NL1009844C2 - Plastic composition with improved weather resistance. - Google Patents

Description

- 1 -

PLASTIC COMPOSITION WITH IMPROVED WEATHER RESISTANCE

The invention relates to a plastic composition containing a polymer and at least one hindered-amine light stabilizer.

In what follows, a hindered amine light stabilizer is called a HALS compound.

A plastic composition containing a polymer and at least one HALS compound is known from US-A-3,904,581. Patent US-A-3,904,581 discloses a plastic composition containing a polymer and a 4-aminopiperidine compound, being a HALS compound, whereby the plastic composition is stabilized against heat and light degradation. It is generally known that by stabilizing a plastic composition against degradation under the influence of heat and light, in particular against degradation under the influence of UV radiation, the weather resistance of the plastic composition improves, making the plastic composition suitable for certain applications. , for example for outdoor applications. : 25 Although a plastic composition that:

polymer and at least one HALS compound already contains good weather resistance property, there is still need I.

to a plastic composition that has an improved I.

weather resistance.

The object of the invention is to provide a plastic composition which has such an improved weather resistance.

According to the invention, this object is achieved in that the plastic composition according to the invention contains a polymer, at least one HALS compound and at least one bridged amine compound with at least one N-bridgehead.

Indeed, it has surprisingly been found that a plastic composition containing a polymer, at least one HALS compound and at least one bridged amine compound with at least one N bridgehead exhibits a weather resistance significantly better than that of the known plastic composition containing the bridged amine compound with at least one N-10 bridgehead. It was also found that in a plastic composition containing a polymer, at least one HALS compound and at least one bridged amin compound with at least one N bridgehead, it has a weather resistance better than the sum of the contributions of the HALS compound and expects the bridged amine compound. This is all the more surprising because it has also been found that a plastic composition containing a polymer and only a bridged amine compound is hardly stabilized against degradation under the influence of heat and light.

Thus, with certain choices of the components of the plastic composition of the invention, it was found that the weather resistance of the plastic composition of the invention could exhibit a weather resistance that was more than double the weather resistance of the known plastic compositions.

As a measure of weather resistance, a Xenon test 30 is used in the context of this invention. The Xenon test determines the resistance of a plastic composition to light degradation from a filtered (borosilicate glass) Xenon lamp at a black panel temperature of 62 ° C with an intensity of 0.35 W.m'2.nm "1, at a wavelength 1 G 0 9 o 'i · ό - 3 - of 340 nra and at a relative humidity of 55 vol.% In a wet / dry cycle of 18 minutes wet and 102 minutes dry. The degradation of the plastic composition is measured as the difference of the carbonyla absorption at 1713 cm -1 and the absorption at 1860 cm -1 as a function of the time during which the plastic composition is subjected to the said combination of light, temperature and humidity. as 10 the difference between the measured carbonyl absorbances for the films before and after 2500 hours of aging according to the said combination of light, temperature and .1 humidity.

A hindered-amine light stabilizer 15 is understood to mean compounds of the following general formulas: 1 - 4 - 5 and combinations thereof.

Herein, R 1 through R 5 are independent substituents. Examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, the substituents being in turn may contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination thereof. A hindered amine light stabilizer can also be part of a polymer.

Preferably, as the HALS compound, a compound is selected which is derived from a substituted piperidine compound, in particular any compound which is derived from an alkyl substituted piperidyl, piperidinyl or piperazinone compound, and substituted alkoxy piperidinyl compounds. Examples of such compounds are: - 2,2,6,6-tetramethyl-4-piperidone; - 2,2,6,6-tetramethyl-4-piperidinol; 30- bis- (1,2,2,6,6-pentamethylpiperidyl) - (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) -butyl malonate; - di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770); - oligomer of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin® 622); ! r 'r \'; I '* r

... 2 J

1 - 5 - oligomer of cyanoic acid and N, N-di (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine; bis (2,2,6,6-tetramethyl-4-piperidinyl) succinate; bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) -5 sebacate (Tinuvin® 123); bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin® 765); - tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate; 10 - N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexane-1,6-diamine (Chimassorb® T5); - oligomer of cyanoic acid and N, N-di (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine (Chimassorb® 944); 15 - N-butyl-2,2, 6,6-tetramethyl-4-piperidinamine; - 2,2 '- [(2,2,6,6-tetramethyl-piperidinyl) imino] bis- [ethanol]; - poly ((6-morpholine-S-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) -iminohexamethylene- (2,2,6,6-tetramethyl-4- piperidinyl) imino) (Cyasorb® UV 3346); 5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cycloundecyl-oxazole) (Hostavin® N20); - 1,1 '- (1,2-ethanedi-yl) -bis- (3,3', 5,5'-tetramethyl-piperazinone); 25-8 acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5) decane-2,4-dione; polymethylpropyl-3-oxy- [4 (2,2,6,6-tetramethyl) -piperidinyl) -siloxane (Uvasil® 299); 1,2,3,4-butane-tetracarboxylic acid 1,2,3-tris (1,2,6,6,6-pentamethyl-4-piperidinyl) -4-tridecyl ester; copolymer of alpha-methylstryrene-N- (2,2,6,6-tetramethyl-4-piperidinyl) maleimide and N-stearyl maleimide; in1 "? - 6 - - 1,2,3,4-Butanetetracarboxylic acid, polymer with beta, beta, beta ', beta'-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3.9- diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark® LA63) 5 - 2,4,8,10-Tetraoxaspiro [5.5] undecane-3,9-diethanol, beta, beta, beta1 , beta'-tetramethyl, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Mark® LA68) - D-Glucitol, 1.3: 2, 4-bis-O- (2,2,6,6-tetramethyl-4-10 piperidinylidene) - (HALS 7) - oligomer of 7-Oxa-3,20-diazadispiro [5.1.11.2] heneicosan-21-one, 2,2,4,4-tetramethyl-20- (oxiranylmethyl) - (Hostavin® N30) - Propanedioic acid, [(4-methoxyphenyl) methylene] -15, bis (1,2,2,6,6-pentamethyl- 4-piperidinyl) ester (Sanduvor® PR 31) - Formamide, N, N'-1,6-hexanediylbis [N- (2,2,6,6-tetramethyl-4-piperidinyl (Uvinul® 4050H).

- 1,3,5-Triazine-2,4,6-triamine, N, N - [1,2-20 ethanediyl bis [[[4,6-bis [butyl (1,2,2,6,6-pentamethyl) -4-iperidinyl) amino] -1,3,5-triazin-2-yl] imino] -3,1-propanediyl]] -bis [Ν ', N "' - dibutyl-N", N '' - bis (1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb® 119) 25 - 1,5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6, 6-tetramethyl-4-peridinyl) ester (Cyasorb® UV-500) - 1,5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4 -peridinyl) ester (Cyasorb® 30 UV-516).

- N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-acryloyloxy-1,2,6,6,6-pentamethyl-4-piperidine.

- 1,5,8,12-tetrakis [2 *, 4'-bis (1 ", 2", 2 ", 6", 6 "-pentamethyl-4" -piperidinyl (butyl) amino) -1 ', 3 5'-35-triazin-6'-yl] -1,5,8,12-tetraazadodecane.

1 0098 4 4 '- 7 - NECK PB-41 (Clariant Huningue S.A.)

Nylostab® S-EED (Clariant Huningue SA) 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidin-2,5-dione 5 Uvasorb® HA88 1,1 '- (1 , 2-ethane-di-yl) -bis- (3,3 ', 5,5'-tetra-methyl-piperazinone) (Good-rite® 3034) 1.1', 1 "- (1,3.5 -Triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,5, διό tetramethylpiperazinone); (Good-rite® 3150) 1.1 '- (l 3,5-Triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,4,5,5-tetramethylpiperazinone) (Good-rite® 3159) Preferred di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (also known under the trade name TinuvinR 770), oligomer of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl- 4-piperidinol and succinic acid (Tinuvin® 622); bis- (1-octyloxy-2,2,6,6-20-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 123); bis- (1,2,2, 6,6-pentamethyl-4-piperidinyl) sebacate

(Tinuvin® 765); N, N'-bis- (2,2,6,6-tetramethyl-4-I

piperidyl) -hexane-1,6-diamine (Chimassorb® T5); poly ((6-morpholine-S-triazine-2,4-diyl) (2,2,6,6-25 tetramethyl-4-piperidinyl) iminohexamethylene- (2,2,6,6-tetramethyl-4-piperidinyl imino) (Cyasorb® UV 3346); 5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cycloundecyl oxazole) (Hostavin® N20); polymethylpropyl-3-oxy- [4 (2,2,6,6-tetrametyl) -30 piperidinyl) -siloxane (Uvasil® 299), - 1,2,3,4-Butanetetracarboxylic acid, polymer with 7 beta, beta, beta ', beta'-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, 1,2,2,6,6- "

pentamethyl-4-piperidinyl ester (Mark® LA63) I.

:: - 8 - - 2,4,8,10-Tetraoxaspiro [5.5] undecane-3,9-diethanol, beta, beta, beta ', beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester {Mark® LA68) 5 - D-Glucitol, 1,3: 2,4-bis-0- (2,2,6,6-tetramethyl- 4- piperidinylidene) - (HALS 7) - oligomer of 7-Oxa-3,20-diazadispiro [5.1.11.2] heneicosan-21-one, 2,2,4,4-tetramethyl-20- (oxiranylmethyl) - (Hostavin ® N30) 10 - Propanedioic acid, [(4-methoxyphenyl) methylene] -, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor® PR 31) - Formamide, N, N ' -1,6-hexanediylbis [N- (2,2,6,6-tetramethyl-4-piperidinyl (Uvinul® 4050H).

15 - 1,3,5-Triazine-2,4,6-triamine, N, N '"[1,2-ethanediylbis [[[4,6-bis [butyl (1,2,2,6,6- pentamethyl-4-iperidinyl) amino] -1,3,5-triazin-2-yl] imino] - 3,1-propanediyl]] bis [N, N "-dibutyl-N ', N" -bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb® 20 119) - 1,5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis [2,2,6,6 -tetramethyl-4-peridinyl) ester (Cyasorb® UV-500) - 1,5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, 25 bis (1,2,2,6,6-pentamethyl-4 -peridinyl) ester (Cyasorb® UV516) - mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol and fatty acids (Cyasorb® UV 3853); NAL PB-41 (Clariant Huningue SA) 30 Nylostab® S- EED (Clariant Huningue SA) 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidin-2,5-dione Uvasorb® HA88 1,1 '- (1,2-ethane- di-yl) -bis- (3,3 ', 5,5'-tetra-methyl-. piperazinone) (Good-rite® 3034) 1 00984 4 - 9 - l', l "- (l, 3,5-Triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,5,5-tetramethylpiperazinone), (Good-rite® 3150) 1 , 1 ', 1' '- (1,3,5-Triazine-2,4,6-5 triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,4,5,5-tetraraethylpiperazinone) (Good-rite® 3159) used.

The bridged amine compound with at least one N bridgehead that can be used in the context of this invention is preferably a compound derived from a compound of the general Formula 1 or 2 (see Formula Sheet), where Mi to M4 are bridgeheads and each bridgehead is independently selected from carbon, nitrogen, silicon or phosphorus, with the proviso that at least one bridgehead must always be a nitrogen atom and carbon and silicon may be substituted; an N bridgehead is defined as a bridgehead that is a nitrogen atom; Di, Dm, Dn, Dc, Dp and Dq here represent 20 each for a chain with a length of 1 to 20 atoms,

where the number of atoms that make up the chains are T

is equal to 1, m, n, o, p and q, any number and type of atoms can be chosen independently and 1 where the chains can have different lengths and can be made up of different types of atoms. The chains can also contain side groups, Γ where the number of atoms in the side groups is not

included in the number of atoms in the chain. Suitable I.

choices for the atoms that make up the chains are carbon, nitrogen, oxygen, silicon, and phosphorus.

Preferably, the chains are composed of 1 to 3 carbon atoms.

Preferably, the bridged amine compound having at least one N-bridgehead 35 is used with a HALS compound in a ratio, i · n o; ·· '. · "; Z * !!, (- '- 10 - calculated relative to the amount of HALS compound from about 1:20 (m: m) to about 20: 1 (m: m), more preferably in a ratio from about 1:10 (m: m) to about 10: 1 (m: m), most preferably in a ratio of about 1: 5 (m: m) to about 5: 1 (m: m). Within the limits of the latter ratios, the weather resistance is better than expected from the amounts of the bridged amine compound having at least one N-10 bridgehead and the HALS compound present.

The amount of bridged amine compound with at least one N-bridgehead that can be used in the plastic composition can vary within wide limits, which are easy to determine for those skilled in the art. The limits may vary depending on, for example, the type of polymer, the type of HALS compound, the other additives in the aggregate package, the weather resistance to be achieved or, in general, the type, properties and specific application of the plastic composition.

For example, it is possible that the bridged amine compound having at least one N-bridgehead is present in the plastic composition in an amount, calculated relative to the amount of polymer in the plastic composition, preferably from about 0.01 wt% to about 10, 0 wt%, more preferably in an amount from 0.05 wt% to 5 wt%, most preferably in an amount from 0.1 wt% to 2.5 wt%.

Suitable choices for the bridged amine compound with at least one N-bridgehead are: derivatives of 7-nitro-1,3,5, triazamantane and 7-amino-1,3,5-triazamantane, ·, f: .- ..1 i - 11 - - Derivatives of 7-amino-1,3,5-triazamantane of general structure I or II: R '

N-R

rA

o, 5

NH = CH-R

r / S

00 10 wherein R and R 'are independent substituents; examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, the substituents in turn containing functional groups; examples of functional groups i are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination thereof.

In addition, the substituent can link several of the compounds I and / or II together.

- derivatives obtained by a reaction of 7-amino- - 1,3,5-triazaadamantane with compounds containing one or more functional groups. Examples of these functional groups are: aldehydes, acids, esters, amides, ketones, anhydrides and isocyanates.

triazaadamantane derivatives which are bound to a polymer (preferably a polyolefin) by means of an imide functionality; polymer-bonded compounds obtained by the reaction of 7-amino-1,3,5-triazaadamantane with a maleic anhydride functionalized polymer (preferably a polyolefin); 10 - Hexamethylene tetraamine (HMTA), diazabicyclo [2.2.2] octane (DABCO) or derivatives thereof. HMTA and DABCO are commercially easy to obtain or easy to prepare according to well-known methods. For example, HMTA can be easily prepared from the inexpensive and easily obtainable basic raw materials, ammonia and formaldehyde.

The bridged amine compound having at least one N bridgehead is preferably used as a salt, more preferably as an ammonium salt in combination with a HALS compound having a molecular weight of less than 1000 g / mol. A carboxylic acid is preferably chosen as the salt former. Examples of suitable carboxylic acids are aliphatic carboxylic acids, aliphatic dicarboxylic acids and aromatic carboxylic acids. Suitable choices are stearic acid, sebacic acid, cyclohexane dicarboxylic acid and benzene tricarboxylic acid. Preferably, the bridged amine compound having at least one N-bridgehead is not used as the salt, the salt former containing a halogen or sulfur; Namely, it is well known that halogen or sulfur containing compounds can reduce the action of the HALS stabilizer.

Preferably, the bridged amine compound having at least one N-bridgehead 35 is substituted with at least one substituent having a molecular weight, preferably of at least 50, more preferably of at least 100.

Surprisingly, it has been found that by using the bridged amine compound with at least one N-bridgehead either in its salt form or substituted with at least one substituent with a molecular weight greater than about 50, or in its salt form and substituted with at least one substituent with a molecular weight greater than about 50, a plastic composition is obtained which has an even better weather resistance.

The plastic composition according to the invention preferably contains a thermoplastic polymer selected from the group of polyolefins and 1 styrene polymers. Suitable choices include:

propylene polymers, such as propylene homopolymer, ethylene L

propylene random copolymer, ethylene-propylene block copolymer Γ

and mixtures thereof. Also, as propylene polymers, L

For the purposes of this invention mixtures containing at least 50 wt. % of one of the above-mentioned propylene polymers with, for example, polyethylene or ethylene-propylene-diene copolymers; - ethylene polymers, such as low density polyethylene (LDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE) or ultra high molecular weight polyethylene (UHMWPE) butene polymers, such as polybutene-1.

Suitable choices of styrene polymers are, for example, polystyrene, high impact polystyrene (HIPS), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-maleic anhydride copolymer (SMA), and styrene-maleimide copolymer 35 (SMI).

<η f ·. ·· I

t '\ i' V ·: * i - 14 -

More preferably, the polymer is a propylene polymer or an ABS, even more preferably a propylene polymer.

The bridged amine compound with at least one N-bridgehead can be easily introduced at any time before a plastic article, for example a molded article, foil, film, fiber, coating, foam, tape, latex or powder, is made from the plastic composition in the plastic composition using one of the many standard 10 methods known to those skilled in the art.

According to a first method, the bridged amine compound with at least one N-bridgehead, for example in the form of a powder, solution, emulsion or suspension, is mixed with the other 15 components of the plastic composition, which are for example in the form of a powder or a melt .

According to a second method, the bridged amine compound with at least one N-20 bridgehead is first mixed with at least one HALS compound and optionally other additives in a so-called additive package, for example in the form of a powder, solution, emulsion or suspension and this package is then added to the plastic, for example in the form of powder or as a melt.

The plastic composition containing a polymer, at least one HALS compound and at least one bridged amine compound with at least one N-bridgehead may also contain other additives, eg anti-oxidants, thermal and UV stabilizers, metal deactivators, fillers, pigments, flame extinguishers, optical brighteners and similar additives used in plastic compositions.

.. i - 15 -

The invention will be further elucidated by means of the examples without being limited thereto.

5 Examples

In the examples, the following general procedures were followed.

Preparation of the various browned amines 10 HMTA stearate:

A solution of 28.45 grams (0.1 Mol)

Stearic acid in ethanol was added dropwise with stirring to a solution of 14 grams (0.1 Mol) DABCO in ethanol. The mixture was evaporated with a Rotavap.

7-Nitro-1,3,5-Triazamantane:

To a solution of 140.2 grams (1.0 mole) of Hexamethylene tetraamine in 500 ml of ethanol (80%) was added a mixture of 56.8 ml (1.0 mole) nitromethane and 45 ml (1.2 mole) formic acid with continuous stirring and reflux. The mixture was refluxed for 4 hours and left overnight. The separated crystalline product was washed several times with water and ethanol. After recrystallization in water, the product (white needles) was dried in the vacuum drying oven. (Literature: Collection Czechoslov.

Chem. Commun [vol. 40], 1975, pp. 2179-82).

30 7-Amino-l, 3,5-Triazamantane:

In a Parr autoclave (160 ml content) with stirrer and shanks, 15.0 grams of 7-nitro-

1,3,5-triaza amantane, 100 ml Methanol and 1.5 grams T.

wet Raney Cobalt as a catalyst. The hydrogenation was run at max.

- 16 - speed, carried out under hydrogen at 80 bar pressure and 80 ° C. After filtering off the catalyst, the methanol was removed by rotary evaporation. The crystalline product was dried in a vacuum desiccant.

7-Dodecylideneamino-1,3,5-triazamantane:

In a Parr autoclave (160 ml content) equipped with stirrer and beffels, 8.4 grams of 7-amino-10 l, 3,5-triazamantane, 10.0 grams of dodecanal, 85 ml

Methanol, 10 ml of Toluene and 2.0 grams of wet Raney Cobalt were introduced as a catalyst. The reaction was carried out at max speed and 80 ° C for one hour under nitrogen medium {2 bar). After filtering off the catalyst, the filtrate was evaporated with a rotary evaporator and dried in a vacuum drying oven.

Preparation of a plastic composition

A polymer powder (PP) was mixed with a dichloromethane solution containing an amount of a HALS compound. This mixture was dried in an oven (Hereaus Vacutherm) for 24 hours at a temperature of 28 ° C and a pressure of about 20 mm Hg. Subsequently, a dichloromethane solution of the bridged amine compound having at least one N bridgehead was added to the plastic composition. This plastic composition was also dried in the same manner as described above.

30 Production of PP films and pictures

The PP composition was pressed into a film with a Fontijne press (type TP200, preheating for 5 minutes without pressure at 190 ° C, followed by applying a pressure of 100-120 kNewton, followed by 1 noq. 1 -t '· - 17 - cool by 10 minutes at said pressure). The thickness was checked with a Heidenhain electronic meter. On average, a thickness of 120-150 μτα for the films was obtained.

5

Determination of weather resistance

The weather resistance of a plastic composition was determined in a weather resistance test conducted in an Atlas 10 Material Testing Technology Weather-0 meter (type Ci65) according to the method described in the previous description. The degradation was measured using FT-IR. Weather resistance is then expressed as the difference between the measured carbonyl absorbances for the 15 films before and after 2500 hours of aging according to the said combination of light, temperature and humidity.

In the examples, the following abbreviations and 1 brand names were used: PP: polypropylene HMTA: hexamethylene tetraamine. ^ HMTA stearate: mono-salt of stearic acid and HMTA. Seed: 7-amino-1,3,5-triazamantane Dodecylidene seed: 7-dodecylideneamino-1,3,5-25 triazamantane.

Example 1

A series of plastic compositions were prepared by the method described above. Here, the composition of the plastic composition was varied.

PP was chosen as the polymer (StamylanR, type P83ml8, DSM, The Netherlands). Films were prepared from the plastic compositions using the method as described above. The films were subjected to a weather resistance test and the weather resistance was determined as described above. The results are summarized in Table 1.

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This shows that the plastic composition according to the invention preferably contains a salt of a bridged amine compound with at least one N-bridgehead and a HALS compound with a molecular weight of less than 1000 g / mol, or a bridged amine compound with at least one N bridgehead which is not salt and a HALS compound having a molecular weight of greater than 1000 g / mol.

. . ); ·· .; fc .. Z

Claims (14)

1. Plastic composition containing a polymer and at least one hindered-amine light stabilizer, characterized in that the plastic composition also contains at least one bridged amine compound with at least one N-bridgehead. A plastic composition according to claim 1, wherein the ratio between the bridged amine compound 10 having at least one N bridged head and the HALS compound is between 1: 5 (m: m) and 5: 1 (m: m). Plastic composition according to claim 1 or 2, wherein the amine compound having at least one N-bridgehead is present in an amount calculated from the total amount of polymer in the plastic composition of 0.1 to 2.5% by weight. A plastic composition according to any one of claims 1 to 3, wherein the hindered amine light stabilizer is 20 di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (also known under the trade name Tinuvin® 770), oligomer of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin® 622); bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 123); bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin® 765); N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexane-1,6-diamine (Chimassorb® T5); poly ((6-morpholine-S-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) iminohexamethylene- (2,2,6,6-tetramethyl-4-piperidinyl) imino) (Cyasorb® UV 3346); 5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cycloundecyl oxazole) (Hostavin® N20); i - 23 - Polymethylpropyl-3-oxy- [4 (2,2,6,6-tetrametyl) - •! piperidinyl) -siloxane (Uvasil® 299), 1,2,3,4-Butanetetracarboxylic acid, polymer with beta, beta, beta ', beta'-tetramethyl-2,4,8,10-5 tetraoxaspiro [5.5] undecane -3,9-diethanol, 1.2.2.6.6-pentamethyl-4-piperidinyl ester (Mark LA63) - 2,4,8,10-Tetraoxaspiro [5.5] undecane-3,9-diethanol, beta, beta, beta ' , beta'-tetramethyl, ~ 10 polymer with 1,2,3,4-butanetetracarboxylic acid, 2.2.6.6-tetramethyl-4-piperidinyl ester (Mark ~ LA68) - - D-Glucitol, 1.3: 2.4 -bis-O- (2,2,6,6-tetramethyl- - 4-piperidinylidene) - (HALS 7) - 15. Oligomer of 7-Oxa-3,20-diazadispiro [5.1.11.2] heneicosan-21- one, 2,2,4,4- 1 tetramethyl-20- (oxiranylmethyl) - (Hostavin N30) 1 - Propanedioic acid, [(4-methoxyphenyl) methylene] - -, bis (1,2,2,6,6 pentamethyl-4-piperidinyl) ester ~ 20 (Sanduvor PR 31) - Formamide, N, N1-1,6-hexanediylbis [N- (2,2,6,6- = tetramethyl-4-piperidinyl (Uvinul 4050H). - 1,3,5-Triazine-2,4,6-triamine, N, N - [1,2-ethanediylbis [[[4,6-bis [butyl (1,2,2,6,6-f 25 pentamethyl-4-iperidi nyl) amino] -1,3,5-triazin-2- = yl] imino] -3,1-propanediyl]] - bis [Ν ', Ν' "- dibutyl-N ', N" -bis (1 , 2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb 119) - 1,5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic = 30 acid, bis (2,2,6,6- tetramethyl-4-peridinyl) ester = (Cyasorb UV-500) - 1,5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic = acid, bis (1,2,2,6,6-pentamethyl-4- peridinyl) = ester (Cyasorb® UV516) 1009844 'I - 24 - - mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol and fatty acids (Cyasorb® UV 3853); NECK PB-41 (Clariant Huningue SA) Nylostab S-EED (Clariant Huningue SA) 5 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidin-2,5-dione Uvasorb HA88 1.1 '- (1,2-ethane-di-yl) -bis- (3,3', 5,5'-tetra-methyl-piperazinone) (Good-rite® 3034) 10 1.1 ', 1 "- (1,3,5-Triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,5,5-tetramethylpiperazinone); (Good-rite® 3150) 1 , 1 ', 1 "- (1,3,5-Triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-15 ethanediyl) tris (3,3,4,5,5-tetramethylpiperazinone) ( Good-rite® 3159) Plastic composition according to any one of claims 1 to 4, characterized in that the bridged amine compound with at least one N-bridgehead is hexamethylene tetraamine, diazabicyclo [2.2.2] octane or a derivative of either compound. Plastic composition according to any one of claims 1 to 5, characterized in that the bridged amine compound with at least one N-bridgehead 25 is not salt and the HALS compound has a molecular weight of more than 1000 g / mol. Plastic composition according to any one of claims 1 to 6, characterized in that the bridged amine compound with at least one N bridgehead 30 is a salt and the HALS compound has a molecular weight of less than 1000 g / mol. Plastic composition according to claim 7, characterized in that the salt is an ammonium salt. Plastic composition according to any one of claims 35 to 8, characterized in that the bridged 1 Gü '4 1 - 25 amine compound is substituted with at least one N bridgehead with at least one aliphatic or aromatic substituent having a molecular weight of at least 50. Plastic composition according to any one of claims 1 to 9, characterized in that the polymer is selected from the group comprising propylene polymers and acrylonitrile-butadiene-styrene copolymer (ABS). I 11. Use of a bridged amine compound having at least one N-bridgehead, not being a salt, in combination with a hindered-amine light stabilizer having a molecular weight of greater than 1000 g / mol as a stabilizer for a plastic composition with improved weather resistance. 12. Use of a salt of a bridged amine compound with at least one N-bridgehead, in combination with a hindered-amine light stabilizer having a molecular weight of less than 1000 g / mol as a stabilizer for a plastic composition with improved weather resistance. 13. Articles made from the plastic composition according to any one of claims 1-10. 15. Plastic composition with improved weather resistance, as described and illustrated by the examples. ,. B 'J. COOPERATION CONVENTION (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE OF IDENTIFICATION OF NATIONAL APPLICATION Characteristic of the applicant ol of the representative 9761NL Dutch application no. Filing date 1009844 12 August 1998 Priority date claimed Applicant (Name) DSM NV Date of the request International Type Study Assigned by the International Research Initiative (ISA) to the request for an International Type Study No. SN 31667 EN I. SUBSTANTIVE CLASSIFICATION £ RP [When using different classifications, indicate all classification symbols] According to the International classification (IPC) Int. Cl. 6: C 08 K 5/34, C 08 L 23/10, C 08 L 55/02 II. FIELDS OF TECHNIQUE EXAMINED Minimum documentation examined Classification system Classification symbols Int. Cl.6 C 08 K Documentation examined other than the minimum documentation to the extent that such documents are included in the areas investigated HL 1 I CANNOT EXAMINE CERTAIN CONCLUSIONS (comments o supplement sheet) ^ <V · I 1 LACK OF UNITY OF INVENTION (remarks also supplementary sheet) Form PCT / ISA / ZOKjl 07.1979