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US20050038245A1 - Naphthyltriazines as stabilizers for organic material - Google Patents

Naphthyltriazines as stabilizers for organic material Download PDF

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Publication number
US20050038245A1
US20050038245A1 US10/492,721 US49272104A US2005038245A1 US 20050038245 A1 US20050038245 A1 US 20050038245A1 US 49272104 A US49272104 A US 49272104A US 2005038245 A1 US2005038245 A1 US 2005038245A1
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Prior art keywords
alkyl
phenyl
formula
alkenyl
substituted
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Inventor
Vien Toan
Georges Metzger
Thomas Schafer
Stephane Biry
Christophe Bulliard
Dieter Reinehr
Peter Michaelis
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BASF Corp
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Individual
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Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: REINEHR, DIETER, MICHAELIS, PETER, METZGER, GEORGES, BIRY, STEPHANE, SCHAFER, THOMAS, TOAN, VIEN VAN, BULLIARD, CHRISTOPHER
Publication of US20050038245A1 publication Critical patent/US20050038245A1/en
Priority to US11/098,640 priority Critical patent/US7087753B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms

Definitions

  • the invention relates to novel compounds of the 2-hydroxyphenyl-1,3,5-triazine type that comprise one or two ⁇ - or ⁇ -bonded naphthyl groups, to the use of those compounds for stabilising organic material, especially in plastics materials, surface-coatings, cosmetic preparations, sun protection agents or photographic material, against damage by light, oxygen and/or heat, and to correspondingly stabilised organic material.
  • a light stabiliser is usually added.
  • a class of light stabilisers that is very often employed comprises the UV absorbers, which protect the material by absorbing harmful radiation by way of chromophores.
  • An important group of UV absorbers is formed by the 2-hydroxyphenyl-1,3,5-triazines (U.S. Pat Nos. 3,118,887, 3,242,175, 3,244,708, GB-A-1 321 561).
  • the invention therefore relates to a compound of formula I wherein
  • radicals R 2 to R 10 , R 12 to R 14 , R 16 and R 17 as alkyl are branched or unbranched alkyl, such as e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl
  • the radicals R 2 , R 3 to R 9 , R 12 as C 5 -C 12 cycloalkyl include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclodocecyl. Cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl are preferred.
  • R 2 to R 8 , R 9 , R 11 , and R 12 as alkenyl include, within the scope of the definitions given, inter alia allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl and n-octadec-4-enyl.
  • Substituted alkyl, cycloalkyl or phenyl radicals may be mono- or poly-substituted and may carry substituents at the binding carbon atom (in the ⁇ -position) or at other carbon atoms; if a substituent is bonded by a hetero atom (such as e.g. alkoxy), it is preferably not in the ⁇ -position and the substituted alkyl radical comprises 2, especially 3, or more carbon atoms.
  • a plurality of substituents is preferably bonded to different carbon atoms.
  • Alkyl interrupted by —O—, —NH—, —NR 7 — and/or by —S— may be interrupted by one or more of the mentioned groups, in each case normally one group being inserted into a bond and hetero-hetero bonds, such as, for example, O—O, S—S, NH—NH etc. not occurring; if the interrupted alkyl is, in addition, substituted, the substituents are not normally in the ⁇ -position with respect to the hetero atom. If a plurality of interrupting groups of the type —O—, —NH—, —NR 7 — and —S— occurs in a radical, those groups are usually identical.
  • Aryl is generally an aromatic hydrocarbon radical, for example phenyl, biphenylyl or naphthyl, with phenyl and biphenylyl being preferred.
  • Aralkyl generally denotes alkyl substituted by aryl, especially by phenyl;
  • C 7 -C 20 aralkyl therefore includes, for example, benzyl, ⁇ -methylbenzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl;
  • C 7 -C 11 phenylalkyl preferably comprises benzyl, ⁇ -methylbenzyl and ⁇ , ⁇ -dimethylbenzyl.
  • Alkylphenyl and alkylphenoxy are alkyl-substituted phenyl and phenoxy, respectively.
  • a halogen substituent is —F, —Cl, —Br or —I; —F or —Cl, and especially —Cl, is preferred.
  • Haloalkyl is especially chloroalkyl or trifluoromethyl; trifluoromethyl is of particular importance industrially.
  • Alkylene is e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene, etc.
  • the alkyl chain may also be branched in that case, such as e.g. in isopropylene.
  • Cycloalkenyl is e.g. 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2,4-cyclopentadien-1-yl, 2-cyclohexen-1-yl, 2-cyclohepten-1-yl or 2-cycloocten-1-yl.
  • C 6 -C 15 Bicycloalkyl is e.g. bornyl, norbornyl, 2.2.2-bicyclooctyl. Bornyl and norbornyl, and especially bornyl and norborn-2-yl, are preferred.
  • C 6 -C 15 Bicycloalkoxy is, for example, bornyloxy or norborn-2-yl-oxy.
  • Bicycloalkyl-alkyl or -alkoxy is alkyl or alkoxy substituted by bicycloalkyl, the total number of carbon atoms being 6-15; examples are norbornane-2-methyl and norbornane-2-methoxy.
  • Bicycloalkenyl is e.g. norbornenyl, norbornadienyl.
  • Norbornenyl and especially norborn-5-enyl, is preferred.
  • Bicycloalkenyl-alkoxy is alkoxy substituted by bicycloalkenyl, the total number of carbon atoms being 6-15; an example is norborn-5-enyl-2-methoxy.
  • Tricycloalkyl is e.g. 1-adamantyl, 2-adamantyl; 1-adamantyl is preferred.
  • Tricycloalkoxy is e.g. adamantyloxy.
  • C 3 -C 12 Heteroaryl is preferably pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thiophenyl or quinolinyl.
  • Typical compounds of formula I include those wherein
  • the compounds of formula I can be prepared by Friedel-Crafts addition of halotriazines to corresponding aromatic compounds and phenols analogously to one of the methods specified in EP-A-434 608 or in one of the publications mentioned at the beginning or analogously to one of the methods specified in the publication by H. Brunetti and C. E. Lüthi, Helv. Chim. Acta 55, 1566 (1972); see also U.S. Pat. Nos. 5,726,310, 6,057,444, 6,225,468, and EP-A-941 989, WO 00/29392.
  • That procedure can be followed by a further reaction according to known methods to form compounds of formula I wherein R 7 is not hydrogen; such reactions and processes are described, for example, in EP-A-434 608, page 15, line 11, to page 17, line 1. That route is especially suitable for the preparation of compounds according to the invention of formula I wherein the naphthyl group is bonded in the ⁇ -position (1-naphthyl).
  • cyanuric chloride is used as starting material and is reacted with approximately one equivalent each of naphthalene or a suitable naphthalene compound, a further aromatic compound and a phenol, such as, for example, resorcinol.
  • Suitable aromatic starting materials must have at least one C—H bond on the aromatic compound; at least one of the phenols used must contain an ortho-position unsubstituted in that manner.
  • the further aromatic compound may be identical to the naphthalene compound or the phenol, or may be benzene or a substituted benzene, such as, for example, toluene, xylene, mesitylene, tert-butylbenzene, biphenyl or methoxybenzene.
  • the naphthalene compound is preferably naphthalene, or alkyl- or alkoxy-naphthalene, especially ⁇ - or ⁇ -naphthol, ⁇ - or ⁇ -methylnaphthalene, ⁇ - or ⁇ -meth-oxynaphthalene.
  • the phenol is preferably phenol, resorcinol, or resorcinol substituted by alkyl or by phenylalkyl, especially resorcinol.
  • the reaction is carried out in a manner known per se by reacting the starting materials with the cyanuric halide in an inert solvent in the presence of anhydrous AlCl 3 .
  • Aluminium trichloride can be used in excess and/or in admixture with HCl, for example conc. aqu. hydrochloric acid.
  • the naphthyl compound is reacted first and the phenol compound is added last.
  • reaction product of cyanuric halide and naphthyl compound can be further reacted directly or can also be isolated in known manner.
  • a number of such intermediates are novel; the invention therefore relates also to the compounds
  • Suitable solvents are, for example, hydrocarbons, chlorinated hydrocarbons, hydrocarbons containing SO or SO 2 groups, or nitrated aromatic hydrocarbons; high-boiling hydrocarbons, such as ligroin, petroleum ether, toluene or xylene, or sulfolane are preferred.
  • the temperature is generally not critical; the temperatures used are usually from ⁇ 20° C. to the boiling point of the solvent, for example from 0° C. to 100° C.
  • the ⁇ - or ⁇ -naphthyltriazines according to the invention can also be prepared by means of Grignard processes analogously to known compounds, see U.S. Pat. No. 5,438,138 and publications mentioned therein.
  • the compounds according to the invention can furthermore be obtained analogously to processes described in U.S. Pat. Nos. 5,545,863, 5,478,935, 6,020,490, WO 96/28431, or by ring-closing reactions analogously to H. Brunetti and C. E. Lüthi, Helv. Chim. Acta 55, 1566 (1972).
  • compounds according to the invention of formula I can be obtained analogously to WO 96/28431 by replacing one or also both of the biphenyl starting compounds described in WO 96/28431 on pages 9-13 by a corresponding naphthyl compound in each case.
  • Free phenolic hydroxyl groups of the reaction product in the p-position with respect to the triazine ring can be further modified in known manner, for example etherified.
  • Working-up can be carried out by customary methods, e.g. by extraction and separation steps, filtration and drying; if necessary, further purification steps can be performed, e.g. recrystallisation.
  • the reactions can be carried out with the exclusion of oxygen, for example by flushing with an inert gas, such as argon; oxygen is not troublesome in every case, however, and therefore the reaction can also be carried without the mentioned measure.
  • an inert gas such as argon
  • working-up can be carried out according to customary methods.
  • the compounds according to the invention are especially suitable for stabilising organic materials against damage by light, oxygen or heat.
  • the compounds according to the invention are most especially suitable as light stabilisers (UV absorbers).
  • the materials to be stabilised may be e.g. oils, fats, waxes, surface-coatings, cosmetics, photographic materials, textiles and their dyestuffs, or biocides.
  • a particularly interesting application is in polymeric materials of the kind present in plastics materials, rubbers, coating materials, photographic material or adhesives.
  • cosmetic preparations the skin or hair to which the preparation is applied is especially also protected against damage by light.
  • organic materials that can be stabilised in that manner are as follows:
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • Homopolymers and copolymers from 1.)-4.) may have any stereostmucture including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • the invention further relates therefore to a composition
  • a composition comprising A) an organic material that is sensitive to oxidative, thermal or/and actinic degradation/formation and B) as stabiliser at least one compound of formula I, and to the use of compounds of formula I for stabilising organic material against oxidative, thermal or actinic degradation/formation.
  • the invention also includes a method of stabilising organic material against thermal, oxidative or/and actinic degradation/formation, which comprises applying or adding at least one compound of formula I to that material.
  • the amount of the stabiliser to be used depends upon the organic material to be stabilised and upon the intended use of the stabilised material.
  • the composition according to the invention comprises from 0.01 to 15, especially from 0.05 to 10, and more especially from 0.1 to 5, parts by weight of stabiliser (component B) per 100 parts by weight of component A.
  • the stabiliser (component B) may be a single compound of formula I or also a mixture.
  • compositions according to the invention may comprise as additional component (C) one or more conventional additives, such as, for example, antioxidants, further light stabilisers, metal deactivators, phosphites or phosphonites.
  • additional component (C) one or more conventional additives, such as, for example, antioxidants, further light stabilisers, metal deactivators, phosphites or phosphonites. Examples of these are as follows:
  • Tris(2,4-di-tert-butylphenyl)phosphite (Irgafoso®168, Ciba-Geigy), tris(nonylphenyl) phosphite,
  • the nature and amount of the further stabilisers added is determined by the nature of the substrate to be stabilised and its intended use; from 0.1 to 10% by weight, for example from 0.2 to 5% by weight, based on the material to be stabilised, are often used.
  • the invention therefore includes a synergistic stabiliser mixture comprising (a) a compound of formula I and
  • Preferred sterically hindered amines are, for example, those mentioned in the above list in 2.6 or hereinafter as additives to the coating compositions according to the invention.
  • the organic materials to be protected are preferably natural, semi-synthetic or synthetic organic materials.
  • the compounds according to the invention can also be used as sun protection agents for human or animal skin or hair.
  • the invention therefore relates also to a cosmetic preparation comprising a UV absorber of formula I, preferably in an amount of from 0.25 to 5% by weight, based on the total weight of the preparation, and a skin- and hair-tolerable carrier or excipient.
  • the stabiliser mixtures according to the invention can be used especially advantageously in compositions comprising as component A a synthetic organic polymer, especially a thermoplastic polymer, a binder for coatings, such as, for example, surface-coatings, or a photographic material.
  • Suitable thermoplastic polymers are, for example, polyolefins, especially polyethylene (PE) and polypropylene (PP) and copolymers thereof, and polymers comprising hetero atoms in the main chain (see e.g. U.S. Pat. No. 5,288,778, columns 2 and 3).
  • additives according to the invention can be added to the material individually or as a mixture. If desired, the individual components can be mixed with one another before being incorporated into the polymer, for example in a dry state, by compacting or as a melt.
  • incorporación of the additives according to the invention and optionally further components into the polymer is carried out according to customary methods, such as, for example, dry mixing in powder form or wet mixing in the form of solutions, dispersions or suspensions, for example in inert solvents, water or oil.
  • Incorporation of the additives according to the invention and optionally further components can be carried out, for example, before or after shaping, or by applying or adding the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent removal of the solvent or suspension agent/dispersant. Addition directly into the processing apparatus (e.g. extruder, mixer etc.), for example from a dry mixture or powder or as a solution or dispersion, suspension or melt, is possible.
  • the incorporation can be carried out in principle in any heatable vessel equipped with stirring apparatus, for example in closed apparatuses, such as kneaders, mixers or stirred vessels. Incorporation is preferably carried out in an extruder or kneader. The incorporation can be carried out under an inert atmosphere or equally in the presence of oxygen.
  • Any conventional apparatus for melting and mixing the polymer can be used for the addition of the additive or additive mixture.
  • Suitable apparatuses such as, for example, those mentioned above, are known in the art.
  • the additives are added during the processing step in the extruder.
  • Especially preferred processing apparatuses are single-screw extruders, twin-screw extruders running in opposite directions or in the same direction, planetary gear extruders or kneaders.
  • Processing machines can be equipped with one or more degassing vessels to which a negative pressure can be applied.
  • the screw length may, for example, be 1-60, preferably 35-48, screw diameters.
  • the rotation speed of the screw is preferably 10-600 revolutions per minute (rpm), especially 25-300 rpm.
  • the maximum throughput depends upon the screw diameter, the rotation speed and the driving force.
  • the process according to the invention can also be operated at less than the maximum throughput by altering the mentioned parameters or by the use of metering machines.
  • the additives according to the invention and optionally further components can be added to the polymer material also by spraying. They are suitable for diluting other additives (for example the above-mentioned conventional additives) or melts thereof, making it possible to spray them on together with the latter. Especially advantageous is addition of the additives according to the invention by spraying during the deactivation of the polymerisation catalyst; in that case, the evolution of vapour can be utilised for deactivation. For example, addition by spraying, optionally together with other additives, can be advantageous in the case of spherically polymerised polyolefins.
  • the additives according to the invention and optionally further additives can be added to the polymer also in the form of concentrates (master batches) that comprise those components, for example, in a concentration of from 1 to 40%, preferably from 2 to 20%, relative to the weight of the polymer. That polymer does not necessarily have to have the same structure as the polymer to which the additives are finally added.
  • the polymer may be used in the form of a powder, granules, solutions, suspensions or in the form of latices.
  • Incorporation can be carried out before or during shaping, or by applying the dissolved or dispersed compound to the polymer, where applicable with subsequent evaporation of the solvent. In the case of elastomers, these may also be stabilised in the form of latices.
  • a further possibility of incorporating the compounds of formula I into polymers comprises adding them before, during or immediately after polymerisation of the corresponding monomers or before crosslinking.
  • the compounds of formula I can be added as such or alternatively in encapsulated form (e.g. in waxes, oils or polymers).
  • the stabilised polymer compositions obtained in that manner can be converted into shaped articles, such as e.g. into fibres, films, monofilaments, tapes, non-woven fabrics, surface-coatings, panels, web panels, vessels, tubes and other profiles, by the usual methods, such as e.g. hot-pressing, spinning, extrusion, blow-moulding, rotomoulding, spraying or injection-moulding.
  • a polymer composition according to the invention having a relatively high content of stabiliser according to the invention, for example 5-15% by weight, is applied in a thin layer (10-100 ⁇ m) to a shaped article made from a polymer containing little or no stabiliser of formula I.
  • Application can be carried out simultaneously with the shaping of the basic body, e.g. by so-called coextrusion.
  • Application can also be carried out, however, to the ready-shaped basic body, e.g. by lamination with a film or by coating with a solution.
  • the outer layer or layers of the finished article have the function of a UV filter which protects the interior of the article from UV light.
  • the outer layer contains preferably 5-15% by weight, especially 5-10% by weight, of at least one compound of formula I.
  • the UV absorber can also be present in a different layer or in the single polymer layer.
  • the materials stabilised in that manner are distinguished by high resistance to weathering, especially by high resistance to UV light.
  • the polymers retain their mechanical properties and also their colour and gloss for a long time even when used outside.
  • Compounds of the present formula I can be used advantageously in plastics films, for example polyethylene films, of the kind used in agriculture especially as a covering for hothouses.
  • a particular advantage of hothouse films or agrofilms stabilised according to the invention is that it is possible to filter out the portion of UV radiation that directly damages the crops and/or that favours the spread of a number of pathogenic microorganisms, such as fungi and viruses, and pathogenic insects, such as e.g. whitefly, aphids, thrips etc. Those pests can be significantly reduced if the admission of UV radiation to the plants is prevented or reduced. [R. Reuveni et al., Plasticulture No. 102, p. 7 (1994); Y.
  • the hydroxyphenyl UV absorbers of the present invention exhibit good compatibility and persistence in the polyolefin.
  • the present invention accordingly also contributes to the improvement of agrofilms and describes a method for suppressing microbial infestation of cultivated plants, such as, for example, tomatoes, cucumbers, gourds, melons, citrus fruit, roses, strawberries, grapes, paprika etc.
  • the coating composition preferably contains 0.01-10 parts by weight, especially 0.05-10 parts by weight, more especially 0.1-5 parts by weight, of the stabiliser according to the invention (component B) per 100 parts by weight of solid binder (component A).
  • Multilayer systems are possible here as well, it being possible for the concentration of the stabilisers in the top layer to be higher, for example from 1 to 15 parts by weight, especially from 3 to 10 parts by weight, based on 100 parts by weight of solid binder.
  • the use of the compounds as stabiliser in coatings is accompanied by the additional advantage that delamination, i.e. flaking-off of the coating from the substrate, is prevented.
  • Substrates may in this case be, for example, wood, ceramic materials, metals, plastics materials, surface-coated articles and articles primer-coated with organic materials.
  • the binders may in principle be any binders that are customary in the art, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A18, pp. 368-426, VCH, Weinheim 1991.
  • the binder will generally be a film-forming binder, based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.
  • Suitable catalysts which accelerate full curing of the binder, are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim 1991.
  • component A is a binder consisting of a functional acrylate resin and a crosslinking agent.
  • coating compositions with specific binders are:
  • They may also be coating systems based on siloxanes. Such coating systems are described, for example, in WO 98/56852, WO 98/56853, DE-A-2 914 427 and DE-A-4 338 361.
  • the coating composition preferably comprises as further component (C) a light stabiliser of the sterically hindered amine type, the 2-(2-hydroxyphenyl)-1,3,5-triazine type and/or of the 2-hydroxyphenyl-2H-benzotriazole type, for example those mentioned in the above list in Sections 2.1, 2.6 and 2.8.
  • a light stabiliser of the sterically hindered amine type the 2-(2-hydroxyphenyl)-1,3,5-triazine type and/or of the 2-hydroxyphenyl-2H-benzotriazole type, for example those mentioned in the above list in Sections 2.1, 2.6 and 2.8.
  • Further examples of light stabilisers of the 2-(2-hydroxyphenyl)-1,3,5-triazine type which can be used advantageously are listed inter alia in the publications U.S. Pat. No. 4,619,956, EP-A-434 608, U.S. Pat. Nos.
  • the invention therefore relates also to a coating composition that comprises, in addition to the binder A and the stabiliser B, as further component C a light stabiliser of the sterically hindered amine type.
  • the latter is preferably a 2,2,6,6-tetraalkylpiperidine derivative or a derivative of 3,3,5,5-tetraalkyl-morpholin-2-one that contains at least one group of the formula wherein R is hydrogen or methyl, especially hydrogen.
  • Component C is preferably used in an amount of 0.05-5 parts by weight per 100 parts by weight of the solid binder.
  • tetraalkylpiperidine derivatives that can be used as component C are to be found in EP-A-356 677, pp. 3-17, sections a) to f).
  • the said sections of that EP-A are regarded as forming part of the present description. It is especially advantageous to use the following tetraalkylpiperidine derivatives:
  • the coating composition may comprise further components, e.g. solvents, pigments, dyes, plasticisers, stabilisers, rheology additives, such as, for example, thixotropic agents, drying catalysts or/and flow improvers.
  • solvents e.g. solvents, pigments, dyes, plasticisers, stabilisers, rheology additives, such as, for example, thixotropic agents, drying catalysts or/and flow improvers.
  • Possible components are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A18, pp. 429-471, VCH, Weinheim 1991.
  • Possible drying catalysts and curing catalysts are, for example, free (organic) acids or bases or also (organic) blocked acids or bases that can be activated by thermal energy or light energy, organic metal compounds, amines, amino-group-containing resins or/and phosphines.
  • Organic metal compounds are e.g. metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metals Al, Ti, Zr or Hf, or organometal compounds, such as e.g. organotin compounds.
  • metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.
  • metal chelates are the aluminium, titanium, zirconium or hafnium chelates of acetyl acetone, ethylacetyl acetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl-trifluoroacetyl acetate and the alkoxides of those metals.
  • organotin compounds are dibutyltin oxide, dibutyltin dilaurate and dibutyltin dioctoacte.
  • quaternary ammonium salts such as e.g. trimethylbenzylammonium chloride.
  • Amino-group-containing resins are simultaneously binders and curing catalysts. Examples thereof are amino-group-containing acrylate copolymers.
  • phosphines such as e.g. triphenylphosphine
  • the coating compositions may also be radiation-curable coating compositions.
  • the binder consists substantially of monomeric or oligomeric compounds having ethylenically unsaturated bonds (prepolymers) which after application are cured by actinic radiation, i.e. converted into a crosslinked, high-molecular-weight form.
  • a system is UV-curing, it generally comprises a photoinitiator in addition.
  • the stabilisers can be employed also without the addition of sterically hindered amines.
  • the coating compositions can be applied to any desired substrates, for example to metal, wood, plastics material or ceramic materials. They are preferably used as topcoat in the finishing of automobiles. If the topcoat consists of two layers of which the bottom layer is pigmented and the top layer is not pigmented, the coating composition can be used for the top layer or the bottom layer or for both layers, but preferably for the top layer.
  • the coating compositions can be applied to the substrates by the usual methods, for example by coating, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A18, pp. 491-500.
  • curing of the coatings can be carried out at room temperature or by heating.
  • the coatings are preferably cured at 50-150° C., and in the case of powder coating compositions or coil-coating compositions also at higher temperatures.
  • the resulting coatings exhibit excellent resistance to the damaging effects of light, oxygen and heat; special mention is to be made of the good light stability and weathering resistance of the resulting coatings, for example surface-coatings.
  • the coating compositions may comprise an organic solvent or solvent mixture in which the binder is soluble.
  • the coating composition may also, however, be an aqueous solution or dispersion. It may also be a mixture of an organic solvent and water.
  • the coating composition may also be a high solids surface coating or may be solvent-free (e.g. a powder coating composition). Powder coating compositions are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., A18, pages 438-444.
  • the powder coating composition may also be in the form of a powder slurry, i.e. a dispersion of the powder preferably in water.
  • the pigments may be inorganic, organic or metallic pigments.
  • the coating compositions contain no pigments and are used as clear surface-coatings.
  • topcoat for applications in the automobile industry, especially as the pigmented or unpigmented top layer of the finish. Its use for underlying layers is, however, also possible.
  • the compounds of formula I can also be applied to a substrate by plasma-enhanced deposition. Numerous possible methods of obtaining plasmas under vacuum conditions are described in the literature.
  • the electrical energy can be coupled in inductively or capacitatively. Direct current or alternating current may be used, it being possible for the frequency of the alternating current to vary from a few kHz to the megahertz range. Feeding-in in the microwave range (gigahertz) is also possible.
  • Preferred substrates are metals, semi-conductors, glass, quartz or thermoplastic, crosslinked or structurally crosslinked plastics materials.
  • silicon especially is to be mentioned, which may, for example, be in the form of wafers.
  • metals especially aluminium, chromium, steel and vanadium are to be mentioned, which are used for the manufacture of high-quality mirrors, such as, for example, telescope mirrors or automobile headlamp mirrors. Aluminium is especially preferred.
  • stabilisers As primary plasma gases it is possible to use, for example, He, argon, xenon, N 2 , O 2 or air, non-reactive gases such as He, argon and xenon being preferred.
  • non-reactive gases such as He, argon and xenon being preferred.
  • the deposition process with the stabilisers is not per se sensitive to the gas supplied and the coupling-in of the electrical energy.
  • the crucial factor is that it is carried out at a relatively low pressure.
  • the pressure is preferably from 10 ⁇ 6 mbar to 10 ⁇ 2 mbar, especially from 10 ⁇ 3 to 10 ⁇ 4 mbar.
  • the material may, for example, be applied to a plasma electrode and vaporised directly from there.
  • the material to be vaporised will be on a separately heatable plate or in a crucible located outside the plasma discharge.
  • the crucible or the plate may be at a positive or negative electrical potential with respect to the plasma.
  • the temperature at which the stabilisers are vaporised is preferably from 20° C. to 350° C., especially from 100° C. to 250° C.
  • the process is especially suitable for depositing thin layers.
  • the deposited layer preferably has a thickness of from 10 nm to 1000 nm, especially from 50 nm to 500 nm and more especially from 100 nm to 300 nm.
  • recording materials are to be understood as being, for example, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reproduction techniques.
  • Recording materials such as e.g. photographic material and components present therein, are described, for example, in U.S. Pat. No. 6,184,375 from column 34, line 9, to column 63, line 52, or in GB-A-2 343 007 from page 22, last paragraph, to page 106, line 35.
  • the compounds according to the invention of formula I can be used therein analogously to the UV absorbers described in GB-A-2 343 007 from page 97, 3rd paragraph, to page 110, in place of those UV absorbers or in combination therewith, or analogously to the compounds of formula I described in U.S. Pat. No. 6,184,375.
  • the compounds according to the invention can also be used advantageously as UV absorbers in protective coatings, films and foils in liquid crystal displays for protection against UV radiation and to protect polymer material and other components in the liquid crystal displays against damage by UV light. Examples of such fields of application and materials are to be found inter alia in:
  • the compounds according to the invention can also be used advantageously in optical recording layers and recording media in which laser radiation, e.g. by short-wave irradiation by means of blue laser diodes (wavelength for example 405 nm), causes a change in the optical characteristics, by means of which digital information can be stored and subsequently retrieved from the storage layer or the storage medium.
  • laser radiation e.g. by short-wave irradiation by means of blue laser diodes (wavelength for example 405 nm)
  • causes a change in the optical characteristics by means of which digital information can be stored and subsequently retrieved from the storage layer or the storage medium.
  • Examples of such fields of application and materials are to be found interalia in JP-A-2001-277720; JP-A-2002-160452.
  • reaction mixture After 2 h, the reaction mixture, which is then solid, is comminuted and the solid is filtered off. Dilute hydrochloric acid is added to the solid and the mixture is heated to boiling. The solid is filtered off.
  • the product (or the hydrochloric acid addition product thereof) can be purified by treatment with ethyl methyl ketone.
  • Example 20 is obtained analogously to Example 20 described in WO 00/29392.
  • the product is prepared analogously to Example 20 described in Patent WO 00/29392 and is used for the subsequent reactions without further purification.
  • reaction mixture is stirred for 1 h, the temperature being increased from 65° C. to 90° C.
  • the solid reaction mixture is then hydrolysed with ice-water.
  • the crude product is filtered off, dried at 110° C. in vac. and used for the further reaction without further purification.
  • the product is prepared analogously to Example 18 described in patent WO 00/29392 and is used for the subsequent reactions without further purification.
  • a solution of 228 g of 1-bromonapthalene in 250 ml of THF is added dropwise to a suspension of 28.0 g of magnesium in 100 ml of anhydrous THF in such a manner that the reaction temperature remains at from 50 to 65° C.
  • a small quantity of iodine is added and heating is carried out until the reaction commences.
  • the reaction mixture is heated to boiling for 15 min. It is then cooled to 25° C.
  • a solution of 299 g of 1-bromo-4-methoxy-naphthalene in 190 ml of tetrahydrofuran (THF) is added dropwise to a suspension of 33.7 g of magnesium in 126 ml of anhydrous THF in such a manner that the reaction temperature remains at from 60 to 65° C.
  • THF tetrahydrofuran
  • a small quantity of iodine is added and heating is carried out until the reaction commences.
  • the reaction mixture is heated to boiling for a further 1 h. It is then cooled to 25° C.
  • the resulting solution is added dropwise at 25° C.
  • reaction temperature is maintained at from 20 to 25° C.
  • reaction mixture is stirred at 25° C. for a further 18 h.
  • the reaction mixture is then poured into ice-water and acidified with hydrochloric acid.
  • the product is filtered off, washed with water and recrystallised from toluene; melting point: 142-145° C.
  • UVAs according to the invention of formula I are used:
  • compositions according to the invention may comprise, in addition, one or more known UVAs.
  • UVAs the following compounds inter alia are used:
  • a gelatin layer of the following composition (per m 2 ) is applied in the usual manner to a polyester support: component: amount: gelatin 1200 mg tricresyl phosphate 150 mg curing agent 40 mg wetting agent 100 mg compound of formula I 300 mg
  • the potassium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine is used as curing agent, and sodium 4,8-diisobutyl-naphthalene-2-sulfonate is used as wetting agent.
  • gelatin layers are dried at 20° C. for 7 days.
  • compounds 1 to 3 according to the invention are used, clear transparent layers are obtained which are suitable for a photographic recording material, for example as a UV filter layer.
  • UVA The long-wave absorption maximum ( ⁇ max ) and the optical density at ⁇ max (OD max ), of the UV filter layers so produced are measured with a Lambda 15 spectrophotometer produced by Perkin-Elmer. The results are given in the following Table. UVA according to the invention from sample Example: ⁇ max OD max 1-1 A2 347.0 1.48 1-2 A3 346.6 1.39 1-3 A5 357.0 1.23
  • Clear transparent layers are obtained which are suitable for a photographic recording material, for example as a UV filter layer.
  • UV filter layers are produced as described in Examples B1 and B2.
  • the corresponding samples are exposed with 60 kJ/cm 2 in an Atlas exposure apparatus and the decrease in density at the long-wave absorption maximum ( ⁇ max ) is determined.
  • ⁇ max long-wave absorption maximum
  • UVA of decrease in sample formula I other UVA mass ratio ⁇ max density 3-1 A2 — — 347.0 5% 3-2 A3 — — 346.6 7% 3-3 A2 HBT-1 70/30 348.2 4% 3-4 A2 HBT-2 50/50 347.1 8% 3-5 A2 HPT-1 70/30 350.0 4% 3-6 A2 HPT-2 50/50 345.0 3% 3-7 A3 HBT-1 70/30 348.3 6% 3-8 A3 HBT-2 50/50 347.4 8% 3-9 A3 HPT-1 70/30 349.3 7% 3-10 A3 HPT-2 50/50 346.0 6%
  • UV filter layers are produced as described in Examples B1 and B2.
  • the corresponding samples are stored in a climatic test cabinet at 80° C. and 70% humidity for 14 days and the decrease in density at the long-wave absorption maximum ( ⁇ max ) is determined.
  • ⁇ max long-wave absorption maximum
  • UVA according decrease sample to the invention other UVA mass ratio ⁇ max in density 4-1 — HBT-2 — 347.6 30% 4-2 A2 — — 347.0 ⁇ 1% 4-3 A3 — — 346.6 ⁇ 1% 4-4 A5 — — 358.8 4% 4-5 A2 HBT-1 70/30 348.2 1% 4-7 A2 HPT-1 70/30 350.0 1% 4-8 A2 HPT-2 50/50 345.0 2% 4-9 A3 HBT-1 70/30 348.3 2% 4-11 A3 HPT-1 70/30 349.3 ⁇ 1% 4-12 A3 HPT-2 50/50 346.0 1% 4-13 A5 HBT-1 70/30 355.2 2% 4-14 A5 HBT-2 50/50 352.1 8% 4-15 A5 HPT-1 70/30 356.6 ⁇ 1% 4-16 A5 HPT-2 50/50 348.6 1%
  • Example B1 The procedure is the same as that described in Example B1 but with the compounds according to the invention being employed in such a manner that a filter of optical density 2.0 (measured at the long-wave absorption maximum ⁇ max ) is obtained. Clear, transparent layers are obtained which are suitable for a photographic recording material.
  • the required total amount of UVA is listed in the following Table. sample UVA total amount 5-1 A2 400 mg/m 2 5-2 A3 420 mg/m 2
  • the potassium salt of 2,4-dichloro-6-hydroxytriazine is used as curing agent, and the sodium salt of diisobutylnaphthalenesulfonic acid is used as wetting agent.
  • the layers are dried at 20° C. for 7 days.
  • a step wedge having a density difference of 0.3 log E per step is exposed onto each of the layers so obtained and is then processed in the Agfa P-94 processing process for negative colour papers according to the manufacturer's instructions.
  • the samples so produced are exposed behind UV filters produced in accordance with Example B3 and B5, in an Atlas exposure apparatus. Before and after exposure, the reflection density is measured (in the green region for magenta layers and in the blue region for yellow layers). The results for an initial density of 1.0 are entered in the following Table. Samples having filter layers not containing any UVA ( ⁇ ) and samples having filter layers containing only the conventional HBT-2 compounds (*) are used as comparisons.
  • a photographic material having the following layer structure is produced: top layer red-sensitive layer second gelatin intermediate layer green-sensitive layer first gelatin intermediate layer blue-sensitive layer polyethylene support
  • gelatin layers consist of the following components (per m 2 of support material):
  • the top layer is produced with and without UV absorber
  • 2,4-Dichloro-6-hydroxytriazine potassium salt solution is used as curing agent, and the sodium salt of diisobutylhaphthalenesulfonic acid is used as wetting agent.
  • the reflection densities are measured in red for the cyan step, in green for the magenta step and in blue for the yellow step at a density of from 0.9 to 1.1 of the wedges.
  • the wedges are then exposed with a total of 15 kJ/cm 2 in an Atlas exposure apparatus and the reflection densities are re-measured.
  • the reflection density before and after exposure is also measured in blue for yellowing.
  • the presence of the compound according to the invention reduces the density loss of the cyan, magenta and yellow image-producing colours and also the yellowing of the magenta layer.
  • the UV absorbers according to the invention are tested in an application concentration of 1.5% (based on binder solids) in a 2-component polyurethane clear surface-coating. Testing is carried out with and without the addition of the sterically hindered amine Tinuvin® 292 (HALS; Ciba Specialty Chemicals; main component bis(1,2,2,6,6-pentamethylpiperidyl)sebacate), application concentration 1% based on binder solids.
  • HALS sterically hindered amine Tinuvin® 292
  • HALS sterically hindered amine Tinuvin® 292
  • main component bis(1,2,2,6,6-pentamethylpiperidyl)sebacate main component bis(1,2,2,6,6-pentamethylpiperidyl)sebacate
  • the UV absorbers according to the invention are stirred into the polyol component.
  • a clear surface-coating formulation not containing any light stabiliser is used as a reference.
  • the isocyanate component is added.
  • the finished clear surface-coaung is applied, after dilution to spraying viscosity, to prefabricated aluminium sheets (Uniprime Epoxy, silver-metallic base coating) and then dried at 80° C. /45 min. A dry layer thickness of 40 ⁇ m is obtained.
  • the samples are then subjected to accelerated weathering (UVCON® weathering apparatus of Atlas Corporation, UVB—313—lamps, cycle 8 hours' exposure at 70° C. and 4 hours' condensation at 50° C.).
  • UVCON® weathering apparatus of Atlas Corporation UVB—313—lamps, cycle 8 hours' exposure at 70° C. and 4 hours' condensation at 50° C.
  • the gloss (20° gloss, DIN 67 530) is measured.
  • Table 8a results obtained with UVA according to the invention alone are reproduced in Table 8a and those obtained in combination with HALS are reproduced in Table 8b.
  • the numbers of the compounds according to the invention refer to the Preparation Examples A. TABLE 8a 20° gloss after 0 h, 1200 h and 2000 h weathering (UVCON ®, UVB-313) 0 h 1200 h 2000 h unstabilised 91 16 1.5% comp. A2 92 91 83 1.5% comp. A5 92 92 79 1.5% comp. A3 91 86 72

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  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Plural Heterocyclic Compounds (AREA)
US10/492,721 2001-10-18 2002-10-10 Naphthyltriazines as stabilizers for organic material Abandoned US20050038245A1 (en)

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US20060052491A1 (en) * 2002-10-02 2006-03-09 Adalbert Braig Synergistic uv absorber combination

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US7122299B2 (en) * 2002-11-06 2006-10-17 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
JP2007507567A (ja) * 2003-05-26 2007-03-29 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 高適合性及び非移行性ポリマー状ｕｖ−吸収剤
US20060252857A1 (en) * 2003-05-27 2006-11-09 Schaefer Thomas Aminoaryl-1-3-5-triazines and their use as uv absorbers
CN102292397B (zh) 2009-01-19 2014-12-10 巴斯夫欧洲公司 有机黑色颜料及其制备
JP5756877B2 (ja) * 2014-06-27 2015-07-29 三菱樹脂アグリドリーム株式会社 農業用フィルム
US10479882B2 (en) 2017-09-14 2019-11-19 Teknor Apex Company Rotational moldable composition comprising polyethylene, and a blend of a pigment and a polyethylene copolymer
US12289992B2 (en) 2018-10-05 2025-04-29 Samsung Display Co., Ltd. Display apparatus and light absorber included in display apparatus
CN112805844B (zh) * 2018-10-05 2025-06-10 三星显示有限公司 显示设备和包括在该显示设备中的光吸收剂
KR20220121794A (ko) * 2019-12-24 2022-09-01 토요잉크Sc홀딩스주식회사 수지 조성물, 및 성형체
JP7147827B2 (ja) * 2019-12-24 2022-10-05 東洋インキＳｃホールディングス株式会社 紫外線吸収剤、組成物、成形体および積層体
JP7673384B2 (ja) * 2020-11-13 2025-05-09 ａｒｔｉｅｎｃｅ株式会社 樹脂組成物、および成形体
CN113299178B (zh) * 2021-04-26 2022-08-26 允昌特种印刷(深圳)有限公司 点光源识读激光加密纸质防伪标识及其制备方法

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US20060052491A1 (en) * 2002-10-02 2006-03-09 Adalbert Braig Synergistic uv absorber combination
US7332105B2 (en) 2002-10-02 2008-02-19 Ciba Specialty Chemicals Corporation Synergistic UV absorber combination

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