Stabilizing shaped polymer articles to resist degradation induced by artificial UV-C light

Abstract

The present invention relates to the use of a stabilizer selected from compounds (1) to (7), a mixture of a compound (8) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), a mixture of a compound (9) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12) for stabilizing shaped polymer articles against degradation induced by artificial UV-C light; and to a method for stabilizing a shaped polymeric article against degradation induced by artificial UV-C light, the method comprising incorporating a stabilizer selected from these stabilizers into the shaped polymeric article.

Description

[0001] The present invention relates to the use of a stabilizer selected from compounds (1) to (7), a mixture of compound (8) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), a mixture of compound (9) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12) for stabilizing a shaped polymer article against degradation induced by artificial UV-C light; and to a method for stabilizing a shaped polymer article against degradation induced by artificial UV-C light, the method comprising incorporating a stabilizer selected from these stabilizers into a shaped polymer article. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.

[0002] Artificial UV-C light is increasingly used for the disinfection of polymeric articles. As a result, an increase in yellowing, microcracking, or blooming is observed in such polymeric articles. Therefore, there is a need to develop suitable plastic additives that provide low application rates, are compatible with other plastic additives, and reduce yellowing, microcracking, or blooming.

[0003] These objects are achieved by the use of a stabilizer selected from the group consisting of:

[0004] Compound (1)

[0005]

[0006] Compound (2)

[0007]

[0008] Compound (3)

[0009]

[0010] Compound (4)

[0011]

[0012] Compound (5)

[0013]

[0014] Compound (6)

[0015]

[0016] Compound (7)

[0017]

[0018] Compound (8)

[0019]

[0020] A mixture of a hydroxyphenyl triazine selected from the group consisting of compounds (10), (11) or (12)

[0021] or

[0022] Compound (9)

[0023]

[0024] A mixture with a hydroxyphenyltriazine selected from compound (10), (11) or (12).

[0025] These objects are also achieved by a method for stabilizing a shaped polymer article against degradation induced by artificial UV-C light, which method comprises incorporating a stabilizer into the shaped polymer article.

[0026] In a preferred form, the stabilizer is selected from compound (1).

[0027] In another preferred form, the stabilizer is selected from compound (2).

[0028] In another preferred form, the stabilizer is selected from compound (3).

[0029] In another preferred form, the stabilizer is selected from compound (4).

[0030] In another preferred form, the stabilizer is selected from compound (5).

[0031] In another preferred form, the stabilizer is selected from compound (6).

[0032] In another preferred form, the stabilizer is selected from compound (7).

[0033] In another preferred form, the stabilizer is selected from compound (1), (2), (3), (4), (5), (6), or (7).

[0034] In another preferred form, the stabilizer is selected from compound (2), (3), or (4).

[0035] In another preferred form, the stabilizer is selected from compound (6) or (7).

[0036] Mixtures of stabilizers selected from compounds (1), (2), (3), (4), (5), (6), or (7) are also possible. Typically, the mixture of these stabilizers comprises two of these stabilizers. A mixture of two stabilizers selected from compounds (1), (2), (3), (4), (5), (6), or (7) may comprise them in a weight ratio of 10:1 to 1:10, preferably 7:1 to 1:7.

[0037] In another preferred form, the stabilizer is selected from a mixture of compound (1) and an additional stabilizer selected from compounds (2) to (7), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0038] In another preferred form, the stabilizer is selected from a mixture of compound (2) and an additional stabilizer selected from compounds (1) or (3) to (7), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0039] In another preferred form, the stabilizer is selected from a mixture of compound (3) and an additional stabilizer selected from compounds (1) to (2) or (4) to (7), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0040] In another preferred form, the stabilizer is selected from a mixture of compound (4) and an additional stabilizer selected from compounds (1) to (3) or (5) to (7), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0041] In another preferred form, the stabilizer is selected from a mixture of compound (5) and an additional stabilizer selected from compounds (1) to (4) or (6) to (7), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0042] In another preferred form, the stabilizer is selected from a mixture of compound (6) and an additional stabilizer selected from compounds (1) to (5) or (7), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0043] In another preferred form, the stabilizer is selected from a mixture of compound (7) and an additional stabilizer selected from compounds (1) to (6), and wherein the weight ratio may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0044] In another preferred form, the stabilizer is selected from

[0045] A mixture of compound (7) and compound (11),

[0046] A mixture of compound (5) and compound (11),

[0047] A mixture of compound (2) and compound (10),

[0048] A mixture of compound (2) and compound (11),

[0049] A mixture of compound (3) and compound (11),

[0050] A mixture of compound (4) and compound (11), or

[0051] A mixture of compound (6) and compound (11).

[0052] In another preferred form, the stabilizer is selected from a mixture of compound (8) and a hydroxyphenyl triazine selected from compound (10), (11) or (12).

[0053] In another preferred form, the stabilizer is selected from a mixture of compound (9) and a hydroxyphenyl triazine selected from compound (10), (11) or (12).

[0054] In another preferred form, the stabilizer is selected from a mixture of compound (8) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), wherein the weight ratio is 100:1 to 1:3, preferably 50:1 to 2:1.

[0055] In another preferred form, the stabilizer is selected from a mixture of compound (9) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), wherein the weight ratio is 100:1 to 1:3, preferably 50:1 to 2:1.

[0056] In another preferred form, the stabilizer is selected from

[0057] A mixture of compound (8) and at least one of compounds (10), (11) or (12); and

[0058] A mixture of compound (9) and at least one of compound (10), (11) or (12).

[0059] In another preferred form, the stabilizer is selected from

[0060] A mixture of compound (8) and one of compounds (10), (11) or (12); and

[0061] A mixture of compound (9) and one of compounds (10), (11) or (12).

[0062] In another preferred form, the stabilizer is selected from

[0063] A mixture of compound (8) and one of compounds (10), (11) or (12), wherein the weight ratio is 100:1 to 1:3, preferably 50:1 to 2:1; or

[0064] A mixture of compound (9) and one of compounds (10), (11) or (12), wherein the weight ratio is 100:1 to 1:3, preferably 50:1 to 2:1.

[0065] In another preferred form, the stabilizer is selected from

[0066] A mixture of compound (8) and compound (10); and

[0067] A mixture of compound (9) and compound (10).

[0068] In another preferred form, the stabilizer is selected from

[0069] A mixture of compound (8) and compound (11); and

[0070] A mixture of compound (9) and compound (11).

[0071] In another preferred form, the stabilizer is selected from

[0072] A mixture of compound (8) and compound (12); and

[0073] A mixture of compound (9) and compound (12).

[0074] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (10).

[0075] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (11).

[0076] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (12).

[0077] In another preferred form, the stabilizer is selected from a mixture of compound (9) and compound (10).

[0078] In another preferred form, the stabilizer is selected from a mixture of compound (9) and compound (11).

[0079] In another preferred form, the stabilizer is selected from a mixture of compound (9) and compound (12).

[0080] In another preferred form, the stabilizer is selected from

[0081] A mixture of compound (8) and compound (10),

[0082] A mixture of compound (8) and compound (11), or

[0083] A mixture of compound (9) and compound (12).

[0084] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (10), wherein the weight ratio is 30:1 to 1:1, preferably 20:1 to 3:1.

[0085] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (11), wherein the weight ratio is 30:1 to 1:1, preferably 20:1 to 3:1.

[0086] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (12), wherein the weight ratio is 30:1 to 1:1, preferably 20:1 to 3:1.

[0087] In another preferred form, the stabilizer is selected from a mixture of compound (9) and compound (10), wherein the weight ratio is 30:1 to 1:1, preferably 20:1 to 3:1.

[0088] In another preferred form, the stabilizer is selected from a mixture of compound (9) and compound (11), wherein the weight ratio is 30:1 to 1:1, preferably 20:1 to 3:1.

[0089] In another preferred form, the stabilizer is selected from a mixture of compound (9) and compound (12), wherein the weight ratio is 30:1 to 1:1, preferably 20:1 to 3:1.

[0090] The shaped polymer articles generally contain 0.01 to 5 wt%, preferably 0.1 to 3 wt% of each of these stabilizers.

[0091] The shaped polymer articles generally contain a total amount of 0.01 to 5 wt%, preferably 0.1 to 3 wt% of stabilizers.

[0092] The stabilizer is typically present within the shaped polymer article, for example, the stabilizer is uniformly distributed within the shaped polymer article. In another form, the stabilizer is typically incorporated into the shaped polymer article, for example, the stabilizer is uniformly incorporated into the shaped polymer article.

[0093] The artificial UV-C light may have a wavelength of 100 to 290 nm, preferably 200 to 275 nm. For example, the UV-C light has a wavelength of 250-260 nm, or 220-230 nm, or 210-220 nm, or 260-270 nm, or 200-220 nm.

[0094] UV-C light is artificial, which generally means it is produced by a lamp, such as a mercury lamp, an excimer lamp, a pulsed xenon lamp, or a light-emitting diode (LED).

[0095] Degradation is usually induced by UV-C disinfection targeting microorganisms of molded polymer articles. UV-C disinfection is a method of disinfecting surfaces by irradiating them with artificial UV-C light.

[0096] UV-C disinfection typically results in the reduction of microorganisms such as archaea, bacteria, fungi, protozoa or viruses. When microorganisms are exposed to UV-C light, the cell nucleus may be altered due to the photolysis process. Thus, cell division and, in turn, reproduction may be prevented.

[0097] Examples of bacteria are the following genera: Chlamydia, Clostridium, Escherichia, Helicobacterium, Lactobacillus, Legionella, Leuconostoc, Listeria, Pediococcus, Salmonella, Shigella, Staphylococcus, Vibrio and Yersinia.

[0098] Examples of fungi are the following genera: Aspergillus, Penicillium, Saccharomyches and Candida.

[0099] Examples of viruses are the following genera and groups: coronavirus (e.g., SARS-CoV-1 (severe acute respiratory syndrome coronavirus), MERS-CoV (Middle East respiratory syndrome coronavirus), SARS-CoV-2), rotavirus, norovirus, human papillomavirus, herpes virus, hepatitis virus, influenza virus and HIV.

[0100] UV-C disinfection of surfaces generally requires high intensity UV-C light, and the lamp is typically close to the surface to keep it free of microorganisms.

[0101] The dosage of UV-C light generally determines the effectiveness of UV-C disinfection.

[0102] The dose is the product of the UV intensity (expressed as energy per unit surface area, e.g., microwatts per square centimeter) and the exposure time (e.g., seconds). The dose is usually expressed as 1 mJ / cm2 = 1000 microwatt seconds per square centimeter.

[0103] According to the literature, the dose range for 90% killing of most bacteria and viruses is usually between 2,000 and 8,000 μW·s / cm2. Some typical doses (mJ / cm2) for controlling certain microorganisms can be found in the literature:

[0104]

[0105] Typically, the surface of the shaped polymer article receives a dose of at least 100, 500, 1000, 1500, 2000, 3000, or 5000 μW·s / cm2 of UV-C light within 24 hours. For example, the surface receives a dose of at least 500 μW·s / cm2 per day, such as surfaces in subways, which are disinfected with UV-C light every morning, or surfaces in taxis, which are disinfected with a dose of UV-C light after each passenger during the day.

[0106] Degradation caused by UV-C light, preferably induced by UV-C disinfection, is typically induced frequently, such as at least once a second, a minute, an hour, a day, or a week. The term "frequently" generally means at certain time intervals.

[0107] The degradation caused by UV-C light is usually induced indoors, such as in public buildings (e.g., schools, hospitals, libraries), industrial offices (open offices, cubicles), industrial production buildings (warehouses, assembly halls), private buildings (single-family houses, multi-storey houses, skyscrapers), or indoors in transport vehicles (cars, taxis, buses, trams, subways, trains, airplanes, ships). Preferably, the degradation caused by UV-C light is induced indoors in public buildings or transport vehicles.

[0108] The shaped polymer article is typically an article present indoors, such as in public buildings (e.g., schools, hospitals, libraries), industrial offices (open offices, cubicles), industrial production buildings (warehouses, assembly halls), private buildings (single-family homes, multi-storey homes, skyscrapers), or in the interior of transport vehicles (cars, taxis, buses, trams, subways, trains, airplanes, ships). Preferably, the shaped polymer article is present indoors in a public building or a transport vehicle.

[0109] Suitable shaped polymer articles are:

[0110] - Articles in transport vehicles, for example, dashboards, hat racks, seats, trunk linings, interior linings, dashboard panes, dashboards, interior trim, door panels, seat backs, pillar covers, fasteners, consoles, dashboards, seats, frames, housings;

[0111] - general purpose appliances, for example, boxes and housings, electronic devices (personal computers, telephones, portable mobile phones, printers, televisions, audio and video devices), or electrical appliances (for example, washing machines, drums, ovens (microwave ovens), dishwashers, blenders and irons);

[0112] - Bathroom products, such as portable toilets, shower cubicles, toilet seats, covers, sinks, shower curtains, brushes, mats, bathtubs, portable toilets, toothbrushes and bedpans;

[0113] - fabrics, for example, carpets, curtains, blinds, nets, ropes, cables, cords, threads, threads, clothes, underwear, gloves, shoes, sportswear, umbrellas, tents, air mattresses, bags;

[0114] - Storage systems such as boxes (crates), suitcases, bottles, cabinets, household boxes, pallets, containers, racks, rails, screw boxes, packages and jars.

[0115] -Medical devices such as plungers, plastic syringes, ophthalmic applications, diagnostic devices, and packaging for drug blisters.

[0116] - furniture, for example, foam products (cushions, buffers), dishcloths, mats, chairs, tables, sofas;

[0117] -Office supplies, e.g., ballpoint pens, stamps, mice, racks, rails.

[0118] Preferably, the shaped polymeric article is an article in a transportation vehicle or a medical device.

[0119] Shaped polymer articles are generally opaque articles.

[0120] Shaped polymer articles generally have, at least in part, a non-porous surface.

[0121] Typically, the non-porous surfaces of shaped polymeric articles are stabilized against degradation.

[0122] Typically, the opaque surface of a shaped polymeric article is stabilized against degradation.

[0123] Stabilization against degradation usually involves

[0124] Reduction of yellowing of molded articles, or

[0125] Reduction of microcracks on the surface of molded articles, or

[0126] Reduction of blooming of molded articles.

[0127] The reduction can be determined by comparison to a shaped polymer article without the stabilizer.The stabilizer can stabilize the areas of the shaped article that are exposed to the UV-C light.

[0128] Shaped polymer articles are often made from synthetic polymers. Examples of synthetic polymers are:

[0129] 1. Polymers of monoolefins and dienes, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or poly-butadiene, polyhexene, polyoctene, and polymers of cycloolefins, for example cyclopentene, cyclohexene, cyclooctene or norbornene, polyethylene (which may optionally be crosslinked), for example high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0130] Polyolefins, ie polymers of monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be prepared by different processes and in particular by the following process:

[0131] a) Free radical polymerization (usually under high pressure and at elevated temperature).

[0132] b) Catalytic polymerization using a catalyst which generally contains one or more than one metal of group IVb, Vb, VIb or VIII of the periodic table. These metals generally have one or more than one ligand, typically oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be π-coordinated or σ-coordinated. These metal complexes may be in free form or fixed on a substrate, typically on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst itself may be used in the polymerization, or another activator may be used, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide or metal alkyloxane, the metal being an element of group Ia, IIa and / or IIIa of the periodic table. The activator may conveniently be modified with another ester, ether, amine or silyl ether group. These catalyst systems are often referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0133] 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, mixtures of polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).

[0134] 3. Copolymers of monoolefins and dienes with each other or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), very low density polyethylene, propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinyl cyclohexane copolymers, ethylene / cyclic olefin copolymers (e.g. ethylene / norbornene like COC), ethylene / 1-olefin copolymers (wherein the 1-olefin is generated in situ); propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinyl cyclohexane copolymers, ethylene / propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

[0135] 4. Hydrocarbon resins (eg C5-C9), including hydrogenated modifications thereof (eg tackifiers) and mixtures of polyalkylenes and starches.

[0136] Homopolymers and copolymers from 1.) to 4.) may have any stereostructure, including syndiotactic, isotactic, hemi-isotactic or atactic; atactic polymers are preferred. Stereoblock polymers are also included. Copolymers from 1.) to 4.) may be random or block copolymers, homogeneous or heterogeneous, or highly crystalline homopolymers.

[0137] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0138] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers, including styrene, α-methylstyrene, all isomers of vinyl toluene (especially p-vinyl toluene), ethyl styrene, propyl styrene, vinyl biphenyl, all isomers of vinyl naphthalene and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure, including syndiotactic, isotactic, hemi-isotactic or atactic; atactic polymers are preferred. Stereoblock polymers are also included.

[0139] 6a. Copolymers comprising the above vinyl aromatic monomers and a comonomer selected from the group consisting of ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic acid derivatives and mixtures thereof, such as styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (interpolymers), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact mixtures of styrene copolymers and another polymer such as a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / isoprene / butadiene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene, HIPS, ABS, ASA, AES.

[0140] 6b. Hydrogenated aromatic polymers derived from hydrogenation of the polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, usually referred to as polyvinylcyclohexane (PVCH).

[0141] 6c. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers mentioned under 6a.).

[0142] Homopolymers and copolymers may have any stereostructure, including syndiotactic, isotactic, hemi-isotactic or atactic; atactic polymers are preferred. Stereoblock polymers are also included.

[0143] 7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on poly(alkyl acrylates) or poly(alkyl methacrylates), styrene and acrylonitrile on acrylate / butadiene copolymers, and mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0144] 8. Halogen-containing polymers, such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and vinyl chloride, homopolymers and copolymers of epichlorohydrin, in particular polymers of halogen-containing vinyl compounds, for example polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers. The polyvinyl chloride may be rigid or flexible (plasticized).

[0145] 9. Polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; poly(methyl methacrylate) impact-modified with butyl acrylate, polyacrylamide and polyacrylonitrile.

[0146] 10. Copolymers of the monomers mentioned under 9) with one another or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

[0147] 11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; and copolymers thereof with the olefins mentioned above under 1).

[0148] 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with diglycidyl ethers.

[0149] 13. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0150] 14. Polyphenylene ethers and polyphenylene sulfides and mixtures of polyphenylene ethers with styrene polymers or polyamides.

[0151] 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof. Polyurethanes formed by the reaction of (1) diisocyanates with short-chain diols (chain extenders) and (2) diisocyanates with long-chain diols (thermoplastic polyurethanes, TPU).

[0152] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6 / 6, 6 / 10, 6 / 9, 6 / 12, 4 / 6, 12 / 12, polyamide 11, polyamide 12, aromatic polyamides starting from meta-xylene diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic acid or / and terephthalic acid with or without elastomers as modifiers , such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as block copolymers with polyethylene glycol, polypropylene glycol or polybutylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). The polyamides may be amorphous.

[0153] 17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

[0154] 18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones or lactides, for example polyethylene terephthalate (PET), polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polytrimethylene terephthalate, polyalkylene naphthalates and polyhydroxybenzoates, and copolyetheresters derived from hydroxyl-terminated polyethers, and also polyesters modified with polycarbonate or MBS. Copolyesters may include, for example - but not limited to - polybutylene succinate / terephthalate, polybutylene adipate / terephthalate, polytetramethylene adipate / terephthalate, polybutylene succinate / adipate, polybutylene succinate / butylene carbonate, poly-3-hydroxybutyrate / octanoate copolymers, poly-3-hydroxybutyrate / hexanoate / decanoate terpolymers. Furthermore, aliphatic polyesters may include, for example but not limited to, poly(hydroxyalkanoates), in particular poly(propiolactone), poly(butyrolactone), poly(neopentalactone), poly(valerolactone) and poly(caprolactone), polyethylene succinate, polypropylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene furanoate and polylactic acid (PLA) and corresponding polyesters modified with polycarbonate or MBS. The term "polylactic acid (PLA)" means any of homopolymers of preferably poly-L-lactide and its blends or admixtures with other polymers; copolymers of lactic acid or lactide with other monomers such as hydroxy-carboxylic acids, such as, for example, glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6-hydroxy-hexanoic acid and cyclic forms thereof; the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, i.e., L-lactide, D-lactide, meso-lactide and any mixtures thereof. Preferred polyesters are PET, PET-G, PBT.

[0155] 19. Polycarbonates and polyester carbonates. Polycarbonates are preferably prepared by reaction of bisphenol compounds with carbonic acid compounds, in particular phosgene, or in the melt transesterification process, diphenyl carbonate or dimethyl carbonate. Homopolycarbonates based on bisphenol A and copolycarbonates based on the monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) are particularly preferred. These and further bisphenols and diol compounds which can be used for the synthesis of polycarbonates are disclosed in particular in WO 08037364 (page 7, line 21 to page 10, line 5), EP 1582549 (

[0018] to

[0034] ), WO 02026862 (page 2, line 23 to page 5, line 15), WO 05113639 (page 2, line 1 to page 7, line 20). The polycarbonates may be linear or branched. Mixtures of branched and unbranched polycarbonates can also be used. Suitable branching agents for polycarbonates are known from the literature and are described, for example, in the patent specifications US 4185009 and DE 2500092 (3,3-bis-(4-hydroxyaryl-oxindole according to the invention, in each case see the entire document), DE 4240313 (see page 3, lines 33 to 55), DE 19943642 (see page 5, lines 25 to 34) and US 5367044 and the literature cited therein. The polycarbonates used may additionally be inherently branched, without adding branching agents in the context of the polycarbonate preparation. Examples of inherent branching are so-called Fries structures, as described in EP 4240313. Chain terminators can additionally be used in the polycarbonate preparation as disclosed in 1506249 for melt polycarbonates. Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof are preferably used as chain terminators. Polyester carbonates are obtained by reacting the bisphenols already mentioned, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone-dicarboxylic acid. A portion of the carbonate groups in the polycarbonate, up to 80 mol-%, preferably 20 to 50 mol-%, can be replaced by aromatic dicarboxylic acid ester groups.

[0156] 20. Polyketone.

[0157] 21. Polysulfone, polyethersulfone and polyetherketone.

[0158] 22. Crosslinked polymers derived from aldehydes on the one hand and from phenols, ureas and melamine on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

[0159] 23. Drying and non-drying alkyd resins.

[0160] 24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinkers, and also their low-flammability halogen-containing modifications.

[0161] 25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

[0162] 26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

[0163] 27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example the products of the diglycidyl ethers of bisphenol A, bisphenol E and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines with or without accelerators.

[0164] 28. Natural polymers, such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers, such as methylcellulose; and rosin and its derivatives.

[0165] 29. Blends of the abovementioned polymers (polymer blends), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0166] 30. Naturally occurring and synthetic organic materials, which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratio (typically those used as spinning compositions) and aqueous emulsions of such materials.

[0167] 31. Aqueous emulsions of natural or synthetic rubber, for example natural latex or latices of carboxylated styrene / butadiene copolymers.

[0168] 32. Adhesives, for example block copolymers such as SIS, SBS, SEBS, SEPS (S stands for styrene, I stands for isoprene, B stands for polybutadiene, EB stands for ethylene / butylene block, EP stands for polyethylene / polypropylene block).

[0169] 33. Rubbers, for example polymers of conjugated dienes, for example polybutadiene or polyisoprene, copolymers of monoolefins and dienes with each other or with other vinyl monomers, copolymers of styrene or α-methylstyrene with dienes or with acrylic acid derivatives, chlorinated rubber, natural rubber.

[0170] 34. Elastomers, for example natural polyisoprene (cis-1,4-polyisoprene natural rubber (NR) and trans-1,4-polyisoprene gutta-percha), synthetic polyisoprene (IR for isoprene rubber), polybutadiene (BR for butadiene rubber), chloroprene rubber (CR), polychloroprene, chloroprene rubber, Baypren, etc.; butyl rubber (copolymer of isobutylene and isoprene, IIR), halogenated butyl rubber (chlorobutyl rubber: CIIR; bromobutyl rubber: BIIR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), also known as Buna N rubber hydrogenated nitrile rubber (HNBR) Therban and Zetpol; EPM (ethylene propylene rubber, copolymer of ethylene and propylene) and EPDM rubber (ethylene propylene diene rubber, a terpolymer of ethylene, propylene and diene components), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluorosilicone rubber (FVMQ), fluoroelastomers (FKM and FEPM) Viton, Tecnoflon, Fluorel, Aflas and Dai-El; perfluoroelastomers (FFKM) Tecnoflon PFR, Kalrez, Chemraz, Perlast; polyether block amide (PEBA), chlorosulfonated polyethylene (CSM), (Hypalon), ethylene vinyl acetate (EVA), thermoplastic elastomers (TPE), knotty elastin and elastin, polysulfide rubber, elastic olefins, elastic fibers used in fabric production.

[0171] 35. Thermoplastic elastomers, for example styrenic block copolymers (TPE-s), thermoplastic olefins (TPE-o), elastomeric blends (TPE-v or TPV), thermoplastic polyurethanes (TPU), thermoplastic copolyesters, thermoplastic polyamides, reactor TPO (R-TPO), polyolefin plastomers (POP), polyolefin elastomers (POE).

[0172] Preferred synthetic polymers are polymers of classes 1, 5, 6, 6a, 6b, 6c, 7, 8, 16, 18 and 19 above.

[0173] In another preferred form, the synthetic polymer is polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene, or polycarbonate.

[0174] In another preferred form, the synthetic polymer is polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyvinyl chloride, polyamide, polyurethane, poly(methyl methacrylate) or polyethylene terephthalate.

[0175] In another preferred form, the synthetic polymer is polyethylene, polypropylene, poly(methyl methacrylate), polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyvinyl chloride, polyamide, polyurethane, or polyethylene terephthalate.

[0176] In another preferred form, the synthetic polymer is polyethylene, polypropylene, acrylonitrile butadiene styrene, polyurethane, poly(methyl methacrylate).

[0177] In another preferred form, the synthetic polymer is polyethylene.

[0178] In another preferred form, the synthetic polymer is polypropylene.

[0179] In another preferred form, the synthetic polymer is polystyrene.

[0180] In another preferred form, the synthetic polymer is acrylonitrile butadiene styrene copolymer.

[0181] In another preferred form, the synthetic polymer is polycarbonate.

[0182] In another preferred form, the synthetic polymer is polyvinyl chloride.

[0183] In another preferred form, the synthetic polymer is a polyamide.

[0184] In another preferred form, the synthetic polymer is polyethylene terephthalate.

[0185] In another preferred form, the synthetic polymer is polyurethane.

[0186] In another preferred form, the synthetic polymer is poly(methyl methacrylate).

[0187] Preferably, the synthetic polymer is polypropylene or polyvinyl chloride and the shaped article is an article in a transportation vehicle, such as an instrument panel.

[0188] In another preferred form, the synthetic polymer is a polyurethane and the shaped article is an article for use in a transportation vehicle, such as a steering wheel.

[0189] In another preferred form, the synthetic polymer is polyethylene terephthalate and the shaped article is an article for use in transportation vehicles, such as a fiber for upholstery or interior linings.

[0190] In another preferred form, the stabilizer is compound (2) and the shaped polymer article is made of a polyolefin such as polypropylene.

[0191] In another preferred form, the stabilizer is compound (2) and the shaped polymer article is made of a polyolefin such as polypropylene, and the shaped polymer article comprises 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0192] In another preferred form, the stabilizer is compound (1) and the shaped polymer article is made from acrylonitrile butadiene styrene copolymer.

[0193] In another preferred form, the stabilizer is compound (2) and the shaped polymer article is made from acrylonitrile butadiene styrene copolymer.

[0194] In another preferred form, the stabilizer is compound (4) and the shaped polymer article is made from acrylonitrile butadiene styrene copolymer.

[0195] In another preferred form, the stabilizer is compound (6) and the shaped polymer article is made from acrylonitrile butadiene styrene copolymer.

[0196] In another preferred form, the stabilizer is compound (1), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and the shaped polymer article contains 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0197] In another preferred form, the stabilizer is compound (2), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and the shaped polymer article contains 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0198] In another preferred form, the stabilizer is compound (4), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and the shaped polymer article contains 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0199] In another preferred form, the stabilizer is compound (6), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and the shaped polymer article contains 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0200] In another preferred form, the stabilizer is a mixture of compound (1) and compound (13) and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer.

[0201] In another preferred form, the stabilizer is a mixture of compound (2) and compound (13) and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer.

[0202] In another preferred form, the stabilizer is a mixture of compound (4) and compound (13) and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer.

[0203] In another preferred form, the stabilizer is a mixture of compound (6) and compound (13) and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer.

[0204] In another preferred form, the stabilizer is a mixture of compound (1) and compound (13), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and wherein the weight ratio is 10:1 to 1:10, 5:1 to 1:5, or 3:1 to 1:3.

[0205] In another preferred form, the stabilizer is a mixture of compound (2) and compound (13), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and wherein the weight ratio is 10:1 to 1:10, 5:1 to 1:5, or 3:1 to 1:3.

[0206] In another preferred form, the stabilizer is a mixture of compound (4) and compound (13), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and wherein the weight ratio is 10:1 to 1:10, 5:1 to 1:5, or 3:1 to 1:3.

[0207] In another preferred form, the stabilizer is a mixture of compound (6) and compound (13), and the shaped polymer article is made of acrylonitrile butadiene styrene copolymer, and wherein the weight ratio is 10:1 to 1:10, 5:1 to 1:5, or 3:1 to 1:3.

[0208] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polyethylene.

[0209] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10) and the shaped polymer article is made of a polyolefin such as polyethylene.

[0210] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and the shaped polymer article is made of a polyolefin such as polyethylene.

[0211] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 10:1 to 1:5, or 5:1 to 1:1.

[0212] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 10:1 to 1:5, or 5:1 to 1:1.

[0213] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 10:1 to 1:5, or 5:1 to 1:1.

[0214] In another preferred form, the stabilizer is compound (3) and the shaped polymer article is made of a polyolefin such as polyethylene.

[0215] In another preferred form, the stabilizer is compound (4) and the shaped polymer article is made of a polyolefin such as polyethylene.

[0216] In another preferred form, the stabilizer is compound (5) and the shaped polymer article is made of a polyolefin such as polyethylene.

[0217] In another preferred form, the stabilizer is compound (7) and the shaped polymer article is made of a polyolefin such as polyethylene.

[0218] In another preferred form, the stabilizer is compound (3) and the shaped polymer article is made of a polyolefin such as polyethylene, and the shaped polymer article comprises 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0219] In another preferred form, the stabilizer is compound (4) and the shaped polymer article is made of a polyolefin such as polyethylene, and the shaped polymer article comprises 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0220] In another preferred form, the stabilizer is compound (5) and the shaped polymer article is made of a polyolefin such as polyethylene, and the shaped polymer article comprises 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0221] In another preferred form, the stabilizer is compound (7) and the shaped polymer article is made of a polyolefin such as polyethylene, and the shaped polymer article contains 0.01-1 wt%, preferably 0.01-0.5 wt% of the stabilizer.

[0222] In another preferred form, the stabilizer is a mixture of compound (5) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polyethylene.

[0223] In another preferred form, the stabilizer is a mixture of compound (7) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polyethylene.

[0224] In another preferred form, the stabilizer is a mixture of compound (5) and compound (11), and the shaped polymer article is made of a polyolefin such as polyethylene.

[0225] In another preferred form, the stabilizer is a mixture of compound (7) and compound (11), and the shaped polymer article is made of a polyolefin such as polyethylene.

[0226] In another preferred form, the stabilizer is a mixture of compound (5) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 20:1 to 1:1, or 20:1 to 5:1.

[0227] In another preferred form, the stabilizer is a mixture of compound (7) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 20:1 to 1:1, or 20:1 to 5:1.

[0228] In another preferred form, the stabilizer is a mixture of compound (5) and compound (11), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 20:1 to 1:1, or 20:1 to 5:1.

[0229] In another preferred form, the stabilizer is a mixture of compound (7) and compound (11), and the shaped polymer article is made of a polyolefin such as polyethylene, and wherein the weight ratio is 20:1 to 1:1, or 20:1 to 5:1.

[0230] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polypropylene.

[0231] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10) and the shaped polymer article is made of a polyolefin such as polypropylene.

[0232] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and the shaped polymer article is made of a polyolefin such as polypropylene.

[0233] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of a polyolefin such as polypropylene, and wherein the weight ratio is 20:1 to 1:1, or 15:1 to 4:1.

[0234] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), and the shaped polymer article is made of a polyolefin such as polypropylene, and wherein the weight ratio is 20:1 to 1:1, or 15:1 to 4:1.

[0235] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and the shaped polymer article is made of a polyolefin such as polypropylene, and wherein the weight ratio is 20:1 to 1:1, or 15:1 to 4:1.

[0236] In another preferred form, the stabilizer is compound (2) and the shaped polymer article is made of poly(methyl methacrylate).

[0237] In another preferred form, the stabilizer is compound (3) and the shaped polymer article is made of poly(methyl methacrylate).

[0238] In another preferred form, the stabilizer is compound (4) and the shaped polymer article is made of poly(methyl methacrylate).

[0239] In another preferred form, the stabilizer is compound (6) and the shaped polymer article is made of poly(methyl methacrylate).

[0240] In another preferred form, the stabilizer is compound (2) and the shaped polymer article is made of poly(methyl methacrylate), and the shaped polymer article contains 0.1-5 wt%, preferably 0.3-3 wt% of the stabilizer.

[0241] In another preferred form, the stabilizer is compound (3) and the shaped polymer article is made of poly(methyl methacrylate), and the shaped polymer article contains 0.1-5 wt%, preferably 0.3-3 wt% of the stabilizer.

[0242] In another preferred form, the stabilizer is compound (4) and the shaped polymer article is made of poly(methyl methacrylate), and the shaped polymer article contains 0.1-5 wt%, preferably 0.3-3 wt% of the stabilizer.

[0243] In another preferred form, the stabilizer is compound (6) and the shaped polymer article is made of poly(methyl methacrylate), and the shaped polymer article contains 0.1-5 wt%, preferably 0.3-3 wt% of the stabilizer.

[0244] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate).

[0245] In another preferred form, the stabilizer is a mixture of compound (3) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate).

[0246] In another preferred form, the stabilizer is a mixture of compound (4) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate).

[0247] In another preferred form, the stabilizer is a mixture of compound (6) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate).

[0248] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate).

[0249] In another preferred form, the stabilizer is a mixture of compound (3) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate).

[0250] In another preferred form, the stabilizer is a mixture of compound (4) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate).

[0251] In another preferred form, the stabilizer is a mixture of compound (6) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate).

[0252] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0253] In another preferred form, the stabilizer is a mixture of compound (3) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0254] In another preferred form, the stabilizer is a mixture of compound (4) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0255] In another preferred form, the stabilizer is a mixture of compound (6) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0256] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0257] In another preferred form, the stabilizer is a mixture of compound (3) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0258] In another preferred form, the stabilizer is a mixture of compound (4) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0259] In another preferred form, the stabilizer is a mixture of compound (6) and compound (11), and the shaped polymer article is made of poly(methyl methacrylate), and wherein the weight ratio is 100:1 to 1:1, or 70:1 to 5:1, or 50:1 to 10:1.

[0260] In another preferred form, the stabilizer is compound (6) and the shaped polymer article is made of polyurethane.

[0261] In another preferred form, the stabilizer is compound (6), and the shaped polymer article is made of polyurethane, and the shaped polymer article contains 0.1-5 wt%, preferably 0.3-3 wt% of the stabilizer.

[0262] In another preferred form, the stabilizer is a mixture of compound (9) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of polyurethane.

[0263] In another preferred form, the stabilizer is a mixture of compound (9) and compound (12), and the shaped polymer article is made of polyurethane.

[0264] In another preferred form, the stabilizer is a mixture of compound (9) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of polyurethane, and wherein the weight ratio is 20:1 to 1:1, or 10:1 to 1:1, or 8:1 to 2:1.

[0265] In another preferred form, the stabilizer is a mixture of compound (9) and compound (12), and the shaped polymer article is made of polyurethane, and wherein the weight ratio is 20:1 to 1:1, or 10:1 to 1:1, or 8:1 to 2:1.

[0266] In another preferred form, the stabilizer is compound (2) and the shaped polymer article is made of polyurethane.

[0267] In another preferred form, the stabilizer is compound (2), and the shaped polymer article is made of polyurethane, and the shaped polymer article comprises 0.1-5 wt%, preferably 0.3-3 wt% of the stabilizer.

[0268] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyl triazine selected from compounds (10), (11) or (12), and the shaped polymer article is made of polyurethane.

[0269] In another preferred form, the stabilizer is a mixture of compound (2) and compound (10), and the shaped polymer article is made of polyurethane.

[0270] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), and the shaped polymer article is made of polyurethane.

[0271] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyl triazine selected from compound (10), (11) or (12), and the shaped polymer article is made of polyurethane, and wherein the weight ratio is 20:1 to 1:1, or 15:1 to 1:1, or 10:1 to 2:1.

[0272] In another preferred form, the stabilizer is a mixture of compound (2) and compound (10), and the shaped polymer article is made of polyurethane, and wherein the weight ratio is 20:1 to 1:1, or 15:1 to 1:1, or 10:1 to 2:1.

[0273] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), and the shaped polymer article is made of polyurethane, and wherein the weight ratio is 20:1 to 1:1, or 15:1 to 1:1, or 10:1 to 2:1.

[0274] The shaped polymer article is prepared or shaped, for example, by one of the following processing steps:

[0275] Injection blow molding, extrusion, blow molding, rotational molding, in-mold decoration (back injection), slush molding, injection molding, co-injection molding, blow molding, forming, compression molding, resin transfer molding, pressing, film extrusion (cast film; blown film), fiber spinning (woven, nonwoven), stretching (uniaxial, biaxial), annealing, deep drawing, calendaring, mechanical transformation, sintering, coextrusion, lamination, cross-linking (radiation, peroxide, silane), vapor deposition, welding together, gluing, vulcanization, thermoforming, tube extrusion, profile extrusion, sheet extrusion; sheet casting, lap splicing, foaming, recycling / remaking, visbreaking (peroxide, thermal), fiber meltblowing, spunbonding, surface treatment (corona discharge, combustion, plasma), sterilization (by gamma rays, electron beam), tape extrusion, pultrusion, SMC processing or plastisol.

[0276] The shaped polymer article may be an extruded, molded or calendered shaped polymer article.

[0277] The shaped polymer article can have any shape, such as film, foil, fiber, fabric, plate, device.

[0278] Examples

[0279] Example 1: Polypropylene compression molded film

[0280] PP / TPO(Borealis EE013AE) was formulated with 0.1% of a blend of 80% tris(2,4-di-tert-butylphenyl)phosphite and 20% octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 0.05% calcium stearate, and the additives listed in Table 1. The listed formulation components were premixed in a high-speed mixer. The well-blended formulation was melt compounded in a Collin ZK25 x 42D twin-screw extruder at a set temperature of 230°C and 160 rpm under nitrogen. The pelletized sample was compression molded in a press at 230°C for 3 minutes to form a 170 micron thick film.

[0281] UV-C aging device: The samples were exposed to UV-C radiation in a climate chamber equipped with 2 stainless steel lamp stands housing 5 UVC 253.7 nm emitting lamps TUV T8F17 1SL / 25 from Signify GmbH, Hamburg, Germany. The sample holder was located 57 cm below the lamp stand and the sample was placed only in the center of the sample stand (30×40 cm). The conditions in the chamber were maintained at a temperature of 65°C ± 3°C and a relative humidity of 20 ± 10% rh. The irradiance in the range of 250 to 260 nm measured at the level of the sample stand was 7.7 W / m 2 .

[0282] The parameters were measured using a FT-IR spectrophotometer Nicolet iN10MX from Thermo Fisher Scientific Inc. at 1721 cm -1 The intensity change of the C=O absorption (carbonyl absorption) measured at 1 Å is used to measure the oxidative damage in the sample. The time (in hours) to reach a carbonyl value of 0.1 is reported in Table 1.

[0283] Table 1

[0284]

[0285] The data show that samples B and C better stabilize the polymer against degradation induced by artificial UV-C light compared to sample A.

[0286] Example 2: ABS compression molded substrate

[0287] ABS (acrylonitrile butadiene styrene copolymer, Terluran GP-22 from INEOS Styrolution, 100 wt%) was formulated with 0.1 wt% of a blend of 80% tris(2,4-di-tert-butylphenyl)phosphite and 20% octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 0.03 wt% of a hindered amine light stabilizer (N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-diformylhexamethylenediamine, CAS 124172-53-8) in samples B to E and the additives listed in Table 2. Compound (13) is 2-(2-hydroxy-5-methylphenyl)benzotriazole, CAS 2440-22-4.

[0288] The well-blended formulation was dried in a vacuum oven at 80°C for 3 hours and then melt compounded in a Collin ZK25 x42D twin screw extruder at a set temperature of 220°C and 160 rpm under nitrogen. The pelletized sample was dried at 80°C for 3 hours and compression molded in a press at 220°C for 3 minutes to form a 2 mm thick plaque (50×75 mm).

[0289] The substrates were exposed to a UV-C weathering device as described in Example 1. The color change (ΔE) of the substrates with increasing exposure time was tested using a Datacolor 800 spectrophotometer (aperture 20 mm) according to DIN EN ISO / CIE 11664-4. The ΔE values ​​after 12 hours and 18 hours of exposure are summarized in Table 2.

[0290] Table 2

[0291]

[0292] The data show that samples B through E better stabilize the polymer against degradation induced by artificial UV-C light than sample A.

[0293] Example 3: LDPE blown film

[0294] 0.922g / cm 3 A low density polyethylene Riblene FC 30 with a density (ISO 1183) and a melt index (ISO 1133) of 0.25 g / 10 min at 190°C / 2.16 kg was formulated with 1000 ppm of an oligomeric hindered amine light stabilizer (polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol, CAS 65447-77-0) and the additives listed in Table 3.

[0295] Additive loadings are in ppm (parts per million) by weight based on the weight of the polymer. All formulations additionally contained 2000 ppm of erucamide (Crodamide ER-MB-GD) and 1000 ppm of a blend of 80% tris(2,4-di-tert-butylphenyl)phosphite and 20% octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate as antioxidants.

[0296] The additives were blended with the ground polymer powder in a high speed mixer. The well blended formulation was melt compounded in a Berstorff ZE25A x 47D twin screw extruder at a maximum of 200°C, 160 rpm under nitrogen. The pelletized samples were processed into 100 micron thick monolayer films on a laboratory blown film line (Dolci) with a 100 mm die and a set temperature of 180°C.

[0297] As described in Example 1, the film samples were exposed to a UVC weathering device.

[0298] The oxidative damage of polyethylene film samples was measured by the intensity change of C=O absorption (carbonyl absorption) in the IR spectrum. The FT-IR spectrophotometer Nicolet iN10MX from Thermo Fisher Scientific was used at 1721 cm -1 The time (in hours) to reach a carbonyl value of 0.1 is reported in Table 3.

[0299] Table 3

[0300]

[0301] The data show that samples C and D with lower amounts of compound (8) better stabilize the polymer against degradation induced by artificial UV-C light than sample A and sample B with even higher amounts of compound (8).

[0302] Example 4: LDPE blown film

[0303] Low-density polyethylene (0.922 g / cm 3 Riblene FC 30 with a density (ISO 1183) and a melt index (ISO 1133) of 0.25 g / 10 min at 190°C / 2.16 kg) was formulated with 3000 ppm of a blocked oligomeric hindered amine light stabilizer (polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine and N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, CAS 192268-64-7) and the additives listed in Table 4.

[0304] Additive loadings are reported in ppm (parts per million) by weight based on the weight of the polymer.

[0305] The additives were blended with the ground polymer powder in a high speed mixer. The well blended formulation was melt compounded in a Berstorff ZE25A x 47D twin screw extruder at a maximum of 200°C, 160 rpm under nitrogen. The pelletized samples were processed into 5 layers of 100 micron thick films (30 / 5 / 30 / 5 / 30) on a laboratory blown film line (Collin BL) with an 80 mm die and a set temperature of 210°C.

[0306] As described in Example 1, the film samples were exposed to a UV-C weathering device.

[0307] The oxidative damage of polyethylene film samples was measured by the intensity change of C=O absorption (carbonyl absorption) in the IR spectrum. The FT-IR spectrophotometer Nicolet iN10MX from Thermo Fisher Scientific was used at 1721 cm -1 The time (in hours) to reach a carbonyl value of 0.1 is reported in Table 4.

[0308] Table 4

[0309]

[0310] The data show that samples B, C, D, and F better stabilize the polymer against degradation induced by artificial UV-C light than sample A.

[0311] The data show that Sample E with a lower amount of Compound (7) better stabilizes the polymer against degradation induced by artificial UV-C light than Sample A and Sample D with even a higher amount of Compound (7).

[0312] The data show that Sample G with a lower amount of Compound (5) better stabilizes the polymer against degradation induced by artificial UV-C light than Sample A and Sample F with even a higher amount of Compound (5).

[0313] Example 5: Polypropylene Compression Molded Substrate

[0314] A polypropylene homopolymer (Moplen HP500N) was mixed with 0.1% 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (CAS 27676-62-6), 0.1% tris(2,4-di-tert-butylphenyl)phosphite, 0.145% of the reaction product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine and N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (CAS 192268-64-7) and 0.07% N,N'-Bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-diformylhexamethylenediamine (CAS 124172-53-8) and the additives listed in Table 5 were prepared together.

[0315] The listed formulation components were premixed in a high speed mixer. The well blended formulation was melt compounded in a Collin ZK 25 x 42D twin screw extruder at a set temperature of 230°C and 160 rpm under nitrogen. The pelletized samples were injection molded into 1 mm thick plaques (90×85 mm) at 230°C in an Arburg 320S injection molding machine.

[0316] As described in Example 1, the substrate was exposed to a UV-C weathering device.

[0317] The oxidative damage of polyethylene film samples was measured by the intensity change of C=O absorption (carbonyl absorption) in the IR spectrum. The FT-IR spectrophotometer Nicolet iN10MX from Thermo Fisher Scientific was used at 1721 cm -1 The time (in hours) to reach a carbonyl value of 0.1 is reported in Table 5.

[0318] Table 5

[0319]

[0320] The data show that samples B and C (both with lower amounts of compound (8)) better stabilize the polymer against degradation induced by artificial UV-C light than sample A with a higher amount of compound (8).

[0321] Example 6: PMMA solution cast film

[0322] The film was prepared as follows: 10 g of amorphous thermoplastic polymethyl methacrylate ( 7N) was dissolved in 40 g of methyl chloride together with 0.1 g of a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine and N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (CAS 192268-64-7) as an alkaline stabilizer for the integrity of the prepared membrane and 0.103 g of the compounds listed in Table 6.

[0323] The film was stretched with the aid of an automatic blade (Erichsen) at a blade speed of 12 mm / s and a gap height of 120 mm.

[0324] The films were exposed to a UV-C weathering device as described in Example 1. The time (in hours) to film embrittlement is reported in Table 6.

[0325] Table 6

[0326]

[0327] The data demonstrate that Samples A, C, E, and G stabilize the polymer against degradation induced by artificial UV-C light.

[0328] The data also shows that samples B, D, F and H (all with lower amounts of the first additive) better stabilize the polymer against degradation induced by artificial UV-C light than samples A, C, E and G, respectively, with higher amounts of the first additive.

[0329] Example 7: TPU substrate

[0330] Aromatic thermoplastic polyurethane TPU (from Covestro) 385S) was formulated with 0.27% ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (CAS 36443-68-2), 0.17% bis-(2,4-di-tert-butylphenol)pentaerythritol diphosphite, 0.8% polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinolethanol (CAS 65447-77-0) and the additives listed in Table 7.

[0331] The polymer was dried at 80°C under nitrogen and vacuum to a level below 0.05% water before mixing. The listed formulation components were premixed in a high-speed mixer. The well-blended formulation was directly melt compounded in a Berstorff ZE25A x47D twin-screw extruder at a set temperature of 210°C and 160rpm under nitrogen. The pelletized sample was air dried at 80°C for 4 hours (water content below 0.03%) and injection molded into 2 mm thick plaques (44×68 mm) at 210°C in an Engel e-mac 100 injection molding machine.

[0332] The substrates were exposed to a UV-C weathering device as described in Example 1. The time (in hours) at which the substrates had a ΔE value = 12 is reported in Table 7.

[0333] Table 7

[0334]

[0335] The data show that Sample B better stabilizes the polymer against degradation induced by artificial UV-C light compared to Sample A.

[0336] The data show that Sample C better stabilizes the polymer against degradation induced by artificial UV-C light compared to Sample A.

[0337] Example 8: TPU substrate

[0338] Aromatic TPU (from BASF) 1185A 10000) was formulated with 1.0% of a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol (CAS 65447-77-0) and the additives listed in Table 8.

[0339] The polymer was dried at 80°C under nitrogen and vacuum to a level below 0.02% water before mixing. The listed formulation components were premixed in a high-speed mixer. The well-blended formulation was directly melt compounded in a Berstorff ZE25A x47D twin-screw extruder at a set temperature of 205°C and 160rpm under nitrogen. The pelletized sample was air dried at 80°C for 4 hours (water content below 0.02%) and injection molded into 2 mm thick plaques (44×68 mm) at 210°C in an Engel e-mac 100 injection molding machine.

[0340] The substrates were exposed to a UV-C weathering device as described in Example 1. The time (in hours) at which the substrates had a ΔE value = 12 is reported in Table 8.

[0341] Table 8

[0342]

[0343] The data demonstrate that Sample A stabilizes the polymer against degradation induced by artificial UV-C light.

[0344] The data show that samples B, C and D (all with lower amounts of compound (2)) stabilize the polymer even better against degradation induced by artificial UV-C light than sample A with higher amounts of compound (2).

Claims

1. Use of a stabilizer selected from the following for stabilizing a shaped polymer article against degradation induced by artificial UV-C light: Compound (1) Compound (2) Compound (3) Compound (4) Compound (5) Compound (6) Compound (7) Compound (8) A mixture of a hydroxyphenyl triazine selected from the group consisting of compounds (10), (11) or (12) or Compound (9) A mixture with a hydroxyphenyltriazine selected from compound (10), (11) or (12).

2. The use according to claim 1, wherein Degradation by UV-C light is induced frequently, preferably at least once a week.

3. The use according to claim 1 or 2, wherein The stabilizer is present inside the shaped polymer article.

4. The use according to any one of claims 1 to 3, wherein The UV-C light has a wavelength of 200 to 275 nm.

5. The use according to any one of claims 1 to 4, wherein The degradation caused by UV-C light is induced indoors, preferably indoors in public buildings, industrial offices, industrial production buildings, private buildings, or transport vehicles.

6. The use according to any one of claims 1 to 5, wherein The shaped polymer article comprises 0.01-5 wt%, preferably 0.1-3 wt% of each of these stabilizers.

7. The use according to any one of claims 1 to 6, wherein The shaped polymer article is made of a synthetic polymer, preferably polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyvinyl chloride, polyamide, polyurethane, poly(methyl methacrylate) or polyethylene terephthalate.

8. The use according to any one of claims 1 to 7, wherein The weight ratio of the compound (8) or the compound (9) to the hydroxyphenyltriazine selected from the compound (10), (11) or (12) is 100:1 to 1:3, preferably 50:1 to 2:

1.

9. The use according to any one of claims 1 to 8, wherein The degradation caused by UV-C light is induced by UV-C disinfection of the microorganisms of the shaped polymer article.

10. The use according to any one of claims 1 to 9, wherein The surface of the shaped polymer article receives at least 100 μW·s / cm within 24 hours. 2 dosage.

11. The use according to any one of claims 1 to 10, wherein The shaped polymeric article is a film, foil, fiber, fabric, sheet, or device.

12. The use according to any one of claims 1 to 11, wherein The non-porous surface of the shaped polymer article is stabilized against degradation.

13. The use according to any one of claims 1 to 12, wherein The opaque surface of the shaped polymer article is stabilized against degradation.

14. A method for stabilizing shaped polymer articles against degradation induced by artificial UV-C light, the method comprising incorporating into the shaped polymer articles as defined in any one of claims 1 to 13 a stabilizer selected from the stabilizers defined in claim 1.

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