UV-absorber and light sensible organic material containing it.

The present invention relates to new UV absorbers of the anthrone, acridon and xanthone type and light-sensitive organic material containing them.

CH-A-379,760 describes a method for protecting light-sensitive materials from the harmful effects of light, in particular UV rays, in which 1-hydroxyxanthone compounds are used.

It has now been found that certain anthrones, acridones and another class of xanthone compounds can also be used successfully for this purpose.

The present invention relates to compounds of the formula<chemistry id="chem0001" num="0001"><img file="EP0434618A2_D0001.tif" /></chemistry> wherein X, O, NH or CH₂ and R₀ are hydrogen or a radical of the formula - (CH₂)_nIs CO₂R, wherein n is 1 or 2 and R is alkyl having 1 to 18 carbon atoms or <img file="EP0434618A2_D0002.tif" /> is where m is 1 to 12, R₁ alkyl having 1 to 18 carbon atoms or hydroxyl-substituted and / or optionally interrupted alkyl having 4 to 18 carbon atoms, ―COR₄, where R₄ is alkyl or alkenyl each having 2 to 12 carbon atoms,<chemistry id="chem0002" num="0002"><img file="EP0434618A2_D0003.tif" /></chemistry> means, wherein R₅ is alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms and y is 1 to 12, and R₂ and R₃ are independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, ―OR₁, wherein R₁ has the meaning given, or is chlorine, and R₆ is hydrogen or alkyl having 1 to 4 carbon atoms.

The present invention further relates to a process for the preparation of these compounds, light-sensitive organic material which comprises at least one of these compounds in which XO is, and a process for protecting light-sensitive organic materials by using the compounds of the formula (1) in which XO is .

In the compounds of the formula (1), the substituent R₀ in addition to hydrogen denotes a radical of the formula - (CH₂)_n-CO₂R. R is an alkyl radical with 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl and corresponding branched isomers, or a radical of the formula (̵CH₂CH₂O<img file="EP0434618A2_D0004.tif" />where m is an integer from 1 to 12. Index n is 1 or 2. R₁ is alkyl having 1 to 18 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl or octadecyl, where appropriate branched alkyl radicals can also be used. The alkyl radicals R 1, if they contain 4 to 18 carbon atoms, can be substituted with one or more hydroxyl groups. They can also be interrupted by one or more oxygen atoms and, if appropriate, additionally have one or more hydroxyl groups. Examples of such alkyl radicals would be groups such as - (CH₂)_x-O- (CH₂)_yH and - (CH₂)_x-O- (CH₂)_y-O- (CH₂)_e.g.H, the sum of x and y or x, y and z being 4 to 18, and<chemistry id="chem0003" num="0003"><img file="EP0434618A2_D0005.tif" /></chemistry> to be mentioned, wherein r is 0 or 1 and s is 1 to 15.

R₁ also means a radical of the formula ―COR₄, wherein R₄ is alkyl or alkenyl each having 2 to 12 carbon atoms. Examples of such alkyl radicals are mentioned above. Examples of the alkenyl radicals are ethenyl, propenyl, butenyl, hexenyl, octenyl, nonenyl and dodecenyl, where the alkenyl radicals R 1 can also be polyunsaturated. R 1 can also represent the corresponding branched isomers. R₄ also means residues of the formulas<chemistry id="chem0004" num="0004"><img file="EP0434618A2_D0006.tif" /></chemistry> wherein R₅ is alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms (see above for examples) and y is 1 to 12.

Furthermore, R₁ represents a radical of the formula<chemistry id="chem0005" num="0005"><img file="EP0434618A2_D0007.tif" /></chemistry> where R₅ and y have the meaning given.

The substituents R₂ and R₃ independently of one another are hydrogen, alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms (see above for examples), OR₁, wherein R₁ has the meaning given, or chlorine.

X is a divalent radical and means CH₂, NH or O.

Preferably in the compounds of formula (1) the substituents R₂ and R₃ are hydrogen or methyl.

Another group of preferred compounds of formula (1) is characterized in that R₁ optionally substituted with hydroxyl and / or optionally interrupted by oxygen alkyl having 4 to 12 carbon atoms ―COR₄ or<chemistry id="chem0006" num="0006"><img file="EP0434618A2_D0008.tif" /></chemistry> is wherein R₄ is alkyl of 4 to 8 carbon atoms, y is 1 to 4 and R₅ alkyl of 1 to 4 carbon atoms.

Of these, those compounds are particularly suitable in which R 1 is alkyl having 1 to 8 carbon atoms.

Furthermore, those compounds of the formula (1) are preferred in which R₀ is a radical of the formula ―CH₂CH₂CO₂R, in which R is alkyl having 1 to 8 carbon atoms or (̵CH₂CH₂O<img file="EP0434618A2_D0009.tif" />is and m is 6 to 8. According to the invention, photosensitive organic materials can be protected against the damaging influence of UV radiation by providing these materials with a protective layer, for example a lacquer, which contains at least one compound of the formula (1) in which X is O, or on such a compound incorporated in the usual way into the organic material. Analogously, compounds of formula (1) can be used, wherein X is NH or CH₂.

According to the invention, photosensitive organic materials are free from sterically hindered amines or hydroxyphenylbenztriazole derivatives.

Examples of light-sensitive organic materials that can be protected according to the invention from harmful exposure to light are:<ul id="ul0001" list-style="none"><li>1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene as well as polymers of cycloolefins such as cyclopentene or norbornene; also polyethylene (which may or may not be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).</li><li>2nd Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).</li><li>3rd Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as, for example Ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene Copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore mixtures of such copolymers with one another and with polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers and LLDPE / ethylene Acrylic acid copolymers.</li><li>3a. Hydrocarbon resins (e.g. C₅-C₉) including hydrogenated modifications thereof (e.g. tackifier resins).</li><li>4th Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).</li><li>5. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.</li><li>6. Graft copolymers of styrene or a-methylstyrene, such as styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene, styrene and alkyl acrylates or Alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkylacrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the copolymers mentioned under 5), as described, for example, as so-called ABS, MBS, ASA or AES polymers are known.</li><li>7. Halogen-containing polymers, such as, for example, polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.</li><li>8th. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.</li><li>9. Copolymers of the monomers mentioned under 8) with one another or with other unsaturated monomers, such as, for example, acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene-butadiene.</li><li>10th Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallylphthalate, polyallylmelamine; as well as their copolymers with olefins mentioned in point 1.</li><li>11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers.</li><li>12th Polyacetals, such as polyoxymethylene, and also those polyoxymethylenes which contain comonomers, such as, for example, ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.</li><li>13. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.</li><li>14. Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and their precursors.</li><li>15. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides, made from hexamethylenediamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, for example Poly-2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenylene-isophthalamide. Block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Furthermore, polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide systems").</li><li>16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.</li><li>17th Polyesters which are derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters which are derived from polyethers having hydroxyl end groups; furthermore polyesters modified with polycarbonates or MBS.</li><li>18th Polycarbonates and polyester carbonates.</li><li>19th Polysulfones, polyether sulfones and polyether ketones.</li><li>20th Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.</li><li>21. Drying and non-drying alkyd resins.</li><li>22. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications.</li><li>23. Crosslinkable acrylic resins derived from substituted acrylic esters, such as epoxy acrylates, urethane acrylates or polyester acrylates.</li><li>24th Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.</li><li>25th Crosslinked epoxy resins derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.</li><li>26. Natural polymers, such as cellulose, natural rubber, gelatin, and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.</li><li>27 Mixtures (polyblends) of the aforementioned polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.</li></ul>

In addition to the compounds of the formula (1), the light-sensitive organic materials according to the invention can also contain other customary stabilizers and additives, such as:

1. Antioxidants

1.1. Alkylated monophenols

,

e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert .butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol , 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.

1.2. Alkylated hydroquinones

,

e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ether

,

e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6- tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert.butyl-2-methylphenol).

1.4. Alkylidene bisphenols

,

e.g. 2,2'-methylene-bis- (6-tert.butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert. butyl-4-ethylphenol), 2,2'-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylene-bis- (4-methyl-6- cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6-di-tert.butylphenol), 2,2'-ethylidene bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (6-tert.butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (α- methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis- [6- (α, α-di-methylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di -tert.-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl) butane, 2.6 -Bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1 , 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis- [3,3-bis- (3'-tert-butyl-4 ′ -Hydroxyphenyl) -butyrate], Bis- (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -dicyclopentadiene, bis- [2- (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6- tert-butyl-4-methylphenyl] terephthalate.

1.5 benzyl compounds

,

e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) -2,4,6-trimethylbenzene, bis (3,5-di-tert-butyl-4-hydroxy-benzyl) ) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, 1,3,5 -Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, Ca salt of monoethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.6. Acylaminophenols

,

e.g. 4-hydroxy-lauric anilide, 4-hydroxystearic anilide, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, N- (3,5- di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.

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

with mono- or polyhydric alcohols, such as with methanol, octa-decanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide .

1.8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid

with mono- or polyhydric alcohols, such as with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) - oxalic acid diamide.

1.9. Ester of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid

with mono- or polyhydric alcohols, such as with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) - oxalic acid diamide.

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

,

such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

2nd UV absorbers and light stabilizers

2.2. 2-hydroxybenzophenones

,

such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4 , 4'-dimethoxy derivative.

2.3. Esters of optionally substituted benzoic acids

,

such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert.butyl-benzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4-hydroxybenzoic acid - 2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4. Acrylates

,

such as, for example, α-cyano-β, β-diphenylacrylic acid ethyl or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, α-carbomethoxy-p-methoxy cinnamic acid methyl ester, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indoline.

2.5. Nickel compounds

,

such as Nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as 1: 1 or 1: 2-complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methyl-phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6. Oxalic acid diamides

,

such as 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'di -tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.

2.7. 2- (2-hydroxyphenyl) - 1,3,5-triazines

,

such as 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- (2nd -hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) - 1 , 3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3rd Metal deactivators

,

such as N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis- (3,5-di-tert.butyl-4 -hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide.

4th Phosphites and phosphonites

,

such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert.butylphenyl) phosphite, diisodechritol, diisodechritol , 4-di-tert.butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert.butylphenyl) -4,4′-biphenylene diphosphonite, 3,9-bis (2, 4-di-tert.butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane.

5. Peroxide destroying compounds

,

such as esters of β-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol-tetrakis (tetrakis) propionate.

6. Polyamide stabilizers

,

such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers

,

such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K Palmitate, antimony catecholate or tin catecholate.

8th. Nucleating agents

,

such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcing agents

,

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

10th Other additives

,

such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.

Of the organic materials that can be protected against light damage according to the invention, organic polymers are to be emphasized, in particular synthetic polymers. Thermoplastic polymers and, in particular, paint compositions are therefore preferably protected, with the latter in particular stabilizing the polymeric binder against the influence of light.

Lacquer compositions or lacquers which contain the compounds of the formula (1) can be, for example, pigmented or unpigmented lacquers or metallic effect lacquers. They can contain an organic solvent or be solvent-free or be aqueous lacquers

The paints can contain at least one of the polymers listed above as a binder. Examples of varnishes with special binders are the following:<ul id="ul0002" list-style="none"><li>1. Paints based on cold or hot crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, optionally with the addition of an acidic curing catalyst;</li><li>2nd Two-component polyurethane lacquers based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic polyisocyanates;</li><li>3rd One-component polyurethane varnishes based on blocked polyisocyanates, which are deblocked during baking;</li><li>4th Two-component paints based on (poly) ketimines and aliphatic or aromatic polyisocyanates;</li><li>5. Two-component paints based on (poly) ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methyl acrylamidoglycolate methyl ester;</li><li>6. Two-component lacquers based on polyacrylates and polyepoxides containing carboxyl or amino groups;</li><li>7. Two-component paints based on acrylate resins containing anhydride groups and a polyhydroxy or polyamino component;</li><li>8th. Two-component paints based on (poly) oxazolidines and acrylate resins containing anhydride groups or unsaturated acrylate resins or aliphatic or aromatic polyisocyanates.</li><li>9. Two-component paints based on unsaturated polyacrylates and polymalonates;</li><li>10th thermoplastic polyacrylate varnishes based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;</li><li>11. Coating systems based on siloxane-modified acrylic resins; and</li><li>12th Coating systems based on fluorine-modified acrylic resins.</li></ul>

The paints can also be radiation-curable paints. In this case, the binding agent consists of monomeric or oligomeric compounds which contain ethylenic double bonds and are converted into a crosslinked high-molecular form by irradiation with actinic light or with electron beams. This is usually a mixture of such compounds.

The lacquers can be applied as single-layer or two-layer lacquers, the stabilizers according to the invention preferably being added to the top layer.

The lacquers can be applied to the substrates (metal, plastic, wood, etc.) by the usual methods, for example by brushing, spraying, pouring, dipping or electrophoresis.

Paints that are applied to automobiles (car paints) are particularly preferred. If the photosensitive organic materials according to the invention are coating compositions, the latter preferably contain no alkyd resins as binders.

The compounds of the formula (1) can be incorporated into the lacquers or lacquer compositions and other light-sensitive organic materials by customary, known methods. As a rule, the proportions are from 0.01 to 5.0, in particular from 0.02 to 3.0,% by weight of UV absorber, based on the organic material, the amounts of UV absorber to be chosen depending on the nature of the material and depend on the requirements for its stability.

The components of stabilizer combinations can be added to the organic material individually or as a mixture. The compounds of the formula (1) and, if appropriate, further stabilizers are preferably added before or during the shaping of the material, provided that they are, for example, thermoplastics. However, the addition can also take place during the polymerization or before this to the starting monomers.

The compounds of the formula (1) can be prepared by methods known per se, for example by heating a mixture of the compounds of the formulas<chemistry id="chem0007" num="0007"><img file="EP0434618A2_D0010.tif" /></chemistry> wherein R₀, R₂, R₃, R₆ and X have the meaning given, the intermediate compound of the formula<chemistry id="chem0008" num="0008"><img file="EP0434618A2_D0011.tif" /></chemistry> are obtained, which can be converted into the compound of formula (1) by reaction with, for example, R₁-Cl or R₁-Br, in which R₁ has the meaning given.

The following examples further illustrate the invention. Unless otherwise stated, parts or percentages are based on weight.

Manufacturing examples

:

Example 1:

22.8 g 1,3-dihydroxyxanthone (manufactured according to Grover, J. Chem. Soc. <u style="single">1955</u>, 3982) are refluxed in 250 ml of methyl ethyl ketone with 15.2 g of K₂CO₃ and 21.2 g of 1-bromooctane for 15 hours. After cooling, the salt is filtered off and the methyl ethyl ketone solution is evaporated in vacuo. Crystallization of the residue from heptane gives 1-hydroxy-3-octoxyxanthone with a melting point of 98 ° C.

Example 2:

22.8 g 1,3-dihydroxyxanthone (manufactured according to Grover, J. Chem. Soc. <u style="single">1955</u>, 3982) are placed in 300 ml of absolute ethanol. Add slowly, in portions, 11.2 g of potassium tert-butoxide and then 0.5 g of potassium iodide. At room temperature, 12.3 g of ethyl chloroacetate are added dropwise in about 15 minutes and the reaction mixture is then heated under reflux for 6 hours. It is poured into 500 ml of water and acidified with 20 ml of glacial acetic acid. The resulting precipitate is slipped off, dried. The compound of the formula is obtained by recrystallization from hexane<chemistry id="chem0009" num="0009"><img file="EP0434618A2_D0012.tif" /></chemistry> with a melting point of 165 ° C.

Example 3:

22.8 g 1,3-dihydroxyxanthone (manufactured according to Grover, J. Chem. Soc. <u style="single">1955</u>, 3982) are heated to 120 ° C. in 200 ml of xylene. After the addition of 1.5 g of tetrabutylammonium bromide, 20.5 g of 2-ethylhexyl glycidyl ether are added dropwise in about 10 minutes and the reaction mixture is then stirred at 120 ° for 24 hours. 5 g of Tonsil AC are then added to the reaction solution, the mixture is stirred at 110 ° for 5 minutes and filtered. The filtrate is evaporated, the residue is taken up in 300 ml of hexane and 50 g are filtered through silica gel. After evaporation, the compound of the formula is obtained<chemistry id="chem0010" num="0010"><img file="EP0434618A2_D0013.tif" /></chemistry> in the form of a yellowish resin that slowly crystallizes. The melting point is 56 to 58 ° C.

Application example 1:

The UV absorbers according to the invention are tested in a 2-layer metallic lacquer.

A clear lacquer with the following composition is produced:<tables id="tabl0001" num="0001"><img file="EP0434618A2_D0014.tif" /></tables>

1 part of the compound from preparation example 1, predissolved in 10 parts of xylene, is added.

This clear coat is diluted with a mixture of xylene (13 parts), butanol (6 parts) and butyl glycol acetate (1 part) to make it sprayable and onto a prepared aluminum sheet (coil coat-coated, automotive filler, silver metallic basecoat based on polyester / cellulose acetate butyrate / melamine resin) sprayed and baked at 130 ° C for 30 minutes. The result is a dry film thickness of 40 to 50 µm clear varnish. For comparison, an equally prepared aluminum sheet is coated with the clear coat defined above, but which is free of UV absorbers.

The samples thus obtained are checked for gloss retention after weathering. In comparison to the sample without UV absorber, the samples stabilized according to the invention show significantly better weathering stability. The results are summarized in Table 1 below.

Table 1:

Evaluation of gloss retention after weathering according to DIN 67530 (20 ° C gloss)<tables id="tabl0002" num="0002"><img file="EP0434618A2_D0015.tif" /></tables> Cycle: 8 hours UV (UVB-313), 70 ° C; 4 hours cond., 50 ° C (UVCON)

Example of use 2:

Application example 1 is repeated, but 0.5 part of the compound of the formula (6) is used as the additional UV absorber<chemistry id="chem0011" num="0011"><img file="EP0434618A2_D0016.tif" /></chemistry>

Table 2:

Evaluation of gloss retention after weathering according to DM 67530 (20 ° gloss)<tables id="tabl0003" num="0003"><img file="EP0434618A2_D0017.tif" /></tables> Cycle: VDA method C (Xenotest 1200)