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CA2032692A1 - Photosensitive organic material containing uv absorbers - Google Patents

Photosensitive organic material containing uv absorbers

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Publication number
CA2032692A1
CA2032692A1 CA 2032692 CA2032692A CA2032692A1 CA 2032692 A1 CA2032692 A1 CA 2032692A1 CA 2032692 CA2032692 CA 2032692 CA 2032692 A CA2032692 A CA 2032692A CA 2032692 A1 CA2032692 A1 CA 2032692A1
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Prior art keywords
carbon atoms
alkyl
formula
hydrogen
compound
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CA 2032692
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French (fr)
Inventor
Godwin Berner
Andreas Valet
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D311/86—Oxygen atoms, e.g. xanthones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Paints Or Removers (AREA)

Abstract

A-17884/+

Photosensitive organic material containing UV absorbers Abstract of the Disclosure Compounds of the formula (1)

Description

-1 2~3~

A-17884/+

Photosensitive organic material containing UV absorbers The present invention relates to photosensitive organic material containing novel UV absorbers, to novel thioxanthone compounds and to the use thereof as UV absorbers.

CH-~-379,760 discloses a process for the protection of photosensitive materials from the harmful effect of light, especially UV rays, wherein 1-hydroxyxanthone compounds are used. It has now been found that certain anthrones, acridones and thioxanthones can also be used successfully for this purpose.

The present invention relates to photosensitive organic material containing as UV absorber at least one compouncl of the formula (1) ! 1! 1 1!
R~ ~ ' OR~
3 Ro wherein X is CHz, NH or S, R is hydrogen or a radical of the formula -~CH2? CO2R, wherein n is 1 or 2 and R is alkyl having 1 to 18 carbon atoms or -~CH2CH20~-H
wherein m is 1 to 12, R1 is hydrogen, alkyl having 1 to 12 carbon atoms, alkyl having 2 to 18 carbon atoms which is substituted by hydroxyl and/or interrupted by oxygen, alkenyl having 2 to 12 carbon atoms or -COR4, wherein R4 is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, -(CH2) -CRs or -O-CH2CH(OH)CHzO-CRs, or R1 -(CH2) O-~Rs, .. . : .
~ : , . . ;
. ,: . ... .

~ ?2 wherein R5 is alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms and y is 1 to 12, R2 and R2 independently of the other are hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, -OR1, wherein R1 is as defined, or chlorine, and R6 is hydrogen or alkyl having 1 to 4 carbon atoms.

The present invention further relates to a process for the protection of photosensitive organic materials from UV radiation by using the compounds of formula (1), if desired in combination with sterically hindered amines, to thioxanthone compounds of formula (1) and to a process for their preparation.
In the compounds of formula (1) present in the materials of the invention, the substituent R is either hydrogen or a radical of the formula -(CH2) -C02R. In said formula, R is an alkyl radical having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl, as well as corres-ponding branched isomers, or a radical of the formula -~CH2CH20~-H, wherein m is an integer from 1 to 12. The index n is 1 or 2. Apart from hydrogen, R1 is alkyl having 1 to 18 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl or octadecyl, corresponding branched alkyl radicals also being possible.
Alkyl radicals R1 having 2 to 18 carbon atoms can bo substituted by one or more hydroxyl groups. They can also be interrupted by one or more oxygen atoms and, if desired, can additionally have one or more hydroxyl groups. Examples of such alkyl radicals are groupings such as -(CH2)x-0-(CH2)yH and -(CH2)x-0-(CH2)y~0~(CH2)zH, the sum of x and y or of x, y and z being 2 or, respectively, 3 to 18, and -ClH2CHCH2(0)r(CH2)sH wherein r is 0 or 1 and s is 1 to 15.

R1 is also alkenyl having 2 to 12 carbon atoms, such as ethenyl, propenyl, butenyl, hexenyl, octenyl, nonenyl and dodecenyl, it also being possible for the alkenyl radicals R1 to be polyunsaturated. R1 can also be the corresponding branched isomers.

3 ~ 2`~ 2 If R1 is a radical of the formula -COR4, R4 is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, examples of appropriate radicals being listed above, or else -(CH2) -~Rs, or -O-CH2CH(OH)CHzO-CRs, wherein Rs 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.

R1 is also -(CHz) O-CRs, wherein Rs and y are as defined.

The substituents Rz and R3 independently of the other are hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms (see above for examples), -OR1, wherein R1 is as defined, or chlorine.

Apart from hydrogen, R6 is alkyl having 1 ~o 4 carbon atoms, such as methyl, propyl, isopropyl, butyl or t-butyl.

The divalent group X is CHz, NH or S. If the compounds of formula (1) are used in combination with sterically hindered amines or hydroxy-phenylbenzotriazole derivatives, X can additionally be O.

In the compounds of formula (1), the substituents R2 and R2 are preferably hydrogen.

Other preferred compounds of formula (1) are those in which R -CHzCHzCOzR wherein R is alkyl having 1 to 18 carbon atoms or -~CH2CH20~-H in which m is 4 to 8, and those in which R is a radical of the formula -CH2CH2CO2CH3.

In another group of compounds of formula (1) which are preferably used,the substituent Rl is hydrogen, alkyl having 4 to 8 carbon atoms, alkyl having 2 to 12 carbon atoms which is substituted by hydroxyl and/or interrupted by oxygen, alkenyl having 4 to 12 carbon atoms or -COR4 in which R4 is alkyl having 4 to ô carbon atoms.

: - ,, ~........... . :
`' . :
' , ' ' ':.. ~

~32~

Of these compounds, those in which the substituent Rl is hydrogen or alkyl or alkenyl each having 4 to 8 carbon atoms are especially suitable.

It is possible to protect photosensitive organic materials from the harmful effect of ~V radiation by providing these materials with a protective layer, e.g. a lacquer, which contains at least one compound of formula (1), or by incorporating such a compound into the organic material in a manner conventional per se. Combinations of such compounds of formula (1), wherein X is CH2, NH, O or S, with the known light stabilizers of the sterically hindered amine type, or with hydroxy-phenylbenzotriazole derivatives, can also be used successfully for this purpose.

Examples of the wide variety of photosensitive organic materials which can be protected according to the invention from the harmful effect of light arc:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-l-ene, polymethylpent-l-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, e.g. of cyclopentene or norbornene, and polyethylene (which can be uncrosslinked or cross-linlced), e.g. high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), e.g. mixtures of poly-propylene with polyisobutylene and of polypropylene with polyethylene (e.g. PPIHDPE, PP/LDPE) and mixtures of different types of polyethylene (e.g. LDPEIHDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, e.g. ethylenelpropylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-l-ene copolymers, propylene/isobutylene copolymers, ethylenelbut-l-ene copolymers, ethylenelhexene copolymers, ethylenelmethylpentene copolymers, ethylenelheptene 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), as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and also mixtures of such copolymers with each other and with polymers mentioned under 1), e.g.
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.

3a. Hydrocarbon resins (e.g. Cs-Cg)~ including hydrogenated modifi-cations thereof (e.g. tackifiers).
4. Polystyrene, poly(p-methylstyrene) and poly(-methylstyrene).
5. Copolymers of styrene or -methylstyrene with dienes or acrylic derivatives, e.g. styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/maleic anhydride and styrene/acrylonitrile/methyl acrylate; high-impact mixtures of styrene copolymers and another polymer, e.g. a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, e.g. styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or styrene/ethylene-propylene/styrene.
6. Graft copolymers of styrene or -methylstyrene, e.g. styrene on polybutadiene; styrene on polybutadiene/styrene or polybutadiene/acrylo-nitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on poly-butadiene, 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 polyalkyl acrylates or polyalkyl methacrylates; and styrene and acrylo-nitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 5), e.g. the mixtures known as ABS, MBS, ASA or AES polymers.

- ~
.. . . . .

, 7. Halogenated polymers such as polychloroprene, chlorinated rubber, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, and epichlorohydrin homopolymers and copolymers, and especially polymers of halogenated vinyl compounds, e.g. polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride and polyvinylidene fluoride; as well as copolymers thereof, such as vinyl chloride/vinyl-idene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.
8. Polymers derived from ~,B-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamides and poly-acrylonitriles.
9. Copolymers of the monomers mentioned under X) with each other or with other unsaturated monomers, e.g. acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers or acrylonitrile/vinyl halide copolymers, or acrylo-nitrile/alkyl methacrylate/butadiene terpolymers.
10. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoat~3, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polya:Llylmelamine; as well as copolymers thereof with olefins mentioned in section 1.
11. ~omopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
12. Polyacetals such as polyoxymethylene, and polyoxymethylenes con-taining comonomers, e.g. ethylene oxide; and polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
13. Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

:, :

c~
14. Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and from aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
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 and 4/6, polyamide 11, polyamide 12, and aromatic polyamides obtained from m-xylene, diamine and adipic acid; polyamides prepared from hexa-methylenediamine and isophthalic and/or terephthalic acid and, if desired, an elastomer as modifier, e.g. poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and also polyamides or copolyamides modified with EPDM or ABS, and polyamides condensed during processing ("RIM polyamide systems").
16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
17. Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as poly-ethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoates, as well as block polyether-esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
18. Polycarbonates and polyester-carbonates.
19. Polysulfones, polyether-sulfones and polyether-ketones.
20. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other, such as phenollformaldehyde resins, urea/formaldehyde resins and melaminelformaldehyde resins.
21. Drying and non-drying alkyd resins.

'-: ,,'':'~
.~ `:

, 2~i3~2 22. Unsaturated polyester resins de}ived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and vinyl compounds as crosslinking agents, and also halogenated modifications thereof of low flammability.
23. Crosslinkable acrylic resins derived from substituted acrylic acid esters, e.g. from epoxy acrylates, urethane acrylates or polyester acrylates.
24. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
25. Crosslinked epoxy resins derived from polyepoxides, e.g. from bisglycidyl ethers or from cycloaliphatic diepoxides.
26. Natural polymers such as cellulose, natural rubber and gelatin, and derivatives thereof chemically modified in a polymer-homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl cellulose; and rosins and derivatives.
27. Mixtures (polyblends) of the aforementioned polymers, e.g. PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PCIASA, PC/PBT, PVC/CPE, PVC/acrylates, POMlthermoplastic PUR, PClthermo-plastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 66 and copolymers, PA/HDPE, PA/PP and PA/PPO.

Examples of hindered amines which can be used in combination with the compounds of formula (1~, wherein X is CH2, NH, O or S, are polyalkyl-piperidine compounds containing at least one group of the formula RCH2\!CH3/R
-N~ \-/

9 ~3~13~

wherein R is hydrogen or methyl. ~ is preferably hydrogen. Said compounds are derivatives of polyalkylpiperidines, especially of 2,2,6,6-tetra-methylpiperidine. These compounds preferably carry one or two polar substituents or a polar spiro ring system in the 4-position of the piperidine ring. Said compounds can be low-molecular or oligomeric or polymeric compounds.

The following classes of polyalkylpiperidines are of particular importance:

a) Compounds of formula III

RCH2~ ~ H3~R
RZl- ~ /-_o- -R22 III
RCH2 CH; n wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R21 is hydrogen, oxyl, hydroxyl, Cl-Cl2 alkyl, C3-Cg alkenyl, C~-Ca alkynyl, C7-C12 aralkyl, C1-C18 alkoxy, Cs-C8 cycloalkoxy, C7-Cg phenylalkoxy, Cl-Cg alkanoyl, C3-Cs alkenoyl, C1-C1g alkanoyloxy, benzyloxy, glycidyl or a group -CH2CH(OH~-Z, wherein Z is hydrogen, methyl or phenyl, R2~ preferably being H, C1-C4 alkyl, allyl, benzyl, acetyl or acryloyl, and R22 when n is 1 is hydrogen, Cl-Cl 8 alkyl which may be interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, arali-phatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid, or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 C atoms, of a cycloaliphatic carboxylic acid having 7 to 15 C atoms, of an ~,B-un-saturated carboxylic acid having 3 to 5 C atoms or of an aromatic carboxylic acid having 7 to 15 C atoms, R22 when n is 2 is C1-C12 alkylene, C4-Cl2 alkenylene, xylylene, a divalent radical of an ali-phatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid, or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8 ~2~

- 14 C atoms or of an aliphatic, cyclosliphatic or aromatic dicarbamic acid having 8 -14 C atoms, R2z when n is 3 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a trivalent silyl radical, and Rz2 when n is 4 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Any Cl-C12 alkyl substituents are e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, ~-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Rz1 or R2z as Cl-Cl 8 alkyl can be e.g. the groups listed above and additionally n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, for example.

Rzl as C3-C8 alkenyl can be e.g. prop-l-enyl, allyl, methallyl, but-2-enyl, pent-2-enyl, hex-2-enyl, oct-2-enyl or 4-tert-butylbut-2-enyl.

R21 as C3-Cg alkynyl is preferably propargyl.

R21 as C7-Cl2 aralkyl is especially phenethyl and in particular benzyl.
Rzl as Cl-C8 alkanoyl i5, for example, formyl, propionyl, butyryl or octanoyl, but preferably acetyl, and R21 as C3-Cs alkenoyl is especially acryloyl~

R21 as Cl-Clg alkoxy is e.g. hexyloxy, heptyloxy, octyloxy or decyloxy.R21 as cycloalkoxy is preferably cyclohexyloxy. Rz1 as phenylalkoxy is preferably benzyloxy. Rz1 as alkanoyloxy is e.g. acetoxy, butyroyloxy, hexanoyloxy, octanoyloxy, decanoyloxy or stearoyloxy.

R22 as a monovalent radical of a carboxylic acid is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid radical.

' , , J

R22 as a divalent }adical of a dicarboxylic acid is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical.

R22 as a trivalent radical of a tricarboxylic acid is e.g. a trimellitic acid, citric acid or nitrilotriacetic acid radical.

R22 as a tetravalent radical of a tetracarboxylic acid is e.g. the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyro-mellitic acid.

R22 as a divalent radical of a dicarbamic acid is, for example, a hexamethylenedicarbamic acid or 2,4-toluylenedicarbamic acid radical.

Preferred compounds of formula III are those in which R is hydrogen, R
is hydrogen or methyl, n is 1 and R22 is C1-C1g alkyl or n is 2 and R22 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 C
atoms.

The following compounds are examples of polyalkylpiperidine compounds of this class:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 4) 1-(4-tert-butylbut-2-enyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine 5) 4-stearoyloxy-2,2,6,6 tetramethylpiperidine 6) 1-ethyl-4-salicyloyloxy-2,2,6,6~tetramethylpiperidine 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 8) 1,2,2,6,6-pentamethylpiperidin-4-yl ~-(3,5-di-tert-butyl-4-hydroxy-phenyl)propi^nate 9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate 10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate 11) di(2,2,6,6-tetramethylpiperidin-4-yl) glutarate 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate :, - : .
': , 2 ~

13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate 14) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate 15) di(1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl) sebacate 16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate 17) 1-hydroxy-4-~-cyanoethoxy-2,2,6,6-tetramethylpiperidine 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate 19) tri(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine 21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate 22) di(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate 23) di(1,2,2,6,6-pentamethylpiperidin-4-yl~ butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate 24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 25) di(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 26) hexane-1',6'-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethyl-piperidine) 27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethyl-piperidine) 28) tetra(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetra-carboxylate 29) tetra(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetra-carboxylate 30) tri.s(1-propyl-2,2,6,6-tetramethylpiperidln-4-yl) phosphite 31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate 32) phenyl[bis(1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine 35) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine b) Compounds of formula IV, ~ IV
RCH~ CH3 n wherein n is the number l or 2, R and R21 are as defined under a), Rz3 is hydrogen, Cl-C12 alkyl, C2-Cs hydroxyalkyl, C5-c7 cycloalkyl, C7-C8 aralkyl, C2-C1g alkanoyl, C3-Cs alkenoyl, benzoyl or a group of the formula RCHz\ CH3/R
R~

and R24 when n is l is hydrogen, C1~C1a alkyl, C3-C8 alkenyl, Cs-C7 cycloalkyl, C1-C4 alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl or a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl, R24 when n is 2 is C2-C12 alkylene, C6-C12 arylene, xylylene, a group -CHz-CH(OH)-CH2- or a group -CHz-CH(OH)-CH2-O-D-O-, wherein D is Cz C10 alkylene, C6-C1s arylene or C6-C1z cycloalkylene, or, provided that R23 is not alkanoyl, alkenoyl or benzoyl, R2 4 can also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or the group -CO-, or R23 and Rz4 together, when n is l, can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Any C1-C12 or C1-C1 8 alkyl substituents are as already defined under a).

Any Cs-C7 cycloalkyl substituents are especially cyclohexyl.

R23 as C7-C8 aralkyl is especially phenylethyl or in particular benzyl.R23 as C2-Cs hydroxyalkyl is especially 2-hydroxyethyl or 2-hydroxy-propyl.

R23 as C2-C1g alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, and R23 as C3-Cs alkenoyl is especially acryloyl.

R24 as C2-Cs alkenyl is e.g. allyl, methallyl, but-2-enyl, pent-2-enyl,hex-2-enyl or oct-2-enyl.

.
.: . , ,:

:. . : `'-. .'' ~ 3 Rz4 as C1-C4 alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group can be e.g. 2-hydroxyethyl, 2-hydroxypropyl, 2-cyano-ethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonyl-propyl or 2-(dimethylaminocarbonyl)ethyl.

Any C2-C12 alkylene substituents are e.g. ethylene, propylene, 2,2-di-methylpropylene, tetramethylene, hexamethylene, octamethylene, deca-methylene or dodecamethylene.

Any C6-C1s arylene substituents are e.g. o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

D as C6-Cl2 cycloalkylene is especially cyclohexylene.

Preferred compounds of formula IV are those in which n is 1 or 2, R is hydrogenj Rz1 is hydrogen or methyl, R23 is hydrogen, C1-C12 alkyl or a group of the formula RCH2\ /CH3~
R21-N\ /--RCH 2 CH;

and R24 in the case where n = 1 is hydrogen or C1-C1 2 alkyl and in tho case where n ~ 2 is C2-Cg alkylene.

The following compounds are examples of polyalkylpiperidine compounds of this class:
37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diamine 38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacet-amide 39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine 41) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladipamide 42) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl~-N,N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine 43) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine .
~, :
',' ~ ' . .

.
44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)succindiamide 45) di(2,2,6,6-tetramethylpiperidin-4-yl) N-(2,2,6,6-tetramethyl-piperidin-4-yl)-~-aminodipropionate 46) the compound of ~he formula CH3~ / H3 IC4Hg CH3- N\ /--~- CHz-cH(oH)-cH2- l CH3 CH; ./ ~.
I! !
CH3-¢-CH3 / ~, :
C~13\ C~3 \.
CH3- ~-CH2-CH(OH)-CH2-CH3 CH3 4Hg 47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine 48) 4-(3-methyl-4-hydroxy-5-tert-butylbenzamido)-2,2,6,6-tetramethyl-piperidine 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine c) Compounds of formula V, RCH2\ /CH3/R /O 1 R21- N\ /.\ ~ R2s V
RCHz CH;
wherein n is the number 1 or 2, R and R21 are as defined under a) and R2s when n is 1 is C2-Cg alkylene, C2-Cg hydroxyalkylene or C4-C22 acyloxy-alkylene and when n is 2 is the group (-CHz)2C(CH2-)2.

R2s as C2-Cg alkylene or C2-Cs hydroxyalkylene is, for example, ethylene, l-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethyl-propylene.

Rzs as C4-C2 2 acyloxyalkylene is e.g. 2-ethyl-2-aceto~ymethylpropylene.

'. ,. : ' `~ ~ ' The following compounds are examples of polyalkylpiperidine compounds of this class:
50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5~5]undecane 51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane 52) 8-aza-2,7,7~8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane 53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl 175- :
dioxaspiro[5.5]undecane 55) 2,2,6,6-tetramsthylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5''-(1'',3''-dioxane)-2''-spiro-4'''-(2''',2''',6''',6'''-tetra-methylpiperidine) d) Compounds of formulae VIA, VIB und VIC

RCH2\ /CH3~R ~26 R21- ~ X C ~ - R27 VIA
RCH ~ \C}I 0 n RCH2\ / H3/R ~1 ~-\ X - C=0 VIB

~ RCN 3 \CR ~ Rz~

wherein n is the number 1 or 2, R and R21 are as defined under a), R26 is hydrogen, Cl-C12 alkyl, allyl, benzyl, glycidyl or Cz-C6 alkoxyalkyl, R27 when n is 1 is hydrogen, C1-C12 alkyl, C3-Cs alkenyl, C7-Cg aralkyl, Cs-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C1o aryl, glycidyl or a group of the formula -(CH2) -C00-Q or of the formula -(CH2) -0-C0-Q, wherein p is 1 or 2 and Q is C1-C4 alkyl or phenyl, and ,, ':

: ,. : . ~ ~.: ' R2 7 when n is 2 is Cz-C12 alkylene, C4-C1z alkenylene, C6-C1z arylene, a group -CH2-CH(OH)-CH2-O-D-O-CHz-CH(OH)-CH2-, wherein D is C2-Clo alkylene, C6-C1s arylsne or C6-C12 cycloalkylene, or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2-, wherein Z' is hydrogen, C1-C1g alkyl, allyl, benzyl, C2-C12 alkanoyi or benzoyl, and Tl and T2 independently of the other are hydrogen, C1-Cl8 alkyl or C6-Clo aryl or C7-Cg aralkyl which is unsubstituted or substituted by halogen or C1-C4 alkyl, or T1 and T2 form a Cs-Cl2 cycloalkane ring together with the C atom to which they are bonded.

Any Cl-Clz alkyl substituents are e.g. 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.

Any C1-C1 8 alkyl substituents can be e.g. the groups listed above and additionally n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, for example.

Any Cz-C6 alkoxyalkyl substituents are e.g. methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl~ ethoxypropyl, n-butoxy-ethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

R27 as C3-Cs alkenyl is e.g. prop-1-enyl, allyl, methallyl, but-2-enyl or pent~2-enyl.

R2 7, Tl and T2 as C7-Cg aralkyl are especially phenethyl or in particular benzyl. If T1 and Tz form a cycloalkane ring together with the C a~om, said ring can be e.g. a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

R27 as C2-C4 hydroxyalkyl is e.g. 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

R2 7, T1 and Tz as C6-C1o aryl are especially phenyl or ~- or ~-naphthyl which are unsubstituted or substituted by halogen or C1-C4 alkyl.

.

- 18 - 2 ~ 9 ~

R27 as C2-Cl 2 alkylene is e.g. ethylene, propylene, 2,2-dimethyl-propylene, tet}amethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

R27 as C4-Cl2 alkenylene is especially but-2-enylene, pent-2-enylene orhex-3-enylene.

R27 as C6-Clz arylene is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Z' as C2-Cl2 alkanoyl is, for example, propionyl, butyryl, octanoyl or dodecanoyl, but preferably acetyl.

D as C2-C10 alkylene, C6-Cls arylene or C6-C12 cycloalkylene is as defined under b).

The following compounds are examples of polyalkylpiperidine compounds of this class:
56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione 57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione 58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione 59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione 60) 1,3,7,7,8,9,9-heptamethyl~1,3,8-triazaspiro[4.5]decane-2,4-dione 61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]-heneicosane 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane 65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]-decane-2,4-dione or the compounds of the following formulae:

. . .: : :~

~2~

_. .

~'i i`~
X :r \/
~\~0 r~
æ :~ 2 "\A~
o l S ! ! ~
" ~ ~ X
X
~\ A/" ~ I

T
x ~T ~ . o 5 N .// \. ~ N
N ~ ! ! ~ N
~ 0~

X~ X I I ~ r jX
O

e) Compounds of formula VII, ~ ~28 ~ ~ -R VII
R2s ~ ~ 30 wherein n is the number 1 or 2, R2 a is a group of the formula ~CH3\ /CH2R
-E-(A)x--\ /N- R
CH3 CHzR

wherein R and R21 are as defined under a), E is -0- or -NR21-, A is C2-Cs alkylene or -(CH2)3-O- and x is the number 0 or 1, R2g is the same as R2g or is one of the groups -NR3lR32, -OR33, -NHCH20R33 and -N(CH20R33)2, R30 when n = 1 is the same as R2 8 or R29 and when n = 2 is a group -E-B-E-, wherein B is C2-C6 alkylene which may be interrupted by -N(R31)-, R31 is C1-C12 alkyl, cyclohexyl, benzyl, C1-C4 hydroxyalkyl or a group of the formula ~CH3\ /CH2R
-~/ \N- R

R32 is C1-C12 alkyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl and R33 is hydrogen, Cl-Cl2 alkyl or phenyl, or R31 and R3z together are C4-Cs alkylene or C4-Cs oxaalkylene, for example -CH2CH2\ -CH2CHz /0, or a group of the formula ~ -R
-CHzCH2 -CH2CH2 or R31 and R32 are each a group of the formula .. ~.. .

., . : - ~ :
.

'' , ' ' ' ' '~ ~

f~ ~

H ~ NH- A-CH3 CH3 i C4Hg-~
CH3\i i/CH3 , - CH3 y CH3 Any C1-C12 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.

Any C1-C4 hydroxyalkyl substituents are e.g. 2-hydroxyethyl, 2-hydroxy-propyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

A as C2-C6 alkylene is, for example, ethylene, propylene, 2,2-dimethyl-propylene, tetramethylene or hexamethylene.

If R31 and R32 together are C4-Cs alkylene or C4-Cs oxaalkylene, this is e.g. tetramethylene, pentamethylene or 3-oxapentamethylene.

The compounds of the following formulae are examples of polyalkyl-piperidine compounds of this class:
C,H3 H3C\ ~\ /CH3 H3C !, ,! CH3 70) ~-C4Hg IN
(CH3CH2)2N N N(CH2CH3)2 ~(C4Hs)2 CH3\ / H3 ~-~ CH3\ /CH3 71) CzHs- N/ \~ / \N-C2Hs CH3 CH3 zHs 2Hs CH / \CH

~' . . .

'' .

~ ~ 3 r2 ~ ~3 2 H3C\ ~CH3 72) ~ b where R = -NH-CH2CH2CH2-~-~ CH3 R ~N/ R H ~ C CH 3 ~ ~3 ~

N

.A.
o~

~ZI X
Z,/ \ I / )Z3~ :' '~
A ~ Z
~ x ~ ~, ! ! ~ y "~ ~ ~ ~
\ A ~ i N \~ / Ir~ ,~

Y I c.~ 2 ~
1 3 // ~
~i~
:~
~--~
y N ~

/ \ / \
`! !,U
z/ ~

.
~ I~

.: :

`, 2 ~

75) R-NH-(CH2)3-N-(CH 2 ) 2 - - ( CH 2 ) 3 - NH-R
CH 3~ /CH 3 where R = _ ~ \ ~ 9 / ~NH

C4Xg-~
CH3\i i/CH3 CH3 ~ CH3 H

76) R-NH-(cHz)3-N-(cH2)2-N-(cH2)3-NH-R
CH3\ /CH3 where R = _ ~\~4 9 / \N-CH

C4Hg-~
CH3\i/ \i/CH3 C}13/ ~ \CH3 C,H3 ,R ~ ÇH3 77) R-~-(CHz)3-~-(CH2)2-~-(CH2)3-N-R
CH3\ /CH3 where R = _ ~ \c~ CH3 C4Hg-~
CH3\i/ \i/CH3 C

-:....... . : . ' ,. ' ' ' `'' ' ," ' :,.. ' ' 2~`~2~

CH3\ /CH3 C8H17~ NH
N' ~ CH3 CH3 78) C8H17 ~/ N~ NH(CH2)3 - _ .

ÇH2cH2oH
CH3\ /P\ /CH3 CH3 !, ,! CH3 79) ~-C4H9 CH3\ /CH3 ~ CH3\ /CH3 HO-CH2CH2-N/ \- ~/ \N~ \~ - / \N-CH2CH2-OH
. . 4H9 4H9 .-.
CH3 \CH3 CH3 CH3 ÇH2-CH=CH2 H3C\ /N\ ,CH3 ~13C/I\ /I\CH3 ~-C4H9 (80) H3C\ /CH3 ~ ~ fH3 H2C=HC-H2C- / \--~/ \N~ ;/ \N-CH2-CH=CH2 f) Oligomeric or polymeric compounds whose repeat structural unit contains a 2,2,6,6-tetraalkylpiperidine radical of formula (I), especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof which co`ntain such radicals.

The compounds of the following formulae are examples of 2,2,6,6-poly-alkylpiperidine light stabilizers of this class, m being a number from 2 to about 200:

~ ' :

:' ~

- 26 - 2 ~3 ~

81 )CH3\ ~CH3 C-CHZ-CHZ-C-O-CH2-CHZ-N~

8 2 )CH 3\ /CH3 CH3\ /CH 3 CH 2 - CH 2 - N\ /--O-C-(CH 2 ) 4-C-O--\ ~- CH 2 - CH 2 - O - C - ( CH 2 )4-~
CH3 CH3 CH; CH3 83)CH3\ /C2H5 CH3\ /C2H5 NH-tCH2)3- ~ /--NH-C- i1/ ~i - C - NH--\ /N-(CH2)3-NH-C-i~ i~-C
/ ~ CH3 ~ CH3 ~

84) CH3 CH3 1NH-¢- CH 2 - ¢ - CH3 ~- CH3 CH3 N 1 (CH2)6 1 ] m CH / \ C}l C}5 '/ ~I CH
CH3 H CH3 CH3 ~ CH3 85) [ ~ CHz--CH(OH)--CH2~;;
.
CH3 ~ CH3 86)CH3\ /CH3 CH3\ /CH3 O -.\ ~-CH2-CH=CH-CH2-N\ /--O-C-~ - C
._. ._. 4H9 CH3 CH3 CH3 `CH3 ~," '' ., , ' ~.
.' ~' ', ' . ' , ' i .' .' ;. .. " ' , - 27 - 2 ~ 3 ~ ~ ~2 87) (CH2)6- ~ ~ m ~CH3~I i/CH3 CH3\l i/CH3 ~`

CH3\~ CH3 ~ CH3 CH3 ~ CH3 CH3 ~ CH3 ~.\./._. CH3\ /CH3 _ -0--\ ~ -CHz--~ ~--CHz- ~ \--0- e ( CH2) 4 - e CH3 CH3CH3 CH3 m 89) CH3\ /CH3 [ e ~ C--O--CH2-CHz- ~
C}13/ \CH3 90) ÇH3 [ ~ CH2 ~
¦ CH3\ /CH3 Cl13 CH3 91) - CH2 ~
CH3\ /CH3 C6Hl3- --\ ~- CH3 :

!

': , " "::' :
- 28 - 2Q~ 3~ ~

92) /0\
Y
. (CHz)6 CH3\~ i/CH3 CH3\~ i/CH3 CH3 ~ CH3 CH3 y CH3 93) [ - ~ (CHz)6 ~ CH2-CH2 ~ m CH3\i i/CH3 CH3\i i/CH3 CH3 ~ CH3 CH3 ~ CH3 [ ~ (CH2)6 N! Rc CHz- RC
CH3\~ i/CH3 CH3\~ i/CH3 CH3 ~ CH3 CH / ~ / \C~I

Of thesc classes of compounds, classes a), d), e) and f) are especially suitable, in particular compounds n 10, 13, 14, 23, 24, 28, 29, 63, 65, 75, 77, 81, 84, 92 and 93.

Apart from the compounds of formula (1) in which X is CH2, NH or S, or apart from the combinations of compounds of formula (1) where X = CH2, NH, O or S with hindered amines, the materials of the invention can also contain other conventional stabilizers and additives, e.g. antioxidants, other light stabilizers, metal passivators, processing stabilizers, nucleating agents, fillers and other additives. Examples of such additional ingredients are:

~ ~ ~ 3 ~

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-butylphen 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol.

1.2. Alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-nlethylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).

1.4. Alkylidenebisphenols, e.g. 2,2'-methylenebis(6-tert-butyl-4-methyl-phenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis[4-methyl-6-(~-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-(~-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(,~-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, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, 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-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, ~ 3 bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolterephthalate, 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, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of monoethyl 3,5-di-ter~-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-dicyclo-hexyl-4-hydroxybenzyl) isocyanurate.

1.6. Acylaminophenols, e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.7. Esters of B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. with methanol, octadecanol, hexane-1,6-diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) iso-cyanurate, N,N'-bis(hydroxyethyl)oxalodiamide.

1.8. Esters of B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. with methanol, octadecanol, hexane-1,6-diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) iso-cyanurate, N,N'-bis(hydroxyethyl)oxalodiamide.

1.9. Esters of B-(3,5-dicyclohcxyl-4-hYdroxYPhenYl)propionic acid with monohydric or polyhydric alcohols, e.g. with methanol, octadecanol, hexane-1,6-diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) iso-cyanurate, N,N'-bis(hydroxyethyl)oxalodiamide.

1.10. Amides of B-(3,5-di-tert-butyl-4-hydroxyphenYl)proPionic acid, e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

. : :

.

:
,: -,. - .

_ 31 _ 2~2~ 2 2. UV absorbers and light stabilizers 2.1. 2-(2'-Hydroxyphenyl)ben20triazoles, e.g. the 5'-methyl, 3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octyloxy, 3',5'-di-tert-amyl and 3',5'-bis(~,~-dimethylbenzyl) derivatives.

2.2. 2-Hydroxybenzophenones, e.g. the 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 or unsubstituted benzoic acids, e.g. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, 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.

2.4. AcrYlates, e.g. ethyl or isooctyl ~-cyano-~,~-diphenylacrylate, methyl o-carbomethoxycinnamate, methyl or butyl ~-cyano-B-methyl-p-methoxycinnamate, methyl ~-carbomethoxy-p-methoxycinnamate, N-(B-carbo-methoxy-B-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, e.g. nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclo-hexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, e.g.
of the methyl or ethyl ester, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6. Oxalic acid diamides, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-dioctyl-oxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with .

,7: J ~

2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and of o- and p-ethoxy-disubstituted oxanilides.

2.7. 2-(2-HYdroxyphenyl)-1,3,5-triazines, e.g. 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-propoxy-phenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyl-oxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal passivators, e.g. N,N'-diphenyloxalodiamide, 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 dihydrazide.

4. Phosphites and phosphonites, e.g. triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl penta-erythritol diphosphite, bis(2,4-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-butyl-phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane.

5. Peroxide scavengers, e.g. esters of B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-(B-dodecylmercapto)propionate.

6. Polyamide stabilizers, e.g. copper salts in combination with iodides and/or phosphorus compounds, and salts of divalent manganese.

~ .

7. Basic co-stabilizers, e.g. melamine, polyvinylpyrrolidone, dicyan-diamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

8. Nucleating agents, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9._Fillers and reinforcing agents, e.g. calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, e.g. plasticiæers, lubricants, emulsifiers, pigments, fluorescent whitening agents, flameproofing agents, antistatic agents, blowing agents.

Organic polymers, especially synthetic polymers, are to be singled out among the organic materials which can be protected according to the invention from damage by light. Thermoplastics and especially lacquer compositions are preferably protected; in the latter case, the polymeric binder ln particular is stabilized against the effect of light.

Lacquer compositions or lacquers which contain the compounds of formula(1) can be e.g. pigmented or unpigmented lacquers or metallic lacquers.
They can contain an organic solvent or be solvent-free, or they can be water-based lacquers.

The lacquers can contain at least one of the polymers listed above as abinder. The following are examples of lacquers with special binders:

1. Lacquers based on cold-crosslinking or hot-crosslinking alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, if appropriate with the addition of an acid curing catalyst.

.

2. Two-component polyurethane lacquers based on acrylate, polyester or polyether resins containing hydroxyl groups and on aliphatic or aromatic polyisocyanates.
3. Single-component polyurethane lacquers based on blocked polyiso-cyanates which are unblocked during stoving.
4. Two-component lacquers based on (poly)ketimines and aliphatic or aromatic polyisocyanates.
5. Two-component lacquers based on (poly)ketimines and an unsaturated acrylate resin, a polyacetoacetate resin or a methacrylamidoglycolate methyl ester.
6. Two-component lacquers based on polyacrylates containing carboxyl or amino groups and on polyepoxides.
7. Two-component lacquers based on acrylate resins containing anhydride groups and on a polyhydroxyl or polyamino component.
8. Two-component lacquers based on (poly)oxazolidines and acrylate resins containing anhydride groups, unsaturated acrylate resins or aliphatic or aromatic polyisocyanates.
9. Two-component lacquers based on unsaturated polyacrylates and poly-malonates.
10. Thermoplastic polyacrylate lacquers based on thermoplastic acrylate resins or externally crosslinking acrylate res:Lns in combination with etherified melamine resins.
11. Lacquer systems based on siloxane-modLfied acrylate resins.
12. Lacquer systems based on fluorine-modified acrylate resins.

The lacquers can also be radiation-curable lacquers. In this case, the binder consists of monomeric or oligomeric compounds which contain ethylenic double bonds and are converted to a crosslinked high-molecular form by irradiation with actinic light or with electron beams. Said binder is generally a mixture of such compounds.

The lacquers can be applied as one-coat or two-coat lacquers, the stabilizers of the invention preferably being added to the top coat.

~,~, .... .
:

.
i 2 ~ ~ 2 The lacquers can be applied to the substrates (metal, plastic, wood etc.) by the conventional processes, for example by coating, spraying, pouring, dipping or electrophoresis. Lacquers which can be applied to motor vehicles (automotive finishes) are especially preferred.

The compounds of formula (1) can be incorporated into lacquers or lacquer compositions, as well as other photosensitive organic materials, by conventional known methods. The amount of UV absorber added depends on the organic material and its stability requirements. In general, 0.01 to 5% by weight, especially 0.02 to 3% by weight, of UV absorber is added, based on the material.

The components of stabilizer combinations can be added to the organic material individually or as a mixture. The compounds of formula (1) and, if desired, other stabilizers are preferably added before or during the shaping of the material in the case of e.g. thermoplastics. However, they can also be added to the starting monomers before or during the poly-merization. In the case of lacquer compositions, the stabilizers which can be used according to the invention are mixed especially with the lacquer formulation or parts of the lacquer formulation prior to application.

The compounds of the invention of formula (1) in which X is S, and alsothe compounds used according to the invention of formula (1) in which X
is CH2, NH or 0, prove to be effective UV absorbers distinguished by a high fastness to light. They are therefore suitable for the permanent protection of photosensitive organic materials from the harmful effects of light.

The compounds of formula (1) can be prepared by methods known per se. For example, heating a mixture of the compounds of the formulae (2) ~ .\ / \OH and (3) ~
R H ~ ~- OH

y~

wherein R , Rz, R3 and R6 are as defined and X is CHz, NH, O or S, can give the intermediate of the formula Rz~ 8 1~ /R6 ( 4 ) 1 i1 i1 R~ ~ OH
o which can be converted to the corresponding compound of formula (1) by reaction with, for example, R1-Cl or R~-Br, wherein R1 is as defined.

The following Examples illustrate the invention in greater detail. Parts or percentages are by weight, unless stated otherwise.

Preparatory Examples:

Example 1: 1-Hydroxy-3-octyloxyxanthone 22.8 g of 1,3 dihydroxyxanthone (prepared according to Grover, J. Chem.
Soc. 1955, 3982) are refluxed for 15 hours in 250 ml of methyl ethyl ketone with 15.2 g of K2CO3 and 21.2 g of l-bromooctane. After cooling, the salt is filtered off and the methyl ethyl ketone solution is evaporated under vacuum. Crystallization of th~ residue from heptane gives 1-hy~roxy-3-octyloxyxanthone with a melting point of 98C.

Example 2: 22.8 g of 1,3-dihydroxyxanthone (prepared according to Grover, J. CHem. Soc. 1955, 3982) are introduced into 300 ml of absolute ethanol.
11.2 g of potassium tert-butylate and then 0.5 g of potassium iodide are added slowly in portions. 12.3 g of ethyl chloroacetate are added dropwise in ca. 15 minutes at room temperature and the reaction mixture is then refluxed for 6 hours. It is poured into 500 ml of water and acidified with 20 ml of glacial acetic acid. The precipitate formed is isolated by suction filtration and dried. Recrystallization from hexane gives the compound of the formula 1O~

11 1 11 ~
~- O ~- OCHzCOC2Hs ~' : :

- , ~

2~2 -with a melting point of 165C.

Example 3: 22.8 g of 1,3-dihydroxyxanthone (prepared according to Grover, J. Chem. Soc. 1955, 3982) are heated to 120C in 200 ml of xylene. After the addition of 1.5 g of tetrabutylammonium bromide 9 20.5 g of 2-ethyl-hexyl glycidyl ether are added dropwise in ca. 10 minutes and the reaction mixture is then stirred for 24 hours at 120C. 5 g of Tansil AC
are then added to the reaction solution, which is stirred for 5 minutes at 110C and filtered hot. The filtrate is evaporated, the residue is taken up in 300 ml of hexane and the mixture is filtered on 50 g of silica gel. After evaporation, the compound of the formula ~ 01H
.~-\./-\.~-\.

~-/ \o/ ~- OcH2clHcHzocH28H-cl~H9 H 2Hs is obtained in the form of a yellowish resin, which crystallizes slowly.
The melting pOillt is 56 to 58C.

Application Example 1: The UV absorbers of the inventlon are tested in a 2-coat metallic lacquer.

A transparent lacquer of the following composition is prepared:

Uracron~ 2263 XB (50Y0) 59.2 parts Cymel~ 327 (90%) 11.6 parts Baysilon~ A (1% in xylene) 1.0 part Butyl glycol acetate 5.5 parts Xylene 19.4 parts Butanol 3.3 parts 100.0 parts 1 part of the compo~nd according to Preparatory Example 1, dissolved beforehand in 10 parts of xylene, is added.

';

. :

This transparent lacquer is diluted for sprayability with a mixture of xylene (13 parts), butanol (6 parts) and butyl glycol acetate (1 part), sprayed on to a prepared aluminium sheet (coil-coated, automotive filler, metallic silver base lacquer based on polyester/cellulose acetato-butyrate/melamine resin) and stoved at 130C for 30 minutes. The result is a dry layer thickness of 40 to 50 ~m of transparent lacquer. By way of comparison, an aluminium sheet prepared in ~he same way is coated with the transparent lacquer defined above, except that it is free of UV
absorber.

The samples obtained in this way are tested for gloss retention after weathering. The samples stabilized according to the invention have a markedly better weathering stability than the sample without UV absorber.

Lacquers which, apart from said UV absorbers, contain a sterically hindered amine of the formula ,_. H9C4 . \./
H0-.~ CH2- C- COz--/ ~ -CH3 .=. /-\ 2 ~ HaC- N\ /-- OOC-(CHz)4 ~ or ~ Hl7Cao-N\ /-- OOC-(CH2) also have comparably good properties.

The results are collated in Table 1 below.

, - .

.

2 ~ 3 r~

Table 1:
Evaluation of the gloss retention after weathering according to DIN 67530 (20~ gloss) UV-absorber 20 gloss after . 0 400 8001200 hours none 86 75 45 16 according to Example 184 78 74 81 according to Example 285 75 68 74 according to Example 386 80 80 80 according to formula (5)85 73 70 74 R OIH
formula (5) i i1 i ~i H3C ~- O ~- OCH3 Cycle: 8 hours of UV (UVB-313), 70C
4 hours of conditioning, 50C (UVCON) Application Example 2: Applicatlon Example 1 is repeated, except that 0.5 part of the compound of the formula H3C\ /CH3 ~6) CH3~ o-co-(CH2~4- _ is used as the additional UY absorber. The results are given in Table 2.

, ' ~ .::
.

; :; :::

~ ~ 3 f~

Table 2: Evaluation of the gloss retention after weathering according to DIN 67530 (20 gloss) UV-absorber 20 gloss after 0 400 800 1200 hours none 86 71 52 36 1 part according to example 1 +
0-5 part of (6) 86 70 61 56 1 part according to example 3 +
0 5 art of (6) 86 74 66 57 P
Cycle: VDA method C (Xenotest 1200) .",. ~ .

~, . , ,': :' .:

Claims (17)

1. Photosensitive organic material containing as UV absorber at least one compound of the formula (1) wherein X is CH2, NH or S, R is hydrogen or a radical of the formula -(CH2) wherein n is 1 or 2 and R is alkyl having 1 to 18 carbon atoms or -(CHzCH20)-H
wherein m is 1 to 12, R1 is hydrogen, alkyl having 1 to 12 carbon atoms, alkyl having 2 to 18 carbon atoms which is substituted by hydroxyl and/or interrupted by oxygen, alkenyl having 2 to 12 carbon atoms or -COR4, wherein R4 is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms.
wherein R5 is alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms and y is 1 to 12, R2 and R2 independently of the other are hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, -ORl, wherein Rl is as defined, or chlorine, and R6 is hydrogen or alkyl having 1 to 4 carbon atoms.
2. Material according to claim 1 in which R is a radical of the formula -CH2CH2CO2R, wherein R is alkyl having 1 to 18 carbon atoms or -(CH2CH20)-H in which m is 4 to 8.
3. Material according to claim 1 in which R is a radical of the formula -CH2CH2CO2CH3.
4. Material according to claim 1 in which, in the compound of formula (1) R2 and R3 are hydrogen.
5. Material according to claim 1 in which, in the compound of formula (1), Rl is hydrogen, alkyl having 4 to 8 carbon atoms, alkyl having 2 to 12 carbon atoms which is substituted by hydroxyl and/or interrupted by oxygen, alkenyl having 4 to 12 carbon atoms or -COR4 in which R4 is alkyl having 4 to 8 carbon atoms.
6. Material according to claim 5 in which, in the compound of formula (1), Rl is hydrogen or alkyl or alkenyl each having 4 to 8 carbon atoms.
7. Photosensitive organic material containing as UV absorber at least one compound of formula (1) according to claim 1, wherein X is CH2, NH, O or S, in combination with at least one stericaLly hindered amine or hydroxy-phenylbenzotriazole derivative.
8. Material according to claim 1 or claim 7 which is a lacquer or a thermoplastic polymer.
9. A process for the protection of photosensitive organic materials from UV radiation, wherein these materials are provided with a protective layer containing at least one compound of formula (1) according to claim 1, wherein X is CH2, NH or S, or at least one compound of formula (1) according to claim 1, wherein X is CH2, NH or s, is incorporated into these materials.
10. A process for the protection of photosensitive organic materials from VV radiation, wherein these materials are provided with a protective layer containing at least one compound of formula (1) according to claim 1, wherein X is CH2, NH, O or S, or at least one compound of formula (1) according to claim 1, wherein X is CH2, NH, O or S, is incorporated into these materials, the compound of formula (1) according to claim 1 being used in each case in combination with at least one sterically hindered amine or hydroxyphenylbenzotriazole derivative.
11. A compound of formula (1) according to claim 1 in which X is S, R
is hydrogen or a radical of the formula -(CHz) CO2R, wherein n is 1 or 2 and R is alkyl having 1 to 18 carbon atoms or -(CH2CH2O)-H
wherein m is 1 to 12, Rl is hydrogen, alkyl having 1 to 12 carbon atoms, alkyl having 4 to 18 carbon atoms which is substituted by hydroxyl and/or interrupted by oxygen, alkenyl having 2 to 12 carbon atoms or -COR4, wherein R4 is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, wherein R5 is alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms and y is 1 to 12, R2 and R2 independently of the other are hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, -OR1, wherein R1 is as defined, or chlorine, and R6 is hydrogen or alkyl having 1 to 4 carbon atoms.
12. A compound according to claim 11, wherein R is a radical of the formula -CH2CH2CO2R in which R is alkyl having 1 to 8 carbon atoms or -(CH2CH2O)-H in which m is 6 to 8.
13. A compound according to claim 11, wherein R is a radical of the formula -CH2CHzCO2CH3.
14. A compound according to claim 11, wherein R2 and R3 are hydrogen.
15. A compound according to claim 11, wherein R1 is hydrogen, alkyl having 4 to 8 carbon atoms, alkyl having 2 to 12 carbon atoms which is substituted by hydroxyl and/or interrupted by oxygen, alkenyl having 4 to 12 carbon atoms or -COR4 in which R4 is alkyl having 4 to 8 carbon atoms.
16. A compound according to claim 15, wherein R1 is hydrogen or alkyl or alkenyl each having 4 to 8 carbon atoms.
17. A process for the preparation of the compounds of formula (1) according to claim 1 in which X is S and R is a radical of the formula -ORl, wherein a mixture of the compounds of the formula (2) and (3) wherein R , R2, R3 and R6 are as defined in claim 11, is heated and the intermediate of the formula (4) is reacted with Rl-Cl or R1-Br, wherein Rl is as defined in claim 11, to give the corresponding compound of formula (1), which is isolated.
CA 2032692 1989-12-21 1990-12-19 Photosensitive organic material containing uv absorbers Abandoned CA2032692A1 (en)

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