OH at the 2, 3 or 4 position, an alkoxy group having 1 to 8 carbon atoms, di (1 carbon atom
To represent from 2 carbon atoms substituted by a group represented by 4 alkyl) amino group or the formula (Ie ') 4 alkyl; R ₁₁ has one of the definitions given for R _16. ] It is a compound represented by these.

In these compounds, the terminal group bonded to the triazine residue is, for example, a group B or —N (R ₁₁ ) —
R ₁₂ -B, for example, a chlorine atom or The terminal group bonded to the diamino group may be, for example, a hydrogen atom or a di-B-substituted triazinyl group, for example, Or And a group represented by

It is convenient to replace the chlorine atom attached to the triazine residue with, for example, an —OH or amino group. In Suitable amino groups representative: pyrrolidin-1-yl group, morpholino group, -NH _2, -N (alkyl C 1 -C 8) ₂ and -NY '(alkyl of C 1 -C 8) (Wherein Y ′ is a hydrogen atom or the following formula: Represents a group represented by ).

In the oligomer and polymer compounds shown above, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, n-hexyl group, 1-methylhexyl group, n-heptyl group, isoheptyl group, 1,1, 3,3-tetramethylbutyl group, 1-
Methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, nonyl group, decyl group, undecyl Group, 1-methylundecyl group, dodecyl group, 1,1,3,3,5,5-hexamethylhexyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, eicosyl group and Examples of cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups; examples of 7 to 9 phenylalkyl groups are benzyl groups; and examples of alkylene groups are Ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group 2,2-dimethyl-trimethylene group, hexamethylene group, trimethyl hexamethylene group, octamethylene and decamethylene.

(H ') The following equation (1h) Wherein n ₆ is a number of 1 or 2, G and G ₁₁ are as defined in (a ′), and G ₁₄ is as defined in (b ′). The compound represented.

(I ') The following equation (1i) Wherein the groups G ₃₉ are independently of the following formula (1i-1) Wherein G ₄₀ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, G ₄₁ represents an alkylene group having 2 to 12 carbon atoms, and G ₄₂ represents hydrogen. Atom, alkyl group having 1 to 8 carbon atoms, -O., -CH ₂ CN, alkenyl group having 3 to 6 carbon atoms, phenylalkyl group having 7 to 9 carbon atoms; alkyl having 1 to 4 carbon atoms A phenylalkyl group having 7 to 9 carbon atoms, which is substituted on the phenyl group by a group; or an acyl group having 1 to 8 carbon atoms). ] The compound represented by these.

The alkyl group is, for example, an alkyl group having 1 to 4 carbon atoms, especially a methyl group, an ethyl group, a propyl group or a butyl group. The cycloalkyl group is preferably a cyclohexyl group. The alkylene group is, for example, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a 2,2-dimethyltrimethylene group or a hexamethylene group. An alkenyl group is preferably an allyl group. The phenylalkyl group is preferably a benzyl group. The acyl group is preferably an acetyl group.

The following formula IIIb (Wherein groups A are independently of one another —OR ₁₃ , —N (R ₁₄ )
(R ₁₅ ) or the following formula (IIId) X represents —O— or> N—R ₁₆ ; R ₁₆ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, unsubstituted Or a cycloalkyl group having 5 to 12 carbon atoms substituted by 1, 2 or 3 of an alkyl group having 1 to 4 carbon atoms; 1, 2 or 3 of an unsubstituted or an alkyl group having 1 to 4 carbon atoms A phenylalkyl group having 7 to 9 carbon atoms, which is substituted on the phenyl group by a tetrahydrofurfuryl group; Or —OH, an alkoxy group having 1 to 8 carbon atoms, a di (alkyl having 1 to 4 carbon atoms) amino group or a formula (I)
2 to carbon atoms substituted by a group represented by e ') represents a 4 alkyl; R ₁₁ has one of the definitions given for R _16; and the group B are, independently of one another A Has one of the definitions given with respect to; where the formula (I
e ′) and all other symbols are as defined above for formula Ia. The compound represented by the formula (1) is particularly preferred. The groups B, R ₁₁ and R ₁₂ in the individual repeating units
May be the same or different within the meaning given.

(J ') The following equation (2a) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a C 1-8 alkyl group or a C 1
Represents 5 to 5 hydroxyalkyl groups;
₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ are the same as the carbon atom to which the group is attached. Together they represent a cycloalkyl group having 5 to 12 carbon atoms. ).

Specific examples of the hydrogenation products of the present invention include the following compounds: 1-propoxy-2,2,6,6-tetramethyl-4-piperidone, 1-propoxy-2,2,
6,6-tetramethyl-4-piperidol, bis (1-
Propoxy-2,2,6,6-tetramethyl-4-piperidyl)-(3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) butylmalonate, bis (1-propoxy-2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, bis (1-propoxy-2,2,6,
6-tetramethyl-4-piperidyl) succinate N,
N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine, N-butyl-1-propoxy-2,2,6,6-tetramethyl -4-piperidinamine, 5- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -2-cyclo-undecyloxazole, 1,6-
Hexanediyl-N, N'-bis (1-propoxy-
2,2,6,6-tetramethyl-4-piperidyl-formamide), 1,5-dioxaspiro (5,5) undecane-3,3-dicarboxylic acid bis (1-propoxy-
2,2,6,6-tetramethyl-4-piperidyl) ester, 1,5,8,12-tetrakis (2 ′, 4′-bis (1 ″ -propoxy-2 ″, 2 ″, 6) '' 、
6 "-tetramethyl-4" -piperidyl (butyl)
Amino) -1 ′, 3 ′, 5′-triazin-6′-yl) 1,5,8,12-tetraazadodecane, 1,3
5-tris (N-cyclohexyl-N- (1-propoxy-2,2,6,6-tetramethylpiperazin-3-one-4-yl) amino) -s-triazine,

N, N'-bis (1-propoxy-2,
2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6
Linear or cyclic condensate of dichloro-1,3,5-triazine, tris (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (1-propoxy-2) , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 ′-(1,2-ethanediyl) -bis- (4-propoxy-3) , 3,5
5-tetramethylpiperazinone), 4-benzoyl-1
-Propoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-1-propoxy-2,2,2
6,6-tetramethylpiperidine, 3-n-octyl-
8-propoxy-7,7,9,9-tetramethyl-1,
3,8-Triazaspiro [4.5] decane-2,4-dione, N, N′-bis (1-propoxy-2,2,6,
6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,
Linear or cyclic condensate of 3,5-triazine, 2-chloro-4,6-bis- (4-n-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidyl)-
Condensate of 1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-propoxy-
3-dodecyl-7,7,9,9-tetramethyl-1,
3,8-Triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (1-propoxy-2,2,
6,6-tetramethyl-4-piperidyl) pyrrolidine-
2,5-dione,

A mixture of 4-hexadecyloxy- and 4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (1-propoxy-2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and the condensation product of 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5
N- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) condensation product of -triazine and 4-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidine -N-dodecylsuccinimide, 2-undecyl-8-propoxy-7,7,9,9
-Tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 8-propoxy-7,
7,9,9-tetramethyl-2-cycloundecyl-1
-Oxa-3,8-diaza-4-oxospiro [4,
5] reaction products of decane and epichlorohydrin,
N, N'-bis-formyl-N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, poly [methyl-propyl-3-oxy-4 -(1-propoxy-2,2,6,6
-Tetramethyl-4-piperidyl)] a reaction product of siloxane, maleic anhydride-α-olefin copolymer and 1-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine; or (Where R is It is represented by ).

In order to stabilize organic materials against the detrimental effects of light, oxygen and / or heat, in particular to stabilize synthetic organic polymers or compositions containing them, the compounds of the formulas I, III and V, In particular, the compounds represented by IIIa and IIIb can be effectively used. They are notable for high thermal stability, substrate compatibility and good durability in the substrate.

Examples of polymers which can be stabilized by this method are as follows. 1. Mono- and di-olefin polymers such as 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 be crosslinked as desired), such as high density polyethylene (HDPE), High density and high molecular weight polyethylene (HDPE-HMW),
High density and ultra high molecular weight polyethylene (HDPE-UH
MW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LL
DPE), (VLDPE) and (ULDPE). Polyolefins, ie polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be produced by various methods and in particular by the following methods.

A) Radical polymerization (usually under high pressure and high temperature). b) Usually IVb, Vb, VIb or VII of the periodic table
Catalytic polymerization using a catalyst containing one or more of the Group I metal atoms. These metal atoms are usually one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls which can be co-ordinated, typically π- or σ-. Having. These metal complexes can be fixed in free form or typically on a substrate such as 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 on their own in the polymerization, or typically a metal alkyl,
Further activators such as metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxane can be used, the metal atoms being elements of group Ia, IIa and / or IIIa of the periodic table. Activators can be conveniently modified with additional ester, ether, amine or silyl ether groups.
These catalyst systems are usually based on Phillips.
s), Standard Oil Indiana (Stan
darOil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts
t) named (SSC).

2.1) Mixtures of the above-mentioned polymers, such as mixtures of polypropylene and polyisobutylene, polypropylene and polyethylene (eg PP / HD)
PE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / bute-1- Ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer,
Ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, ethylene / vinyl acetate copolymer and copolymers thereof with carbon monoxide or ethylene / Acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene, and mixtures of such copolymers with one another and with the polymers mentioned above under 1) For example, polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer ( VA), LDPE / ethylene - acrylic acid copolymer (EAA), LLDPE / EVA, L
LDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.

4. Hydrocarbon resins (eg, having 5 to 9 carbon atoms), including their hydrogenated modifications (eg, tackifiers), and mixtures of polyalkylenes and starch. 5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). 6. Copolymers of styrene or α-methylstyrene with a diene or acrylic derivative, such as styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / Acrylonitrile / methyl acrylate, styrene copolymers and other polymers such as polyacrylates, high impact strength mixtures of diene polymers or ethylene / propylene / diene terpolymers, and styrene / butadiene / styrene, styrene / isoprene / styrene,
Block copolymers of styrene, such as styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as styrene, polybutadiene-styrene or polybutadiene-
Styrene and acrylonitrile (or methacrylonitrile) for acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) for polybutadiene, styrene and acrylonitrile and methyl methacrylate for polybutadiene, styrene and maleic anhydride for polybutadiene, styrene for polybutadiene, styrene and acrylonitrile and maleic anhydride or maleimide for polybutadiene and maleimide and polybutadiene. Styrene and alkyl acrylate or methacrylate for polybutadiene, styrene and acrylonitrile for ethylene / propylene / diene terpolymer,
Styrene and acrylonitrile for polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile for acrylate / butadiene copolymers and their mixtures with 6) the copolymers listed below, for example known as ABS, MBS, ASA or AES polymers Copolymer mixture.

8. Halogen containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and Copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers, such as vinyl chloride / vinylidene chloride, vinyl / vinyl acetate or vinylidene chloride / vinyl acetate. Copolymer. 9. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, impact-modified polymethyl methacrylate, polyacrylamide and polyacrylonitrile with butyl acrylate. 10.9) Copolymers of the monomers mentioned below with one another or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylates / Butadiene terpolymer.

11. Polymers or acyl derivatives derived from unsaturated alcohols and amines or their acetal, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine,
And their copolymers with the olefins mentioned above under 1). 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14． Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, and precursors thereof. 16. Polyamides and copolyamides derived from diamines and dicarboxylic and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6
/ 12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamide starting from m-xylenediamine and adipic acid, hexamethylenediamine and isophthalic acid or / and terephthalic acid, using elastomers as modifiers Or without polyamides, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide, and also with the abovementioned polyamides and polyolefins, olefin copolymers, ionomers or chemical bonds or grafts Block copolymers with modified elastomers or polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, and EPDM
Or polyamides or copolyamides modified with ABS and polyamides condensed during processing (RIM polyamide system). 17． Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,
Block copolyetheresters derived from 4-dimethylolcyclohexane terephthalate and polyhydroxybenzoate, and polyethers terminated with hydroxyl end groups, and also polyesters modified with polycarbonate or MBS. 19. Polycarbonate and polyester carbonate. 20. Polysulfone, polyethersulfone and polyetherketone. 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Dry and non-dry alkyd resins. 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinkers, and also low-flammability halogen-containing modifications thereof. 24. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates. 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example the products of diglycidyl ethers of bisphenol A and bisphenol F, which are customary, such as anhydrides or amines Crosslinked with or without curing agents and accelerators. 27. Blends (polyblends) of the above mentioned polymers, for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC
/ MBS, PC / ABS, PBTP / ABS, PC / A
SA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PU
R, POM / acrylate, POM / MBS, PPO /
HIPS, PPO / PA6.6 and copolymer, PA
/ HDPE, PA / PP, PA / PPO, PBT / PC
/ ABS or PBT / PET / PC.

Use of the compounds of the formula IIIa as stabilizers in synthetic organic polymers, such as coatings or bulk polymers or articles formed therefrom, in particular in thermoplastic polymers and corresponding compositions, and in coating compositions. Especially interesting to do. The most important thermoplastic polymers in the compositions of the present invention are polyolefins and their copolymers, such as those described in items 1-3 above, thermoplastic polyolefins (TPO), thermoplastic polyurethanes (TP
U), thermoplastic rubber (TPR), polycarbonate, such as those described in item 19 above, and blends, such as those described in item 28 above. Most important are polyethylene (PE), polypropylene (PP): polycarbonate (PC) and polycarbonate blends, such as PC / ABS blends, and in acid or metal catalyst coating compositions.

In general, 0.1 to 10% (based on the material to be stabilized), preferably 0.01 to 5%
%, Especially from 0.01 to 2%, is added to the material to be stabilized. Especially 0.05 to 1.
It is preferred to use the novel compounds in an amount of 5%, especially 0.1 to 0.5%. When the compounds of the present invention are used as flame retardants, the amount added is usually high, for example stabilized,
And 0.1 for organic materials protected against combustion
To 25% by weight, mainly 0.1 to 10% by weight.

The hybridization to the material can be carried out by methods customary in the art, for example by mixing or applying the compounds of the formulas I, IIIa, IV, V and, if desired, further additives. It is possible. If a polymer, especially a synthetic polymer, is involved, the hybridization can be carried out by using a compound dissolved or dispersed in the polymer before or during the molding operation or with or without subsequent solvent removal. For elastomers,
It can be stabilized as latex. Furthermore, as regards the incorporation of the compounds of the formula IIIa into the polymers, it is also possible to add them before, during or immediately after the polymerization of the corresponding monomers or before crosslinking. In this connection, the compounds of the formula IIIa can be added as such or in encapsulated form (for example, encapsulated in waxes, oils or polymers). When added before or during the polymerization, the compounds of formula IIIa can also act as polymer chain length regulators (chain ends).

The compounds of the formula IIIa can also be added, for example, in the form of masterbatches containing the compounds in a concentration of 2.5 to 25% by weight, based on the polymer to be stabilized.

The compound represented by the formula IIIa can be appropriately mixed by the following method. • As an emulsion or dispersion (eg, latex or emulsified polymer) • As a dry mixture during mixing of additional components or polymer mixtures • Direct introduction into processing equipment (eg, extruders, internal mixers, etc.)・ As solution or melt

The use of the novel polymer compositions in various forms, for example for producing films, fibers, tapes, molding materials, profiles, or as coating materials, adhesives or putty binders, and / or Can be processed to produce a product.

In addition to the compounds of the formula IIIa, the novel compositions may comprise, as additional component C, one or more of the customary additives, for example: 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- (α-methylcyclohexyl) -4,6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-
4-methoxymethylphenol, nonylphenol which is linear or branched in the side chain, for example, 2,6-
Di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol , 2,4-dimethyl-6-
(1′-Methyltridec-1′-yl) phenol and mixtures thereof. 1.2. Alkylthiomethylphenol , for example, 2,
4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- Nonylphenol.

1.3. Hydroquinone and alkylated arsenic
Droquinones , for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert- amylhydroquinone , 2,6-di-phenyl-4 Octadecyloxyphenol, 2,
6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-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 α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E). 1.5. Hydroxylated thiodiphenyl ethers such as 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), 4,4'-thiobis (3,6-di-secondary amylphenol), 4,4'-bis (2 , 6-Dimethyl-4-hydroxyphenyl) disulfide.

[0087] 1.6. Alkylidenebisphenol , for example, 2,2'-methylenebis (6-tert-butyl-4-
Methylphenol), 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′- Methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol), 2,
2′-methylenebis (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- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α
-Dimethylbenzyl) -4-nonylphenol], 4,
4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-
Methylphenol), 1,1-bis (5-tert-butyl-
4-hydroxy-2-methylphenyl) butane, 2,6
-Bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, , 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxy) Phenyl) butyrate], bis (3-tert-butyl-4-hydroxy-
5-methylphenyl) dicyclopentadiene, bis [2
-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl]
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-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-
(Hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzylation
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-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ) Dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate. 1.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5). -Methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3
3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate.

1.9. Aromatic hydroxybenzyl compound
Object, for example, 1,3,5-tris (3,5-di - tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di - Part Tributyl-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 (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4, 6-bis (3,5-
Di-tert-butyl-4-hydroxyanilino) -1,3,3
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-dimethylbenzyl) 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, 1,3,5-tris (3,5-dicyclohexyl) -4-Hydroxybenzyl) isocyanurate.

1.11. Benzyl phosphonates , such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di- Tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate,
Calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. Acylaminophenols , for example, 4-hydroxylauric anilide, 4-hydroxystearic anilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13. β- (3,5-di-tert-butyl
The following monovalent of -4-hydroxyphenyl) propionic acid
Or esters with polyhydric alcohols , examples of alcohols, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol,
Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 1.14. β- (5-tert-butyl-4-hydroxy-3
-Methylphenyl) propionic acid
Esters with polyhydric alcohols , examples of alcohols, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15. β- (3,5-dicyclohexyl
L-4-hydroxyphenyl) propionic acid
Esters with polyhydric or polyhydric alcohols , examples of alcohols,
Methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,
Pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl)
Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-
2,6,7-trioxabicyclo [2.2.2] octane. 1.16.3 3,5-Di-tert-butyl-4-hydroxyp
Phenylacetic acid with the following monohydric or polyhydric alcohol
Ter , alcohol examples, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol,
Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. β- (3,5-di-tert-butyl
Amides of -4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di-tert-butyl-4-
(Hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-
(Hydroxyphenylpropionyl) trimethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N '
-Bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard XL-1 (Naugar registered trademark supplied by Uniroyal)
d XL-1)). 1.18. Ascorbic acid (vitamin C) .

1.19. Amine antioxidants , for example,
N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p
-Phenylenediamine, N, N'-bis (1-ethyl-
3-methylpentyl) -p-phenylenediamine, N,
N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl ) -P-Phenylenediamine, N-isopropyl-N′-phenyl-p-
Phenylenediamine, N- (1,3-dimethylbutyl)
-N'-phenyl-p-phenylenediamine, N- (1
-Methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-
Phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N '
-Di-secondary butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamine such as p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino Phenol, 4-octadecanoylaminophenol, bis (4
-Methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetra Methyl-4,
4'-diaminodiphenylmethane, 1,2-bis [(2
-Methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide,
Bis [4- (1 ′, 3′-dimethylbutyl) phenyl]
Amines, tertiary octylated N-phenyl-1-naphthylamine, mixtures of mono- and dialkylated tertiary butyl / tertiary octyl diphenylamines, mixtures of mono- and dialkylated nonyl diphenylamines, mixtures of mono- and dialkylated dodecyl diphenylamines, Mono
And mixtures of dialkylated isopropyl / isohexyldiphenylamine, mixtures of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-
3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono- and dialkylated tert-butyl /
A mixture of tertiary octylphenothiazines, a mixture of mono- and dialkylated tertiary octylphenothiazines, N-
Allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperidi-4-yl) hexa Methylenediamine, bis (2,2,6,6-
Tetramethylpiperidi-4-yl) sebacate, 2,
2,6,6-tetramethylpiperidino-4-one, 2,
2,6,6-tetramethylpiperidino-4-ol.

[0095] 2. UV absorber and light stabilizer 2.1.2- (2'-hydroxyphenyl) benzotri
Azoles such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (3 ′, 5 ′)
-Di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1 , 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'
-Di-tert-butyl-2'-hydroxyphenyl) -5
Chloro-benzotriazole, 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 (α, α-
Dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole,
-(3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2-
(3′-tert-butyl-2′-hydroxy-5 ′-(2-
Methoxycarbonylethyl) 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'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-
2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl)
Phenyl) benzotriazole, 2,2′-methylene-
Bis [4- (1,1,3,3-tetramethylbutyl)-
6-benzotriazol-2-ylphenol], 2-
[3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H- transesterification products of benzotriazole with polyethylene glycol 300, the formula [R-CH ₂ CH ₂ -COOCH
₂ CH _2- ] _2-wherein R is 3′-tert-butyl-4 ′
-Hydroxy-5'-2H-benzotriazol-2-ylphenyl group. 2- [2′-
Hydroxy-3 ′-(α, α-dimethylbenzyl)-
5 '-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-
3 ′-(1,1,3,3-tetramethylbutyl) -5 ′
-(Α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2.2-Hydroxybenzophenone ,
For example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-
Benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. 2.3. Esters of substituted and unsubstituted benzoic acids such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol , 2,
4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5
Di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl-3,5-di- Tertiary butyl-4-hydroxybenzoate.

2.4. Acrylates , for example ethyl-
α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, butyl -Α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-
(Cyanovinyl) -2-methylindoline. 2.5. A nickel compound , for example, a nickel complex of 2,2′-thio-bis [4- (1,1,3,3-tetramethylbutyl) phenol], for example a 1: 1 or 1: 2 complex, wherein n- With or without additional ligands such as butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3,5-
Monoalkyl esters of di-tert-butylbenzylphosphonic acid, for example nickel salts of methyl or ethyl esters, for example nickel complexes of ketoxime such as 2-hydroxy-4-methylphenylundecylketoxime, 1
Nickel complexes of phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-)
Piperidyl) succinate, bis (1,2,2,6,6)
-Pentamethyl-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, 1- (2-hydroxyethyl) -2,2,
The condensation product of 6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N′-bis (2,2,
Linear or cyclic condensation products of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2 , 6,6-tetramethyl-4-
Piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butane-tetracarboxylate,
1,1 ′-(1,2-ethanediyl) bis (3,3
5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2 2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5
-Di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1 -Octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-
2,2,6,6-tetramethylpiperidyl) succinate, N, N′-bis (2,2,6,6-tetramethyl-
Linear or cyclic condensation products of 4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis (4-n-butyl Amino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,
Condensation product of 2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-
Condensation product of 1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,
3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione,
3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione,
-Hexadecyloxy- and 4-stearyloxy-
A mixture of 2,2,6,6-tetramethylpiperidine,
N, N'-bis (2,2,6,6-tetramethyl-4-
Condensation products of piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro -1,
3,5-triazine and 4-butylamino-2,2,
Condensation product of 6,6-tetramethylpiperidine (CAS
Reg. No. [136504-96-6]), 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-oxospiro [4.5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza- The reaction product of 4-oxospiro [4.5] decane and epichlorohydrin, 1,1-bis (1,2,2
2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethane, N,
N'-bis-formyl-N, N'-bis (2,2,6
6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethylene-malonic acid and 1,2,2
Diester with 2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-
4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1, Reaction product with 2,2,6,6-pentamethyl-4-aminopiperidine.

[0099] 2.7. Oxamides , for example, 4,4'-
Dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5 ′
-Di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylamino Propyl) oxamide, 2-ethoxy-5
-Tert-butyl-2'-ethoxanilide and 2-
Mixtures with ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and o- and p-ethoxy-
Mixtures of disubstituted oxanilides.

2.8.2- (2-hydroxyphenyl)
-1,3,5-triazine , 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-dimethyl Phenyl) -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-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- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -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-ethylhexyl-
1-oxy) -2-hydroxypropyloxy] phenyl {-4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine.

3. Metal quencher , for example, N, N'-diphenyloxamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5- Di-tert-butyl-4-
(Hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N′-diacetyladipoyl Dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

[0102] 4. Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris ( 2,
4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2
4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
Diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2
4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite,
6-isooctyloxy-2,4,8,10-tetra-
Tert-Butyl-12H-dibenz [d, g] -1,3,2
-Dioxaphosphosine, 6-fluoro-2,4,8,1
0-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite , Bis (2,4-di-tert-butyl-6-
Methylphenyl) ethyl phosphite, 2,2 ′,
2 ″ -Nitrilo [triethyl tris (3, 3 ′, 5,
5'-tetra-tert-butyl-1,1'-biphenyl-
2,2′-diyl) phosphite], 2-ethylhexyl (3,3 ′, 5,5′-tetra-tert-butyl-1,1
1'-biphenyl-2,2'-diyl) phosphite.

Particularly preferred are the following phosphites. Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168: Ciba)
Geiba (Ciba-Geigy), tris (nonylphenyl) phosphite.

[0104] 5. Hydroxylamine , eg, N, N
-Dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N
-Ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, hydrogenated tallowamine N, N-dialkylhydroxylamine derived from 6. Nitrones , for example, N-benzyl-α-phenyl-
Nitrone, N-ethyl-α-methyl-nitrone, N-octyl-α-heptyl-nitrone, N-lauryl-α-
Undecyl-nitrone, N-tetradecyl-α-tridecyl-nitrone, N-hexadecyl-α-pentadecyl-nitrone, N-octadecyl-α-heptadecyl-nitrone, N-hexadecyl-α-heptadecyl-nitrone, N-octadecyl-α- Pentadecyl-nitrone,
N-heptadecyl-α-heptadecyl-nitrone, N-
Octadecyl-α-hexadecyl-nitrone, a nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallowamine.

[0105] 7. Thio-synergists such as dilauryl thiodipropionate or distearyl thiodipropionate. 8. Peroxide scavengers , for example esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide , Pentaerythritol tetrakis (β-
Dodecyl mercapto) propionate. 9. Polyamide stabilizers , for example copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

10. Basic co-stabilizers , such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, such as calcium stearate, Zinc stearate, magnesium behenate, magnesium stearate, sodium ricinolate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. 11. Nucleating agents , for example inorganic materials such as talc, metal oxides such as titanium dioxide, magnesium oxide, phosphates, carbonates or sulphates, preferably of alkaline earth metals, such as mono- or polycarboxylic acids Organic compounds and their salts, for example, polymeric compounds such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, ionic copolymers ("ionomers").

12. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural products Powder or fiber, synthetic fiber. 13. Other additives , such as plasticizers, lubricants, emulsifiers, pigments, flow additives, catalysts, flow regulators, optical brighteners, flame retardants, antistatics and foaming agents.

[0108] 14. Benzofuranone and indolino
Down, for example, U.S. Patent No. 4325863, U.S. Patent No. 4338244, U.S. Patent No. 51,753
12, US Pat. No. 5,216,052, US Pat. No. 5,252,643, German Patent 431.
No. 6611, German Patent No. 4,316,622, German Patent No. 4,316,876, European Patent No. 0 589 839 or European Patent No. 05911.
No. 02 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-
On], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert- Butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-
Tert-butyl-benzofuran-2-one, 3- (3,4-
Dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl)-
5,7-ditert-butyl-benzofuran-2-one.

In an amount of 0.1 to 10% by weight, for example 0.2 to 5% by weight, based on the material to be stabilized,
Conventional additives are used reasonably.

The optional co-stabilizer added to the stabilizer mixture according to the invention is preferably a further light stabilizer, for example 2-
Hydroxyphenyl-benzotriazole, 2-hydroxyphenyl-triazole, benzophenone or those of oxalanilides, for example EP 45339
6, EP 434608, U.S. Pat. No. 5,298,067, WO 94/18278.
And British Patent No. 2297091 and W
O 96/28431, and / or (Wherein, G represents a hydrogen atom or a methyl group, particularly a hydrogen atom).
Further tetrahindered amines derived from 6,6-tetraalkylpiperidines and examples of tetraalkylpiperidine derivatives which can be used as co-stabilizers for the mixtures according to the invention are described in EP 356677, It is described on pages 3 to 17, paragraphs a) to f). The preceding document is considered to be part of the present description.

It is likewise particularly interesting to use the novel mixtures containing the compounds of the formula IIIa as stabilizers for coatings, for example paints. Accordingly, the present invention also relates to those compositions wherein component (A) is a film-forming binder for the coating. The novel coating composition is preferably 0.01 to 10 parts by weight of (B), in particular 0.05 to 10 parts by weight of (B), especially 0.1 to 100 parts by weight of solid binder (A). To 5 parts by weight of (B). If the concentration of the novel stabilizer (component (B)) can be relatively high in the outer layer, for example 1 to 15 parts by weight of (B), in particular 3 to 15 parts by weight, per 100 parts by weight of solid binder (A) 10
If it is possible to use parts by weight of (B), here also systems with multiple layers are possible.

The use of novel stabilizers in coatings has the added advantage of preventing delamination, ie, peeling of the coating from the substrate. This advantage is particularly important for metallic substrates that include a system of composite layers on a metallic substrate. In principle, the binder (component (A)) can be any industrially customary binder, for example Ullmann's
s Encyclopedia of Industrial Chemistry, 5th edition, A
18, 368-426, VCH, Weinheim 1991
As described in. Generally, it is a film-forming binder based on a thermoplastic or thermosetting resin, especially a thermosetting resin. Examples are alkyd, acrylic, polyester, polyphenol, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) may be used at room temperature—curable or high temperature—
It can be curable; adding a curing catalyst is effective. Suitable catalysts for accelerating the curing of the binder are, for example, Ullmann's Encyclopedia of Industrial C
hemistry, A18, 469, VCH, Verlagsgesell
schaft, Weinheim 1991. Component (A)
Is a binder composition comprising a functional acrylate resin and a crosslinking agent.

Examples of coating compositions containing a specific binder are shown below. 1. 1. Paints based on cold- or hot-crosslinked alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of these resins, optionally with curing catalysts; 2. two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 3. one-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which have been deblocked during calcination, optionally with the addition of a melamine resin; One-component polyurethane paints based on trisalkoxycarbonyltriazine crosslinkers and hydroxyl-containing resins, such as acrylate, polyester or polyether resins;

[0115] 5. 5. one-component polyurethane paints based on aliphatic or aromatic urethane acrylates or polyurethane acrylates with free amino groups in the urethane structure, optionally with a curing catalyst, and melamine resins or polyether resins; 6. two-component paints based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 7. two-component paints based on (poly) ketimines and unsaturated acrylate resins or polyacetoacetate resins or methacrylamide glycolate methyl ester; Two-component paints based on carboxyl- or amino-containing polyacrylates and polyepoxides;

9. 9. two-component paints based on acrylate resins containing anhydrido groups and a polyhydroxy or polyamino component; 10. two-component paints based on acrylate-containing anhydrides and polyepoxides; 11. two-component paints based on acrylate resins containing (poly) oxazoline and anhydride groups, or on unsaturated acrylate resins, or on aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 12. two-component paints based on unsaturated polyacrylates and polymalonates; 13. thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinked acrylate resins in combination with etherified melamine resins; Paint systems based on siloxane-modified or fluorin-modified acrylate resins

In addition to components (a) and (B), the coating composition of the present invention preferably comprises as component (C) a sterically hindered amine type, 2 (2-hydroxyphenyl)-
Light stabilizers of the 1,3,5-triazine and / or 2-hydroxyphenyl-2H-benzotriazole type include, for example, those mentioned above in items 2.1, 2.6 and 2.8 in the list above. 2- (2) which is advantageously added
Further examples of light stabilizers of the type (-hydroxyphenyl) -1,3,5-triazine are described in the published U.S. Pat.
No. 56, EP 434608, U.S. Pat. No. 5,198,498, U.S. Pat.
No. 68, U.S. Pat. No. 5,369,140, U.S. Pat. No. 5,298,067, WO 94/182.
No. 78, European Patent 704,443, British Patent No. 2,970,091, WO 96/2843.
See No. 1. 2- (2-hydroxyphenyl) -1,3,5-triazine and / or 2-hydroxyphenyl-2H-benzotriazole, especially 2
The addition of-(2-hydroxyphenyl) -1,3,5-triazine is of particular technical interest.

Component (C) is preferably used in an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of solid binder. Apart from components (A), (B) and, if used, (C), the coating composition comprises further components,
For example, it may also contain solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, dry catalysts and / or leveling agents. Examples of possible ingredients are Ullmann's Encyclopedia of Industrial
Chemistry, 5th edition, A18, 429-471
Page, VCH, Weinheim 1991.

Possible drying or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and / or phosphines. Examples of organometallic compounds are metal carboxylates, especially metals Pb, Mn, Co, Z
n, Zr or Cu, or metal chelates, especially those of metal Al, Ti or Zr, or organometallic compounds such as, for example, organotin compounds.

Examples of metal carboxylate are stearate of Pb, Mn or Zn, octoate of Co, Zn or Cu, naphthenate of Mn and Co or the corresponding linoleate, resinate or tallate.
Examples of metal chelates are acetylacetone, ethyl acetyl acetate, salicylaldehyde, salicylaldoxime, aluminum, titanium or zirconium chelates of o-hydroxyacetophenone or ethyl trifluoroacetyl acetate, and alkoxides of these metals. Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.

Examples of amines are in particular tertiary amines such as tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N
-Ethylmorpholine, N-methylmorpholine or diazabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary amine salts, for example trimethylbenzylammonium chloride. The amino group-containing resin is a binder and at the same time a curing catalyst. Examples of these are amino group-containing acrylate copolymers. Phosphines, such as triphenylphosphine, can also be the curing catalyst used.

The novel coating composition can also be a radiation-curable coating composition. In this case, the binder basically consists of monomeric or oligomeric compounds containing ethylenically unsaturated bonds which are cured by actinic radiation after application, ie converted into cross-linked high molecular weights. If the system is UV-curable, it generally also contains a photoinitiator. A corresponding system is described in the above-mentioned publication Ullman.
n's Encyclopedia of Industrial Chemistry, 5th edition,
A18, pages 451-453.
In radiation-curable coating compositions, it is possible to use the novel stabilizer without adding sterically hindered amines.

The coating composition of the present invention can be applied to any desired substrate, for example, metal, wood, plastic or ceramic material. They are preferably used as topcoats in automotive finishes. If the bottom layer is colored and the top layer consists of two uncolored topcoats, the new coating composition can be used for either the top layer or the bottom layer, or for both layers. However, it is preferably used for the upper layer. Conventional methods, such as brushing, spraying,
The novel coating composition can be applied to a substrate by pouring, dipping or electrodynamics; Ullmann's Ency
clopedia of Industrial Chemistry, 5th edition, A18
Volume, pages 491-500.

Depending on the binder system, the coating can be cured at room temperature or by heating. The coating is preferably 50 to 150
C. and at higher temperatures in the case of powder coatings or coil coatings. The coatings obtained according to the invention have good resistance to the detrimental effects of light, oxygen and heat, especially for the good light stability and weatherability of the coatings so obtained, for example paints. Deserves mention.

The invention therefore also relates to coatings, especially paints, which are stabilized against the detrimental effects of light, oxygen and heat by the inclusion of the compounds of the formula F according to the invention. Preferably, the paint is an automotive topcoat. The invention further provides a method for stabilizing a coating based on an organic polymer against damage by light, oxygen and / or heat, comprising a coating composition, ie a mixture comprising a compound of the formula F, The invention also relates to a method comprising mixing and using a mixture comprising a compound of the formula F in a coating composition as a stabilizer against light, oxygen and / or heat damage.

The coating composition can include an organic solvent or solvent mixture in which the binder can be dissolved. Similarly,
The coating composition may be an aqueous solution or dispersion. The vehicle may be a mixture of an organic solvent and water. The coating composition may be a high-solid paint and may be solvent free (eg, a powder coating material). Powder coatings are available, for example, from Ullmann's
Encyclopedia of Industrial Chemistry, 5th edition, A1
8, pages 438-444. Here, for example, in the specification of EP 856563, in particular, page 22, line 21 to page 26, page 29
The additives of the invention can be used as described in the line, as well as in the documents cited by reference in said prior document. The powder coating material can also have the form of a powder-slurry, preferably a dispersion of the powder in water.

Examples of resins for powder coating are as follows. 1. Carboxy- or hydroxy-functionality based on monomers such as terephthalic acid, isophthalic acid, neopentyl glycol, 2-methyl-1,3-propanediol, tris-1,1,1- (hydroxymethyl) propane and the like. Polyester resin 2. Bisphenol A or Novolak® (Nov) for thermal or UV curing with a cationic photoinitiator
olac) An epoxy resin based on bisphenol, such as an epoxy resin. 3. Hydroxy-, carboxy- or glycidyl-functional acrylate polymers and copolymers. Suitable comonomers include styrene, alkyl methacrylate, acrelamide, acrylonitrile, and the like. 4. Unsaturated polyester resins for UV-curable polymer coatings typically used with multifunctional vinyl ethers or acrylate esters.

Powder coatings based on resins having carboxy functionality are typically used with the following types of crosslinkers: 1) Polyfunctional epoxy compounds, such as epoxy resins, triglycidyl isocyanurate, epoxidized unsaturated fatty acid esters (eg, Uranox® from DSM)
(Uranox) resins) and esters and ethers of glycidol (eg, Ciba Specialty Chemicals (Ciba)
Specialty Chemicals)
ldit) PT 910). 2) β-Hydroxyalkylamides such as Primid type XL552 and QM1260 from EMS Chemie. 3) Melamine, benzoguanimine and glycoluril, such as American Cyanamid
Derivatives of Powderlink® 1174 from Ricoh.

Crosslinking agents for hydroxy-functional resins include anhydrides and especially blocked diisocyanates and uretdione. Powder coatings based on resins with epoxy functionality are typically crosslinkers,
For example, divalent acids (eg, 1,12-dodecanedioic acid), carboxy-functional polyesters of acrylates and methacrylates, carboxy-functional copolymers, anhydrides (eg, anhydrides prepared from 1,12-dodecanedioic acid) Used with Other additives that can be used with the compounds of the present invention in powder coatings include degassing agents, flow enhancers, tribocharging additives curing catalysts, sensitizers, cationic and free radicals. It contains a photoinitiator as well as typically a liquid paint additive.

The low basicity of the compounds of the present invention is particularly beneficial since basic compounds often catalyze the crosslinking reaction of powder coatings, causing poor flow and outgassing and reduced storage stability. is there. This is particularly effective in highly reactive formulations, such as glycidyl methacrylate-functional acrylic acid. Here, the combination of the compounds according to the invention together with UV absorbers, in particular those of the hydroxyphenyltriazines, can be used for improving the weather resistance in the absence of a catalyst to cause it. Significant effects in weatherability have also been demonstrated with other binder systems, as well as with other types of UV absorbers, such as those mentioned above, especially for use in automotive paints.

In powder coatings, the compounds of the present invention can also be used to improve oxidative stability and to reduce yellowing on curing and overbaking. Here, there is not only the benefit of low basicity, but also the stability of sterically hindered morpholinones which resists and prevents yellowing caused by oxides of nitrogen in gas-fired furnaces. In particular, European Patent No. 81
It is particularly advantageous to use phosphite and phosphonite co-stabilizers as described in US Pat. No. 6,442, and dialkyl esters of dithiopropionic acid. Where appropriate, the compounds according to the invention can also be used for stabilizing the polyester at the production stage as well as at all subsequent stages of use.

The pigments can be inorganic, organic or metallic pigments. The novel coating composition is preferably free of pigments and is used as a transparent coating. Similarly, it is preferred to use the coating composition as a topcoat for applications in the automotive industry, especially as a colored or unpigmented topcoat in paint finishing. However, use as a primer coating is also possible. Some of the products of the present invention are novel compounds.

The present invention therefore relates to compounds of the formula I, in particular
To R_Five, R₆, R₇, R₈And R ₉Are independent of each other
Hydrogen atom, alkyl group having 1 to 8 carbon atoms, carbon atom
An alkenyl group having 3 to 8 carbon atoms, 5 to 1 carbon atoms
2 aryl groups, electron-withdrawing groups; 1 to 4 carbon atoms
An alkyl group, an alkoxy group having 1 to 4 carbon atoms,
C 6 -C 12 substituted by a logen atom
Represents an aryl group, and R_Five, R₆, R₇, R₈And
And R₉Of the formula Ia in which at least one of the above does not represent a hydrogen atom
It also relates to the compounds represented. The present invention provides a compound represented by formula I
Compound, especially R_Five, R₆, R₇, R₈And R₉But each other
Independently an alkyl group having 1 to 8 carbon atoms, carbon atom
An alkenyl group having 3 to 8 carbon atoms, 5 to 12 carbon atoms
An aryl group or an electron withdrawing group; an alkyl group having 1 to 4 carbon atoms
Alkyl group, alkoxy group having 1 to 4 carbon atoms, halo
C 6 -C 12 carbon atoms substituted by a gen atom
Represents a reel group; and all other symbols are as defined above.
It also relates to a compound of formula Ia as described above.

Preferred compounds of the formula I are of the formula Ia Wherein the index n ranges from 1 to 15, especially 3
R ₅ to R ₉ are as defined for formula I; R ₁₂ is 2 to 12 carbon atoms
An alkylene group having 4 to 12 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, a cycloalkylene di (alkylene having 1 to 4 carbon atoms) group having 5 to 7 carbon atoms, A 1-4 alkylenedi (cycloalkylene having 5 to 7 carbon atoms) group, a phenylene (alkylene having 1 to 4 carbon atoms) group, a 1,4-piperazinediyl group, -O-
Or> NX ₁ (wherein X ₁ has 1 to 1 carbon atoms)
Represents 2 acyl groups or (C 1 -C 12 alkoxy) carbonyl group or has one of the definitions of R ₁₄ given below, excluding the hydrogen atom. Represents an alkylene group of 4 to 12 carbon atoms interrupted by); or R ₁₂ is of the formula (Ib ′) or (Ic ′) Wherein m is 2 or 3, and X ₂ is a carbon atom having 1 to 18 carbon atoms, an unsubstituted or substituted by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms. An unsubstituted or substituted phenyl group substituted by one, two or three of an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; an unsubstituted or carbon atom Represents a phenylalkyl group having 7 to 9 carbon atoms which is substituted on the phenyl group by 1, 2 or 3 of the alkyl groups having 1 to 4 groups; and the radicals X ₃ independently of one another have 2 to 12 carbon atoms. . that of an alkylene group represents a group represented by); group a independently of one another -OR ₁₃ and, -N
(R ₁₄ ) (R ₁₅ ) or the following formula (Id ′) R ₁₃ , R ₁₄ and R ₁₅ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; one of an unsubstituted or an alkyl group having 1 to 4 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, substituted by 2 or 3 carbon atoms; an unsubstituted or an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms A phenyl group substituted by 1, 2 or 3 alkoxy groups; unsubstituted or 7 to 9 carbon atoms substituted on the phenyl group by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms A phenylalkyl group; a tetrahydrofurfuryl group, or —O at the 2, 3 or 4 position
H, an alkoxy group having 1 to 8 carbon atoms, a di (alkyl having 1 to 4 carbon atoms) amino group or the following formula (I
e ') (Wherein Y represents —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ), and represents an alkyl group having 2 to 4 carbon atoms substituted by a group represented by the formula: Or —N (R ₁₄ ) (R ₁₅ ) additionally represents a group of formula (Ie ′); X represents —O— or> N—R ₁₆ ;
₁₆ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
An alkenyl group having 3 to 18 carbon atoms, an unsubstituted or an alkyl group having 1 to 4 carbon atoms, 1, 2 or 3
C 5 -C 12 cycloalkyl substituted by C; C 7 -C 9 cycloalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 of C 1 -C 4 alkyl; Phenylalkyl group; tetrahydrofurfuryl group, the following formula (If ′) Or -OH at the 2, 3 or 4 position, an alkoxy group having 1 to 8 carbon atoms, di (1 carbon atom
R 4 represents an alkyl) amino group or a C 2 -C 4 alkyl group substituted by a group of the formula (Ie ′); R ₁₁ has one of the definitions given for R ₁₆ And the radicals B independently of one another have one of the definitions given for A. ] Is represented by;
And in each individual repeating unit represented by the formula (Ia), each of the groups B, R ₁₁ and R ₁₂ may have the same or different definitions.

Further, a novel product obtained by the method of the present invention has the following formula:
IIIc, IVa and Va[Where R is the following formulaE represents an organic crosslinking group represented by_TwoIs -CO- or-
(CH_Two)_p-(Wherein P is 0, 1 or 2)
E;₁Is the two residues R_{twenty four}And R_{twenty five}Carbon with
Represents an atom, or> NR _{twenty five}Represents or
Represents an oxygen atom, and R_{twenty four}And R_{twenty five}Is a hydrogen atom or
Represents an organic residue, and a total of 2 to 500 crosslinking groups R
And the group is directly attached
Substituted together with carbon and nitrogen atoms
Forming a 5-, 6- or 7-membered cyclic structure
R₁, R_Two, R_ThreeAnd R_FourAre independent of each other
No alkyl group having 1 to 8 atoms or 1 carbon atom
5 represents a hydroxyalkyl group;₁You
And R_TwoTogether with the carbon atom to which the group is attached
Represents a cycloalkyl group having 5 to 12 carbon atoms,
Or R_ThreeAnd R_FourIs the carbon atom to which the group is attached
Together with cycloalkyl having 5 to 12 carbon atoms
R;_Five, R₆, R₇, R₈And R₉Are each other
Independently represents a hydrogen atom, an alkyl having 1 to 8 carbon atoms
Group, alkenyl group having 2 to 8 carbon atoms, number of carbon atoms
5 to 12 aryl groups, C1 to C4
A loalkyl group, an electron withdrawing group;
4 alkyl groups, alkoxy having 1 to 4 carbon atoms
Group, substituted by a residue selected from a halogen atom
R 6 represents an aryl group having 6 to 12 carbon atoms;₂₀And
And R_{twenty one}Represents a halogen atom; and R_{twenty two}And R_{twenty three}Is
Represents a hydrogen atom or forms a chemical bond together
Where R in the formula IIIc is(Where R_{twenty four}And R_{twenty five}Together represent = O, or
Or where R_{twenty four}Represents a hydrogen atom;_{twenty five}Is a hydrogen atom,
OH, or phenoxy group, or alkylphenoxy
It is an alkanoyloxy group substituted by a silyl group. )
Does not represent a crosslinking group represented by ]. E₁Is placed
When representing a substituted carbon atom,_TwoIs mainly-(CH_Two)
_p-Especially CH_TwoE;₁Is an oxygen atom or NR_{twenty five}
To represent E_TwoRepresents mainly a carbonyl group.

Accordingly, formula IIIc, IVa or Va wherein R is a divalent hydrocarbon group having 7 to 500 carbon atoms, or a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a silicon atom and a halogen atom. 2 to 50 carbon atoms containing 1 to 200 heteroatoms
Represents a hydrocarbon group of 0 and Or Wherein p is 0, 1 or 2; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are an alkyl group having 1 to 8 carbon atoms or a carbon atom 1 atom
Represents 5 to 5 hydroxyalkyl groups;
₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ are the same as the carbon atom to which the group is attached. together they are a cycloalkyl group having 5 to 12 carbon atoms; R ₅ and R ₆ represents a hydrogen atom or a methyl group independently of one another, and R _7, R ₈ and R
₉ is independently of each other a haloalkyl group having 1 to 4 carbon atoms, phenyl group, vinyl group, nitro group, CN, COO
R _{10 wherein} R ₁₀ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms or a phenyl group; R ₂₄ and R ₂₅ each independently represent a hydrogen atom or And R ₂₆ is a hydrogen atom or, together with the remaining structure of formula (VIb), a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a silicon atom or a halogen atom And an organic residue forming a hydrocarbon group having 2 to 500 carbon atoms containing 1 to 200 heteroatoms selected from atoms.].

Most preferably, formulas IIIc, IVa or Va, wherein R ₅ and R ₆ independently of one another represent a hydrogen atom or a methyl group; and R ₇ , R ₈ and R ₉ independently of one another a carbon atom A bromoalkyl group having 1 to 4 carbon atoms, a phenyl group, CN, COOR ₁₀ (wherein R ₁₀ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms or a phenyl group) Especially R ₅ , R ₆ , R ₇ , R ₈ and R ₉ represent a hydrogen atom; R ₂₀ and R ₂₁ represent a bromine atom;
Is compatible with the structure of formula VIa, p is 1 and R ₁ , R ₂ , R ₃ and R ₄ independently of one another represent a methyl or ethyl group; R ₁ , R ₂ , R ₃ and R ₄
Represents, independently of one another, a methyl or ethyl group; or R ₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group; If R is compatible with the structure represented by formula VIc;; R ₃ and R ₄ represents a cycloalkyl group having 5 to 12 carbon atoms together with the carbon atoms to which said radicals are attached R _1, R ₂ , R ₃ and R ₄ independently represent an alkyl group of 1 to 8 carbon atoms or a hydroxyalkyl group of 1 to 5 carbon atoms, or R ₁ and R ₂ are Together with the carbon atom present represents a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ together with the carbon atom to which the group is attached, have 5 to 12 carbon atoms. Represents a cycloalkyl group ).

Of particular interest is the following formula IIIc Wherein R comprises 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen and, together with two carbon and nitrogen, is substituted Represents a hydrocarbon group having 7 to 500 carbon atoms forming a 5- or 6-membered cyclic structure; and R ₁ , R ₂ , R ₃ and R ₄ are as defined above.) With the proviso that R
Is Does not represent Formula IIIc, which forms the structure represented by Compounds of the formula IIIc shown above are particularly preferred.

Accordingly, the novel sterically hindered amines are usually
Equivalent to equation (1a), (1b) or (2a)
Or at least a group represented by the following formula (3) or (4)
Also includes a kind;[Wherein, n₁Is a number from 1 to 4, G and G₁Is
Each independently represents a hydrogen atom or a methyl group;₁₁Is
n-propoxy group, O-CH = C = CH_Two, O-CH =
CH-CH_ThreeOr halogenated n-propoxy groups, especially
n-propoxy group or brominated n-propoxy group
And n₁If is 1, then G₁₂Is one of the oxygen atoms or
Charcoal uninterrupted or interrupted by more
An alkyl group having 1 to 18 atoms, a cyanoethyl group,
Benzoyl group, glycidyl group; aliphatic, alicyclic, unsaturated
Or containing aromatic carboxylic acid, carbamic acid or phosphorus
No monovalent or monovalent silyl group of the acid, preferably 2
Aliphatic carboxylic acid radicals having 18 carbon atoms, 7
Alicyclic carboxylic acids having from 15 to 15 carbon atoms
Group, or an α, β-unsubstituted group having 3 to 5 carbon atoms.
Represents a group of saturated carboxylic acids, each carboxylic acid,
Aliphatic, cycloaliphatic or aromatic moieties, if present
-COOZ in minutes₁₂Substituted by one to three of the groups
Where Z₁₂Is the number of hydrogen atoms and carbon atoms
1 to 20 alkyl groups, 3 to 12 carbon atoms
Alkenyl group, cycloalkyl having 5 to 7 carbon atoms
Group, phenyl group or benzyl group, n₁Place of 2
If G₁₂Is an alkylene group having 2 to 12 carbon atoms,
Alkenylene group having 4 to 12 atoms, xylylene
Group; aliphatic, cycloaliphatic, aromatic aliphatic or aromatic dical
Divalent radicals of boric acid, dicarbamic acid or phosphorus-containing acids
Or a divalent silyl group, preferably 2 to 36 carbon atoms
Groups of aliphatic dicarboxylic acids having atoms, or 8 to
Alicyclic or aromatic dicals having 14 carbon atoms
Having a boric acid group or 8 to 14 carbon atoms
Represents aliphatic, alicyclic or aromatic dicarbamic acid groups
Where each dicarboxylic acid is -COOZ ₁₂Base
An aliphatic, alicyclic or aromatic moiety according to one or two of
And n₁If is 3, G₁₂
Is -COOZ₁₂Aliphatic, cycloaliphatic or aromatic moiety depending on the group
Aliphatic, cycloaliphatic or
Is a trivalent group of an aromatic tricarboxylic acid,
Trivalent groups of formic acid or trivalent groups or of phosphorus-containing acids
A divalent silyl group; and n₁If is 4, G₁₂Is fat
Tetravalent group of aliphatic, alicyclic or aromatic tetracarboxylic acid
And R₁, R_Two, R_ThreeAnd R_FourAre independent of each other
An alkyl group having 1 to 8 carbon atoms or 1 carbon atom
Represents 5 to 5 hydroxyalkyl groups;
₁And R_TwoTogether with the carbon atom to which the group is attached
Represents a cycloalkyl group having 5 to 12 carbon atoms
Or R_ThreeAnd R_FourIs the carbon to which the group is attached
A cycloalkyl having 5 to 12 carbon atoms together with an atom
G represents a hydrogen atom or a methyl group;
G₁And G_TwoIndependently represent a hydrogen atom or a methyl group
Or together represent the substituent = O; and
G_ThreeRepresents a direct bond or a methylene group;
And the open bond of (4) is the carbon of the organic residue defined above.
Bonds with an atom, nitrogen atom or oxygen atom,₁₃Is hydrogen field
, An alkyl group having 1 to 12 carbon atoms,
2-5 hydroxyalkyl groups, no 5 carbon atoms
A cycloalkyl group having 7 to 7 carbon atoms;
Alkyl group, alkanoyl having 1 to 18 carbon atoms
Groups, C 3 -C 5 alkenoyl groups, benzoy
Or the following formula (1b-1)Represents a group represented by_TwoIs the number 1, 2 or 3;
And n_TwoIf is 1, G₁₄Is the number of hydrogen atoms and carbon atoms
An alkyl group having 1 to 18 carbon atoms, an alkyl group having 3 to 8 carbon atoms,
Lucenyl group, cycloalkyl having 5 to 7 carbon atoms
Groups; hydroxyl, cyano, alkoxycarbonyl or
C1 -C4 substituted by a carbamide group
Alkyl group; glycidyl group, formula -CH_Two-CH (OH)
-Z or the formula CONH-Z (where Z is a hydrogen atom, methyl
Represents a phenyl group or a phenyl group. ) Represents a group represented by;
n_TwoIs 2, G₁₄Is an alkyl having 2 to 12 carbon atoms
A kylene group, an arylene group having 6 to 12 carbon atoms,
Silylene group, -CH_Two-CH (OH) -CH_TwoGroup or
-CH_Two-CH (OH) -CH_Two—O—D—O— group (formula
Wherein D is an alkylene group having 2 to 10 carbon atoms,
C 6 -C 15 arylene group, no C 6
And 12 cycloalkylene groups. ) Or is
Ih G₁₃Is an alkanoyl group, an alkenoyl group or a ben
Provided that they do not represent a zoyl group,₁₄Is instead
1-oxo-alkylene having 2 to 12 carbon atoms
Group, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarboxylic acid
The divalent group of carbamic acid or alternatively the group -CO
-Can be represented, and n_TwoIf is 3, G₁₄IsRepresents a group represented by_TwoIf is 1, G₁₃You
And G₁₄Are aliphatic, alicyclic or aromatic together
Represents a divalent group of 1,2 or 1,3-dicarboxylic acid
be able to. ].

Preferred novel sterically hindered amines of the formula IIIc are as described above in paragraphs (b ') to (j') and are preferably indicated there. Formula III
The novel compounds represented by c are effective as stabilizers for organic materials against decomposition by light, oxygen and / or heat. The material to be stabilized can be, for example, an oil, a fat, a wax, a cosmetic or a biocide. Of particular interest is the use in polymeric materials such as plastics, rubber, coating materials, photographic materials or adhesives: for example, organic polymers as described above, and electronic reproductions, especially colored photographic materials, for example GB 23195.
No. 23, German Patent No. 19750906, page 23, line 20 to page 105, line 32, or US Pat. No. 5,538,840,
Column 5, line 60 to column 106, line 31; the relevant part of U.S. Pat. No. 5,539,940 is incorporated herein by reference. In addition, those described above for the compounds of the formulas I and III are preferred.

[0141]

The following examples further illustrate the present invention. In the examples and claims which follow hereafter, all parts or percentages are by weight unless otherwise indicated. Unless otherwise stated, room temperature refers to a temperature in the range of 20-30 ° C. The following abbreviations are used in the examples. m. p. Melting point or range; Mn number average molecular weight (g / mol); Mw weight average molecular weight (g / mol); GPC gel permeation chromatography

Example 1: The following equation Preparation of the starting compound of the formula Stage 1: 74.3 g (0.35 mol) in 50 ml of water
Of N- (2,2,6,6-tetramethyl-4-piperidinyl) -n-butylamine was slowly added to a solution of 64.5 g (0.35 mol) of cyanuric chloride in 500 ml of xylene at 0 ° C. The temperature is constant during the addition and for an additional hour. After 2 hours at room temperature, the mixture was cooled to 0 ° C. and 14.7 g (0.368 mol
1) Add aqueous sodium hydroxide solution. 1 / at 0 ° C
After 2 hours and a further 2 hours at room temperature, the aqueous solution is separated off and 69.2 g (0.175 mol) of N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl)
Add -1,6-hexanediamine.

The mixture is heated to 50 ° C. for 1 hour and 48.4 g (0.35 mol) of crude potassium carbonate are added and heated to 60 ° C. for 4 hours. After washing with water, the organic layer is concentrated under vacuum at 60-70 ° C./10 mbar and 250 ml of xylene are recovered. 138.1
g (0.35 mol) of N, N'-bis (2,2,6,
6-tetramethyl-4-piperidinyl) -1,6-hexanediamine is added and the mixture is kept at 150 ° C. for 2 hours.
And cooled again, and 14g (0.35mo
1) Add crude sodium hydroxide.

The mixture is heated to 140 ° C. for a further 4 hours,
The residual water of the reaction is removed azeotropically and
And heat for another 4 hours. After cooling to 60 ° C., the mixture is
Diluted with 00 ml xylene, filtered and 100m
Wash three times with 1 liter of ethylene glycol. This solution can be used for the isolation of the compound described in Example 6.

Step 2: After concentration under vacuum at 60 ° C./10 mbar, 54.4 g (0.147 mol) of 2-chloro-4,6-bis (dibutylamino) -1,3,5-
Add the triazine. The mixture is heated to 140 ° C. for 3 hours and 20.3 g (0.147 mol) of crude potassium carbonate are added, the mixture is heated to reflux and the reaction water is removed azeotropically. The mixture is heated to 160 ° C. for 4 hours, a further 20.3 g (0.147 mol) of crude potassium carbonate are added and again heated to 160 ° C. for 2 hours. After cooling to 60 ° C., the mixture is diluted with 300 ml of xylene, filtered and concentrated under vacuum at 140 ° C./1 mbar. After drying, a solid having a melting range of 130 to 136 ° C. is obtained; Mn (by GPC
) : 2830 g / mol.

Example 2: The method of the present invention; Step 1: Preparation of a compound represented by : In a 1 liter stainless steel autoclave equipped with a heating device and a mechanical stirrer,
A solution of 150 g (0.05 mol) of the product of Example 1 in 400 ml of xylene, 66.5 g (0.55 mol)
l) allyl bromide and 114 g (0.825 mo
1) Add potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 5 hours, and cooled to 60 ° C. 3
Add 00 ml of water and stir the mixture vigorously. The organic layer is then collected and placed in a 1 liter round bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel. After cooling to -15 ° C, 32
128 g of a solution by weight of peracetic acid are added under stirring over a period of 30 minutes. The temperature is raised to 0 ° C. and the reaction mixture is allowed to react for 4 hours. A solution of 250 g of K ₂ CO _{3 in} 500 ml of water is added and kept at 0 ° C. with stirring for 30 minutes. The organic layer is collected, washed three times with 100 ml of water and dried over sodium sulfate.

Step 2: Put the solution in a 1 liter stainless steel autoclave. After addition of 3 g of 5% by weight of platinum on carbon, the autoclave is filled with 40 bar of hydrogen and maintained at 70 ° C. for 6 hours with stirring. The autoclave is then cooled to 20 ° C. and opened. After removing the catalyst by filtration, the solution was
Concentrate at 0 ° C. and 1 mbar. White solid, melting point 12
7 to 135 ° C., Mn (GPC) = 3580 g / mo
1, the product is obtained with Mw / Mn = 1.33.

Example 3 The method of the present invention; In a round-bottomed flask, 20 g of 1-allyl-2,2,6,6
- tetramethyl - piperidin-4-ol, 40 ml of methanol, 35% (v / v) H 2 O 2 solution 118g of
Insert The mixture is heated to 65 ° C., reacted for 5 hours, concentrated under vacuum until the methanol has distilled off, and 40 ml of CH ₂ Cl ₂ are added. The mixture is stirred and the organic layer is collected and concentrated. The product is obtained as a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
5.90-5.80 (m, 1H); 5.21-4.97
(M, 2H); 4.24 (m, 2H); 3.87 (m,
1H); 1.75 (m, 2H); 1.42 (m, 2
H); 1.15 (s, 3H); 1.11 (s, 3H).

Example 4a: In a stainless steel autoclave was charged 20 g of the product of Example 3, 0.2 g of nickel Raney and 100 ml of toluene; the autoclave was filled with 8 bar of hydrogen and stirred for 8 hours. Maintain at 25 ° C for a while. The autoclave is then opened, the catalyst is removed by filtration and the mixture is concentrated under vacuum. The product is obtained as a white solid. ¹ H NMR (300 MHz,
_{CDCl 3) /ppm:3.96 (m, 1H} ); 3.6
6 (t, 2H); 1.57 (m, 4H); 1.22
(M, 2H); 1.13 (s, 12H); 0.89
(T, 3H).

Example 4b: In a round-bottomed flask, 20 g of the product of Example 4a),
6 g of methyl sebacate, 100 ml of xylene and 0.25 g of di-butyl-tin-oxide are charged. The mixture is heated to 145 ° C., reacted with stirring for 6 hours, cooled and concentrated under vacuum to give the above product as an oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
4.95 (t, 4H); 3.66 (t, 4H); 2.2
1. (t, 4H); 1.77 (m, 4H); 1.63-
1.42 (m, 12H); 1.28-1.18 (m, 3
6H); 0.90 (t, 6H). Other analytical data: HPLC evaluation: 80%

Example 5: The method of the present invention; In a stainless steel autoclave, 20 g of bis (2,2,6,6-tetramethyl-piperidine-sebacate) was added.
4-yl) ester (trade name: registered trademark Tinuvin)
in) 770), 24 g of allyl bromide, 6 g of potassium carboxylate and 100 ml of toluene; the mixture is heated to 120 ° C. and reacted with stirring for 5 hours,
Cool and filter to remove salts. Excess allyl bromide is removed by distillation. The solution is placed in a round bottom flask and 8 g of metachloroperbenzoic acid dissolved in 50 ml of toluene are added over a period of 30 minutes or more, keeping the temperature below 25 ° C.

A solution of 13 g of potassium carbonate in 100 ml of water is then added to the reaction mixture and left under stirring for 30 minutes. The organic layer is collected and washed with the potassium carbonate solution prepared as described above. The organic layer is then dried over sodium sulfate and placed in a stainless steel autoclave. 1 g of 5% by weight platinum on carbon
After the addition, the autoclave is filled with 8 bar of hydrogen,
Then, it is maintained at 25 ° C. for 4 hours with stirring. After removal of the catalyst by filtration, the solution is concentrated under vacuum. The product is obtained as a pale yellow oil; ¹ H NMR (300 MHz,
_{CDCl 3) /ppm:4.95 (m, 2H} ); 3.6
6 (t, 4H); 2.21 (t, 4H); 1.77
(M, 4H); 1.63-1.42 (m, 12H);
1.28-1.18 (m, 36H); 0.90 (t, 6
H). Other analytical data: HPLC evaluation: 78%

Embodiment 6: The following equation With an intermediate This compound represented is prepared according to the method described by Step 1 of Example 1. The solution obtained from step 1 is then concentrated at 140 ° C. and 1 mbar and 2555
g / mol average Mn (by GPC), m.p.
p. A solid at 138-143 ° C. is obtained.

Example 7: To a solution of 150 g of the product of Example 6 in 400 ml of xylene is added 66.5 g of allyl bromide and 114 g of potassium carbonate. The mixture is heated to 150 ° C, allowed to react for 5 hours, and cooled to 60 ° C. 30
0 ml of water is added and the mixture is stirred vigorously. The organic layer was then collected, cooled to -15 ° C and 3 in acetic acid.
128 g of a 2% by weight solution of peracetic acid are added under stirring over a period of 30 minutes. The temperature is raised to 0 ° C. and the reaction mixture is allowed to react for 4 hours. 250 g of K ₂ CO _{3 in} 500 ml of water
And keep at 0 ° C. for 30 minutes with stirring. The organic layer is collected, washed three times with 100 ml of water and dried over sodium sulfate. The solution is placed in a 1 liter stainless steel autoclave. After addition of 3 g of 5% by weight of platinum on carbon, the autoclave is filled with 40 bar of hydrogen and kept at 70 ° C. with stirring for 6 hours. The autoclave is then cooled to 20 ° C. and opened. After removing the catalyst by filtration, the solution is concentrated at 140 ° C. and 1 mbar. White solid, melting point 125-135 ° C., Mn (GPC) = 29
The product is obtained at 79 g / mol.

Embodiment 8: The following equation A compound represented by 300ml of 93g toluene 2-chloro-4,6
To a solution of bis (Nn-butyl-N- (2,2,6,6-tetramethylpiperidin-4-yl))-1,3,5-triazine, 42 g of allyl bromide and 71.7.
g of potassium carbonate are added. The mixture was heated to 150 ° C., reacted for 10 hours, cooled to 60 ° C., and
00 ml of water are added under stirring. The organic layer is then collected and cooled to -5 ° C and 39% by weight in acetic acid
64 g of a solution of peracetic acid are added under stirring for 30 minutes. The temperature is raised to 0 ° C. and the reaction mixture is allowed to react for 2 hours. Add 90 g of sodium carbonate solution in 500 ml of water and keep at 0 ° C. for 30 minutes with stirring. Collect the organic layer and dry over sodium sulfate. The solution is placed in a 1 liter stainless steel autoclave. 5
After adding 3 g of platinum on carbon by weight, the autoclave was
Fill with 0 bar of hydrogen and maintain at 70 ° C. for 6 hours with stirring. The autoclave is then cooled to 20 ° C. and opened. After removing the catalyst by filtration, the solution is concentrated at 140 ° C. and 1 mbar. The product is obtained as a white solid. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
4.97 (m, 2H); 3.67 (t, 4H); 3.2
9 (m, 4H); 1.80-1.30 (m, 20H);
1.31-1.08 (m, 28H); 0.92-0.8
0 (m, 12H).

Embodiment 9: The following equation In Example 8 compound according of the compound represented by 64.5 g, of 200ml xylene, potassium carbonate 20.4g and 4.6g of N-
1- [2- (3-amino-propylamino) -ethyl]
Heating the mixture consisting of propane-1,3-diamine to 140 ° C. for 10 hours, cooling to 20 ° C. and
Wash with 0 ml of water. The collected organic layer is concentrated at 140 ° C. and 1 mbar. The resulting solid has a m.p. p. Having.

Embodiment 10: The following equation In represented by N in toluene 30g of compound 240 ml,
To a solution of N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine, 50
g of allyl bromide and 63 g of potassium carbonate are added. The resulting mixture is heated to 150 ° C and 6
Reaction, cooled to 20 ° C., filtered and
The solvent volume is reduced by 100 ml by solvent evaporation at 0 ° C. and a vacuum of 1 mbar. 150 for concentrated solution
After cooling to −10 ° C., 200 m
A solution of 82 g of m-chloroperbenzoic acid in 1 toluene is added with stirring over 1 hour. After heating the mixture to 0 ° C., a solution of 100 g of potassium carbonate in 300 ml of water is added with stirring and allowed to reach 20 ° C. The organic layer is collected, dried over sodium sulphate and hydrogenated at 70 ° C. for 8 h using 40 bar of hydrogen with 2 g of 5% platinum on carbon. The catalyst is recovered by filtration and the solution is concentrated at 110 ° C. under 1 mbar. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
3.75 (t, 4H); 3.54 (t, 4H); 2.8
2. (m, 2H); 2.63 (t, 4H); 1.78-
1.45 (m, 20H); 1.42-1.23 (m, 4
H); 1.16 (s, 12H); 1.10 (s, 12H);
H); 0.89 (m, 6H).

Embodiment 11: The following equation In toluene in 90g of the compound represented 200ml benzoic acid 1-but -2
To a solution of -enyl-2,2,6,6-tetramethyl-piperidin-4-yl ester was added 70 g of 4-bromo-2.
-Add butene and 100 g of potassium carbonate. The mixture was heated to 140 ° C. and reacted under stirring for 10 hours,
Cool to 20 ° C., pour into 200 ml of water and stir. The organic layer is then collected and concentrated by removing 100 ml of solvent at 110 ° C. and 20 mbar, then adding 100 ml of pure toluene. The resulting solution is cooled to −15 ° C. and a solution of 100 g of m-chloroperbenzoic acid in 200 ml of toluene is added over 30 minutes with stirring. The mixture is reacted at 0 ° C. for 2 hours and then a solution of 40 g of potassium carbonate in 300 ml of water is added with stirring. Collect the organic layer and evaporate the solution under vacuum. The product obtained is a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
7.99 (d, 2H); 7.49 (m, 1H); 7.3
7 (m, 2H); 5.85 (m, 1H); 5.26
(M, 1H); 5.06-5.00 (m, 2H);
28 (m, 1H); 1.94 (m, 2H); 1.71
(M, 2H); 1.25-1.17 (m, 15H).

Embodiment 12: The following equation To a solution of 52 g of 2,2,6,6-tetramethylpiperidine in 250 ml of hexane is added 102 g of potassium carbonate and 135 g of propargyl bromide. The mixture was heated to 140 ° C. and reacted under stirring for 10 hours,
Cool to 20 ° C., pour into 300 ml of water and stir. The organic layer is then collected, dried over sodium sulfate and distilled under vacuum at 64 ° C and 10 ° C.
The fraction is collected at mmHg, dissolved in 250 ml of dichloromethane and cooled to -15 ° C. To the resulting solution is added a solution of 100 g of m-chloroperbenzoic acid in 200 ml hexane under stirring for 30 minutes. Mix 0
C. for 2 hours, then a solution of 40 g of potassium carbonate in 300 ml of water is added with stirring. Collect the organic layer, dry over sodium sulfate and evaporate the solvent under vacuum. The product obtained is a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
6.82 (t, 1H); 5.49 (d, 2H); 1.5
2 (s, 6H); 1.13 (s, 12H).

Embodiment 13: The following equation A mixture of 16 g of the compound of the formula (11), 500 ml of ethanol and 0.9 g of Lindlar catalyst is placed in an autoclave. The autoclave is filled with 10 bar of hydrogen and maintained at 40 ° C. under stirring for 6 hours, then it is cooled to 20 ° C. and opened. After removal of the catalyst by filtration, the solution is concentrated under vacuum. The resulting product is obtained as a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
6.29 (d, 1H); 4.01 (m, 1H); 1.5
7 (d, 3H); 1.45 (m, 6H); 1.12
(S, 12H).

Embodiment 14: The following equation A mixture of 38 g of the compound of formula 11 described in Example 11, 300 ml of toluene and 1 g of 5% by weight of platinum supported on carbon is placed in an autoclave. 30 in autoclave
Fill with bar of hydrogen and maintain at 40 ° C. under stirring for 6 hours, then cool it to 20 ° C. and release. After removal of the catalyst by filtration, the solvent was removed at 110 ° C and 3 ° C.
Remove by vacuum concentration at 5 mbar. The resulting product is obtained as a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
3.69 (t, 2H); 1.45 (m, 8H); 1.1
5 (s, 12H); 0.92 (t, 3H).

Embodiment 15: The following equation In 4-hydroxy-2,2,6,6-tetramethylpiperidine of the compound represented by 207 g, 100 g of DBE-2 ^O (mixture of 75% glutaric acid dimethyl ester and 25% adipic acid dimethyl ester, DuPont (DuPont) -USA) is dissolved in 500 ml of toluene, 2 g of lithium amide are added and heated and reflux is continued for 6 hours while azeotropically distilling off the methanol formed during the reaction. Then the mixture is cooled to 20 ° C., washed with water and dried over sodium sulfate. The resulting solution was then treated with allyl bromide, according to a similar method and similar stoichiometry described for the preparation of the compound of Example 5.
React with sodium carbonate, peracetic acid, hydrogen and 5% by weight platinum on carbon. The product is obtained as a pale yellow oil. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm:
4.95 (m, 2H); 3.63 (t, 4H); 2.2
4 (m, 2H); 1.86-1.71 (m, 4H-6)
H); 1.57-1.44 (m, 8H); 1.15
(M, 28H); 0.89 (m, 6H).

Embodiment 16: The following equation A compound represented by Step 1: in toluene 64g of 300 ml 2,4,6
In a solution of tris- (Nn-butyl-N- (2,2,6,6-tetramethylpiperidin-4-yl))-1,3,5-triazine 48 g of allyl bromide and 55.
Add 8 g of potassium carbonate. The mixture is heated to 150 ° C., reacted for 5 hours, cooled to 60 ° C. and 300 ml of water are added with stirring. The organic layer is then collected, concentrated by removing 100 ml of solvent at 110 ° C. and 20 mbar, adding 400 ml of pure toluene, cooling to −5 ° C. and 39% by weight in acetic acid.
Of peracetic acid are added over 30 minutes with stirring. The temperature is raised to 0 ° C. and the reaction mixture is allowed to react for 2 hours. A solution of 80 g of sodium carbonate in 500 ml of water is added and kept at 0 ° C. for 30 minutes with stirring. Collect the organic layer and dry over sodium sulfate. Step 2: Place the solution in a 1 liter stainless steel autoclave. After addition of 2 g of platinum supported on carbon at 5% by weight, the autoclave is filled with 40 bar of hydrogen, kept at 70 ° C. with stirring for 6 hours, cooled to 20 ° C. and opened. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C. and 1 mbar. The product is obtained as a white solid, m.p. p. 92-100 ° C.

Embodiment 17: The following equation A solution in 43g of bromine was obtained in the stage 1 of the compound of Example 14 represented below 25 ° C. stirring, in the dark under 30 minutes. Mix for 6 hours 2
React at 5 ° C., wash with a solution of 54 g of potassium carbonate in 500 ml of water, collect, dry over sodium sulfate and concentrate at 100 ° C. under reduced pressure (10 mbar). The resulting pale pink solid has a melting point of 106-110 ° C.

Embodiment 18: The following equation To the solution obtained in step 1 of Example 2 is added 88 g of bromine under stirring at 25 ° C. in the dark for 30 minutes. Mix for 6 hours 25
C., wash with a solution of 108 g of potassium carbonate in 1000 ml of water, collect, dry over sodium sulphate and concentrate under reduced pressure (10 mbar) at 120.degree. The resulting pale yellow solid has a melting point above 250 ° C. (decomposition). Bromine content: 32.1% by weight; Mn (by GPC): 2
862.

Use Examples Example 20: Light stabilizing action on PP tapes 1 g of each of the compounds reported below and tris (2,4-di-tert-butylphenyl) phosphite 1
g, pentaerythritol tetarakis (3- (3,
0.5 g of 5-di-tert-butyl-4hydroxyphenyl) propionate) and 1 g of calcium stearate,
It has a melt index of 2.1 g / 10 min (measured at 230 ° C. and 2.16 Kg) and already has a tris (2,4
1 g of di-tert-butylphenylphosphite) and pentaerythritol tetrakis (3- (3,5-di-
Mix in a turbomixer with 1000 g of polypropylene powder containing 10.5 g of tert-butyl-4-hydroxyphenyl) propionate). Mix 200 to 2
Extrusion at 20 ° C. produces polymer particles, then the equipment of a semi-industrial type (Leonard-Sumirag
o) Using (VA) -Italy) and converting to stretched tape 50 microns thick and 2.5 mm wide under the following conditions: Extruder temperature: 210 to 230 ° C Head temperature: 240 to 260 ° C Stretching ratio: 1: 6

The tape thus manufactured was placed on a white card, and a weatherometer 65 WR (ASTM G26-96D 2565-) having a black panel temperature of 63 ° C.
85). The remaining tensile strength is measured on samples taken after various exposure times by the method of constant speed tensiometer, and the exposure time (time) (T50) required to reach half of the initial tensile strength is calculated. I do. Tapes were prepared and exposed under the same conditions as indicated above for comparison, but without the addition of the stabilizers of the present invention. The results obtained are shown in the table below.

[0168]

Example 21: Light Stabilizing Action in LDPE Film Each compound reported below was compared with 0.921
LDPE pellets characterized by a density of g / cm ³ and a melt flow index of 0.60 g / 10 min (190 ° C./2.16 Kg) (Riblene provided by Enichem, Milan, Italy; FF
29) and are mixed with a gentle mixer via a master batch. A masterbatch is prepared in advance by extruding 10% by weight of powdered LDPE and the compounds of the items reported below. The mixture is blow extruded at 210 ° C. and a film of 150 microns thickness is obtained. The film is placed on a white cardboard in a metal frame, and according to ASTM G26-96, with a black panel temperature of 63 ° C and a continuous dry cycle, Atlas Ci.
Exposure in a 65 Xenon Arc Weather O-meter.

During the exposure, the increase in carbonyl (iCO; increase in carbonyl concentration) is measured by FT-IR spectrophotometer, and the samples are tested for embrittlement to evaluate performance periodically. For some samples, the residual tensile strength was measured on samples taken after various exposure times by the method of constant velocity tensiometers; thus, the exposure time required to reach half of the initial tensile strength (time ) (T50) is calculated. The results are summarized in the table below. A low increase in carbonyl concentration and a high T50 time indicate good stability.

[0171]

Example 22 L treated with a Bordeaux mixture
Light stabilizing action in DPE film Each of the compounds reported below,
LDPE pellets characterized by a density of g / cm ³ and a melt flow index of 0.60 g / 10 min (190 ° C./2.16 Kg) (Riblene provided by Enichem, Milan, Italy; FF
29) is mixed through a masterbatch with a gentle mixer. A masterbatch is prepared beforehand by extruding powdered LDPE and 10% by weight of the compounds reported below. The mixture is blow extruded at 210 ° C. and a film of 150 microns thickness is obtained.

For pesticide treatment, 24 films were placed in a Bordeaux mixture (a widely used pesticide based on copper sulphate) and a suspension of water (10 g of a mixture in 1 liter of water). Hold for hours. The treated film is poured into a quartz tube and subjected to ASTM G26-9.
Exposure according to 6 in a Atlas Ci65 Xenon Arc Weather O-meter with a black panel temperature of 63 ° C. and a continuous dry cycle. During exposure, FT-IR
Performance is evaluated periodically by measuring the increase in carbonyl (iCO; increase in carbonyl concentration) with a spectrophotometer. The results are summarized in the table below.

[0174]

Example 23: Light Stabilizing Effect on LDPE Film Treated with VAPAM Each compound of the items reported below was tested with 0.921
LDPE pellets characterized by a density of g / cm ³ and a melt flow index of 0.60 g / 10 min (190 ° C./2.16 Kg) (Riblene provided by Enichem, Milan, Italy; FF
29) is mixed through a masterbatch with a gentle mixer. A masterbatch is prepared beforehand by extruding powdered LDPE and 10% by weight of the compounds reported below. The mixture is blow extruded at 210 ° C. and a film of 150 microns thickness is obtained.

For pesticide treatment, 2 liters of an aqueous solution containing 50% of VAPAM (Baslini SpA, Treviglio / BG, Italy), ie of the formula CH ₃ -NH-CS 20 days in the presence of steam generated by an aqueous solution of 382 g / l of meta-sodium with SNa
Keep inside the dryer at 0 ° C. The treated film was poured into a quartz tube, and the black panel temperature was 63 ° C and the atlas (A) was used in a continuous dry cycle according to ASTM G26-96.
tlas) Exposure in a Ci65 Xenon Arc Weather O-meter. During exposure, the carbonyl increase is measured by an FT-IR spectrophotometer and the samples are tested for embrittlement to evaluate performance periodically. The results are summarized in the following table; low increases in carbonyl concentration and high T50 time indicate good stability.

[0177]

Example 24: Light Stabilizing Action in Greenhouse Films Each of the compounds reported below, and 0.921
LDPE pellets characterized by a density of g / cm ³ and a melt flow index of 0.60 g / 10 min (190 ° C./2.16 Kg) (Riblene provided by Enichem, Milan, Italy; FF
29) is mixed through a masterbatch with a gentle mixer. 10% by weight of powdered LDPE and the sterically hindered hydroxylamine ethers of the invention (Compound A) and components B (= metal co-stabilizer containing oxo and / or hydroxyl groups) and C (further co-stabilizer;
A masterbatch is prepared in advance by extruding an appropriate amount of a carboxylic acid salt). Mix 210
Blow extrusion at <RTIgt; C </ RTI> and obtain a film 150 microns thick. Pontecchio Marconi
In Bologna, Italy, the film is exposed on a roof facing the south of the greenhouse.

VAPAM (Baslin)
i) SpA, Torebigurio (Treviglio) / BG, Italy), namely metam having the formula CH ₃ -NH-CS-SNa - Aqueous solution of sodium (metam-sodium) 382g / liter; Sesumetorin (SESMETRIN) (Bimekkusu (Bim
ex) SpA, Isola / VI, Italy): 23.75% (% w / w) aqueous solution of permethrin having With a solution of 4 liters of VAPAM in 10 liters of water every 6 months and monthly with SESMETRIN (5 g of 5 liters of water)
Treat the greenhouse. During the exposure, the performance is periodically evaluated by measuring the increase in carbonyl by FT-IR spectrophotometer. Exposure is measured in kilo Wrangler (Klys; energy per unit area); 1100 Klys corresponds to one year of exposure.

[0180]

Example 25: Wood coating a) Impregnation: A commercially available impregnating agent ("Xylamon®" with a solids content of 5.2% from Sepam)
on) Impregnate the substrate (pine) using Incolore "). Impregnate with a brush (one application) and dry at room temperature for 24 hours. b) Topcoat: Topcoat Is made from the following material: 73.8 parts of alkyd resin (Jagol®)
(Jagol) PS21, E. Jaguar (E.Jager KG),
0.52 parts of anti-skinning agent (Exkikin®)
n) 2, Servo Delden
V. ), 20.8 parts of an aliphatic hydrocarbon solvent (Exxsol D40, Exxon Chemical, Germany)
(Deutsche Exxon Chemical Co., Ltd.), 4.16 parts of metal desiccant (registered trademark Jager Antihydro-Trockner) E. Jag
er) KG), 0.70 part of PE-wax, 21 in solvent
% (Registered trademark LancoGlidd AH,
G. FIG. M. Langer & Co).

The top coat was treated with 2% UVA (the following formula: A compound represented by the formula: Ciba Specialty Chemicals (Cib
a UV absorber from Specialty Chemicals) and 1% of the inventive stabilizers shown in the table below. All concentrations are by weight based on the solids of the binder. A topcoat is applied to the impregnated pine board with a brush (two applications) and dried at room temperature for 24 hours after each application. Accelerated exposure conditions (QUV, light irradiation at 70 ° C for 8 hours, compression at 50 ° C for 4 hours,
The plate is exposed to a UV-A lamp. The gloss (60 °) is measured according to DIN 67530 every 400 hours of exposure. An unexposed pine board with an unstabilized topcoat is used as a reference. The results are summarized in the table below.

[0183] The initial gloss (60 °) for all samples is 92-93. The results show that good retention of gloss is achieved with the stabilizers of the present invention.

Example 26: Stabilization of a 2-coat metallic finish Dissolve the light stabilizer to be tested in 30 g of Solvesso 100® and the following composition (parts by weight)
The test is performed with a clear coat having Synthacryl SC303 ¹⁾ 27.51 Synthacryl SC370 ²⁾ 23.34 Maprenal 650 ³⁾ 27.29 Butyl acetate / butanol (37/8) 4.33 Isobutanol 4.87 Solvesso 150 (registered trademark ⁾ 2.72 Crystal oil K-30 ⁵⁾ 8.74 Leveling aid Registered trademark Baysilon MA ⁶⁾ 1.20──────────── ──────────────────── 100.00 ¹ acrylate resin, trademark Hoechst (Hoechst) AG; xylene / butanol Le (26: 9) 65% solution ² acrylate in resin, trademark Hoechst (Hoechst) AG; R Solvesso (Solvesso) 100 in a 75% solution ³ melamine resin, trademark Hoechst (Hoechst) AG; iso 55% solution ⁴ aromatic-butanol Hydrocarbon mixture, boiling range: 182 to 203 ° C. (R sorbet Tsu Seo (Solvesso) 150) or 161 to 178 ° C. (R Solvesso (Sol vesso) 100): Manufacturer: R Esso (Esso) ⁵ R 1% in Solvesso 150; manufacturer: Bayer AG

Based on the solids content of the varnish, 1% of the stabilizers indicated in the table below and the UVA 1.5 of Example 25
% To the clear coat. As a comparison, a clear coat without light stabilizer is used. The clear coat is diluted with Solvesso® 100 to spray the viscosity and the top coat is sprayed on a prepared aluminum plate (Uniprime Epoxy®, silver-metallic base coat). Adapt and bake at 130 ° C. for 30 minutes to obtain a transparent coated dry film with a thickness of 40-50 μm. Next, Atlas Xe-
Expose the sample on a Wom Weather O-meter (CAM 180) in the cycle indicated below; 40 'UV light,
Light with 20 ′ rain (front), 60 ′ light, dark with 60 ′ rain (both sides), light at 70 ° C., dark at 40 ° C. (filter: quartz / boron; 0.55 at 340 nm)
W / cm ² ). Then, at regular intervals, the surface gloss of the sample (20 ° gloss as defined in DIN 67530)
Is measured; high values indicate good stabilization.
The results are summarized in the table below.

[0186]

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Gianluca Ferri, Italy, 40011 Anzola Emiria (BIO), 13, Via Don Landi (72) Inventor, Massimiliano Sala, Italy, 41100 Modena Via e Instain 136

Claims (18)

[Claims] 1. The following formula I (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a C 1-8 alkyl group or a C 1
Represents 5 to 5 hydroxyalkyl groups;
₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ are the same as the carbon atom to which the group is attached. R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently of one another are independently a hydrogen atom, a C 1 -C 8 alkyl group, An alkenyl group having 2 to 8 atoms, an aryl group having 5 to 12 carbon atoms, and 1 to 4 carbon atoms
A haloalkyl group or an electron withdrawing group; or an aryl group having 6 to 12 carbon atoms substituted by a residue selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. R ₇ and R ₈ may together form a chemical bond; and R contains 2 to 500 carbon atoms;
And represents an organic bridging group that, together with the carbon and nitrogen atoms to which it is directly attached, forms a substituted 5, 6 or 7 membered cyclic structure. A method for producing a compound of the formula II Wherein all residues R and R ₁ to R ₉ are as defined in formula I. 2. The method according to claim 1, wherein the oxidation reaction is carried out in the presence of a solvent and an oxidizing agent selected from oxygen, peroxide, nitrate, permanganate and chlorate. 3. A compound of the formula II wherein R ₁ , R ₂ , R ₃ and R ₄ independently represent a C 1-8 alkyl group or a C 1-5 hydroxyalkyl group. Or R ₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ are the groups to which the group is attached 5 carbon atoms together with carbon atoms
To 12 cycloalkyl groups; R ₅ , R ₆ , R
₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 5 to 12 carbon atoms,
An electron withdrawing group; or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms substituted by a halogen atom; A substituted 6-membered ring containing from 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen and, together with two carbon and nitrogen, Represents a hydrocarbon group having 3 to 500 carbon atoms which forms a structure. A process for the preparation of compounds of the formula I by oxidizing the compounds of the formula
The described method. 4. Compounds of formula I and formula II,
R ₁ , R ₂ , R ₃ and R ₄ independently of one another preferably represent a methyl or ethyl group, R ₅ and R ₆ independently of one another represent a hydrogen atom or a methyl group;
₇ , R ₈ and R ₉ independently represent a haloalkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a nitro group, CN, COOR ₁₀ or R ₇ and R 9
₈ together form a chemical bond, and the bridging group R is a hydrocarbon group having 2 to 500 carbon atoms or a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, silicon and halogen. 1 or 2 atoms
2. The process according to claim 1, which represents a C2-C500 hydrocarbon group containing 00. 5. The following equation V (Wherein, R, R ₁ , R ₂ , R ₃ and R ₄ , R ₅ , R ₆
And R ₉ are as defined for formula I in claim 1 and R ₇ and R ₈ are hydrogen, C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C ₇ Selected from an aryl group having 5 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, and an electron-withdrawing group; or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Represents an aryl group having 6 to 12 carbon atoms, which is substituted by a substituted residue; and both R ₂₀ and R ₂₁ represent either a hydrogen atom or a halogen atom. A process for the preparation of a compound of the formula (I);
A process characterized in that the compound of formula I is oxidized and the resulting intermediate of formula I is hydrogenated and / or halogenated. 6. A) oxidation, thermal and / or actinic radiation
An organic polymer susceptible to degradation by the following formulas: and B)[Wherein each of R ′ and R isE represents an organic crosslinking group represented by_TwoIs -CO- or-
(CH_Two)_p-(Wherein P is 0, 1 or 2)
E;₁Is the two residues R_{twenty four}And R_{twenty five}Carbon with
Represents an atom, or> NR _{twenty five}Represents or
Represents an oxygen atom, and R_{twenty four}And R_{twenty five}Is a hydrogen atom or
Represents an organic residue, and a total of 2 to 500 crosslinking groups R
R;₁, R_Two, R_ThreeYou
And R_FourAre independently of each other an alkyl having 1 to 8 carbon atoms
Alkyl or hydroxyalkyl having 1 to 5 carbon atoms
Or a group represented by R₁And R_TwoIs the group
5 to 12 carbon atoms together with
Represents a cycloalkyl group of_ThreeAnd R_Four
Is a carbon atom together with the carbon atom to which the group is attached
R 5 represents a cycloalkyl group of the formulas 5 to 12;_Five,
R₆, R₇, R₈And R₉Are independent of each other
, An alkyl group having 1 to 8 carbon atoms, 2 carbon atoms
An alkenyl group having 8 to 8 carbon atoms, an alkyl group having 5 to 12 carbon atoms
Reel group, haloalkyl group having 1 to 4 carbon atoms,
A child withdrawing group; or an alkyl group having 1 to 4 carbon atoms,
An alkoxy group having 1 to 4 carbon atoms or a halogen atom
6 or more carbon atoms replaced by a residue selected from
R represents 12 aryl groups;₂₀And R_{twenty one}Is a halogen field
Represents a child; and R_{twenty two}And R_{twenty three}Represents a hydrogen atom,
Or together form a chemical bond. ]
A composition comprising at least one compound. 7. The composition according to claim 6, wherein the organic polymer comprises a thermoplastic organic polymer or a binder for coating. 8. Component B, based on the material to be stabilized
7. The composition according to claim 6, comprising 0.1 to 10% by weight of a stabilizer. 9. A solvent, pigment, dye, plasticizer, antioxidant, stabilizer, thixotropic agent, leveling aid, further light stabilizer, metal deactivator, phosphite and phosphonite. The composition of claim 6, comprising the following components: 10. Hydroxyphenyl-benzotriazole, 2-hydroxyphenyl-s-triazine,
10. The composition according to claim 9, comprising an additional component which is an ultraviolet absorber selected from benzophenone. 11. The following formula Ia Wherein the index n ranges from 1 to 15; R ₅ ,
R ₆ , R ₇ , R ₈ and R ₉ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 5 to 12 carbon atoms, an electron-withdrawing group Or an alkyl group having 1 to 4 carbon atoms,
R ₁₂ represents an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms substituted by a halogen atom; R ₁₂ represents an alkylene group having 2 to 12 carbon atoms;
An alkenylene group having 4 to 12 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, a cycloalkylenedi (alkylene having 1 to 4 carbon atoms) group having 5 to 7 carbon atoms, Alkylenedi (C 5 -C 7 cycloalkylene) group, phenylene (C 1 -C 4 alkylene) group or 1,4-piperazinediyl group, —O— or> N—X ₁
(Wherein X ₁ represents an acyl group having 1 to 12 carbon atoms or an (carbonyl having 1 to 12 carbon atoms) carbonyl group, or one of the definitions of R ₁₄ given below except for a hydrogen atom. C 4 -C interrupted by) having a represents a 12 alkylene group;. or R ₁₂
Is the following formula (Ib ′) or (Ic ′) Wherein m is 2 or 3, and X ₂ is a carbon atom having 1 to 18 carbon atoms, an unsubstituted or substituted by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms. An unsubstituted or substituted phenyl group substituted by one, two or three of an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; an unsubstituted or carbon atom Represents a phenylalkyl group having 7 to 9 carbon atoms which is substituted on the phenyl group by 1, 2 or 3 of the alkyl groups having 1 to 4 groups; and the radicals X ₃ independently of one another have 2 to 12 carbon atoms. . that of an alkylene group represents a group represented by); group a independently of one another -OR ₁₃ and, -N
(R ₁₄ ) (R ₁₅ ) or the following formula (Id ′) R ₁₃ , R ₁₄ and R ₁₅ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; one of an unsubstituted or an alkyl group having 1 to 4 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms substituted by 2 or 3 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; an unsubstituted or an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms A phenyl group substituted by 1, 2 or 3 alkoxy groups; unsubstituted or 7 to 9 carbon atoms substituted on the phenyl group by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms A phenylalkyl group; a tetrahydrofurfuryl group, or —O at the 2, 3 or 4 position
H, an alkoxy group having 1 to 8 carbon atoms, a di (alkyl having 1 to 4 carbon atoms) amino group or the following formula (I
e ') (Wherein Y represents —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ), and represents an alkyl group having 2 to 4 carbon atoms substituted by a group represented by the formula: Or —N (R ₁₄ ) (R ₁₅ ) additionally represents a group of formula (Ie ′); X represents —O— or> N—R ₁₆ ;
₁₆ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
An alkenyl group having 3 to 18 carbon atoms; 1, 2 or 3 of an unsubstituted or an alkyl group having 1 to 4 carbon atoms
C 5 -C 12 cycloalkyl substituted by C; C 7 -C 9 cycloalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 of C 1 -C 4 alkyl; Phenylalkyl group; tetrahydrofurfuryl group, the following formula (If ′) Or -OH at the 2, 3 or 4 position, an alkoxy group having 1 to 8 carbon atoms, di (1 carbon atom
R 4 represents an alkyl) amino group or a C 2 -C 4 alkyl group substituted by a group of the formula (Ie ′); R ₁₁ has one of the definitions given for R ₁₆ And the radicals B independently of one another have one of the definitions given for A. ] The compound represented by these. 12. A compound of the formula IIIc, IVa or Va[Where R is the following formulaE represents an organic crosslinking group represented by_TwoIs -CO- or-
(CH_Two)_p-(Wherein P is 0, 1 or 2)
E;₁Is the two residues R_{twenty four}And R_{twenty five}Carbon with
Represents an atom, or> NR _{twenty five}Represents or
Represents an oxygen atom, and R_{twenty four}And R_{twenty five}Is a hydrogen atom or
Represents an organic residue, and the crosslinking group R has a total of 2 to 500
A carbon containing carbon atoms and to which the group is directly attached
Substituted together with an elementary atom and a nitrogen atom
Forming a 6- or 7-membered cyclic structure; R
₁, R_Two, R_ThreeAnd R_FourAre independently of each other
1 to 8 alkyl groups or 1 to 5 carbon atoms
Represents a hydroxyalkyl group, or R₁And R
_TwoTogether with the carbon atom to which the group is attached
Represents a cycloalkyl group having 5 to 12 children, or
Is R_ThreeAnd R_FourTogether with the carbon atom to which the group is attached
To form a cycloalkyl group having 5 to 12 carbon atoms
Represents; R_Five, R₆, R₇, R₈And R₉Are independent of each other
A hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Alkenyl group having 2 to 8 carbon atoms, not having 5 carbon atoms
12 aryl groups, haloalk having 1 to 4 carbon atoms
A kill group, an electron withdrawing group; or an alkyl group having 1 to 4 carbon atoms.
Alkyl group, alkoxy group having 1 to 4 carbon atoms, halo
Carbon atom replaced by a residue selected from the gen atom
R represents an aryl group of the number 6 to 12;₂₀And R_{twenty one}Is
Represents a halogen atom; and R_{twenty two}And R_{twenty three}Is a hydrogen atom
Or together form a chemical bond,
R in the formula IIIc is(Where R_{twenty four}And R_{twenty five}Together represent = O, or
Or where R_{twenty four}Represents a hydrogen atom;_{twenty five}Is a hydrogen atom,
OH or phenoxy group or alkylphenoxy
An alkanoyloxy group substituted by a group. )so
It does not represent the crosslinking group represented. ] The compound represented by these. 13. R is a divalent C 7 -500 carbon atom.
A hydrocarbon group, or a nitrogen atom, an oxygen atom, a phosphorus atom,
Represents a hydrocarbon group having 2 to 500 carbon atoms and containing 1 to 200 heteroatoms selected from a sulfur atom, a silicon atom and a halogen atom; Or Wherein p is 0, 1 or 2; R ₁ , R ₂ , R ₃ and R ₄ independently of one another are an alkyl group having 1 to 8 carbon atoms or a carbon atom 1 atom
Represents 5 to 5 hydroxyalkyl groups;
₁ and R ₂ together with the carbon atom to which the group is attached represent a C 5 -C 12 cycloalkyl group, or R ₃ and R ₄ are the same as the carbon atom to which the group is attached. R ₅ and R ₆ independently of one another represent a hydrogen atom or a methyl group; and R ₇ , R ₈ and R
₉ is independently of each other a haloalkyl group having 1 to 4 carbon atoms, phenyl group, vinyl group, nitro group, CN, COO
R ₁₀ (wherein R ₁₀ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms or a phenyl group); R ₂₄ and R ₂₅ independently represent hydrogen Represents an atom or an organic residue as defined, and R ₂₆ is a hydrogen atom, or together with the remaining structure of formula (VIb), a nitrogen, oxygen, phosphorus, sulfur, 13. The compound according to claim 12, which represents an organic residue forming a hydrocarbon group having 2 to 500 carbon atoms containing 1 to 200 heteroatoms selected from a silicon atom or a halogen atom. 14. The following formula (1a), (1b) or (2)
a) or in the following equation (3) or (4)
13. The compound according to claim 12, comprising at least one of the groups represented.
Compound;[Wherein, n₁Is a number from 1 to 4, G and G₁Is
Each independently represents a hydrogen atom or a methyl group;₁₁Is
n-propoxy group, O-CH = C = CH_Two, O-CH =
CH-CH_ThreeOr halogenated n-propoxy groups, especially
n-propoxy group or brominated n-propoxy group
And n₁If is 1, then G₁₂Is one of the oxygen atoms or
Charcoal uninterrupted or interrupted by more
An alkyl group having 1 to 18 atoms, a cyanoethyl group,
Benzoyl group, glycidyl group; aliphatic, alicyclic, unsaturated
Or containing aromatic carboxylic acid, carbamic acid or phosphorus
No monovalent or monovalent silyl group of the acid, preferably 2
Aliphatic carboxylic acid radicals having 18 carbon atoms, 7
Alicyclic carboxylic acids having from 15 to 15 carbon atoms
Group, or an α, β-unsubstituted group having 3 to 5 carbon atoms.
Represents a group of saturated carboxylic acids, each carboxylic acid,
Aliphatic, cycloaliphatic or aromatic moieties, if present
-COOZ in minutes₁₂Substituted by one to three of the groups
Where Z₁₂Is a hydrogen atom, carbon
C 1 -C 20 alkyl, C 3 -C 3
12 alkenyl groups, cycloalkyl having 5 to 7 carbon atoms
Represents a alkyl group, a phenyl group or a benzyl group;₁But
In case of 2, G₁₂Is alkylene having 2 to 12 carbon atoms
Groups, alkenylene groups having 4 to 12 carbon atoms, xylyl
Rene group; aliphatic, alicyclic, aromatic aliphatic or aromatic di
Divalent of carboxylic, dicarbamic or phosphorus-containing acids
Or a divalent silyl group, preferably from 2 to 36
Groups of aliphatic dicarboxylic acids having carbon atoms, or 8
Alicyclic or aromatic dicarbons having 14 carbon atoms
Having carboxylic acid groups or 8 to 14 carbon atoms
Aliphatic, alicyclic or aromatic dicarbamic acid groups
Where each dicarboxylic acid is -COOZ ₁₂
An aliphatic, alicyclic or aromatic moiety according to one or two of the radicals
Min, and n₁Place of 3
If G₁₂Is -COOZ₁₂Aliphatic, cycloaliphatic or
Aliphatics, fats that can be substituted in the aromatic moiety
A trivalent group of a cyclic or aromatic tricarboxylic acid,
Trivalent groups of licarbamic acid or phosphorus-containing acids
Or represents a trivalent silyl group;₁Place of 4
If G₁₂Is aliphatic, alicyclic or aromatic tetracarboxylic
Represents a tetravalent group of an acid;₁, R_Two, R_ThreeAnd R_FourAre
Independently of one another an alkyl group having 1 to 8 carbon atoms or
Represents a hydroxyalkyl group having 1 to 5 carbon atoms
Or R₁And R_TwoIs the carbon to which the group is attached
A cycloalkyl having 5 to 12 carbon atoms together with an atom
Represents a alkyl group, or R_ThreeAnd R_FourIs the group
Together with the combined carbon atoms have 5 to 5 carbon atoms
12 represents a cycloalkyl group; G represents a hydrogen atom or
Represents a tyl group; G₁And G_TwoAre independent of each other
Or a methyl group, or together form a substituent ＯO
And G_ThreeRepresents a direct bond or a methylene group
And the open bonds of equations (3) and (4) are defined above.
Bonds with carbon, nitrogen or oxygen atoms of organic residues
Then G₁₃Is a hydrogen atom, an alkyl having 1 to 12 carbon atoms
A hydroxyalkyl group having 2 to 5 carbon atoms,
Cycloalkyl group having 5 to 7 carbon atoms, number of carbon atoms
7 to 8 aralkyl groups, having 1 to 18 carbon atoms
An alkanoyl group, an alkenoy having 3 to 5 carbon atoms
Or a benzoyl group or the following formula (1b-1)Represents a group represented by_TwoIs the number 1, 2 or 3;
And n_TwoIf is 1, G₁₄Is hydrogen atom, carbon atom number 1
An alkyl group having 18 to 18 carbon atoms and an alkyl group having 3 to 8 carbon atoms
A kenyl group, a cycloalkyl group having 5 to 7 carbon atoms;
Hydroxyl, cyano, alkoxycarbonyl or cal
Alkyl having 1 to 4 carbon atoms substituted by a bamide group
Kill group; glycidyl group, formula -CH_Two-CH (OH) -Z
Or a formula -CONH-Z (where Z is a hydrogen atom, methyl
Represents a phenyl group or a phenyl group. ) Represents a group represented by;
_TwoIs 2, G₁₄Is alkyl having 2 to 12 carbon atoms
An alkylene group, an arylene group having 6 to 12 carbon atoms,
Rylene group, -CH_Two-CH (OH) -CH_TwoGroup or-
CH_Two-CH (OH) -CH_Two—O—D—O— group (formula
Wherein D is an alkylene group having 2 to 10 carbon atoms,
C 6 -C 15 arylene group, no C 6
And 12 cycloalkylene groups. ) Or is
Ih G₁₃Is an alkanoyl group, an alkenoyl group or a ben
Provided that they do not represent a zoyl group,₁₄Is also 1-
Oxo-alkylene group having 2 to 12 carbon atoms;
Aromatic, cycloaliphatic or aromatic dicarboxylic acids or dicarbamides
May represent a divalent radical of the acid or alternatively a radical -CO-
Can, n_TwoIf is 3, G₁₄IsRepresents a group represented by_TwoIf is 1, G₁₃You
And G₁₄Are aliphatic, alicyclic or aromatic together
Represents a divalent group of 1,2 or 1,3-dicarboxylic acid
be able to. ]. 15. A compound of the formula IIIb (Wherein groups A are independently of one another —OR ₁₃ , —N (R ₁₄ )
(R ₁₅ ) or the following formula (IIId) X represents —O— or> N—R ₁₆ ; R ₁₆ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; unsubstituted Or a cycloalkyl group having 5 to 12 carbon atoms substituted by 1, 2 or 3 of an alkyl group having 1 to 4 carbon atoms; 1, 2, or 3 of an unsubstituted or an alkyl group having 1 to 4 carbon atoms A phenylalkyl group having 7 to 9 carbon atoms, which is substituted on the phenyl group by a tetrahydrofurfuryl group; Or —OH, an alkoxy group having 1 to 8 carbon atoms, a di (alkyl having 1 to 4 carbon atoms) amino group or a formula (I)
2 to carbon atoms substituted by a group represented by e ') represents a 4 alkyl; R ₁₁ has one of the definitions given for R _16; and the group B are, independently of one another A Has one of the definitions given for; and here, formula (Ie ') and all other symbols are as defined in claim 11 with respect to formula Ia. Claim 1 represented by:
2. The compound according to 2. 16. A compound of the formula Ia according to claim 11 and / or a compound of the formula IIIc, IVa, Va according to claim 12, as a stabilizer for organic materials against decomposition by light, oxygen and / or heat. Methods using the compounds represented. 17. A method for stabilizing an organic material against decomposition by light, oxygen and / or heat by applying a stabilizer to the organic material or blending the stabilizer with the organic material. The method according to claim 11, wherein the stabilizer is a compound represented by formula Ia according to claim 11 and / or a compound represented by formula IIIc, IVa or Va according to claim 12. 18. A flame retardant for an organic polymer,
A method using the compound represented by the formula IIIc or Va according to claim 12.