DE10311063A1 - UV stabilizer composition for transparent plastic packaging, e.g. for cosmetics or food, contains pentaerythritol tetrakis-2-cyano-3,3-diphenylacrylate and a hydroxybenzophenone derivative - Google Patents

Abstract

Compositions containing 1,3-bis-[2-cyano-3,3-diphenyl-acryloyl)oxy]-2,2-bis-{[ (2-cyano-3,3-diphenylacryloyl)oxy]methyl}-propane and benzophenone derivative(s) with hydroxy and/or organyloxy group(s) are used as UV stabilizers which are effective at up to 400 nm in visibly transparent thermoplastic molding materials for UV-protective packaging. The use of stabilizer compositions (SC) containing 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis-{[2-cyano-3,3-diphenylacryloyl)oxy]methyl}-propane (II) and benzophenone-type UV stabilizer(s) of formula (I) which are effective at up to 400 nm, in thermoplastic molding materials with a glass transition point (Tg) above 20[deg]C and light transmission values of not more than 20% at 300-370 nm and not less than 80% at 410-800 nm (in the stabilized material), for packaging to protect products against the action of light. [Image] one of the groups R1>-R5> and R1>->R5>OR6> and the others = R6>, OR6>, COOR6>, COO-> M+>, CONR6>R7>, SO3R6>, SO3-> M+> or NR6>R7>; R6>, R7>H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl; M : a cation equiv. Independent claims are also included for (1) a method for protecting packaged products from the effects of UV light by using thermoplastic molding materials containing (SC) in the production of the packaging (2) thermoplastic molding materials containing (SC) (3) packaging containing such thermoplastic molding material.

Description

The present invention relates to the use of a stabilizer mixture in thermoplastic molding compositions to protect the packaged products against the effects of ultraviolet Radiation and a method for protecting packaged products ultraviolet radiation.

Find plastic containers and plastic films in large Scope of use as packaging material. Win for aesthetic reasons increasingly transparent packaging materials made of plastics high light transmission in the visible wavelength range from 400 to 750 nm in importance. However, they are transparent, too possibly slightly colored Plastics in general for the amount of ultraviolet (UV) radiation contained in daylight permeable, so that the mechanical, chemical, olfactory, gustatory and / or aesthetic Properties of the packaged products due to the action of UV light deteriorate. The negative change appears in different ways depending on the packaged content, for example in a change of appearance like yellowing and discoloration, in one change of taste and / or smell and / or in the breakdown of ingredients. When it comes to food, perfumes and cosmetics, the shelf life can be strong be reduced. For economic and aesthetic reasons also the packaging material if possible thin-walled his. In addition, for aesthetic reasons Packaging material in the visible area none or one if possible have low self-absorption. Show thin-walled, transparent plastic containers but the disadvantage that due to the small wall thickness of the container the path length for UV radiation is relatively short. Therefore, damaging UV radiation reaches the packaged product. To avoid damage to the packaged product by the action of UV light can the product packed in a transparent plastic packaging Contain sunscreen. Because of the required in many cases official Approval of such ingredients, for example in food, Pharmaceutical and cosmetic sector, as well as due to the skepticism that many consumers bring such additives however, in many cases not possible, the packaged product directly by using a UV absorber to protect.

WO 01/92395 describes compositions which is a transparent thermoplastic polymer and at least one 2-cyanoacrylates included, as well as the use of the compositions for the preparation of shaped objects. As a suitable 2-cyanoacrylic acid ester becomes 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane called. Possibly contains the thermoplastic molding compound also other UV absorbers such as benzotriazoles and substituted triazines.

The US 6,297,300 describes carbonate polymers which, as UV absorbers, contain cyanoacrylic esters such as 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3' , 3'-diphenylacryloyl) oxy] methyl} propane, together with a benzotriazole derivative and / or a hydroxyphenyltriazine derivative, and the use thereof for the production of shaped articles.

WO 01/57124 describes the use of light stabilizers in clear or slightly colored plastic packaging to protect the packaged products against the effects of light. The sunscreen is among hydroxyphenylbenzotriazoles and tris-aryl-s-triazines selected. In addition to a variety of combinations with the described UV absorbers suitable components are also very general Hydroxybenzophenones and α-cyanoacrylates called. An embodiment with this combination is not in the registration.

WO 96/15102 describes 2-cyanoacrylic acid esters as a light stabilizer for organic materials such as cosmetic or dermatological preparations, Plastics or paints. In general, without evidence from an embodiment, will also be a possible one Combination of the 2-cyanoacrylic acid esters with other costabilizers mentioned, in addition to a variety others are also called 2-hydroxybenzophenones.

worin Y für H, OH oder COOR' steht, Z für OR' oder NR'R'' steht (worin R' und R'' für H, C₁-C₂₀-Alkyl, C₂-C₁₀-Alkenyl, C₃-C₁₀-Cycloalkenyl etc. stehen) und A für Wasserstoff oder SO₃H steht, und d) Zimtsäureestern sowie Gemischen davon. Als geeigneter Cyanacrylsäureester wird 1,3-Bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis{[2'-cyano-3',3'-diphenylacryloyl)oxy]methyl}propan genannt. Aus den Formmassen lassen sich beispielsweise Verpackungen und Folien für Kosmetika und Lebensmittel herstellen.The DE-A 100 58 290 describes a process for the preparation of polyolefins which are exposed to water and which are stabilized against visible and ultraviolet light. Light stabilizers which are selected from a) cyanoacrylic acid esters, b) 4,4-diarylbutadienes, c) benzophenones of the formula 1 are added to the polyolefin,

where Y is H, OH or COOR ', Z is OR' or NR'R '' (where R 'and R''are H, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkenyl etc.) and A represents hydrogen or SO ₃ H, and d) cinnamic acid esters and mixtures thereof. A suitable cyanoacrylic acid ester is 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] called methyl propane. The molding compounds can be used, for example, to produce packaging and films for cosmetics and food.

Unsatisfactory in the state of the art Technology disclosed stabilizers or stabilizer compositions is common short duration of the protective effect. There is therefore still a Need for stabilizer compositions that act as UV filter substances for packaging made of plastic. The stabilizer composition should preferably absorb with high extinction, be photostable and thermostable and no or only a little intrinsic color in the visible area exhibit.

Surprisingly it has now been found that when using a stabilizer composition, containing 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane and at least one benzophenone better pre-packaged product Protected against UV radiation is as with conventional UV absorbers or UV absorber mixtures.

worin
wenigstens einer der Reste R¹, R², R³, R⁴, R⁵, R¹', R²', R³', R⁴' und R⁵' für einen Rest OR⁶ steht und
die übrigen unabhängig voneinander ausgewählt sind unter R⁶, OR⁶, COOR⁶, COO^-M⁺, CONR⁶R⁷, SO₃R⁶, SO₃ ^-M⁺ und NR⁶R⁷,
worin
R⁶ und R⁷ unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Heterocycloalkyl, Aryl oder Hetaryl stehen und
M⁺ für ein Kationäquivalent steht,
in thermoplastischen Formmassen, wobei die Glasübergangstemperatur T_G der thermoplastischen Formmasse oberhalb 20 °C liegt und die Transmission der stabilisierten thermoplastischen Formmasse für elektromagnetische Strahlung der Wellenlängen zwischen 300 und 370 nm nicht größer als 20 % und für elektromagnetische Strahlung der Wellenlängen zwischen 410 und 800 nm nicht kleiner als 80 % ist, für Verpackungen zum Schutz der verpackten Produkten gegen die Einwirkung von Licht.An object of the present application is therefore the use of a stabilizer composition containing 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3 ', 3'-diphenylacryloyl) oxy] methyl} propane and at least one further compound protecting against radiation in the ultraviolet radiation range up to 400 nm, selected from benzophenones of the formula I.

wherein
at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ', R ² ', R ³ ', R ⁴ ' and R ⁵ 'represents a radical OR ⁶ and
the rest are independently selected from R ⁶ , OR ⁶ , COOR ⁶ , COO ^- M ⁺ , CONR ⁶ R ⁷ , SO ₃ R ⁶ , SO ₃ ^- M ⁺ and NR ⁶ R ⁷ ,
wherein
R ⁶ and R ⁷ independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl and
M ^{+ stands} for a cation equivalent,
in thermoplastic molding compositions, the glass transition temperature T _{G of} the thermoplastic molding composition being above 20 ° C. and the transmission of the stabilized thermoplastic molding composition for electromagnetic radiation of the wavelengths between 300 and 370 nm not greater than 20% and for electromagnetic radiation of the wavelengths between 410 and 800 nm is not less than 80%, for packaging to protect packaged products against the effects of light.

For the purpose of explaining the present invention, the term "alkyl" includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₁₂ alkyl, particularly preferably C ₁ -C ₈ alkyl groups Examples of alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl , 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1 , 3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpro pyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, Nonyl, decyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

The term "alkyl" also includes substituted alkyl groups which can carry, for example, 1, 2, 3, 4 or 5 substituents. Suitable substituents are, for example, cycloalkyl, aryl, hetaryl, nitro, cyano, halogen, NE ¹ E ² , NE ¹ E ² E ³⁺ (wherein E ¹ , E ² , E ^{3 represent} hydrogen, alkyl, cycloalkyl, aryl), carboxyl, carboxylate, -SO ₃ H and sulfonate. The term "alkyl" also includes those The aforementioned groups are different alkyl groups which are interrupted by at least one heteroatom or a heteroatom-containing group. These include, for example, polyalkylene oxides and polyalkyleneimines of the formulas (CHR ^b CH ₂ O) _y R ^c , (CH ₂ N (E ¹ )) _y R ^c , (CH ₂ CH ₂ N (E ¹ )) _y R ^c , in which R ^b represents hydrogen, methyl or ethyl, R ^c and E ¹ each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl and y represents an integer from 1 to 250.

For the purposes of the present invention, the term “alkenyl” encompasses straight-chain and branched alkenyl groups which, depending on the chain length, can carry one or more double bonds. Preferred are C ₂ -C ₂₀ -, especially C ₂ -C ₁₀ -alkenyl groups, such as vinyl, Allyl or methallyl. The term "alkenyl" also includes substituted alkenyl groups which, for. B. can carry 1, 2, 3, 4 or 5 substituents. Suitable substituents are e.g. B. cycloalkyl, aryl, hetaryl, nitro, cyano, halogen, NE ¹ E ² , NE ¹ E ² E ³⁺ (wherein E ¹ , E ² , E ^{3 represent} hydrogen, alkyl, cycloalkyl, aryl), carboxyl, carboxylate , -SO ₃ H and sulfonate.

For the purposes of the present invention, the term “cycloalkyl” encompasses unsubstituted and substituted cycloalkyl groups, preferably C ₃ -C ₈ cycloalkyl groups, particularly preferably C ₅ -C ₇ cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl. The cycloalkyl groups can be substituted , generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituents which are preferably selected from those mentioned above for the alkyl groups.

For the purposes of the present invention, the term “cycloalkenyl” embraces non-aromatic, unsubstituted or substituted cyclic groups. They are preferably C ₃ -C ₈ -cycloalkenyl groups which, depending on the ring size, can carry one or more double bonds.

The term "heterocycloalkyl" in the sense of the present Invention includes saturated, cycloaliphatic groups with generally 4 to 8, preferably 5 or 6 ring atoms in which 1, 2 or 3 of the ring carbon atoms selected by heteroatoms from the elements oxygen, nitrogen and sulfur and which may optionally be substituted, wherein in the case of a Substitution, these heterocycloaliphatic groups 1, 2, 3 or 4 substituents, preferably selected from those mentioned for the alkyl groups, can wear. Exemplary for such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, Oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, Piperazinyl-, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, Called dioxanyl.

The term "aryl" includes mononuclear or polynuclear aromatic Hydrocarbon residues that are unsubstituted or substituted can. The term "aryl" is preferably used for phenyl, Tolyl, xylyl, mesityl, duryl, naphthyl, fluorenyl, anthracenyl, Phenanthrenyl or naphthacenyl, particularly preferred for phenyl or Naphthyl, these aryl groups in the case of a substitution in Generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 of the above for the Can carry substituents mentioned alkyl groups.

The term "hetaryl" in the sense of the present invention includes unsubstituted or substituted, heterocycloaromatic, mono- or polynuclear groups, preferably the groups pyridyl, quinolinyl, acridinyl, Pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, Indolyl, purinyl, indazolyl, benzotriazolyl, 1,2,3-triazolyl, 1,3,4-triazolyl and carbazolyl, these heterocycloaromatic groups in the case of a Substitution generally 1, 2 or 3 substituents, preferably selected from the previously for can carry the alkyl groups mentioned.

In the context of this invention, carboxylate and sulfonate preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function. These include e.g. B. the esters with C ₁ -C ₆ alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and n-hexanol.

M ⁺ stands for a cation equivalent, ie for a monovalent cation or the portion of a multivalent cation corresponding to a positive single charge. M ⁺ is preferably an alkali metal cation, such as. B. Li ⁺ , Na ⁺ or K ⁺ or for an alkaline earth metal cation, for NH ₄ ⁺ or a quaternary ammonium compound, as can be obtained by protonation or quaternization of amines. Alkali metal cations are preferred, in particular sodium or potassium ions.

Halogen stands for fluorine, chlorine, bromine or iodine.

The use of the stabilizer composition comprising 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxyj-2,2-bis {[2'-cyano-3', 3'- diphenylacryloyl) oxy] methyl} propane and at least one benzophenone of the formula I in thermoplastic molding compositions, the glass transition temperature T _G of thermoplastic molding compound is above 20 ° C, the product packed therein is effectively protected against the damaging influence of ultraviolet radiation. It is particularly advantageous that the use according to the invention in the thermoplastic molding composition generally means that additional W filter substances can not be used in the packaged product itself. This aspect plays an important role particularly in the case of food, cosmetics, perfumes and pharmaceuticals.

The stabilizer composition used according to the invention comprises the compound 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl ) oxy] methyl} propane, the production of which is described in WO 96/15102. The connection is ^® 3030 commercially available under the name Uvinul® by BASF AG.

In a first embodiment, the stabilizer composition used according to the invention contains at least one benzophenone of the formula I. If the compound of the formula I has several substituents R ⁶ , these can have the same or different meanings. Preferred benzophenones of the formula I are those in which at least one of the radicals R ¹ and R ¹ 'is OR ⁶ , in particular hydroxyl or O- (C ₁ -C ₁₀ alkyl). The radicals R ¹ and R ¹ 'are preferably both selected from hydroxy and O- (C ₁ -C ₁₀ alkyl). The radicals R ¹ and R ¹ 'are both particularly preferably hydroxyl.

worin
R⁸, R⁹, R⁸' und R⁹' unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Heterocycloalkyl, Aryl oder Hetaryl stehen.Also preferred are benzophenones of the general formula I in which two of the radicals R ¹ to R ⁵ and two of the radicals R ¹ 'to R ⁵ ' each represent OR ⁶ , the radicals R ⁶ independently of one another being hydrogen, alkyl, alkenyl , Cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl. The radicals R ¹ to R ⁵ and R ¹ 'to R ⁵ ', which are not OR ^6, are preferably hydrogen. The stabilizer composition used according to the invention then contains at least one benzophenone of the formula Ia

wherein
R ⁸ , R ⁹ , R ⁸ 'and R ⁹ ' independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl.

In the formula Ia, the radicals R ⁸ , R ⁸ ', R ⁹ and R ⁹ ', independently of one another, are preferably selected from hydrogen or C ₁ -C ₁₀ alkyl. One of the radicals R ⁸ or R ⁸ 'is particularly preferably hydrogen and the other radical is hydrogen or methyl. One of the radicals R ⁹ or R ⁹ 'is particularly preferably hydrogen and the other radical is hydrogen or methyl. In a very particularly preferred embodiment of the invention, R ⁸ , R ⁸ ', R ⁹ and R ⁹ ' each represent hydrogen.

Particularly preferred are those benzophenones of the general formula Ia in which the OR ⁸ and OR ⁸ 'radicals are each arranged ortho to the carbonyl group. Furthermore, the residues OR ⁹ and OR ⁹ 'are each arranged para to the carbonyl group. Particularly suitable benzophenones of the general formula I are 2,2 ', 4,4'-tetrahydroxybenzophenone, commercially available e.g. B. as Uvinul ^® 3050 from BASF AG, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, commercially z. B. available as Uvinul ^® 3049 from BASF AG.

The benzophenones of the formula I are preferably capable in the wavelength range absorb below 400 nm. Benzophenones usually exhibit however, an inherent color in the visible wavelength range. This is for use in transparent plastic packaging disadvantageous because the plastic through the natural color of the benzophenone is colored. Surprisingly, that is Own color of those used according to the invention Stabilizer composition usually less than the own color of benzophenone. Moreover are characterized by good compatibility with 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy) -2,2-bis {[2'-cyano-3', 3'- diphenylacryloyl) oxy] methyl} propane out.

Transmission is preferred the stabilized thermoplastic molding compound for electromagnetic radiation of the wavelengths between 300 nm and 370 nm not greater than 10%. Preferably is the transmission of the stabilized thermoplastic molding compound for electromagnetic Radiation of wavelengths between 420 nm and 800 nm larger than 90%.

In principle, all thermoplastics with a glass transition temperature T _G of above 20 ° C., which are usually transparent in the visible wavelength range, are suitable as thermoplastic molding compositions. These include both homo- and copolymers as well as polymer blends.

A suitable method for estimating the glass transition temperature T _G of polymer blends is e.g. B. from Fox (TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 [1956]). According to this, the glass transition temperature of copolymers with large molar masses is a good approximation 1 / T G = X 1 / T G 1 + X 2 / T G 2 + ..... X n / T G n where X ¹ , X ² , ..., X ^{n are} the mass fractions 1, 2, ..., n and T _g ¹ , T _g ² , ..., T _g ^{n are} the glass transition temperatures of only one of the monomers 1 , 2, ..., n mean polymers in degrees Kelvin. The latter are e.g. For example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A21 (1992) p 169 or from J. Brandrup, EH Immergut, Polymer Handbook 3 ^rd ed, J. Wiley, New York 1989 known.

Thermoplastic molding compositions with a glass transition temperature T _G above 20 ° C. are not to be understood in the context of this invention as homopolymers of a polyolefin or copolymers of a polyolefin as the main monomer with other monomers as comonomers.

In the first embodiment of the invention the thermoplastic molding composition preferably at least one polymer, that selected is among homopolymers and copolymers of polyesters such as polyalkylene terephthalate, Polycarbonates, poly (meth) acrylates, homo- and copolymers of polyvinyl aromatics, halogen-containing polymers, polymers that differ from unsaturated Alcohols and amines or their acrylic derivatives or acetals derive polysulfones, polyether sulfones and polyether ketones. Polymers and polymer mixtures (polymer blends) which are preferred can be processed into highly transparent, crystal-clear packaging.

In a preferred embodiment of the invention, the thermoplastic molding composition contains at least one polyester, preferably at least one linear polyester, as the polymer. Suitable polyesters and copolyesters are in the EP-A-0678376 . EP-A-0 595 413 and US 6,096,854 described, what is hereby incorporated by reference. As is known, polyesters are condensation products of one or more polyols and one or more polycarboxylic acids. In linear polyesters, the polyol is a diol and the polycarboxylic acid is a dicarboxylic acid. The diol component can be selected from ethylene glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1, 2-Cyclohexanediol, 1,4-Cyclohexanediol, 1,2-Cyclohexanedimethanol and 1,3-Cyclohexanedimethanol can be selected. Also suitable are diols whose alkylene chain is interrupted one or more times by non-adjacent oxygen atoms. These include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like. As a rule, the diol contains 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be used in the form of their cis or trans isomers or as a mixture of isomers. The acid component can be an aliphatic, alicyclic or aromatic dicarboxylic acid. The acid component of linear polyesters is generally selected from terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof. Of course, the functional derivatives of the acid component, such as anhydrides or halides, preferably chlorides, can also be used. Preferred polyesters are polyalkylene terephthalates and polyalkylene naphthalenes, which can be obtained by condensation of terephthalic acid or naphthalenedicarboxylic acid with an aliphatic diol.

Particularly preferred polyalkylene terephthalates are polyethylene terephthalates (PET), which are obtained by condensation of terephthalic acid with diethylene glycol. PET is also by transesterification of dimethyl terephthalate with ethylene glycol with elimination of methanol to give bis (2-hydroxyethyl) terephthalate and its polycondensation with the release of ethylene glycol available. Other preferred polyesters are polybutylene terephthalate (PBT), which can be obtained by condensation of terephthalic acid with 1,4-butanediol, Poly (ethylene-2,6-naphthalate) e (PEN), poly (1,4-cyclohexamdimethylene terephthalate (PCT), and copolyesters of polyethylene terephthalate with cyclohexanedimethanol (PDCT), copolyester of polybutylene terephthalate with cyclohexanedimethanol. Copolymers and transesterification products are also preferred and mixtures (blends) of the aforementioned polyalkylene terephthalates. Particularly suitable thermoplastic molding compositions are selected from Poly- or copolycondensates of terephthalic acid such as poly- or copoylethylene terephthalate (PET or Co-PET or PETG), poly (ethylene-2,6-naphthalate) s (PEN) or PEN / PET copolymers and PEN / PET blends. The copolymers and blends mentioned can be used in dependence parts of transesterification products from their manufacturing process contain.

In a further preferred embodiment of the invention, the thermoplastic molding composition contains polycarbonates as polymers. Polycarbonates arise e.g. B. by condensation of phosgene or carbonic acid esters such as diphenyl carbonate or dimethyl carbonate with dihydroxy compounds. Suitable dihydroxy compounds are aliphatic or aromatic dihydroxy compounds. Examples of aromatic dihydroxy compounds are bisphenols such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A), tetraalkylbisphenol-A, 4,4- (meta-phenylenediisopropyl) diphenol (bisphenol M), 4,4- ( para-phenylenediisopropyl) diphenol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC), 2,2-bis (4-hydroxyphenyl) -2-phenylethane, 1,1 -Bis (4-hydroxyphenyl) cyclohexane (bisphenol-Z) and, if appropriate, mixtures thereof. The polycarbonates can be branched by using small amounts of branching agents. Suitable branching agents include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) - heptane; 1,3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri (4-hydroxyphenyl) Hep tan; 1,3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) ethane; Tri- (4-hydroxyphenyl) phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl] propane; 2,4-bis (4-hydroxyphenylisopropyl) phenol; 2,6-bis (2-hydroxy-5'-methyl-benzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane; hexa- (4- (4- hydroxyphenyl-isopropyl) phenyl) orthoterephthalic acid ester; tetra- (4-hydroxyphenyl) methane; tetra- (4- (4-hydroxyphenyl-isopropyl) phenoxy) methane; α, α ', α''- tris- ( 4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 1 , 4-bis (4 ', 4''- dihydroxytriphenyl) methyl) benzene and in particular 1,1,1-tri (4-hydroxyphenyl) ethane and bis (3-methyl-4-hydroxyphenyl) - 2-oxo-2,3-dihydroindole.

For example, are suitable for chain termination Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, Chlorophenol, bromophenol, cumylphenol or mixtures thereof. The Proportion of chain breakers usually 1 to 20 mole%, per mole of dihydroxy compound.

In another suitable embodiment of the invention the thermoplastic molding compound polymers, which differ from α, β - unsaturated acids and derive their derivatives, e.g. B. poly (meth) acrylates such as polymethyl methacrylate (PMMA) and polyethyl methacrylate.

In another suitable embodiment of the invention the thermoplastic molding compound as a polymer is a vinyl aromatic homo- or copolymers such as polystyrene (PS) or copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as. B. styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile methacrylate, Acrylonitrile butadiene styrene (ABS) or methymethacrylate butadiene styrene (MBS).

In a further suitable embodiment of the invention the thermoplastic molding compound halogen-containing polymers such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl fluoride, polyvinylidene fluoride and their copolymers with, for example, (meth) acrylate (s), acrylonitrile Etc.

In a further suitable embodiment of the invention the thermoplastic molding compound polymers that differ from unsaturated Alcohols and amines or their acrylic derivatives or acetals derived like polyvinyl acetate (PVAC) and polyvinyl alcohol (PVAL).

In a further suitable embodiment of the invention the thermoplastic molding compound as a polymer polysulfone, polyether sulfone or polyether ketones.

• a') 4,4-Diarylbutadiene,
• b') Zimtsäureester,
• c') Triazinverbindungen,
• d') 2-(2'-Hydroxyphenyl)-benzotriazole,
• e') 2-Hydroxybenzophenone,
• f') Diphenylcyanacrylate,
• g') Oxamide,
• h') 2-(2-Hydroxyphenyl)-1,3,5-triazine und
• i') sterisch gehinderte Amine.

Optionally, the stabilizer composition used according to the invention additionally contains at least one further light stabilizer which absorbs light radiation in the UV-A (320 to 400 nm) and / or UV-B range (280 to 320 nm) and / or further stabilizers, the use of Stabilizers then serve to protect the thermoplastic molding composition. The further light stabilizer preferably absorbs UV-A radiation, in particular in the wavelength range from 370 to 400 nm. Of course, the additionally used light stabilizer must be compatible with the stabilizer composition. It is preferably colorless in the visible range or has only a slight intrinsic color. The light stabilizers or stabilizers that are optionally used preferably have high migration fastness and temperature resistance. Suitable light stabilizers and other stabilizers are selected, for example, from groups a ') to i'):

• a ') 4,4-diarylbutadienes,
• b ') cinnamic acid ester,
• c ') triazine compounds,
• d ') 2- (2'-hydroxyphenyl) benzotriazoles,
• e ') 2-hydroxybenzophenones,
• f ') diphenyl cyanoacrylates,
• g ') oxamides,
• h ') 2- (2-hydroxyphenyl) -1,3,5-triazines and
• i ') sterically hindered amines.

Group a ') of the 4,4-diarylbutadienes includes, for example, compounds of the formula II.

The connections are from the EP-A-916 335 known. The substituents R ¹⁰ and / or R ^{11 are} preferably C ₁ -C ₈ alkyl and C ₅ -C ₈ cycloalkyl.

Group b ') of the cinnamic acid esters include, for example, 2-isoamyl 4-methoxycinnamate, 4-Me 2-ethylhexyl thoxycinnamate, methyl-α-methoxycarbonylcinnamate, methyl-α-cyano-β-methylp-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate.

Group c ') of the triazine compounds include, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di -tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) - 1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4- hydroxybenzyl) isocyanurate and 1,3,5-tris (2-hydroxyethyl) isocyanurate.

Group d ') of the 2- (2'-hydroxyphenyl) benzotriazoles includes, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5' - (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2 - (3 ', 5'-Di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro -benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-Tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] - 2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2- isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the esterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) ₃ ] ₂ , with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl and mixtures thereof.

Group e ') of the 2-hydroxybenzophenones includes, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

The group f ') of the acrylates include, for example, ethyl-α-cyano-β, β-diphenyl acrylate and isooctyl-α-cyano-β, β-diphenyl acrylate, To group g ') the Count oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butoxanilide, 2,2'-dodecyloxy-5,5-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides.

To group h ') of 2- (2-hydroxyphenyl) -1,3,5-triazines counting for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2nd , 4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-Hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-butyloxy propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- ( dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5- triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

Group i ') of the sterically hindered amines includes, for example, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1 , 2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6 -pentamethylpiperidin-4-yl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product from 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butane tetracarboxylate, 1.1 ' - (1,2-ethylene) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, Bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl- 7,7,9,9-tet ramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) succinate, the condensation product of N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2,6-dichloro -1,3,5-triazine, the condensation product of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl) - 1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] - decane-2,4-dione, 3-dode cyl-1- (2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidin-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethylpiperidin-4-yl) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensation product of N, N'-bis (2,2,6,6-tetramethylpiperidine -4-yl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro- 1,3,5-triazine, 4-butylamino-2,2,6,6-tetramethylpiperidine, N- (2,2,6,6-tetramethylpiperidin-4-yl) -n-dodecylsuccinimide, N- (1,2 , 2,6,6-pentamethylpiperidin-4-yl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] -decane, the condensation product from 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4.5] decane and epichlorohydrin, the condensation products from 4-amino-2, 2,6,6-tetramethylpiperidine with tetramethylolacetylene diureas and poly (methoxypropyl-3-oxy) - [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane, copolymers from (partially) N-piperidin-4-yl substituted maleimide and a mixture of α-olefins such as. B. Uvinul 5050H (BASF AG). The sterically hindered amines added serve to protect the thermoplastic molding composition.

Usually one adds the thermoplastic molding compound 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl }propane in an amount of 0.01 to 5% by weight, preferably 0.01 to 2% by weight and particularly preferably 0.02 to 1.5% by weight, based on the Total weight of the thermoplastic molding compound. Under the total weight The thermoplastic molding compound is the weight of the the stabilizer composition offset thermoplastic molding composition (thermoplastic molding compound + sum of all stabilizers). Contains the stabilizer composition used according to the invention 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane; refer to at least one benzophenone and other stabilizers the quantities indicated on the sum of all stabilizers.

The weight ratio of 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl }propane to compound I is usually in the range from 30: 1 to 1:10, preferably 10: 1 to 1: 5 and in particular 8: 1 to 1: 1.

Will at least one more light stabilizer or stabilizer of groups a 'to i 'used, so it is usually in an amount of 0.1 to 50, preferably 1 to 20 wt .-%, based on the total weight of the stabilizer composition mitver uses. When using at least one sterically hindered Amine is the concentration of sterically hindered amine in the Rule between 0.01 to 5.0% by weight, preferably 0.05 to 3.00% by weight and especially 0.20-1.5 % By weight, based on the total weight of the thermoplastic molding composition.

Surprisingly it was found that the benzophenones of the general formula Ia also for use in stabilizer compositions suitable for use are determined in thermoplastic molding compositions whose glass transition temperature 20 ° C or is less.

worin
R⁸, R⁹, R⁸' und R⁹' unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
in thermoplastischen Formmassen, wobei die Transmission der stabilisierten Formmasse für elektromagnetische Strahlung der Wellenlängen zwischen 300 und 370 nm nicht größer als 20 % und für elektromagnetische Strahlung der Wellenlängen zwischen 410 und 800 nm nicht kleiner als 80 % ist, für Verpackungen zum Schutz der verpackten Produkte gegen die Einwirkung von Licht.Another object of the present invention is therefore the use of a stabilizer composition containing 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano- 3 ', 3'-diphenylacryloyl) oxy] methyl} propane and at least one further compound protecting against radiation in the ultraviolet radiation range up to 400 nm, selected from benzophenones of the formula Ia,

wherein
R ⁸ , R ⁹ , R ⁸ 'and R ⁹ ' independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl,
in thermoplastic molding compositions, the transmission of the stabilized molding composition for electromagnetic radiation of the wavelengths between 300 and 370 nm not greater than 20% and for electromagnetic radiation of the wavelengths between 410 and 800 nm not less than 80%, for packaging to protect the packaged products against the influence of light.

Regarding more suitable and preferred Compounds of formula Ia is based on the previous comments Referred.

When using a stabilizer composition containing 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane and at least one benzophenone of the formula Ia, the thermoplastic molding composition preferably contains at least one polymer which is selected from polyolefins, polyesters, polycarbonates, polyacrylates, polymethacrylates, polystyrene, copolymers of styrene or α-methylstyrene with dienes and / or Acrylic derivatives, halogen-containing polymers, polymers which are derived from unsaturated alcohols and amines or from their acrylic derivatives or acetals, poly sulfones, polyether sulfones, polyether ketones.

Regarding more suitable and preferred Polyester, polycarbonate, polyacrylate, polymethacrylate, polystyrene, Copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, halogen-containing polymers, polymers, which is different from unsaturated Alcohols and amines or their acrylic derivatives or acetals deduce polysulfones, polyether sulfones and polyether ketones expressly referred to what was said earlier.

Within the scope of the present invention the term "polyolefin" includes all polymers that are constructed from olefins without further functionality, such as polyethylene low or high density, polypropylene, linear polybutene-1 or polyisobutylene or polybutadiene and copolymers of mono- or diolefins. Preferred polyolefins are the homopolymers and Copolymers of ethylene, as well as the homopolymers and copolymers of Propylene.

Ethylene polymers:

• – PE-LD (LD = low density), erhältlich z. B nach dem Hochdruckverfahren (ICI) bei 1000 bis 3000 bar und 150 bis 300°C mit Sauerstoff oder Peroxiden als Katalysatoren in Autoklaven oder Rohrreaktoren. Stark verzweigt mit unterschiedlich langen Verzweigungen, Kristallinität 40 bis 50 %, Dichte 0,915 bis 0,935 g/cm³, mittlere Molmasse bis 600 000 g/mol.
• – PE-LLD (LLD = linear low density), erhältlich mit Metallkomplex-Katalysatoren im Niederdruckverfahren aus der Gasphase, aus einer Lösung (z. B. Benzin), in einer Suspension oder mit einem modifizierten Hochdruckverfahren. Schwach verzweigt mit in sich unverzweigten Seitenketten, Molmassen höher als bei PE-LD.
• – PE-HD (HD = high density), erhältlich nach dem Mitteldruck-(Phillips) und Niederdruck-(Ziegler)-Verfahren. Nach Phillips bei 30 bis 40 bar, 85 bis 180°C, Chromoxid als Katalysator, Molmassen etwa 50 000 g/mol. Nach Ziegler bei 1 bis 50 bar, 20 bis 150°C, Titanhalide, Titanester oder Aluminium alkyle als Katalysatoren, Molmasse etwa 200 000 bis 400 000 g/mol. Durchführung in Suspension, Lösung, Gasphase oder Masse. Sehr schwach verzweigt, Kristallinität 60 bis 80 %, Dichte 0,942 bis 0,965 g/cm³.
• – PE-HD-HMW (HMW = high molecular weight), erhältlich nach Ziegler-, Phillips- oder Gasphasenmethode. Hohe Dichte und hohe Molmasse.
• – PE-HD-UHMW (UHMW = ultra high molecular weight) erhältlich mit modifizierten Ziegler-Katalysator, Molmasse 3 000 000 bis 6 000 000 g/mol.

Suitable polyethylene (PE) homopolymers include:

• - PE-LD (LD = low density), available e.g. B by the high pressure process (ICI) at 1000 to 3000 bar and 150 to 300 ° C with oxygen or peroxides as catalysts in autoclaves or tubular reactors. Heavily branched with branches of different lengths, crystallinity 40 to 50%, density 0.915 to 0.935 g / cm ³ , average molecular weight up to 600,000 g / mol.
• - PE-LLD (LLD = linear low density), available with metal complex catalysts using the low pressure process from the gas phase, from a solution (e.g. petrol), in a suspension or with a modified high pressure process. Weakly branched with unbranched side chains, molecular weights higher than with PE-LD.
• - PE-HD (HD = high density), available according to the medium pressure (Phillips) and low pressure (Ziegler) process. According to Phillips at 30 to 40 bar, 85 to 180 ° C, chromium oxide as a catalyst, molar masses about 50,000 g / mol. According to Ziegler at 1 to 50 bar, 20 to 150 ° C, titanium halides, titanium esters or aluminum alkyls as catalysts, molar mass about 200,000 to 400,000 g / mol. Carried out in suspension, solution, gas phase or mass. Very weakly branched, crystallinity 60 to 80%, density 0.942 to 0.965 g / cm ³ .
• - PE-HD-HMW (HMW = high molecular weight), available according to the Ziegler, Phillips or gas phase method. High density and high molecular weight.
• - PE-HD-UHMW (UHMW = ultra high molecular weight) available with modified Ziegler catalyst, molecular weight 3,000,000 to 6,000,000 g / mol.

Particularly suitable is polyethylene (usually supported) catalysts in a gas phase fluidized bed process using catalysts is prepared, for example Lupolen ^® (Basell).

Polyethylene, which is produced using metallocene catalysts, is particularly preferred. Such polyethylene is commercially available, for example, as Luflexen ^® (Basell).

Suitable ethylene copolymers all commercially available ethylene copolymers are suitable, for example, Luflexen ^® grades (Basell), Nordel ^® and Engage ^® (Dow, DuPont). As comonomers such. B. α-olefins with 3 to 10 carbon atoms, in particular propylene, but-1-ene, hex-1-ene and oct-1-ene, and also alkyl acrylates and methacrylates with 1 to 20 carbon atoms in the alkyl radical, especially butyl acrylate. Other suitable comonomers are dienes such as butadiene, isoprene and octadiene. Other suitable comonomers are cycloolefins, such as cyclopentene, norbornene and dicyclopentadiene.

The ethylene copolymers it usually is statistical copolymers or block or impact copolymers. suitable Block or impact copolymers of ethylene and comonomers are e.g. B. Polymers in which a homopolymer of Comonomers or a random copolymer of the comonomer, for example with up to 15 wt .-% ethylene and then in the second stage a comonomer-ethylene copolymer with ethylene contents from 15 to 80 % By weight polymerized. As a rule, so much of the comonomer-ethylene copolymer polymerized in that the copolymer produced in the second stage has a share of 3 to 60% by weight in the end product.

The polymerization for production the ethylene comonomer copolymers can be by means of a Ziegler-Natta catalyst system respectively. It can but also catalyst systems based on metal tallocene compounds or used on the basis of polymerization-active metal complexes become.

Propylene polymers:

The term polypropylene is understood below to mean both homopolymers and copolymers of propylene. Copolymers of propylene contain minor amounts of monomers copolymerizable with propylene, for example C ₂ -C ₈ -alk-1-enes such as ethylene, but-1-ene, pent-1-ene or hex-1-ene. Two or more different comonomers can also be used.

Suitable polypropylenes include Homopolymers of propylene or copolymers of propylene with up 50% by weight of other alk-1-enes polymerized with up to 8 carbon atoms. The copolymers of propylene are statistical copolymers or block or impact copolymers. If the copolymers of propylene are statistically constructed, they generally contain up to 15% by weight, preferably up to 6% by weight, other alk-1-enes with up to 8 carbon atoms, especially ethylene, but-1-ene or a mixture of Ethylene and but-1-ene.

Suitable block or impact copolymers of propylene are e.g. B. Polymers in which in the first stage a propylene homopolymer or a random copolymer of propylene with up to 15 wt .-%, preferably up to 6 wt .-%, other alk-1-enes with up to 8 carbon atoms produces and then in the second stage a propylene-ethylene copolymer with ethylene contents of 15 to 80 wt .-%, wherein the propylene-ethylene copolymer may additionally contain other C ₄ -C ₈ -alk-1-enes, polymerized. As a rule, so much of the propylene-ethylene copolymer is polymerized in that the copolymer produced in the second stage has a proportion of 3 to 60% by weight in the end product.

The polymerization for production of polypropylene can be achieved using a Ziegler-Natta catalyst system respectively. In particular, such catalyst systems are used which, in addition to a titanium-containing solid component a), also contain cocatalysts in the form of organic aluminum compounds b) and electron donor compounds c) have.

But catalyst systems can also be used on the basis of metallocene compounds or on the basis of polymerization-active metal complexes are used.

The production of the polypropylenes is usually carried out by polymerization in at least one, often also in two or more reaction zones connected in series (reactor cascade), in the gas phase, in a suspension or in a liquid phase (bulk phase). The usual reactors used for the polymerization of C ₂ -C ₈ -alk-1-enes can be used. Suitable reactors include continuously operated stirred tanks, loop reactors, powder bed reactors or fluidized bed reactors.

The polymerization for production The polypropylene used is under normal reaction conditions at temperatures from 40 to 120 ° C, especially from 50 to 100 ° C and press from 10 to 100 bar, in particular from 20 to 50 bar.

Suitable polypropylenes have usually a melt flow rate (MFR), according to ISO 1133, from 0.1 to 200 g / 10 min., In particular from 0.2 to 100 g / 10 min., At 230 ° C and under a weight of 2.16 kg.

In a further preferred embodiment of the invention the thermoplastic molding composition at least one polyolefin. preferred Polyolefins contain at least one copolymerized polymer which is selected under ethylene, propylene, but-1-ene, isobutylene, 4-methyl-1-pentene, Butadiene, isoprene and mixtures thereof. Homopolymers are suitable Copolymers from the olefin monomers mentioned and copolymers at least one of the olefins mentioned as the main monomer and others Monomers (such as vinyl aromatics) as comonomers.

Particularly preferred polyolefins are low density polyethylene homopolymers (PE-LD) and polypropylene homopolymers. A preferred polypropylene homopolymer is, for example, biaxial oriented polypropylene (BOPP).

If as thermoplastic molding compounds Polyolefins come into consideration, so they are usually steric hindered amines, as mentioned above, stabilized.

Regarding the proportion of 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane in the thermoplastic molding compound, the weight ratio of 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane to the benzophenone of the formulas Ia and the use of other Light stabilizers or stabilizers are expressly on what has been said before.

Furthermore, regarding the Transmission of the thermoplastic molding composition in this embodiment the invention expressly referred to what was said earlier.

Another subject of the present Invention is a method of protecting packaged products from ultraviolet Radiation, in which one uses a thermoplastic to manufacture the packaging Molding compound that uses a stabilizer composition according to the invention contains.

The light stabilizers used according to the invention and, if available, the other stabilizers, the thermoplastic Molding compound added. Adding takes place in the usual Way, for example by mixing with the thermoplastic Molding compound. So you can the light stabilizers used according to the invention and optionally the other stabilizers also the starting monomer Add (olefin monomers) and polymerize the mixture of monomers and stabilizers. You can also use the stabilizers during the polymerization of the Add olefin monomers. requirement for an encore before or during The polymerization is that the stabilizers under the polymerization conditions are stable, i.e. do not decompose or decompose only slightly.

The light stabilizers used according to the invention and, if present, those are preferably added other stabilizers, the finished thermoplastic molding compound. This is done in the usual way according to mixing methods known per se, for example with melting at temperatures of 150 to 300 ° C. However, the components can also be mixed "cold" without melting, and the powdery or granular mixture is only melted and homogenized during processing.

It is understood that 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane and at least one benzophenone of the formulas I and Ia and optionally other stabilizers together or separately from each other, all at once, in portions or continuously, over the Time constant or along a gradient. For example part of the used according to the invention Stabilizer composition already during the polymerization of the Add olefin monomers and add the rest to the finished polymer, or you can add the whole Add stabilizer composition to the finished polymer.

Mixing is preferably carried out in a usual Extruder, where the components are mixed or individually, for example completely about one Funnel inserted into the extruder or proportionately at a later point of the extruder to the melted or solid one located in the extruder Product introduced can be. For the Melt extrusion are, for example, single or twin screw extruders particularly suitable. A twin screw extruder is preferred.

The mixtures obtained can, for example pelletized or granulated, or by generally known methods, for example by extrusion, injection molding, foaming with Blowing agents, deep drawing, blow molding or calendaring can be processed.

Moldings (also Semi-finished products, foils, films and foams) manufacture all types, for example packaging and foils, for example for textiles, especially packaging for Cosmetics, perfumes and pharmaceuticals and packaging and films for food, beverage bottles or Packaging for Cleaning supplies. Furthermore, stretch films can be made from the molding compounds produce. Stretch films can for example as outer packaging for wrapping already packaged goods Find use. The outer packaging then mainly protects the Packaging of the product against the damaging influence of UV radiation, for example before fading.

Basically, every product can go through a packaging containing the stabilizer composition used in the invention contains protect. That is preferably to be protected Product selected among cosmetic products, pharmaceutical products, perfumes, food and detergents. To the suitable cosmetic products belong Soap, body lotion, Skin cream, shower bath, bubble bath, body spray, make-up, eyeliner, Mascara, blush, lipstick, hair shampoo, hair conditioner, Hair gel, hair wax, hair tonic, nail polish, nail polish remover, etc. Suitable pharmaceutical products include pharmaceutical compositions or drugs in the form of tablets, pills, coated tablets, suppositories, Solutions, Dry juice, suspensions and the like. To the suitable foods belong carbonated and non-carbonated soft drinks such as lemonade, carbonated beverages like beer or fruit juice / carbonated Water, non-carbonated beverages such as wine, fruit juice, tea or coffee, fruit, meat, sausage, milk products such as milk, yogurt, butter or cheese, animal and vegetable Fats, baked goods, pasta, spices, sauces, Pastes, pestos, funds, marks, ketchups, dressings etc. To the appropriate Detergents include Household cleaners and industrial cleaners.

It is particularly preferred to use the according to the invention for use upcoming stabilizer composition in thermoplastic molding compounds which contain polyolefins for agricultural films and packaging films, in biaxially oriented polypropylene for stretch wrapping films, in polyethylene terephthalate or polyethylene naphthalate for Bottles and other packaging containers, in polystyrene for blister packaging and other packaging, in polycarbonate for bottles, flacons and others Packaging containers, in polyvinyl chloride for packaging containers and foils or in polyvinyl alcohol for the production of films.

If necessary, the foils can be made of different Polymers by lamination or as extrusion laminates with each other can be combined into composite films. By mono- or biaxial stretching if necessary, the properties can be improved. You use this for example for the production of shrink films. shrink films can be made, for example, from polyethylene terephthalate, polyethylene, Make polyvinylidene chloride or polyvinyl chloride.

The using the stabilizer composition according to the invention Draw packaging made from thermoplastic molding compounds through special quality features out. In comparison to the packaging stabilized with the comparison composition finds damage of the packaged products to a lesser extent due to UV radiation.

The invention is illustrated by the following Examples closer illustrated.

• 1,3-Bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis{[2'-cyano-3',3'-diphenylacryloyl)oxy]methyl}propan
  
  Es wurde das Produkt Uvinul^® 3030 von BASF AG verwendet.
• – Benzophenonon der Formel
  
  Es wurde das Produkt Uvinul^® 3050 von BASF AG verwendet.

The following were used as light stabilizers:

• 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane
  
  It was the product Uvinul ^® 3030 used by BASF AG.
• - Benzophenonone of the formula
  
  The product Uvinul ^® 3050 from BASF AG was used.

I. Production of the blends and specimen

Slide 1

As a thermoplastic molding compound a polyethylene terephthalate, Polyclear T 94, from Terhell & Co GmbH is used. The polyethylene terephthalate was 0.13 wt .-% of the light stabilizer A and 0.07 wt .-% of the light stabilizer B and cold premixed. The mixture was then melted at 275 ° C. and homogenized. The melt was discharged, granulated and approximately 300 μm thick Foils extruded.

Slide 2 (control):

The production took place on the previously described manner, but no stabilizer was used.

Slide 3 (comparison)

The production took place as for Slide 1 described, however, 0.2% by weight was used as stabilizer of stabilizer A.

Slide 4 (comparison)

The production took place as for Slide 1 described, however, 0.2% by weight was used as stabilizer of stabilizer B.

II. Application technology exam of the slides

Tabelle 2: Wollgewebe mit einer Lichtechtheit von 5

The protective effect against ultraviolet radiation was determined by determining the color change of wool samples of known light fastness according to the wool scale EN ISO 105-B01, which were protected by a film as described above. For this purpose, the films 1 and 2 were placed on wool fabrics of light fastness 4 and 5 and then the wool fabric protected by the film was irradiated in accordance with DIN 54004. The light fastness scale ranges from 1 to 8, 1 for an insufficient light fastness and 8 for a high one Lightfastness stands. The film 2 contained no light stabilizer and served as a control. In addition, wool samples of light fastness 4 and 5 which were not protected by a film as described above were irradiated as a control. The color change of the wool sample was determined after every 200, 400, 600, 800 and 1000 h. The smaller the numerical value determined, the less the color change. Accordingly, a high numerical value means a large color change. The higher the protective effect of the film, the less the color change of a wool sample with low light fastness, ie the better the film is able to protect the dye and thus also a product from the damaging influence of ultraviolet radiation. The results are summarized in Tables 1 and 2. Table 1: Wool fabric with a light fastness of 4

Table 2: Wool fabric with a light fastness of 5

The with the film of the invention protected Samples showed only a slight change in color when irradiated compared to samples protected by the control film. The advantageous properties of the film are clearly evident in the Protection of samples with low light fastness. Rehearsals with a low light fastness, for example of 4, are still effective before the damaging Protected from the influence of UV radiation. The films according to the invention are characterized by a particularly long-lasting effect when irradiated.

III. Yellowness index and transmission of the foils

Furthermore, the transmission and the yellowness index (YI) is determined. Served as the specimen slides 1 to 4.

• a) farbmetrisch nach DIN 6167 und DIN 5033 Die erfindungsgemäße Folie 1 weist unterhalb von 370 nm nur eine geringe Transmission auf und ist zudem farblos. Vergleichsfolie 3 weist zwar nur eine geringe Färbung auf, zeigt jedoch unterhalb von 370 nm eine unakzeptabel hohe Transmission. Bei Vergleichsfolie 4 liegt die Transmission zwar in dem erwünschten Bereich, die Folie zeigt jedoch eine deutliche Eigenfarbe wie der hohe YI-Index belegt.

A yellowness index of zero means that the specimen is pure white. Negative YI values mean that the specimen is bluish (the more negative YI is, the more blue it is). Positive YI values mean that the specimen is yellowish. The more positive the YI, the more yellow the sample appears to the viewer.

• a) Colorimetric according to DIN 6167 and DIN 5033. The film 1 according to the invention has only a low transmission below 370 nm and is also colorless. Comparative film 3 has only a slight coloration, but shows an unacceptably high transmission below 370 nm. In comparison film 4, the transmission is in the desired range, but the film shows a clear inherent color, as evidenced by the high YI index.

Claims (14)

Use of a stabilizer composition containing 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy ] methyl} propane and at least one more against radiation protective compound in the ultraviolet radiation range up to 400 nm, selected from benzophenones of the formula I,

wherein at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ', R ² ', R ³ ', R ⁴ ' and R ⁵ 'represents a radical OR ⁶ and the rest independently are selected from R ⁶ , OR ⁶ , COOR ⁶ , COO ^- M ⁺ , CONR ⁶ R ⁷ , SO ₃ R ⁶ , SO ₃ ^- M ⁺ and NR ⁶ R ⁷ , where R ⁶ and R ^{7 are} independently hydrogen, alkyl , Alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl and M ^{+ stands} for a cation equivalent, in thermoplastic molding compositions, the glass transition temperature T _{G of} the thermoplastic molding composition being above 20 ° C. and the transmission of the stabilized thermoplastic molding composition for electromagnetic radiation of the wavelengths between 300 and 370 nm is not greater than 20% and for electromagnetic radiation of the wavelengths between 410 and 800 nm is not less than 80%, for packaging to protect the packaged products against the effects of light. Use of a stabilizer composition according to claim 1, wherein in formula I at least one of R ¹ or R ¹ 'is hydroxy. Use of a stabilizer composition containing 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy ] methyl} propane and at least one further compound protecting against radiation in the ultraviolet radiation range up to 400 nm, selected from benzophenones of the formula Ia,

wherein R ⁸ , R ⁹ , R ⁸ 'and R ⁹ ' independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl, in thermoplastic molding compositions, the transmission of the stabilized molding composition for electromagnetic radiation of the wavelengths between 300 and 370 nm is not greater than 20% and for electromagnetic radiation of the wavelengths between 410 and 800 nm is not less than 80%, for packaging to protect the packaged products against the effects of light. Use according to one of the preceding claims, wherein the benzophenone of the formulas I and Ia under 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and mixtures thereof selected is. Use according to one of the preceding claims, wherein the transmission for electromagnetic radiation of wavelengths between 300 and 370 nm not bigger than Is 10%. Use according to one of the preceding claims, wherein the transmission for electromagnetic radiation of wavelengths between 420 and 800 nm larger than Is 90%. Use according to one of the preceding claims, wherein the thermoplastic molding composition contains at least one polymer which selected is among polyesters, polycarbonates, poly acrylates, polymethacrylates, Polystyrene, copolymers of styrene or α-methylstyrene with dienes and / or Acrylic derivatives, halogen-containing polymers, polymers that differ from unsaturated Alcohols and amines or their acrylic derivatives or acetals derive, polysulfones, polyether sulfones, polyether ketones. Use according to claim 3, wherein the thermoplastic Molding composition contains at least one polymer which is selected among polyolefins, polyesters, polycarbonates, polyacrylates, polymethacrylates, Polystyrene, copolymers of styrene or α-methylstyrene with dienes and / or Acrylic derivatives, halogen-containing polymers, polymers that differ from unsaturated Alcohols and amines or their acrylic derivatives or acetals derive, polysulfones, polyether sulfones, polyether ketones. Use according to one of the preceding claims, wherein the proportion of 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl }propane in the thermoplastic molding composition 0.01 to 5 wt .-%, based on the total weight of the thermoplastic molding composition is. Use according to one of the preceding claims, wherein the weight ratio of 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis {[2'-cyano-3', 3'-diphenylacryloyl) oxy] methyl} propane to the benzophenones of the formulas I and Ia in the range from 30: 1 to 1:10. Process for protecting packaged products from ultraviolet Radiation, in which one uses a thermoplastic to manufacture the packaging Molding composition containing a stabilizer composition such as in one of the claims 1 to 10 defined. The method of claim 11, wherein the product to be protected selected is among cosmetic products, perfumes, pharmaceutical products, Food, textiles and cleaning agents. Thermoplastic molding composition containing a stabilizer composition as in one of the claims 1 to 10 defined. Packaging containing a thermoplastic molding compound as defined in claim 13.