HK97084A - 2-(3.5-disubstituted-2-hydroxyphenyl)-2h-benzotriazoles and stabilized compositions containing them - Google Patents

2-(3.5-disubstituted-2-hydroxyphenyl)-2h-benzotriazoles and stabilized compositions containing them

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Publication number
HK97084A
HK97084A HK970/84A HK97084A HK97084A HK 97084 A HK97084 A HK 97084A HK 970/84 A HK970/84 A HK 970/84A HK 97084 A HK97084 A HK 97084A HK 97084 A HK97084 A HK 97084A
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HK
Hong Kong
Prior art keywords
acid
butyl
fillers
acetylene
alkyl
Prior art date
Application number
HK970/84A
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German (de)
French (fr)
Inventor
Martin Dexter
Roland Winter
Original Assignee
Ciba Specialty Chemicals Holding Inc.
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Publication date
Priority claimed from US05/918,984 external-priority patent/US4226763A/en
Priority claimed from US06/036,914 external-priority patent/US4278589A/en
Priority claimed from US06/038,768 external-priority patent/US4275004A/en
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Publication of HK97084A publication Critical patent/HK97084A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

1. A compound of the formula see diagramm : EP0006564,P31,F2 wherein T1 is hydrogen or chlorine and each of T2 and T3 independently of the other is the group see diagramm : EP0006564,P31,F3 wherein T4 is hydrogen or lower alkyl, whilst one of T2 and T3 can also be t-octyl.

Description

The present invention relates to 2-aryl-2H-benzotriazoles, their use as a light-protecting agent for organic material, and stabilised mixtures.
The invention also relates to a process for the production of o-nitroazobenzene intermediates which can be converted into the corresponding 2-aryl-2H-benzotriazole.
UV absorbers of the o-hydroxyphenyl-2H-benzotriazole type have long been of considerable economic interest as photostabilisers for organic material.
Such compounds, the manufacture and use of which of these valuable 2-aryl-2H benzotriazoles are known from the following patents, e.g. US 3004896, US 3055896, US 3072585, US 3074910, US 3189615 and US 3230194. However, these stabilizers show poor tolerance in certain substrates. They are highly prone to sweat, sublimation and/or volatilization during processing into films, films, fibres, etc. at high temperatures. This causes an unreasonably high loss of the benzotriazolator, especially in extremely thin films and coatings. This also applies if the films or coatings are exposed to high temperatures during use.
Attempts have been made to improve tolerability and reduce stabilizer loss by structural modification of benzotriazole.
US-PS 3230194 describes benzotriazole substituted with a long-chain alkyl group in place of a methyl group, in particular 2- ((2-hydroxy-5-tert-octylphenylethyl) --2H-benzotriazole, which has excellent tolerability and stabilizing activity in polyethylene.
USPS 4127586 describes other modifications of 2-aryl-2H-benzotriazoles to improve processing properties, such as the compound 2-[2-hydroxy-3-(1-phenylethyl)-5-methylphenyl]-2H-benzotriazole showing better tolerability and lower loss by evaporation during processing than the previously known benzotriazole compounds.
Benzotriazole-type photostimulators are also known from JP Kokai 158588/75, such as 2-[2-Hydroxy-3-a,a-dimethylbenzyl-5-methylphenyl]-2H-benzotriazole.
Efforts are still being made to improve the processing characteristics of benzotriazoles during processing at high temperatures.
The compounds of the invention, such as 2-[Hydroxy-3,5-di- ((a,a-dimethylbenzyl) phenyl) --2H-benzotriazole, show surprisingly low loss during high temperature processing or in their final use, where the stabilised mixtures are subjected to constant weathering and light exposure as films and coatings.
US-PS 4041 044 describes an improved process for the manufacture of 2-aryl-2H-benzotriazole, but not the compounds of the invention.
The present invention relates to 2-aryl-2H-benzotriazole as a light-saving agent and to an organic monomer and polymer stabilized with 2-aryl-2H-benzotriazol.
The invention relates in particular to compounds of formula 1
Compounds of formula 1
wherein T is hydrogen or chlorine, T2 and T3 independently of each other the group means in which T4 is hydrogen or low alkyl, wherein either T2 or T3 can also be t-octyl.
If T4 is a low alkyl, it is in particular in the meta- or para-position, preferably in the para-position.
Preference is given to compounds where T2 and T3 have the same meaning and T4 is hydrogen or p-methyl.
T4 hydrogen is particularly preferred.
The compound 2-[2-hydroxy-3,5-di- ((α,α-dimethyl-benzyl) -phenyl]-2H-benzotriazole is particularly preferred.
The compounds of particular preference are 2-[2-Hydroxy-3-t-octyl-5- ((a,a-dimethyl-benzyl) -phenyl]-2-H-benzotriazole and 2-[2-Hydroxy-3-(α,α-dimethyl-benzyl) -5-t-octylphenyl]-2H-benzotriazole.
Err1:Expecting ',' delimiter: line 1 column 159 (char 158)
Stage 1 - The coupling of the diazonium compound can be carried out in an acidic or alkaline environment. If the coupling phenol carries an aralkyl group in ortho position to the hydroxyl group and the reaction is carried out in an acidic environment, the yield of o-nitroazobenzene Vl. is 50% below the theory.
Surprisingly, over 80% of the theory is obtained from the intermediate VI when the coupling reaction is carried out in a highly alkaline environment (pH > 11).
Stage 2 - The reductive cycling of VI to 2-aryl-2H-benzotriazole by one of the known reduction methods, e.g. zinc and NaOH, hydrazine or catalytic hydration with a precious metal catalyst, yields good benzotriazole.
The invention also relates to a process for the production of o-nitroazobenzene intermediates which can be converted into the corresponding 2-aryl-2H-benzotriazole.
The method of the invention relates to the coupling of a substituted phenol with diazotized aniline in a highly alkaline alkanol.
The method of the present invention differs from the state of the art in that it uses an excess of alkali hydroxide far in excess of the stoichiometric amount necessary to neutralize the resulting diazonium salt and to form the salt of the phenol.
The state of the art teaches to avoid highly alkaline coupling processes, so the success with which the current coupling process has been carried out is particularly surprising.
The coupling of phenols with diazonium salt under weakly alkaline conditions is a well-known method for the production of aromatic azo derivatives. Basic Principles of Organic Chemistry by J. D. Roberts and M. C. Caserio, W. A. Benjamin, Inc. New York (1965), pp. 893-895 emphasizes that the coupling process is optimal at about pH 10 but virtually ceases at higher pH values.
It is also known that o-nitrobenzol sodium salt solutions are unstable in the presence of alcohol and alkali metal hydroxide and decompose rapidly under N2 development.
H. Zollinger Azo and Diazo Chemistry, Interscience, New York (1961), pp. 249-250 reports that in the case of strongly alkaline coupling the balance shifts from the side of the diazonium lones.
SU-PS 360 357 describes the coupling of a sodium phenolate in a weakly alkaline solution with excess diazonium acid salt, so that the pH rapidly falls below 11 during the reaction, contrary to the reaction conditions of the invention.
Contrary to the teachings of the state of the art, o-nitroazobenzene is obtained at high yield and in high purity when the reaction is carried out in a highly alkaline environment and in the presence of a low alkanol as a solvent.
The manufacture of o-nitroazobenzene intermediate used for the manufacture of 2-aryl-2H-benzotriazole photo-stabilizers is the subject of a partial notification.
The compounds of the invention are effective photostabilizers for a large number of organic polymers, such as:
Polymers derived from mono- or diolefins, e.g. cross-linked polyetylene, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polyisoprene and polybutadiene, where applicable.2. Mixtures of homopolymers of 1), e.g. mixtures of polypropylene and polyethylene, potypropylene and polybutene-1, polypropylene and polyisobutylene.3. Copolymers from the monomers for the homopolymers of 1), e.g. ethylene/propylene-C butyric acid, propylene/acetylene-1-C butyric acid, propylene/acetylene-C butyric acid, acetylene/acetylene-1-C butyric acid, and polymer of polymers of styrene and styrene, e.g. polymers of styrene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acetylene/acStyrene graft copolymers, e.g. the graft polymer of styrene to polybutadin, the graft polymer of styrene with acrylonitrile to polybutadin and their mixtures with the copolymers of 5), known as acrylonitrile/butadine/styrene or ABS.7. Halogenated vinyl polymers, e.g. polyvinyl chloride, polyvinyl chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, vinyl chloride/vinyl chloride copolymer, vinyl chloride/vinyl polybutadin, Polyvinyl acetate/vinyl polyvinyl acetate.8. Polymers derived from vinyl acetate, polyvinyl acetate and their derivatives.9. Polymers consisting of acrylonitrile, polyvinyl acetate and its derivatives, and their salts, and their salts, are obtained from polymers of vinyl acetate, polyvinyl acetate, and their derivatives.9.Polyacetates, such as polyoxymethylene, and polyoxymethylene containing ethylene oxide as a comonomer.12. Polyalkylenoxides, such as polyoxymethylene, polypropylene oxide or polyisobutylenoxide.13. Polyphenylenoxide.14. Polyethanes and polyharmonic materials, such as those in polyethylene oxide or the polymers of bis-glycidyl ethers.15. Polycarbonates.16. Polycyclenes.17. Polyamides and copolyamides, made from polyamides and diethylamino acids and diethylamino acids/diethylamino acids, or their halogenated, diethylamino acids, such as polyamides, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, diethylamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamino acids, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamine, dilamineAlkyd resins such as glycerol/phthalic acid resins and their mixtures with melamine/formaldehyde resins.21. unsaturated polyester resins from the copolyesters of saturated and unsaturated dicarboxylic acids with polyvalent alcohols and from vinyl compounds as binders and their halogenated flame retardant modifications.22. natural polymers such as cellulose, rubber and their chemically modified homologous derivatives such as cellulose acetate, cellulose phenopropane and cellulose ether, e.g. cellulose methyl cellulose
The compounds of the invention are not only effective photosensitizers, such as 2-aryl-2H-benzotriazole in general, but also particularly valuable for stabilizing polymer substrates that need to be processed at high temperatures, thanks to their surprisingly low loss by evaporation at high temperature.
The compounds of the invention are therefore particularly suitable for the stabilization of polymers such as polyethylene terephthalate, polybutylene terephthalate or their copolymers, polycarbonates such as bisphenol A and phosgene or their copolymers, polysulfones, polyamides such as nylon-6, nylon-6, nylon-6/10 etc. and copolyamides, duroplastic acrylic resins, thermoplastic acrylic resins, polyolefins such as polyethiles, polypropylene, copolyolefins, etc. and other polymers requiring high temperature processing and production.
The stabilisers of formulae I and 11 are incorporated into the polymer by the conventional methods at any stage during the manufacture of moulded products.
The stabilized polymer mixtures of the invention may be used, where appropriate, in a range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight of the usual additives, in particular antioxidants, photo-stabilizers or mixtures thereof. Antioxidants, UV-absorbers and photosensitizers such as 2- ((2'-hydroxyphenyl) benztriazole, 2,4-bis- ((2'-hydroxyphenyle) -6-aiky) -s-triazine, 2-hydroxybenzophenone, 1,3-bis- ((2'-hydroxybenzoyl) benzole, esters of benzoic acids, where substituted, acrylates, other nickel compounds, sterically inhibited amines, oxalic acid diamides, metal desactivators, phosphites, peroxide-resistant compounds polymer stabilisers, basic co-stabilisers, lubricants or other additives such as plasticizers, emulsifiers, fillers, rubber, talc, pigments, optical fillers, flame retardants, optical fillers, such as polymers, polymers, emulsifiers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fillers, fil
Certain hydrophobic, non-diffusing hydroxyphenyl benzotriazoles are known to be UV absorbers in photographic gelatin (US-PS 3253921 and US 4042394). The compounds of the invention are particularly suitable for stabilizing colour images by their low volatility, good UV absorption properties and photographic inactivity.
Of particular interest are the duroplastic and thermoplastic acrylic resins used in car coatings, which are described in the Encyclopedia of Polymer Science and Technology, Interscience Publishers, New York, Volume 1 (1964), pages 273-276 and Volume 13 (1970), pages 530-532, and in Understanding Paint by W.R. Fuller, in American PaintJournal Co., St. Louis, 1965, pages 124-135.
Acrylic resin lacquers which, according to the invention, are stabilized against the action of light, oxygen and moisture are the usual incineration lacquers, as described, for example, in H. Kittel's "Textbook of Paints and Coatings", Volume 1, Part 2, pages 735 and 742 (Berlin, 1972) and in H. Wagner, H. F. Sarx, "Paint Art Resins", pages 229-235.
The stabilization of the compounds of the invention on the basis of heat-interlacing acrylic resin and styrene is of particular interest. Metal effect varnishes made from these resins are not suitable, despite their excellent physical and chemical properties, as the existing styrene leads to cracking.
To achieve the metal effect, the usual aluminium pigments are used in 1-10% by weight relative to the solvent-free binder (lacquer resin). The stabilised paint can be applied using the traditional one-layer or two-layer process. In the latter case, the pigment-containing template paint is first applied and then coated with clear paint.
Other additives that may be present in the paint are other common light-saving agents, phenolic antioxidants, pigments, dyes, metal deactivators, etc.
Generally, the stabilizers used in accordance with the invention are between 0.1 and 5% by weight, preferably between 0.5 and 3% by weight, depending on the lacquer resin.
The combination of sterile inhibited amines and the stabilizers of the invention allows both excellent gloss preservation and resistance to defoliation of the metallized acrylic resin-based auto-top coating.
The sterically inhibited amines are effective in acrylic resin coatings as light stabilizers and are responsible for their maintenance of gloss in weathered conditions, but UV light can pass through the cover layer unhindered if no UV absorber is present and cause damage to the lower epoxy ester layer.
Thus, the combination of sterically inhibited amines with benzotriazoles provides both gloss preservation and defoliation resistance in metallized coatings based on acrylic resins.
The amines used are effective in 0,1 to 5% by weight, preferably in 0,5 to 2% by weight, in particular in 0,5 to 1% by weight, in relation to the acrylic resin.
The benzotriazoles of the invention are effective in 0,1 to 5% by weight, preferably in 0,5 to 2% by weight, especially at 0,5 to 1% by weight, with respect to the acrylic resin.
The amine photo-stabilizers used in addition to the present invention are those of formula XI. where q is 1 or 2, p is 2 to 14, G1, G2, G3 and G4 independently mean an alkyl, or G and G3 together mean an alkyl, or each carboalkoxy or carbophenethoxy is an alkyl, or G and G2 or G3 and G4 independently mean an alkyl or azaalkyl; where q is 1, M is hydrogen, hydroxy, Oxy 1, substituted alkyl, alkenyl, alkynyl, aralkyl, alkenyl, alkenyl, benzoyl, glycidyl or -CH2CHOZ, where Z is hydrogen, methyl or phenyl, where q is 2 means alkenyl, M is alkenyl, alkenyl, alkenyl, arylen, alkenyl, and the same group has the same meaning as q=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=OOCH (OOCH) x=CH (OOCH) x=CH (OH) x=CH (OH) x=CH (OH) x=CH (OH) x=CH (OH) x=CH (OH) x=CH (OH) x=CH (OH) x=OH (OH) x=OH (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH (OH) x (OH) x (OH) x (OH) x (OH) x (OH) x (OH (OH) x (OH) = NO (OH (OH
L is a bivalent organic residue that complements the N-containing ring to a 5- to 7-ring, or two monovalent radicals, and
L1 a bivalent organic residue which complements the N-containing ring to a 5- to 7-ring and which may additionally be linked to other amine groups by a binding group.
The amine is composed of the following compounds: where G5 is hydrogen, alkyl or phenethyl and M2 is hydrogen, hydroxy, oxyl, alkyl, 2-methoxyethyl, alkenyl or propagyl.
Preferably 2,2,6,6-tetralkylpiperidine compounds are used, preferably containing a group of formula XIII R is for hydrogen or methyl.
The light-protective devices to be used in accordance with the invention include in particular the following classes of connectors: (a) Formal protective equipment of formula XIV where n is 1 to 4, preferably 1 or 2, T is hydrogen or -CONH2, R has the meaning given in formula XIII, R1 is hydrogen, oxyl, C1-C18 alkyl, C3-C8 alkenyl, C3-Cs alkynyl, C7-C12 aralkyl, C1-C8 alkenyl, glycidyl, a group -CH2CH(OH) Z, where Z is hydrogen, methyl, ethyl or phenyl, where R1 is preferably hydrogen, C1-C12 alkyl, allyl, benzyl, acetyl, acrylic and when R2, n=1, hydrogen, where appropriate by one or more oxygen atoms C1-C18 alkyl, c1-Cyl, benzyl, benzyl, glycyl, a cyclic resin containing aliphatic hydrocarbon, a heterocyclic or a heterocyclic carboxylic acid, or a carboxylic or heterocyclic carboxylic acid, a heterocyclic or a heterocyclic carboxylic acid,preferably a residue of an aliphatic carbonic acid containing 2-18 C atoms, a cycloaliphatic carbonic acid containing 5-12 C atoms or an aromatic carbonic acid containing z-15 C atoms, if n = 2, C1-C12 alkylines, C4-C12 alkenylines, xylenes, a bivalent residue of an aliphatic, cycloaliphatic, araliphic, aromatic or heterocyclic dicarboxylic acid, dicarboxylic acid or phosphoric acid or a bivalent silyl residue, preferably a residue of an aliphatic carbonic acid containing 2-36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid containing one to three C atoms, an aliphatic, cycloaliphatic or aromatic dicarboxylic acid containing 8-10 aliphatic, cycloaliphatic or heterocyclic acids, or a tricyclic aromatic dicarboxylic acid, if a heterocyclic acid, or a tricyclic acid, or a heterocyclic acid, or a tricyclic acid, or a heterocyclic acid, if a tricyclic acid, or a phenylate of aliphoric acid, or a heterocyclic acid, or a tricyclic acid, or a heterocyclic acid, or a tricyclic acid, or a tricyclic acid, or a dicarboxylic acid, or a dicarboxylic acid, if a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, or a tricyclic acid, a tricyclic acid, a tricyclic acid, or a tricyclic acid, a tricyclic acid, a tricyclic or a tricyclic acid, a tricyclic or a tricyclic acid, a tricyclic acid, a, a, a, a, a, a,where n = 4, a four-value residue of aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
If any substituents are C1-C12 alkyl, they are e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
In the sense of C1-C18 alkyl, R or R2 may represent, for example, the above groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
If R, C2-C8 means alkenyl, it may be, for example, 1-propenyl, allyl, methylyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-ter-butyl-2-butenyl.
R1 is preferred as C3-C8 alkynyl propargyl.
As a C7-C12 aralkyl, R is particularly phenethyl or especially benzyl.
R1 is C1-C8 alkanoyl, e.g. formaldehyde, propionyl, butyryl, octanoyl but preferred acetyl and C3-CS alkenoyl, especially acryloyl.
If R2 means a single-value residue of a carbonic acid, it is, for example, an acetic acid, stearic acid, salicylic acid, methacrylic acid, maleic acid, benzoic acid or β- ((3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid residue.
If R2 is a bivalent residue of a dicarboxylic acid, it is, for example, an adipic acid, suberic acid, sebacic acid, phthalic acid, dibutylmafonic acid, dibenzylmalonic acid, butyl- ((3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid or bicycloheptane dicarboxylic acid residue.
If R2 is a trivalent residue of a tricarboxylic acid, it means, for example, a trimellitic acid or a nitrilotrienoic acid residue.
R2 may also refer to residues of di- and tri-carboxylic acids produced technically by oligomerisation of higher unsaturated fatty acids or by diels-alder addition of crylcylic acid to linoleic acid, and to residues obtained by transformation of mono-, di- and polypoxides such as biphenol A-diglycidyl ether, butandialdiglycidyl ether, trisglycidyl isocyanate, 1,3-diglycidyl-4,4-dimethylantoin with 4-hydroxy-1,2,2,6,6-pentamethylpiperidine.
If R2 is a tetracarbonic residue, it means, for example, a pyromellic acid residue.
If R2 means a bivalent residue of a dicarbamic acid, it is, for example, a hexamethylenedicarbamic acid or a 2,4-toluylenedicarbamic acid residue.
Examples of polyalkylpiperidine anti-photo-sensitizers in this class are the following compounds: 1) 4-hydroxy-2,2,6,6-tetramethylpiperidin2) 1-allyl-4-hydroxy-2,2,2,6,6-tetramethylpiperidin3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidin4) 1-4-butyl-2-butyric acid (butyric acid) 4-hydroxy-2,2,6,6-tetramethylpiperidin4) 1-4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (butyric acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-butyric acid (acid), 4-acid), 4-acid (acid), 4-acid (acid), 4-acid (acid), 4-acid (acid), 4-acid (acid), 4-acid), 4-acid (acid), 4-acid (acid), 4-acid (acid), 4-acid (acid), 4-acid (acid), 4-acid), 4-acid (acid),
(b) Formal lighting protection products of formula XV
where n is the number 1 or 2, R is the number of elements in formula XIII, R1 is the number in a, R3 is hydrogen, C1-C12Alkyl, C5-C7 Cycloalkyl, C7-C8Alkyl, C2-C18 Alkanoyl, C3-C5, Alkenoyl, Benzoyl and R4 is hydrogen, C1-C18 Alkyl, C5-C7 Cycloalkyl, where R is the number of elements in formula XIII, R1 is the number in formula XIII, R1 is the number in formula XIII, R1 is the number in a, R3 is hydrogen, C1-C12Alkyl, C5-C7 Cycloalkyl, C7-C8Alkyl, C7-C8Alkyl, C7-C18Alkyl, C7-C7Alkyl, R4 is hydrogen, C1-C12Alkyl, C1-C12Alkyl, C1-C12Alkyl, C2-C18Alkyl, C2-C18Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C3-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C1-C12Alkyl, C2-C12Alkyl, C2-C12Alkyl, C1-C12Alkyl, C2-C12Alkyl, C1-C12Alkyl, C1-C12Alkyl, C1-C12 or C1-C12Alkyl, or R2-C12Alkyl, or R2-C12A, or R2-C12 or R2-C12 or R2-C12 or R2-C, but may be an alkyl, or a, but not a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or a, or
If any substituents are C1-C18 alkyl, they shall have the meaning already given in (a).
If any substituents are C5-C7 cycloalkyl, they are in particular cyclohexyl.
As a C7-C8 aralkyl, R3 is particularly phenethyl or especially benzyl.
R3 is a C2-C18 alkanoyl such as propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl but preferably acetyl and as a C3-C5 alkenoyl especially acryloyl.
If R4 means a C2-C8 alkenyl, where applicable, substituted with a cyano, carbonyl or carbamide group, then these are e.g. 1-propenyl, allyl, methyll, 2-butenyl, 2-phentenyl, 2-hexenyl, 2-octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonyl vinyl, 2,2-diacetylaminovinyl.
If any substituents are C2-C12 alkyl, these are e.g. ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
If any substituents are C6-C15 aryls, they are e.g. o-, m- or p-phenylenes, 1,4-naphthyls or 4,4'-diphenyls.
As a C6-C12 cycloalkyl, X is in particular a cyclohexyl.
Examples of polyalkylpiperidine light-protecting agents in this class are the following compounds: The following substances are to be classified in the same category as the active substance: - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of ethyl alcohols, - in the form of a mixture of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, - in the form of ethyl alcohols, in the form of ethyl alcohols, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in the form of ethyl alcohol, in
The compound of formula XVI The value of all the materials of Chapter 9 used does not exceed 20% of the ex-works price of the product
(c) Fluorescent lamps of formula XVII
where n is 1 or 2, R is the value specified for formula XIII, R1 is the value specified for formula XIII, R5 is the value specified for formula XIII, and R5 is the group (-CN2) 2C ((CH2) 2) if n = 1, C2-C8 alkyl or hydroxyalkyl, C4-C22 acyl-oxyalkyl, if n = 2.
If R5 means C2-Ca alkyl or hydroxyalkyl, it is for example ethylene, 1-methyl ethylene, propylene, 2-ethyl propylene, 2-ethyl-2-hydroxymethyl propylene.
As C4-C22 acylxycyclenes, R5 means e.g. 2-ethyl-2-acetoxy-methylpropylene.
Err1:Expecting ',' delimiter: line 1 column 573 (char 572)
(d) Photographic protection products of the forms XVIIIA, XVIIIB and XVIIIC
where n is the number 1 or 2, R has the value given for formula XIII, R1 has the value given for formula a, R6 is hydrogen, C1-C12Alkyl, Allyl, Benzyl, Glycidyl, C2-C6Alkoxy Alkyl and R7 if n = 1, hydrogen, C1-C12Alkyl, C3-C5, Alkenyl, C7-C9Alkyl, C5-C7 Cycloalkyl, C2-C4 Hydroxyalkyl, C2-C6 Alkoxy Alkyl, C6-C10 Aryl, Glycidyl, a group of the formula - (C18-CCOO-CH2) or the substituent group - (C18-CCOO-Q) Benzyl, means 1 or 2 and C1-C18 Alkyl or Phenyl, nCHCH=CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH
If any substituents are C1-C12 alkyl, they are e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
The possible substituents in the sense of C1-C18 alkyl may be, for example, the groups listed above and, in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
If any substituents are C2-C6 alkoxyalkyl, they are e.g. methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyaethyl, ethoxypropyl, n-butoxyaethyl, tert-butoxyaethyl, isopropoxyaethyl or propopoxypropyl.
If R7 is C3-C5 alkenyl, it means e.g. 1-propenyl, allyl, methylyl, 2-butenyl or 2-pentenyl.
As C7-C9 aralalkyl, R7, T1 and T2 are particularly phenethyl or especially benzyl and as C5-C7 cycloalkyl (T1 and T2 together with the C atom binding them) particularly cyclohexyl.
If R7 means C2-C4 hydroxyalkyl, it is e.g. 2-hydroxyaethyl, 2-hydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
As C6-C10 aryl, R7, T1 and T2 mean in particular phenyl, a- or β-naphthyl, where appropriate substituted with halogen or C1-C4 alkyl.
If R7 is C2-C12 alkyl, these are e.g. ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
As C4-C12 alkenylene, R7 means in particular 2-butenylen, 2-pentenylen or 3-hexenylen.
If R7 means C6-C12 aryls, it is for example o-, m- or p-phenylenes, 1,4-naphthyls or 4,4'-diphenyls.
If Z means C2-C12 alkanoyl, it is for example propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl.
X has the meaning given in (b) as C2-C10 alkyl, C6-C15 aryl or C6-C12 cycloalkyl.
Examples of polyalkylpiperidine light-protecting agents in this class are the following compounds: The total value of all the materials of Chapter 9 used does not exceed 20% of the ex-works price of the product and the value of all the materials of Chapter 9 used does not exceed 20% of the ex-works price of the product The following compounds are added: 77) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo- dispiro- [5,1,11,-2]-heneicosan78) 1,3-Di ((2,2,6,6-tetramethyl-4-piperidinyl) -imi-dazolidinone-279) 2,4,6-Tri[N-(2,2,6,6-tetramethyl-4-piperidinyl) -butylamino]-s-triazin80) Di-[2-(2,2,6,6-tetramethyl-1-hiperidino) -eat-all-adipat81) 2,2,6,6-tetramethylpiperidine--leucetic acid n-octester.
Other compounds of the formula: Other
(e) Forms of light protection
where n is 1 or 2 and Ra is a group of the formula where R has the value given for formula (I), R1 has the value given under (a), Y is -0 or -NR11-, A is C2-C6 alkyl or -CH2) 3-O- and m means 0 or 1, R9 means the groups R8, NR11R12, -OR13, -NHCH2-OR13 or -N(CH2OR13) 2, R10 means the groups R8 or R9 if n = 1 and R8 or R9 if n = 1 and where n = 2 means the group -Y-Q-Y- where Q means C2-C6 alkyl, interrupted by -NR14) if applicable, R11 means C1-C12 alkyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl or a group of the formula R12C1-C12 means alkyl, cyclohexyl, benzyl, C1-C4 hydroxyalkyl, R13 hydrogen, C1-C12 alkyl or phenyl and R14 hydrogen, C1-C12 alkyl, cyclohexyl, benzyl, phenyl or R11 and R12 together are C4-C5 alkyl or oxaalkyl or R11 and R12 each a group of the formula I mean.
If any substituents are C1-C12 alkyl, they 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.
If any substituents are C1-C4 hydroxyalkyl, they are e.g. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
If A means C2-C6 alkyl, it is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
If R11 and R12 together are C4-C5 alkyl or oxaalkyl, this means e.g. tetramethylene, pentamethylene or 3-oxa-pentamethylene.
Compounds of the formulae XX or XXI
Err1:Expecting ',' delimiter: line 1 column 100 (char 99)R4 means hydrogen, 0, C1-C12 alkyl, allyl or benzyl,A if m2 is C2-C12 alkyl, C4-C8 alkyl, xylen or a residue of the formula CH2-COO-R5-OOC-CH2, -CH2-CH(OH) -CH2 or -CH2CH(OH) CH2-D-CH2CH(OH) CH2 if m3 is a group of the formula is a group of the formula is B C2-C12 alkyl, C4-C8 alkenes, xylenes or a residue of the formula -CH2-COO-R5-OOC-CH2, -CH2CH(OH) -CH2- or -CH2CH(OH) CH2- is R5 C2-C8 alkyl, C4-C8 oxaalkyl or cyclohexyl,D a bivalent residue of the formula -0-R6-0-, -O-C-O-R7-C-O-O-O-O-O-, -OCHR-O8) CH2O-R6-OCH2CH: or is C6 alkyl, C6 cycloalkyl, C6 cycloalkyl, C6 aryl or -phenylen-Z-phenylen, wherein S02 or -0- means R7 is a direct bond, C1 alkyl, C2 alkyl, C6 alkyl, C6 cycloalkyl, R8 and R9 are hydrogen or C1 alkyl,T' is a three-valued remainder of the formulas or is a three-valued aliphatic hydrocarbon residue with 3-10 C atoms,Q' is a four-valued residue of the formula or R11 is a four-valued aliphatic hydrocarbon residue with 4-10 C atoms and the 'E' and 'E' end groups.R1, R2, R3 and R4 as C1-C12 alkyl can be branched or unbranched alkyl residues, e.g. methyl, ethyl, isopropyl, tert. butyl, hexyl, isooctyl, decyl or dodecyl.R1, R2, R3 as an alkoxyalkyl can be e.g. methoxymethyl, 2-methoxythythyl, 2-methoxythythyl, 2-nopropoxythythyl, 2-nopropoxythythyl, 2-nhydroxy-secreted or tert. butyroxy, butyroxy or 2-butoxycycloxy.R1, R2, R3, R2, R3, 2-hydroxy, 2-hydroxy or 2-butyroxy, butyroxy, 2-hydroxy, 2-cycloxy, 2-cycloxy, 2-cycloxy, 2-cycloxy, 2-cycloxy or 3-cycloxy. buty.R1, R2, R3 as C6-C10 aryl can be phenyl or naphthyl, with phenyl being preferred.R1, R2, R3 as substituted phenyl, for example p.Tolyl, 4-hydroxyphenyl, 4-third butylphenyl or 3,5-third butyl-4-hydroxyphenyl.X as C1-C4 alkyl can be e.g. methyl, ethylene, 1,3-propylene, 1,2-propylene, 1,1-dimethylethylene or 2,2-propylene.A, B or R6 as alkyl can be a branched or unbranched alkyl group, such as alkyl, 4-hydroxyphenyl, 4-hydroxyphenyl, 4-hexaxa-hexa-propylene or D-exylenedioxy-1, 2,2-dimethyl, 1,2-B1,2-B1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, or 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, 1,2-B3, or 1,2-B3, or 1,2-B3, or 1,2-B3, or 1,2-B3, or 1,2-B3, or 1,2-B3, or 1,2-B3, respectively.R7 as an alkyl or alkene can be e.g. methyl, 1,3-propylene, tetramethyl, 2,2-dimethyl-1,3-propylene, octamethylene, dodecamethylene, vinyl or 1,4-butene-2-yl. R7 as a cyclic residue can be for example 1,2-cyclopentylene, 1,2-cyclohexyl, 1,2-cyclohexene-4-yl, 3,6-endylenethylenethylenhexen-4-cyclen-1,2, 1,2-phenylen, 1,4-phenylen or 1,4-naphenylen.
Examples of polyalkylpiperidine light-protecting agents in this class are compounds of the following formulae: Other
(g) Photographic protection of the form XXII
where n is 1 or 2, R has the value specified for formula XIII and R14, when n = 1, C4-C18 alkyl, C7-C12 aryl, the group -CO-R15, C1-C4 alkyl replaced by -CH, -COOR16k -OH, -OCOR17 or where R15 is C1-C12 alkyl, C2-C4 alkenyl or phenyl, R16 is C1-C18 alkyl, R17 is C1-C18 alkyl, C2-C10 alkenyl, cyclohexyl, benzyl or C6-C10 aryl, or, if n = 2, R14 is C4-C12 alkyl, 2-butenylen-1,4, xylen, the group is -CH2) 2-OOC-R18-COO-(CH2) 2- or the group is -CH2-OOC-R19-COO-CH2-, where R18 is C2-C10 alkyl, phenylen or cyclohexyl and R19 is C2-C10 alkyl, xylen or cyclohexyl.
If any substituents are C1-C12 alkyl, they are e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Any substituents that denote C1-C18 alkyl may be, for example, the groups listed above and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
If any C2 to C10 groups are alkyl groups, they mean ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene or decamethylene.
R14 is represented by C4-C18 alkyl, e.g. n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, 1,1-dimethyl-2-tert-butyl ether, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
If R14 means a C1-C4 alkyl substituted by -CN, it is, for example, cyyanomethyl, cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl.
If R14 means C4-C12 alkyl, then these are e.g. 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
If R14 is C7-C12 aralkyl, it means in particular phenethyl, p-methyl benzyl or especially benzyl.
R15 is a C2-C4 alkenyl, for example vinyl, 1-propenyl, allyl, methylyl, 2-butenyl.
R17 means, for example, the groups listed for R15 in the alkenyl meaning as C2-C10 alkenyl, and for example crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.
If R17 is C6-C10 aryl, it means, for example, phenyl substituted with methyl, ethyl, isopropyl, n-butyl or tert-butyl in the o- or p-position, as appropriate.
Examples of polyalkylpiperidine light-protecting agents in this class are the following compounds: The use of a mixture of ethylene glycol and ethylene glycol is permitted.
(h) Photographic protection of the form XXIII
where Q is -N(R3) or -O- where R20 is C1-C3 alkyl, where R4 is hydrogen, methyl or phenyl, where R is hydrogen or methyl, where R1 is hydrogen or methyl, where R1 has the meaning specified in (a), R2 is hydrogen or C1-C18 alkyl, R3 is hydrogen, C1-C18 alkyl, C5-C7 cycloalkyl, C7-C12 aryl, Cyanethyl, C6-C10 aryl, where R4 has the meaning specified above, a group of the formula: or a group of the formula means that R21 can be C2-C6 alkyl or C6-C12 aryl, or R3 a group -R20-CO-NH-CH2-OR2ist.
If any substituents are C1-C18 alkyl, they are e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyle, n-dodecyle, n-tridecyle, n-tetradecyle, n-hexadecyle or n-octadecyle.
If any substituents are C7-C12 aralkyl, they mean, for example, phenethyl or in particular benzyl.
If R1 C3-C8 means alkenyl, it may be for example 1-propenyl, allyl, methylyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-ter-butyl-2-butenyl.
R1 is preferred as C3C8 alkynyl propargyl. As C1-C8 alkanol R1 means for example formyl, propionyl, butyryl, octanoyl but preferred as acetyl and as C3-C5 alkenol, especially acryloyl.
R3 stands for C5-C7 cycloalkyl, specifically cyclohexyl.
As C6-C10 aryl, R3 means phenyl a- or β-naphthyl, which may be substituted with halogens or C1-C4 alkyl.
R21 is represented as C2-C6 alkylenes such as ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene and as C6-C12 arylenes o-, m- or p-phenylenes, 1,4-naphthyls or 4,4'-diphenyls.
Examples of polyalkylpiperidine light-protecting agents in this class are the following compounds: The following substances are to be classified in the same category as the product:
(i) Polymeric compounds the repeating unit of which contains a polyalkylpiperidine residue of formula (I), in particular polyester, polyether, polyamide, polyamine, polyurethane, poly-harnas, polyaminotriazine, poly (meth) acrylate, poly (meth) acrylamide and their copolymers containing such residues. Polyester of amber, sebasic acid, di-butylmalonic acid, oxalic acid or isophthalic acid and 1-hydroxytyl-2,2,6,6-tetramethyl-4-hydroxypiperidin99) Polyamide of amber, adipic acid or phthalic acid and 1- ((3-Aminopropyl)-2,2,6,6-tetramethyl-4-aminopiperidin100) Polyamide of oxalic acid or p-phenylenediesic acid and N,N'-bis ((1,2,2,2,6,6-pentamethyl-4-piperidinyl)-1,6-diaminohexan101) Polyamine 1,2,2,6,6-pentaminylamid-4-aminylamidine-tetramethyl-nope and polyphenols or bisphenol-dihydrochloride-dihydroxyethylenediethylamide-1,2-benzylamide-2,2-benzylamide-2,2-benzylamide-2,2-benzylamide-2,2-benzylamide-2,2-nophenyl-nophenyl-nophenol, and N,2,2,6-6,6-dihydramethylamide-4-nophenol, butyl-4-butyl-4-butyl-4-butyl,2,6-dihydramethylamide-1,2-nophenol and N,6,6-dihydramethylamide-4-butyl-nophenol, and N,2,6-dihydramethylamide-1,2-butyl-butyl-butyl-butyl-butyl-nophenol, and N,6,6-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-but
An example of polyalkylpiperidine light-protecting agents in this class are the compounds of the following formulae, where m is the number 2 to approximately 200. Other
(i) Compounds containing at least one 2- (hydroxyphenyl) benztriazole group or 2-hydroxybenzophenone group and at least one polyalkylpiperidine group in their molecule The Commission has
Examples of polyalkylpiperidine light-preserving agents of this class are compounds of the following formulae: Other
Polyalkyl piperidine derivatives of classes a) to j) which form chemical bonds with the binding agent of the paint may also be used, provided that the polyalkyl piperidine derivative has a suitable reactive group, such as a glycidyl or methyl group.
Examples of such compounds are polyalkylpiperidine derivatives of class h containing methylol or methylol group (s).
Insofar as polyalkylpiperidine compounds are basic compounds, they can form salts with acids, for example inorganic acids or organic carbon, sulphon, phosphon or phosphoric acids, such as hydrochloric acid, boric acid, phosphoric acid, acetic acid, salicylic acid, toluene sulfonic acid or benzoyl phosphoric acid.
The polyalkylpiperidine compounds may form complexes with complex-forming metal compounds, such as with zinc-II acetate, cobalt-II acetyl acetate, nickel-II acetyl acetate, aluminium-III acetyl acetate, nickel-II benzoate or aluminium-III benzoylacetate.
Salt of 1 mole of H3P04 and 1 mole of adipic acid di- (1,2,2,6,6-pentamethyl-4-piperidinyl) ester
Salt of 2 mol of Bis (di-di-tert-butyl-4-hydroxybenzyl) malonic acid and 1 mol of 2,2,6,6-tetramethyl-4-lauroyl-oxypiperidine 1:1 complex of bis (di-di-di-di-tert-butyl-4-piperidinyl) sebacate and nickel-II acetyl acetate The chemical composition of the product is determined by the following equation:
The following examples illustrate the invention. Percentages mean weight percentages.
A. Manufacture in which the value of all the materials of Chapter 9 used does not exceed 30% of the ex-works price of the product
This intermediate product is prepared as described in USPS 2 714120. 705.8 g (7.5 mol) of phenol is mixed with 1772.7 g (15 mol) a-methylstyrol in the presence of 25.7 g (0.135 mol) p-toluol sulphonic acid monohydrate as a catalyst and heated for 2.5 hours at 140 °C below N2. After completion of the reaction, the mixture is cooled to 110 °C and 1125 ml of toluol is added. The resulting solution is then washed at 80 °C with 750 ml of an aqueous solution consisting of 37.5 g NaC03 and 75 NaCI. The organic phase is washed three times with 1000 ml of a durable NaCI solution, which is dried over a sulphur dioxide and is freeze-dried by vacuum distillation and contains 1229,86% of the main gly gland-free product (49,89,12%). The temperature of the water is between 172-175°/0.15-018 mm/Hg.
B. Comparison example: production of the intermediate product 2-nitro-2'-hydroxy-3',5'-di ((a,a-dimethyl-benzyl) azobenzole by acid coupling
Put 90,6 g of a 26% aqueous naphthalic insulin sulphonic acid solution, 1,9 g of Triton X-207 (non-ionic surfactant), 5,6 g of Conoco AAS-90F (sodium dodecylbenzene sulphonate) and 90 ml of water into a 2 I tri-neck round flask with a shaker and thermometer, heat the mixture to 40 °C, mix with 16,5 g of 2,4-Di-a,a-di-methylbenzyl) phenol which has been preheated to 90 °C and stir it vigorously to 40 °C.
A cold o-nitrobenzodiazonium chloride solution is prepared from 49.8 g (0.36 mol) o-nitroaniline and 24.9 g (0.36 mol) sodium nitrite in concentrated HCI at -5 °C to 0 °C. This solution is dripped into the reaction mixture for 3 hours and the resulting dark red to black solution is kept overnight at 40 °C. The temperature is then raised to 65 °C for one hour and then to 95 °C for another 30 minutes. After cooling to 85 °C, the raw product, a deep red viscous mass, is isolated.
The crushed raw product is mixed with 200 ml of hot water (75°C) and then left to stand overnight with 400 ml of methanol. The mixture is stirred with another 400 ml of methanol to a fine granulate.
The thin-film chromatogram shows a homogeneous product with Rf = 0,61 on silica gel in 3 parts cyclohexane and 1 part ethyl acetate as solvent
Example 1: The following substances are to be classified in the same category as the active substance:
In a 5 I tri-neck round flask with gas inlet, stirrer and backflow cooler, add 386 g (0.805 mol) o-nitroazobenzene, produced in example A, and 1200 ml toluene. Add 240 mi isopropane and 240 ml water to this solution. Add 160 ml 50.1% sodium salts to the solution while introducing nitrogen. A bottle of 158.2 g (2.42 gram atoms) zinc is connected to the flask.
The zinc residue is removed by filtration. The organic phase containing the product is washed four times with 340 ml of dilute hydrochloric acid. After removal of the solvent by vacuum distillation, the viscous raw product is obtained, which crystallizes when standing.
To purify the raw product, recrystallize it first from 750 ml of ethyl acetate and then from 1000 ml of acetonitrile/ethyl acetate mixture (4:1) and then dissolve in 1250 ml of toluene.
The result is 219.3 g (60.9% of the theory) of yellowish-white crystals at 140-141 °C. Other
Example 2: It consists predominantly of hydrocarbons having carbon numbers predominantly in the range of C1 through C5.]
In a 500 ml tri-neck flask with agitator, gas inlet and pressure relief, add 13.5 g (0.21 mol) of solid potassium hydroxide and 10 ml of water.
16.5 g (0.05 mol) 2,4-Di- (a-dimethyl-benzyl) phenol and 85 ml of methanol are added under nitrogen and cooled to -4°C. A chilled solution containing 42.9 g (0.06 mol) o-nitrobenzodiazonium chloride in concentrated HCI is added for 15 minutes and stirred and kept at -2°C to 0°C. Immediately a deep red colouration is produced by the azo dye phenoxide formed. The mixture is stirred at -1°C to +1°C for 10 minutes, then slowly (for 2 minutes) with 20 ml of ice and the water is kept at +18°C to +3°C. The suspension is continued for 15 minutes, with a temperature of 160 ml and a water retention of +18°C. The solution can be filtered and filtered with a water and water until the temperature of the mixture reaches +16°C.
The light red raw product is dried in a vacuum at 30°C and 75 mm Hg for 16 hours. The yield is 22.7 g, 82% of the theory.
The raw product is decrystallized from hot n-butanol (5 ml per gram).
Example 3: It consists predominantly of hydrocarbons having carbon numbers predominantly in the range of C1 through C5.]
Using the method in Example 2, dissolve 13,6 g (0.34 mol) of solid sodium salts in 145 ml of methanol, add 16,5 g (0.05 mol) of 2,4-Di- ((a,a-dimethyl-benzyl) phenol and 20 ml of methanol.
The solution is cooled to +2°C. In the meantime, a solution of o-nitrobenzene diazonium chloride is prepared from 8.3 g (0.06 mol) o-nitroaniline and 17.3 g conc. HCI, plus 6 ml of water and 4.3 g of sodium nitrite in 8 ml of water. The diazonium solution is added to the alkaline solution for 2 hours at +2°C. The deep red mixture is stirred for 30 minutes at +2°C, then acidified with 20 ml of ice vinegar and the light red precipitate is isolated by filtration. The product is washed with 3x50 ml of methanol, then with 4x75 ml of water and then dried at 75°C. The yield is 21.6 g (89% Smp. 97% mmol/l, purity: 140-142°C).
Examples 4 to 16: Alkaline coupling
The method is as in example 2, but other phenols are used instead of 2,4-Di- (α,α-dimethylbenzyl) phenol. Other
* The yield is 47% when 4-chloro-2-nitrobenzodiazonium chloride is coupled with this phenol.
Example 17: It consists predominantly of hydrocarbons having carbon numbers predominantly in the range of C1 through C5.]
In example 2, using ethanol instead of methanol results in an N2 development (50% of the theory) and a low yield (50.5%) of the above product.
The same result is obtained when isopropanol is used instead of methanol.
These data indicate that methanol is the most suitable solvent for alkaline coupling.
Example 18: It consists predominantly of hydrocarbons having carbon numbers predominantly in the range of C1 through C5.]
In comparison example B, using a diazonium solution made from 2-nitroaniline in place of diazonium solution made from 4-chloro-2-nitroaniline in an equivalent amount, 47,°% of the dark red product is obtained.
Example 19: It consists predominantly of hydrocarbons having carbon numbers predominantly in the range of C1 through C5.]
If in example 1 2-nitro-2'-hydroxy-3',5'-di- ((α,α-dimethyl-benzyl) -azoben-zo! 4-chlorine-2-nitro-2'-hydroxy-3',5'-di- ((a,a-dimethyl-benzyl) -azobenzol is used instead of 2-nitro-2'-hydroxy-3',5'-di-(α,α-dimethyl-benzyl) -azobenzol, 70.0% of the product is obtained. The light brown crystals melt at 160-161°C (compound no. 2). Other
Example 20: 2- (hydroxy-3-tert-octyl-5-α,α-dimethyl-benzyl) -phenyl-2H-benzotriazole, whether or not containing by weight:
If in example 1 an equivalent amount of 2-nitro-2'-hydroxy-3'-tert-octyl-5'-α,α-dimethyl-benzyl-azobenzene is used instead of the o-nitroazobenzene from comparator example B, the product described above is obtained.
Example 21: Loss resistance of benzotriazoic acid
A number of 2-aryl-2H-benzotriazoles are analysed by tnermalgravimetry, both isothermically at 280°C to measure the time in minutes at which 10%, 50% and 100% of the stabiliser is lost, and by a counting method in which the temperature was continuously increased by 10°C per minute until a stabiliser loss of 10% and 50% respectively was observed.
The test results are summarised in Table A.
The results show the exact amount of stabilizer resistance during processing of the polymer into films, films, fibres, etc. to prevent sweating or evaporation. Other
CYASORB UV-5411 is a 2- ((2-hydroxy-5-tert-octylphenyl) -H-benzotriazole (NL 127.157) which is used in the manufacture of other products.
The compound 333 is 2- (([2-Hydroxy-3- ((1-phenyl-ether) -5-methylphenyl) -2-H-benzotriazole.
The compound S1 is 2-[2-Hydroxy-3-methyl-5- ((a,a-dimethyl-benzyl) -phenyl]-2H-benzotriazole (JP-OS 158.588/75)
The compound S2 is 2-hydroxy-3-α,α-dimethyl-benzyl) -5-methyl-phenvl]-2H-benzotriazole (JP-OS 158.588/75)
The compound S3 is 2-[2-Hydroxy-3- ((a,a-dimethyl-benzyl) -5-tert-butyl-phenyl]-2H-benzotriazole (JP-OS 158.588/75)
The compound S4 is 5-Chloro-2-[2-hydroxy-3-methyl-5- ((a,a-dimethyl-benzyl) -phenyl]-2H-benzotriazole (JP-OS 158.588/75)
Compound 1 (example 1) is clearly more resistant than the other benzotriazoles. Compound 1 incorporated into the polymer would therefore provide the polymer with better protection against harmful light effects and would also show excellent performance during processing.
Example 22: Resistance of benzotriazole stabilizers in polycarbonate during film manufacture.
Polycarbonatharz, (Lexan, General Electric) was equipped with 0.3% (weight) of various 2-aryl-2H-benzotriazole UV absorbers. The formulated resin was extruded at 316°C to thin films. The resulting films were dissolved in methylene chloride and the polycarbonate was precipitated with methanol. The amount of benzotriazole stabilizer remaining in the polycarbonate film after manufacture was determined by gas chromatography analysis. The results are shown in Table B. Other
These data confirm the results of Table A and the resistance to sublimation and exudation of compound 1 during manufacture.
Example 23: Resistance to losses during curing and weathering of benzotriazole stabilizers in thermoset acrylic fluid trains.
A variety of thermoset acrylic resins and an alkyd/acrylic resin system were formulated with 2% (by weight) of different benzotriazole UV absorbers and poured onto glass plates to 1μm thick coatings. The coatings were then cured at elevated temperature for a period of time. The loss of benzotriazole UV absorber was then determined by UV absorption analysis of the coatings. A decrease in coatings absorption can be equated to a loss of benzotriazole stabilizer during curing.
These hardened coats were subjected to the accelerated (quick) weathering test (QUV) which alternated 4 hours of UV exposure at 60°C and 4 hours of condensation (rain) at 50°C over a period of 670 hours. Other
Table C shows that the compound of the invention has a much lower rate of erosion in the thermoset acrylic resin and alkyd/acrylic resin systems than the known benzotriazole.
Example 24: Gloss levels of acrylic enamel and lacquer containing benzotriazole stabilisers and weathering.
Various thermoset acrylic enamels and thermoplastic acrylic paints were formulated with a benzotriazole UV absorber. The gloss values are compared with the original enamel or paint after accelerated weathering (QUV with a cycle of 4 hours UV at 60°C and 4 hours condensation at 50°C). The results are shown in Table D.
Compound 1 formulations consistently produced better gloss after QUV irradiation than those with previously known benzotriazoles.
Example 25: Stabilization of polyethylene terephthalate
0,5% of the compound of Beispie! 1 is given as a stabilizer to molten poietylen terephthalate at 270°C under stirring and a nitrogen atmosphere.
The stabilized mixture is extruded at elevated temperature to a film with low stabilizer loss, then subjected to UV irradiation, and the stabilized film retains its desired physical properties longer than the unstabilized film.
Example 26: Stabilization of polycarbonate
Polycarbonate (Lexan, General Electric) is mixed in an extruder with 0.3% of the compound of example 4. The stabilized mixture is extruded to a film at elevated temperature with little loss of stabilizer. The film retains its physical properties after UV irradiation longer than one without stabilizer.
Example 27: The following shall be indicated in the column 'C' of the column 'C' of the table:
This compound is obtained by coupling o-nitrobenzene diazonium chloride with 2-a-dimethylbenzyl-4-tert-octylphenol as a red crystalline solid, at F 133 to 134 °C, according to the general method of example 3.
Example 28: The following definitions apply to the following substances:
Following the general method of Example 1, an equivalent amount of 2-nitro-2'-hydroxy-3'-α,α-dimethylbenzyl-5'-tert-octylazo-benzol is used instead of the o-nitroazobenzene intermediate of the comparison example B. The above compound was obtained as almost white crystals, F. 88-90°C (compound 3).
Analysis: Calculated for C29H35N3O: Other
Example 29: The substance is to be classified in the immediate vicinity of the active substance.
Following the procedure in Example 1, an equivalent amount of 2-nitro-2'-hydroxy-3'-tert-octyl-5-a,a-dimethylbenzyl azobenzene is used instead of the o-nitroazobenzene intermediate in Comparison Example B, resulting in the above compound.
The delamination of UV-transparent automotive coatings applied to epoxy ester primers is a serious problem for car manufacturers. This problem becomes particularly relevant when the coating thickness is below the prescribed level.
Example 30: Gloss and delamination of thermoplastic acrylate coatings.
A silver metal thermoplastic acrylic paint was formulated with a benzotriazole UV absorber and then applied as a coating to a primer surface made of an epoxy ester on metal plates. The whole was heated for 10 minutes at 48°C and then for 30 minutes at 155°C. The original coating layer thickness was 2.0 b 2.2 mils (50 to 55 microns, 0.0508 to 0.0559 mm).
The plates were exposed to the sun for a year in South Florida in an unheated black box at a 5 degree angle.
The exposed plates were placed in a chamber of constant humidity at 38°C and 100% relative humidity for 96 hours, then dried and immediately examined by the cross-hatch tape adhesion test, then left at room temperature for one hour before the cross-hatch tape adhesion test was repeated at another location on the same plate. The samples generally show a slightly improved delamination resistance after this one-hour rest break, compared to the delamination immediately after the moisture treatment.
The cross-hatch tape adhesion test uses a multi-cutting knife to make cuts through the cover coat on the plate. An acetate-fiber tape is glued over the interfaces and then pulled off. The cover coat is visually assessed whether and how much has been pulled off. This gives a relative assessment of the delamination from 0 (no cross-hatch delamination) to 5 (complete cross-hatch delamination). Other
The data in Table E confirm that compound 1 and the one in Example 10 provide excellent protection against losses during prolonged exposure in the South Florida Black Box test, compared to other benzotriazole protective agents.
The data in Table F show that the compounds of the invention, in particular compound 1, protect a thermoplastic acrylic coating from delamination after 1 year of South Florida Black Box exposure under the most stringent test conditions with immediate moisture treatment.
Example 31: Delamination values of thermoset coatings made of acrylic enamel.
Two silver-metallic thermoset acrylic enamels were formulated with a benzotriazole photosensitive and then sprayed as a coating on a pyrmer surface made of an epoxy ester on a metal plate. The plate was cured for 17 minutes at 130°C to an initial coating film of 1.7 mil thickness (42 microns, 0.0432 mm). The plate was treated for 1200 hours with the QUV weathering test according to example 23.
After the QUV exposure, the plates were moisturized and then delamination was determined, then one hour of recovery was enabled, after which the delamination resistance was again determined as shown in example 30. Other
The combination of sterile amine inhibited light-saving agents with the benztriazole UV absorbers of the invention is particularly suitable for maintaining the shine and preventing delamination, in particular in metallized thermoset acrylic enamels and metallized thermoplastic acrylic coatings for automotive roofs.
The inhibited amines protect the thermoset acrylic enamel and thermoplastic acrylic paint against loss of luster even at low concentrations, but do not act as a UV filter. Accordingly, UV light can pass through the acrylic coating if a UV absorber is absent, such as the benztriazole of the invention, and can cause damage to the epoxy ester primer surface under the coating.
Example 32: Delamination values for coatings made of thermoset acrylic enamel.
Two silver-metallized thermoset acrylic enamels were formulated with both an inhibited amine light shield and a benztriazole UV absorber.
Compound A is bis- ((2,2,6,6-tetramethyl-4-piperidyl) sebacate.
Compound B is bis- ((1,2,2,6-pentamethyl-4-piperidyl)-2-n-butyl-2- ((3,5-di-tert-butyl-4-hydroxybenzyl) -malonate.
Example 33: Delamination and 20° gloss of thermoplastic acrylic paints.
The efficacy of combinations of inhibited amine photosensitives with benztriazole UV absorbers of the invention for protecting automotive roofing coatings is demonstrated in thermoplastic acrylic resins, with both the inhibited amine providing gloss retention after prolonged exposure in South Florida and the bentriazole UV absorbers of the invention protecting the thermoplastic acrylic roofing against delamination.
A silver-metallic thermoplastic acrylic paint was formulated with both an inhibited amine photosensitive and a benztriazole UV absorber.

Claims (12)

1. A compound of the formula wherein T, is hydrogen or chlorine and each of T2 and T3 independently of the other is the group wherein T4 is hydrogen or lower alkyl, whilst one ofT2 and T3 can also be t-octyl.
2. A compound according to claim 1, wherein T, is hydrogen or chlorine, T2 and T3 have the same meaning and T4 is hydrogen or p-methyl.
3. A compound according to claim 1, wherein T4 is hydrogen.
4. 2-[2-Hydroxy-3,5-di-(a,a-dimethylbenzyl)-phenyl]-2H-benzotriazole, according to claim 1.
5. 5-Chloro-2-[2-hydroxy-3,5-di-(a,a-dimethylbenzyl)-phenyl]-2H-benzotriazole according to claim 1.
6. A stabilised organic material containing 0,1-5% by weight of a stabiliser according to any one ot claims 7 to b.
7. A stabilised organic material according to claim 6, wherein the material is a synthetic polymer.
8. A stabilised polymer according to claim 6, wherein the polymer is a polyester, polycarbonate, hot-crosslinkable acrylic resin or polyamide or a polyurethane.
9. A lacquer which has gloss retention and resistance to peeling on weathering, said lacquer containing
a) a hot-crosslinkable acrylic resin and
b) 0,1 to 5% by weight, based on the resin, of a compound of the formula I according to any one of claims 1 to 5 and
c) 0,1 to 5% by weight, based on the resin, of a sterically hindered amine stabiliser.
10. A stabilised organic material according to claim 9, containing 0,5 to 2% by weight of b) and 0,5 to 2% by weight of c).
11. A stabilised organic material according to claim 9, containing, as constituent c), bis-(2,2,6,6-tetramethyl-4-piperidyl) sebacate as light stabiliser.
12. A stabilised organic material according to claim 9, containing, as component c), bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate as light stabiliser.
HK970/84A 1978-06-26 1984-12-13 2-(3.5-disubstituted-2-hydroxyphenyl)-2h-benzotriazoles and stabilized compositions containing them HK97084A (en)

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US05/918,984 US4226763A (en) 1978-06-26 1978-06-26 2-[2-Hydroxy-3,5-di-(.alpha.,α-dimethylbenzyl)-phenyl]-2H-benzotriazole and stabilized compositions
US06/036,914 US4278589A (en) 1978-06-26 1979-05-10 2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole and stabilized compositions
US06/038,768 US4275004A (en) 1978-06-26 1979-05-16 High caustic coupling process for preparing substituted 2-nitro-2'-hydroxyazobenzenes

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EP0031302A3 (en) * 1979-12-21 1981-07-22 Ciba-Geigy Ag Benzotriazole uv absorbers, process for their preparation and stabilized mixtures
EP0317561B1 (en) * 1986-07-28 1991-01-30 AlliedSignal Inc. Sulfonate benzotriazoles and their use in polyamide
EP0418198A1 (en) * 1989-09-11 1991-03-20 Ciba-Geigy Ag Monosulfonated 2-(2'-hydroxyphenyl)-benzotriazoles
JP2971338B2 (en) * 1994-09-09 1999-11-02 帝人株式会社 Easily dyeable meta-type aromatic polyamide fiber
US5574166A (en) * 1995-04-19 1996-11-12 Ciba-Geigy Corporation Crystalline form of 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole
GB2311143B (en) * 1995-04-19 1997-11-05 Ciba Geigy Ag Recording materials stabilized with benzotriazole uv absorbers
US5852087A (en) * 1996-02-13 1998-12-22 Teijin Limited Easily dyeable meta-linkage-containing aromatic polyamide fibers
RU2004120783A (en) * 2001-12-05 2006-01-10 Циба Спешиалти Кемикэлз Холдинг Инк. (Ch) METHOD FOR PRODUCING 2- (2-NITROPHENILAZO) PHENOLS WITHOUT USING ORGANIC SOLVENTS
CN110003126B (en) * 2019-04-17 2022-07-22 威海金威化学工业有限责任公司 Preparation method of ultraviolet absorbent Tinuvin 928

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US3072585A (en) * 1960-01-13 1963-01-08 American Cyanamid Co Vinylbenzyloxy phenylbenzotriazoles
DE2065975C3 (en) * 1970-03-14 1979-11-29 Bayer Ag, 5090 Leverkusen Stabilizing polyurethanes against degradation and discoloration
US4127586A (en) * 1970-06-19 1978-11-28 Ciba-Geigy Corporation Light protection agents
CH529815A (en) * 1970-06-19 1972-10-31 Ciba Geigy Ag Use of 2- (2'-hydroxyphenyl) -benzotriazole compounds as light stabilizers
US3983132A (en) * 1974-08-23 1976-09-28 Gaf Corporation Branched chain dodecyl isomeric mixtures of 2-(5-dodecyl-2-hydroxy phenyl) benzotriazole as stabilizers for heat and light sensitive materials
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