Stabilization of Molded Polymer Articles Against Deterioration Caused by Artificial UV-C Light

Abstract

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

Description

Technical Field

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

Background Art

[0002] Artificial UV-C light is increasingly being used to sterilize polymer articles. As a result, in such polymer articles, an increase in yellowing, microcracking or blooming has been observed. Therefore, there is a need to develop suitable plastic additives that are present in low application amounts, are compatible with other plastic additives, and reduce yellowing, microcracking or blooming.

Summary of the Invention

Means for Solving the Problems

[0003] The object is for Compound (1)

Chemical Formula

Chemical Formula

Chemical Formula

[0004] The object is also achieved by a method of stabilizing a shaped polymer article against degradation caused by artificial UV-C light, the method comprising incorporating a stabilizer into the shaped polymer article. [Embodiments for Carrying Out the Invention]

[0005] In a preferred form, the stabilizer is selected from compound (1).

[0006] In another preferred form, the stabilizer is selected from compound (2).

[0007] In another preferred form, the stabilizer is selected from compound (3).

[0008] In another preferred form, the stabilizer is selected from compound (4).

[0009] In another preferred form, the stabilizer is selected from compound (5).

[0010] In another preferred form, the stabilizer is selected from compound (6).

[0011] In another preferred form, the stabilizer is selected from compound (7).

[0012] In another preferred form, the stabilizer is selected from compound (1), (2), (3), (4), (5), (6) or (7).

[0013] In another preferred form, the stabilizer is selected from compound (2), (3) or (4).

[0014] In another preferred form, the stabilizer is selected from compound (6) or (7).

[0015] Mixtures of stabilizers selected from compound (1), (2), (3), (4), (5), (6) or (7) are also possible. Usually, these mixtures of stabilizers contain two stabilizers. Mixtures of two stabilizers selected from compound (1), (2), (3), (4), (5), (6) or (7) may contain the two stabilizers in a weight ratio of 10:1 to 1:10, preferably 7:1 to 1:7.

[0016] In another preferred form, the stabilizer is selected from a mixture of compound (1) and a further stabilizer selected from compound (2) to (7), and the weight ratio thereof may be 10:1 to 1:10, preferably 7:1 to 1:7.

[0017] In another preferred form, the stabilizer is selected from a mixture of compound (2) and a further stabilizer selected from compounds (1) or (3) to (7), and the weight ratio thereof can be 10:1 to 1:10, preferably 7:1 to 1:7.

[0018] In another preferred form, the stabilizer is selected from a mixture of compound (3) and a further stabilizer selected from compounds (1) to (2) or (4) to (7), and the weight ratio thereof can be 10:1 to 1:10, preferably 7:1 to 1:7.

[0019] In another preferred form, the stabilizer is selected from a mixture of compound (4) and a further stabilizer selected from compounds (1) to (3) or (5) to (7), and the weight ratio thereof can be 10:1 to 1:10, preferably 7:1 to 1:7.

[0020] In another preferred form, the stabilizer is selected from a mixture of compound (5) and a further stabilizer selected from compounds (1) to (4) or (6) to (7), and the weight ratio thereof can be 10:1 to 1:10, preferably 7:1 to 1:7.

[0021] In another preferred form, the stabilizer is selected from a mixture of compound (6) and a further stabilizer selected from compounds (1) to (5) or (7), and the weight ratio thereof can be 10:1 to 1:10, preferably 7:1 to 1:7.

[0022] In another preferred form, the stabilizer is selected from a mixture of compound (7) and a further stabilizer selected from compounds (1) to (6), and the weight ratio thereof can be 10:1 to 1:10, preferably 7:1 to 1:7.

[0023] In another preferred form, the stabilizer is a mixture of compound (7) and compound (11), a mixture of compound (5) and compound (11), a mixture of compound (2) and compound (10), a mixture of compound (2) and compound (11), A mixture of compound (3) and compound (11), a mixture of compound (4) and compound (11), or a mixture of compound (6) and compound (11) is selected from.

[0024] In another preferred form, the stabilizer is selected from a mixture of compound (8) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12).

[0025] In another preferred form, the stabilizer is selected from a mixture of compound (9) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12).

[0026] In another preferred form, the stabilizer is selected from a mixture of compound (8) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the weight ratio thereof is 100:1 to 1:3, preferably 50:1 to 2:1.

[0027] In another preferred form, the stabilizer is selected from a mixture of compound (9) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the weight ratio thereof is 100:1 to 1:3, preferably 50:1 to 2:1.

[0028] In another preferred form, the stabilizer is a mixture of compound (8) and at least one of compounds (10), (11) or (12); and a mixture of compound (9) and at least one of compounds (10), (11) or (12) is selected from.

[0029] In another preferred form, the stabilizer is a mixture of compound (8) and one of compounds (10), (11) or (12); and a mixture of compound (9) and one of compounds (10), (11) or (12) is selected from.

[0030] In another preferred form, the stabilizer is a mixture of compound (8) and at least one of compounds (10), (11) or (12), with a weight ratio of 100:1 to 1:3, preferably 50:1 to 2:1; or a mixture of compound (9) and at least one of compounds (10), (11) or (12), with a weight ratio of 100:1 to 1:3, preferably 50:1 to 2:1 selected from.

[0031] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), and a mixture of compound (9) and compound (10) selected from.

[0032] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and a mixture of compound (9) and compound (11) selected from.

[0033] In another preferred form, the stabilizer is a mixture of compound (8) and compound (12), and a mixture of compound (9) and compound (12) selected from.

[0034] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (10).

[0035] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (11).

[0036] In another preferred form, the stabilizer is selected from a mixture of compound (8) and compound (12).

[0037] In another preferred embodiment, the stabilizer is selected from the mixture of compound (9) and compound (10).

[0038] In another preferred embodiment, the stabilizer is selected from the mixture of compound (9) and compound (11).

[0039] In another preferred embodiment, the stabilizer is selected from the mixture of compound (9) and compound (12).

[0040] In another preferred embodiment, the stabilizer is a mixture of compound (8) and compound (10), a mixture of compound (8) and compound (11), or a mixture of compound (9) and compound (12) selected from.

[0041] In another preferred embodiment, the stabilizer is selected from the mixture of compound (8) and compound (10), and the weight ratio thereof is from 30:1 to 1:1, preferably from 20:1 to 3:1.

[0042] In another preferred embodiment, the stabilizer is selected from the mixture of compound (8) and compound (11), and the weight ratio thereof is from 30:1 to 1:1, preferably from 20:1 to 3:1.

[0043] In another preferred embodiment, the stabilizer is selected from the mixture of compound (8) and compound (12), and the weight ratio thereof is from 30:1 to 1:1, preferably from 20:1 to 3:1.

[0044] In another preferred embodiment, the stabilizer is selected from the mixture of compound (9) and compound (10), and the weight ratio thereof is from 30:1 to 1:1, preferably from 20:1 to 3:1.

[0045] In another preferred embodiment, the stabilizer is selected from the mixture of compound (9) and compound (11), and the weight ratio thereof is from 30:1 to 1:1, preferably from 20:1 to 3:1.

[0046] In another preferred embodiment, the stabilizer is selected from the mixture of compound (9) and compound (12), and the weight ratio thereof is 30:1 to 1:1, preferably 20:1 to 3:1.

[0047] The molded polymer article usually contains each of the stabilizers in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

[0048] The molded polymer article usually contains a total amount of stabilizers in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

[0049] The stabilizer is usually present inside the molded polymer article and is, for example, uniformly distributed inside the molded polymer article. In another form, the stabilizer is usually incorporated into the molded polymer article and is, for example, uniformly incorporated into the molded polymer article.

[0050] Artificial UV-C light can have a wavelength of 100 to 290 nm, preferably 200 to 275 nm. For example, the UV-C light has a wavelength of 250 to 260 nm, or 220 to 230 nm, or 210 to 220 nm, or 260 to 270 nm, or 200 to 220 nm.

[0051] UV-C light is artificial and usually means that it is generated by a lamp such as a mercury lamp, an excimer lamp, a pulsed xenon lamp or a light emitting diode (LED).

[0052] Deterioration is usually caused by UV-C sterilization of the molded polymer article against microorganisms. UV-C sterilization is a method of sterilizing the surface by irradiating the surface with artificial UV-C light.

[0053] UV-C sterilization usually results in a reduction of microorganisms such as archaea, bacteria, fungi, protozoa or viruses. When microorganisms are exposed to UV-C light, the cell nucleus can be denatured by the photo-degradation process. As a result, cell division and thus reproduction can be blocked.

[0054] Examples of bacteria are the following genera: Chlamydia, Clostridium, Escherichia, Helicobacterium, Lactobacillus, Legionella, Leuconostoc, Listeria, Pediococcus, Salmonella, Shigella, Staphylococcus, Vibrio, and Yersinia.

[0055] Examples of fungi are the following genera: Aspergillus, Penicillium, Saccharomyches, and Candida.

[0056] 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 papilloma virus, Herpes virus, Hepatitis virus, Influenza virus, and HIV.

[0057] UV-C sterilization of surfaces typically requires high-intensity UV-C light, and the lamps are typically close to surfaces that are kept free of microorganisms.

[0058] Typically, the effectiveness of UV-C sterilization is determined by the dose of UV-C light.

[0059] 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 generally expressed as 1 mJ / cm2 = 1000 microwatt - seconds / cm2.

[0060] According to the literature, the dose required to kill 90% of most bacteria and viruses usually ranges from 2,000 to 8,000 μW·s / cm2. Some microorganisms: Bacillus subtilis (spores) 12.0 Clostridium tetani 4.9 Legionella Pneumophilla 2.04 Pseudonomas aeruginosa 5.5 Streptococcus feacalis 4.5 Hepatitis A virus 11.0 Hepatitis Poliovirus 12.0 Saccharomyces cervisiae 6.0 Infectious pancreatic necrosis 60.0 Typical doses (mJ / cm2) for controlling [them] can be found in the literature.

[0061] Generally, within 24 hours, a dose of at least 100, 500, 1000, 1500, 2000, 3000, or 5000 μW·s / cm2 of UV - C light is received on the surface of a molded polymer article. For example, the surface receives a dose of at least 500 μW·s / cm2 per day. For example, the surface of the subway is sterilized with UV - C light every early morning, or the surface of a taxi is irradiated with UV - C light for sterilization after each passenger's ride in a day.

[0062] Deterioration by UV-C light, preferably deterioration caused by UV-C sterilization, is usually frequently induced, for example, at least once per second, minute, hour, day, or week. The term "frequently" usually means at regular time intervals.

[0063] Deterioration by UV-C light is usually caused indoors, such as in public buildings (e.g., schools, hospitals, libraries), industrial offices (open-plan offices, small rooms), industrial production facilities (warehouses, meeting rooms), private buildings (detached houses, high-rise buildings, super high-rise buildings), or transportation vehicles (automobiles, taxis, buses, trams, subways, trains, airplanes, ships). Preferably, deterioration by UV-C light is caused indoors in public buildings or transportation vehicles.

[0064] Molded polymer articles are usually articles that exist indoors, such as in public buildings (e.g., schools, hospitals, libraries), industrial offices (open-plan offices, small rooms), industrial production facilities (warehouses, meeting rooms), private buildings (detached houses, high-rise buildings, super high-rise buildings), or transportation vehicles (automobiles, taxis, buses, trams, subways, trains, airplanes, ships). Preferably, molded polymer articles exist indoors in public buildings or transportation vehicles.

[0065] Suitable molded polymer articles are as follows. - Articles for transportation vehicles, such as dashboards, hat shelves, seats, trunk linings, interior linings, dashboard panels, instrument panels, upholstery, door panels, seat backs, pillar covers, fasteners, consoles, instrument panels, seats, frames, skins; - Household appliances, such as cases and covers in general, electronic devices (personal computers, telephones, mobile phones, printers, televisions, audio and video devices), or electrical appliances (e.g., washing machines, tumblers, ovens (microwave ovens), dishwashers, mixers, and irons); - Sanitary products, such as mobile toilets, shower rooms, toilet seats, covers, sinks, shower curtains, brushes, mats, bathtubs, mobile toilets, toothbrushes, and bedpans; - Fabrics, such as carpets, curtains, shades, nets, ropes, cables, strings, cords, threads, clothing, underwear, gloves, shoes, sportswear, umbrellas, tents, air beds, bags; - Storage systems for boxes (crates), luggage, bottles, chests, household boxes, pallets, containers, shelves, trucks, screw boxes, packs, cans, etc. - Medical devices such as pistons, plastic syringes, ophthalmic supplies, diagnostic devices, and blisters for packaging pharmaceuticals. - Furniture, such as foamed products (cushions, shock absorbers), cloths, mats, chairs, tables, sofas; - Office supplies, such as ballpoint pens, ink pads, mice, shelves, trucks.

[0066] Preferably, the molded polymer article is an article within a transport vehicle or a medical device.

[0067] The molded polymer article is typically an opaque article.

[0068] The molded polymer article typically has at least a partially non-porous surface.

[0069] Generally, the non-porous surface of the molded polymer article is stabilized against degradation.

[0070] Typically, the opaque surface of the molded polymer article is stabilized against degradation.

[0071] Stabilization against degradation typically reduces yellowing of the molded article, or reduces microcracks on the surface of the molded article, or reduces blooming of the molded article and includes.

[0072] The reduction can be determined compared to a molded polymer article without a stabilizer. The stabilizer can stabilize regions of the molded article exposed to UV-C light.

[0073] Formed polymer articles are usually made from synthetic polymers. Examples of synthetic polymers are as follows.

[0074] 1. Polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or poly-butadiene, polyhexene, polyoctene and polymers of cycloolefins, such as polymers of cyclopentene, cyclohexene, cyclooctene or nor-bornene, polyethylene (which may optionally be crosslinked), such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0075] Polyolefins, i.e. polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by separate processes, in particular the following processes.

[0076] a) Radical polymerization (usually at elevated temperature under high pressure).

[0077] b) Catalytic polymerization using a catalyst containing one or more metals of Group IVb, Vb, VIb or VIII of the periodic table. These metals usually have one or more ligands which can be either π - coordination or σ - coordination, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls. These metal complexes can be in free form or immobilized on a substrate, usually activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalyst can be used as such in the polymerization or a further activator, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyloxide or metal alkyloxane can be used, and the said metal is an element of Group Ia, IIa and / or IIIa of the periodic table. The activator can be conveniently modified with further ester, ether, amine or silyl ether groups. These catalyst systems are usually called Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single-site catalysts (SSC).

[0078] Mixtures of the polymers described in 2.1), for example mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g., LDPE / HDPE).

[0079] 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), ultra-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 / vinylcyclohexane copolymers, ethylene / cycloolefin copolymers (e.g., ethylene / norbornene such as COC), ethylene / 1-olefin copolymers (the 1-olefin being produced in situ); propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers), terpolymers of ethylene and propylene with a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of the above copolymers with each other and mixtures of the above polymers of 1) with other polymers, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures of them with other polymers, such as polyamides.

[0080] 4. Hydrocarbon resins (e.g., C5 - C9), their hydrogenated modifiers (e.g., tackifiers) and mixtures of polyalkylene and starch are included.

[0081] The homopolymers and copolymers from 1.)~~4.) can have any configuration such as syndiotactic, isotactic, hemi-isotactic or atactic, with atactic polymers being preferred. Stereoblock polymers are also included. The copolymers of 1.)~4.) can be random copolymers or block copolymers, single-phase or multiphase or highly crystalline homopolymers.

[0082] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0083] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including all isomers of styrene, α-methylstyrene, vinyltoluene, especially p-vinyltoluene, all isomers of ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene and vinylanthracene and mixtures thereof. The homopolymers and copolymers can have any configuration including syndiotactic, isotactic, hemi-isotactic or atactic, with atactic polymers being preferred. Stereoblock polymers are also included.

[0084] 6a. The foregoing vinyl aromatic monomer and a comonomer selected from ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, such as copolymers including styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; a mixture of an impact-resistant styrene copolymer and another polymer, such as polyacrylate, diene polymer or 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.

[0085] 6b. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers described in 6.), in particular polycyclohexylethylene (PCHE) prepared by the hydrogenation of atactic polystyrene, which is often referred to as polycyclohexane (PVCH).

[0086] 6c. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers described in 6a.).

[0087] The homopolymers and copolymers can have any steric structure such as syndiotactic, isotactic, hemiisotactic or atactic, and atactic polymers are preferred. Stereoblock polymers are also included.

[0088] 7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene onto polybutadiene, styrene onto polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) onto polybutadiene; styrene, acrylonitrile and methyl methacrylate onto polybutadiene; styrene and maleic anhydride onto polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide onto polybutadiene; styrene and maleimide onto polybutadiene; styrene and alkyl acrylate or methacrylate onto polybutadiene; styrene and acrylonitrile onto ethylene / propylene / diene terpolymer; styrene and acrylonitrile onto poly(alkyl acrylate) or poly(alkyl methacrylate), copolymers grafted with styrene and acrylonitrile onto acrylate / butadiene copolymer, their mixtures with the copolymers listed in 6), for example copolymers grafted with styrene and acrylonitrile onto copolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0089] 8. Halogen-containing polymers, for example polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homopolymers and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and their copolymers, for example vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers. Polyvinyl chloride can be rigid or soft (plasticized).

[0090] 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.

[0091] Copolymers of the monomers described in 10.9) with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

[0092] Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl, polyvinyl butyral, polyallyl phthalate or polyallyl melamine and copolymers of these with the olefins of 1) described above.

[0093] Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide, etc. or copolymers of these with bisglycidyl ether.

[0094] Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyacetals modified by thermoplastic polyurethane, acrylate or MBS.

[0095] Polyphenylene oxides and sulfides and mixtures of polyphenylene oxide with styrene polymers or polyamides.

[0096] Polyurethanes and their precursors derived from one hydroxyl-terminated polyether, polyester or polybutadiene and the other aliphatic or aromatic polyisocyanate. The following: polyurethanes produced by the reaction of (1) diisocyanate with short-chain diol (chain extender), and (2) diisocyanate with long-chain diol (thermoplastic polyurethane, TPU).

[0097] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as 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 m-xylylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid, with or without elastomers as modifiers, such as poly-2,4,4,-trimethylhexamethyleneterephthalamide or poly-m-phenyleneisophthalamide; and block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers, chemically bonded or grafted elastomers; or block copolymers of the aforementioned polyamides with polyethers, such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified by EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). The polyamide can be amorphous.

[0098] 17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

[0099] 18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones or lactides, such as polyethylene terephthalate (PET), polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polypropylene terephthalate, polyalkylene naphthalate, and polyhydroxybenzoate, and copolyether esters derived from hydroxyl-terminated polyethers, and also polyesters modified with polycarbonate or MBS. The copolyesters can include, for example, polybutylene succinate / terephthalate, polybutylene adipate / terephthalate, polytetramethylene adipate / terephthalate, polybutylene succinate / adipate, polybutylene succinate / carbonate, poly-3-hydroxybutyrate / octanoate copolymer, poly-3-hydroxybutyrate / hexanoate / decanoate terpolymer, but are not limited thereto. Further, aliphatic polyesters can include, for example, the class of poly(hydroxyalkanoates), particularly poly(propionolactone), poly(butyrolactone), poly(pivalolactone), 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 the corresponding polyesters modified with polycarbonate or MBS, but are not limited thereto.The term "polylactic acid (PLA)" preferably means a homopolymer of poly-L-lactide and any blend or alloy with other polymers; a copolymer of lactic acid or lactide with other monomers such as hydroxycarboxylic acids such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and their cyclic forms; the terms "lactic acid" or "lactide" include L-lactic acid, D-lactic acid, mixtures thereof and dimers, namely L-lactide, D-lactide, meso-lactide and any mixture thereof. Preferred polyesters are PET, PET-G, PBT.

[0100] 19. Polycarbonates and polyester carbonates. The polycarbonates are preferably prepared by reaction of bisphenol compounds with carbonic acid compounds, in particular phosgene, or in the melt transesterification process by reaction with diphenyl carbonate or dimethyl carbonate. Homopolycarbonates based on bisphenol A and copolycarbonates based on monomeric bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) are particularly preferred. These and further bisphenol and diol compounds which can be used in polycarbonate synthesis are disclosed, inter alia, in WO 08037364 pamphlet (pages 7, line 21 to page 10, line 5), EP 1582549 specification (

[0018] to

[0034] ), WO 02026862 pamphlet (page 2, line 23 to - page 5, line 15), WO 05113639 pamphlet (page 2, line 1 to page 7, line 20). The polycarbonates can be linear or branched. Mixtures of branched and unbranched polycarbonates can also be used. Suitable branching agents for polycarbonates are known from the literature, for example US Pat. No. 4,185,009 and DE 2500092 (3,3-bis-(4-hydroxyallyloxindole according to the invention, see the entire document in each case), DE 4240313 (see page 3, line 33 to line 55), DE 19943642 (see page 5, line 25 to line 34) and US Pat. No. 5,367,044 and the documents cited therein. The polycarbonates used may also originally be branched and no branching agent is added here with respect to the preparation of the polycarbonates. An example of an inherent branch is the so-called Fries structure disclosed in EP 1506249 with respect to melt polycarbonates. Chain terminators can additionally be used in the preparation of polycarbonates. It is preferred to use phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof as chain terminators.Polyester carbonate is obtained by the reaction of the aforementioned bisphenol, at least one aromatic dicarboxylic acid and optionally an equivalent of carbonic acid. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone-dicarboxylic acid. Up to 80 mol% of the carbonate groups in the polycarbonate, preferably 20 - 50 mol% of the portion, can be substituted with aromatic dicarboxylic acid ester groups.

[0101] 20. Polyketone.

[0102] 21. Polysulfone, polyethersulfone and polyetherketone.

[0103] 22. Crosslinked polymers derived from one aldehyde and the other phenol, urea and melamine, such as phenol / formaldehyde resin, urea / formaldehyde resin and melamine / formaldehyde resin.

[0104] 23. Drying and non-drying alkyd resins.

[0105] 24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and halogen-containing modified products thereof having low flammability.

[0106] 25. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylate, urethane acrylate or polyester acrylate.

[0107] 26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

[0108] 27. A crosslinked epoxy resin derived from aliphatic, alicyclic, heterocyclic or aromatic glycidyl compounds, such as diglycidyl ether products of bisphenol A, bisphenol E and bisphenol F, and crosslinked with a conventional curing agent such as an anhydride or an amine, regardless of the presence or absence of an accelerator.

[0109] 28. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, such as cellulose acetate, cellulose propionate and cellulose butyrate or cellulose ethers such as methyl cellulose, and rosin and its derivatives.

[0110] 29. Blends (polyblends) of the aforementioned polymers, such as 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 / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0111] 30. Natural and synthetic organic substances that are pure monomeric compounds or mixtures of such compounds, such as mineral oils, animal and vegetable fats, oils and waxes or synthetic esters (e.g., phthalic esters, adipic esters, phosphoric esters or trimellitic esters)-based oils, fats and waxes, and mixtures of synthetic esters and mineral oils in any weight ratio typically used as spinning compositions, and aqueous emulsions of such materials.

[0112] 31. Aqueous emulsions of natural or synthetic rubbers, such as natural latex or latex of carboxylated styrene / butadiene copolymers.

[0113] 32. An adhesive, such as a block copolymer of SIS, SBS, SEBS, SEPS (where S represents styrene, I represents isoprene, B represents polybutadiene, EB represents an ethylene / butylene block, and EP represents a polyethylene / polypropylene block), etc.

[0114] 33. Rubbers, such as polymers of conjugated dienes like polybutadiene or polyisoprene, copolymers of monoolefins and diolefins with each other or with other vinyl monomers, copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, chlorinated rubbers, natural rubber.

[0115] 34. Elastomers, such as 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, neoprene, biprene, 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), hydrogenated nitrile rubber (HNBR) also called buna N rubber, Therban and Zetpol, EPM (ethylene-propylene rubber, copolymer of ethylene and propylene) and EPDM rubber (ethylene-propylene-diene rubber, terpolymer of ethylene, propylene and diene component), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluorosilicone rubber (FVMQ), fluoroelastomer (FKM and FEPM) Viton, Tecnoflon, Fluorel, Aflas and Dai-El, perfluoroelastomer (FFKM) Tecnoflon PFR, Kalrez, Chemraz, Perlast, polyether block amide (PEBA), chlorosulfonated polyethylene (CSM), (Hypalon), ethylene vinyl acetate (EVA), thermoplastic elastomer (TPE), protein resilin and elastin, polysulfide rubber, elastolefin, elastic fibers used in the production of fabrics.

[0116] 35. Thermoplastic elastomers, such as styrenic block copolymers (TPE-s), thermoplastic olefins (TPE-o), elastomer alloys (TPE-v or TPV), thermoplastic polyurethanes (TPU), thermoplastic copolyesters, thermoplastic polyamides, reactor (Reactor) TPO’s (R-TPO’s), polyolefin plastomers (POP’s), polyolefin elastomers (POE’s).

[0117] Preferred synthetic polymers are the polymers of Classes 1, 5, 6, 6a, 6b, 6c, 7, 8, 16, 18 and 19 described above.

[0118] In another preferred form, the synthetic polymer is polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene copolymer or polycarbonate.

[0119] In another preferred form, the synthetic polymer is polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene copolymer, polycarbonate, polyvinyl chloride, polyamide, polyurethane, poly(methyl methacrylate) or polyethylene terephthalate.

[0120] In another preferred form, the synthetic polymer is polyethylene, polypropylene, poly(methyl methacrylate), polystyrene, acrylonitrile butadiene styrene copolymer, polycarbonate, polyvinyl chloride, polyamide, polyurethane or polyethylene terephthalate.

[0121] In another preferred form, the synthetic polymer is polyethylene, polypropylene, acrylonitrile butadiene styrene copolymer, polyurethane, poly(methyl methacrylate) or polycarbonate.

[0122] In another preferred form, the synthetic polymer is polyethylene.

[0123] In another preferred form, the synthetic polymer is polypropylene.

[0124] In another preferred form, the synthetic polymer is polystyrene.

[0125] In another preferred form, the synthetic polymer is acrylonitrile butadiene styrene copolymer.

[0126] In another preferred form, the synthetic polymer is polycarbonate.

[0127] In another preferred form, the synthetic polymer is polyvinyl chloride.

[0128] In another preferred form, the synthetic polymer is polyamide.

[0129] In another preferred form, the synthetic polymer is polyethylene terephthalate.

[0130] In another preferred form, the synthetic polymer is polyurethane.

[0131] In another preferred form, the synthetic polymer is poly(methyl methacrylate).

[0132] Preferably, the synthetic polymer is polypropylene or polyvinyl chloride, and the molded article is an article inside a transport vehicle such as a dashboard.

[0133] In another preferred form, the synthetic polymer is polyurethane, and the molded article is an article inside a transport vehicle such as a handle.

[0134] In another preferred form, the synthetic polymer is polyethylene terephthalate, and the molded article is an article inside a transport vehicle such as fibers for upholstering or lining a chair.

[0135] In another preferred form, the stabilizer is compound (2), and the molded polymer article is made from a polyolefin such as polypropylene.

[0136] In another preferred form, the stabilizer is compound (2), the molded polymer article is made from a polyolefin such as polypropylene, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0137] In another preferred form, the stabilizer is compound (1), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0138] In another preferred form, the stabilizer is compound (2), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0139] In another preferred form, the stabilizer is compound (4), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0140] In another preferred form, the stabilizer is compound (6), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0141] In another preferred form, the stabilizer is compound (1), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0142] In another preferred form, the stabilizer is compound (2), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0143] In another preferred form, the stabilizer is compound (4), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0144] In another preferred form, the stabilizer is compound (6), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0145] In another preferred form, the stabilizer is a mixture of compound (1) and compound (13), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0146] In another preferred form, the stabilizer is a mixture of compound (2) and compound (13), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0147] In another preferred form, the stabilizer is a mixture of compound (4) and compound (13), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0148] In another preferred form, the stabilizer is a mixture of compound (6) and compound (13), and the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer.

[0149] In another preferred form, the stabilizer is a mixture of compound (1) and compound (13), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the weight ratio thereof is 10:1 to 1:10, 5:1 to 1:5 or 3:1 to 1:3.

[0150] In another preferred form, the stabilizer is a mixture of compound (2) and compound (13), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the weight ratio thereof is 10:1 to 1:10, 5:1 to 1:5 or 3:1 to 1:3.

[0151] In another preferred form, the stabilizer is a mixture of compound (4) and compound (13), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the weight ratio thereof is 10:1 to 1:10, 5:1 to 1:5 or 3:1 to 1:3.

[0152] In another preferred form, the stabilizer is a mixture of compound (6) and compound (13), the molded polymer article is made from an acrylonitrile-butadiene-styrene copolymer, and the weight ratio thereof is 10:1 to 1:10, 5:1 to 1:5 or 3:1 to 1:3.

[0153] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyltriazine selected from compound (10), (11) or (12), and the molded polymer article is made from a polyolefin such as polyethylene.

[0154] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), and the molded polymer article is made from a polyolefin such as polyethylene.

[0155] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and the molded polymer article is made from a polyolefin such as polyethylene.

[0156] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyltriazine selected from compound (10), (11) or (12), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 10:1 to 1:5 or 5:1 to 1:1.

[0157] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 10:1 to 1:5 or 5:1 to 1:1.

[0158] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 10:1 to 1:5 or 5:1 to 1:1.

[0159] In another preferred form, the stabilizer is compound (3), and the molded polymer article is made from a polyolefin such as polyethylene.

[0160] In another preferred form, the stabilizer is compound (4), and the molded polymer article is made from a polyolefin such as polyethylene.

[0161] In another preferred form, the stabilizer is compound (5), and the molded polymer article is made from a polyolefin such as polyethylene.

[0162] In another preferred form, the stabilizer is compound (7), and the molded polymer article is made from a polyolefin such as polyethylene.

[0163] In another preferred form, the stabilizer is compound (3), the molded polymer article is made from a polyolefin such as polyethylene, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0164] In another preferred form, the stabilizer is compound (4), the molded polymer article is made from a polyolefin such as polyethylene, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0165] In another preferred form, the stabilizer is compound (5), the molded polymer article is made from a polyolefin such as polyethylene, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0166] In another preferred form, the stabilizer is compound (7), the molded polymer article is made from a polyolefin such as polyethylene, and the molded polymer article contains 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, of the stabilizer.

[0167] In another preferred form, the stabilizer is a mixture of compound (5) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from a polyolefin such as polyethylene.

[0168] In another preferred form, the stabilizer is a mixture of compound (7) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from a polyolefin such as polyethylene.

[0169] In another preferred form, the stabilizer is a mixture of compound (5) and compound (11), and the molded polymer article is made from a polyolefin such as polyethylene.

[0170] In another preferred form, the stabilizer is a mixture of compound (7) and compound (11), and the molded polymer article is made from a polyolefin such as polyethylene.

[0171] In another preferred form, the stabilizer is a mixture of compound (5) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 20:1 to 1:1 or 20:1 to 5:1.

[0172] In another preferred form, the stabilizer is a mixture of compound (7) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 20:1 to 1:1 or 20:1 to 5:1.

[0173] In another preferred form, the stabilizer is a mixture of compound (5) and compound (11), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 20:1 to 1:1 or 20:1 to 5:1.

[0174] In another preferred form, the stabilizer is a mixture of compound (7) and compound (11), the molded polymer article is made from a polyolefin such as polyethylene, and the weight ratio thereof is 20:1 to 1:1 or 20:1 to 5:1.

[0175] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyltriazine selected from compound (10), (11) or (12), and the molded polymer article is made from a polyolefin such as polypropylene.

[0176] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), and the molded polymer article is made from a polyolefin such as polypropylene.

[0177] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), and the molded polymer article is made from a polyolefin such as polypropylene.

[0178] In another preferred form, the stabilizer is a mixture of compound (8) and a hydroxyphenyltriazine selected from compound (10), (11) or (12), the molded polymer article is made from a polyolefin such as polypropylene, and the weight ratio thereof is 20:1 to 1:1 or 15:1 to 4:1.

[0179] In another preferred form, the stabilizer is a mixture of compound (8) and compound (10), the molded polymer article is made from a polyolefin such as polypropylene, and the weight ratio thereof is 20:1 to 1:1 or 15:1 to 4:1.

[0180] In another preferred form, the stabilizer is a mixture of compound (8) and compound (11), the molded polymer article is made from a polyolefin such as polypropylene, and the weight ratio thereof is 20:1 to 1:1 or 15:1 to 4:1.

[0181] In another preferred form, the stabilizer is compound (2), and the molded polymer article is made from poly(methyl methacrylate).

[0182] In another preferred form, the stabilizer is compound (3), and the molded polymer article is made from poly(methyl methacrylate).

[0183] In another preferred form, the stabilizer is compound (4), and the molded polymer article is made from poly(methyl methacrylate).

[0184] In another preferred form, the stabilizer is compound (6), and the molded polymer article is made from poly(methyl methacrylate).

[0185] In another preferred form, the stabilizer is compound (2), the molded polymer article is made from poly(methyl methacrylate), and the molded polymer article contains 0.1 to 5% by weight, preferably 0.3 to 3% by weight, of the stabilizer.

[0186] In another preferred form, the stabilizer is compound (3), the molded polymer article is made from poly(methyl methacrylate), and the molded polymer article contains 0.1 to 5% by weight, preferably 0.3 to 3% by weight, of the stabilizer.

[0187] In another preferred form, the stabilizer is compound (4), the molded polymer article is made from poly(methyl methacrylate), and the molded polymer article contains 0.1 to 5% by weight, preferably 0.3 to 3% by weight, of the stabilizer.

[0188] In another preferred form, the stabilizer is compound (6), the molded polymer article is made from poly(methyl methacrylate), and the molded polymer article contains 0.1 to 5% by weight, preferably 0.3 to 3% by weight, of the stabilizer.

[0189] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from poly(methyl methacrylate).

[0190] In another preferred form, the stabilizer is a mixture of compound (3) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from poly(methyl methacrylate).

[0191] In another preferred form, the stabilizer is a mixture of compound (4) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from poly(methyl methacrylate).

[0192] In another preferred form, the stabilizer is a mixture of compound (6) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from poly(methyl methacrylate).

[0193] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), and the molded polymer article is made from poly(methyl methacrylate).

[0194] In another preferred form, the stabilizer is a mixture of compound (3) and compound (11), and the molded polymer article is made from poly(methyl methacrylate).

[0195] In another preferred form, the stabilizer is a mixture of compound (4) and compound (11), and the molded polymer article is made from poly(methyl methacrylate).

[0196] In another preferred form, the stabilizer is a mixture of compound (6) and compound (11), and the molded polymer article is made from poly(methyl methacrylate).

[0197] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0198] In another preferred form, the stabilizer is a mixture of compound (3) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0199] In another preferred form, the stabilizer is a mixture of compound (4) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0200] In another preferred form, the stabilizer is a mixture of compound (6) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0201] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0202] In another preferred form, the stabilizer is a mixture of compound (3) and compound (11), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0203] In another preferred form, the stabilizer is a mixture of compound (4) and compound (11), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0204] In another preferred form, the stabilizer is a mixture of compound (6) and compound (11), the molded polymer article is made from poly(methyl methacrylate), and the weight ratio thereof is 100:1 to 1:1 or 70:1 to 5:1 or 50:1 to 10:1.

[0205] In another preferred form, the stabilizer is compound (6), and the molded polymer article is made from polyurethane.

[0206] In another preferred form, the stabilizer is compound (6), the molded polymer article is made from polyurethane, and the molded polymer article contains 0.1 to 5% by weight, preferably 0.3 to 3% by weight, of the stabilizer.

[0207] In another preferred form, the stabilizer is a mixture of compound (9) and a hydroxyphenyltriazine selected from compound (10), (11) or (12), and the molded polymer article is made from polyurethane.

[0208] In another preferred form, the stabilizer is a mixture of compound (9) and compound (12), and the molded polymer article is made from polyurethane.

[0209] In another preferred form, the stabilizer is a mixture of compound (9) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from polyurethane, and the weight ratio thereof is 20:1 to 1:1 or 10:1 to 1:1 or 8:1 to 2:1.

[0210] In another preferred form, the stabilizer is a mixture of compound (9) and compound (12), the molded polymer article is made from polyurethane, and the weight ratio thereof is 20:1 to 1:1 or 10:1 to 1:1 or 8:1 to 2:1.

[0211] In another preferred form, the stabilizer is compound (2), and the molded polymer article is made from polyurethane.

[0212] In another preferred form, the stabilizer is compound (2), the molded polymer article is made from polyurethane, and the molded polymer article contains 0.1 to 5% by weight, preferably 0.3 to 3% by weight, of the stabilizer.

[0213] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), and the molded polymer article is made from polyurethane.

[0214] In another preferred form, the stabilizer is a mixture of compound (2) and compound (10), and the molded polymer article is made from polyurethane.

[0215] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), and the molded polymer article is made from polyurethane.

[0216] In another preferred form, the stabilizer is a mixture of compound (2) and a hydroxyphenyltriazine selected from compounds (10), (11) or (12), the molded polymer article is made from polyurethane, and the weight ratio thereof is 20:1 to 1:1, or 15:1 to 1:1, or 10:1 to 2:1.

[0217] In another preferred form, the stabilizer is a mixture of compound (2) and compound (10), the molded polymer article is made from polyurethane, and the weight ratio thereof is 20:1 to 1:1, or 15:1 to 1:1, or 10:1 to 2:1.

[0218] In another preferred form, the stabilizer is a mixture of compound (2) and compound (11), the molded polymer article is made from polyurethane, and the weight ratio thereof is 20:1 to 1:1, or 15:1 to 1:1, or 10:1 to 2:1.

[0219] The molded polymer article is prepared or molded, for example, by one of the following processing steps: injection blow molding, extrusion molding, blow molding, rotational molding, in-mold decoration (back injection), slush molding, injection molding, co-injection molding, blow molding, molding, compression molding, resin transfer molding, pressing, film extrusion (cast film; inflation film), fiber spinning (woven fabric, non-woven fabric), stretching (uniaxial, biaxial), annealing, deep drawing, calendering, mechanical deformation, sintering, co-extrusion, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, welding, adhesion, vulcanization, thermoforming, pipe extrusion, profile extrusion, sheet extrusion; sheet casting, strap, foaming, recycling / rework, bis-breaking (peroxide, heat), fiber melt blow, spunbond, surface treatment (corona discharge, flame, plasma), sterilization (by gamma rays, electron beam), tape extrusion, draw molding, SMC process or plastisol.

[0220] The molded polymer article can be an extruded, molded or calendered molded polymer article.

[0221] The formed polymer article can have any shape such as a film, foil, fiber, cloth, plate, device, etc.

Example

[0222] Example 1: Polypropylene compression-molded film 80% tris(2,4-di-tert-butylphenyl) phosphite, 20% octadecyl 3-(1,5-di-tert-butyl-4-hydroxyphenyl) propionate blend 0.1%, calcium stearate 0.05% and the additives listed in Table 3 were compounded into PP / TPO (Borealis Daplen® EE013AE). The listed formulation components were premixed in a high-speed mixer. The well-blended formulation was melt-compounded at a set temperature of 230 °C and 160 rpm under nitrogen in a Collin ZK25×42D twin-screw extruder. The pelletized sample was compression-molded into a 170-micron-thick film at 230 °C with a pressure of 3 minutes.

[0223] UV-C aging device: The sample was exposed to UV-C radiation in a climate chamber equipped with two stainless-steel lamp racks holding five UVC 253.7 nm-emitting lamps TUV T8 F17 1SL / 25 from Signify GmbH, Hamburg, Germany. The sample holding rack was placed 57 cm below the lamp rack, and the sample was placed only at the center of the sample rack (30×40 cm). The conditions inside the chamber were maintained at a temperature of 65 ± 3 °C and a relative humidity of 20 ± 10% r.h. The irradiance in the range of 250 - 260 nm measured at the height of the sample rack was 7.7 W / m 2 is.

[0224] The measured parameter was the change in the intensity of the C=O absorption (carbonyl absorption) measured at 1721 cm using a Nicolet iN10MX FT-IR spectrometer from Thermo Fisher Scientific Inc. -1 The change in the intensity of the carbonyl absorption was used to measure the oxidative damage in the sample. The time until the carbonyl value reached 0.1 is reported in Table 1.

[0225]

Table 1

[0226] This data showed that Samples B and C stabilized the polymer better against degradation caused by artificial UV-C light compared to Sample A.

[0227] Example 2: ABS Compression Molding Plate ABS (acrylonitrile-butadiene-styrene copolymer, Terluran GP-22 from INEOS Styrolution, 100 wt%) was blended 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, 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 - E, and the additives listed in Table 2. Compound (13) is 2-(2-hydroxy-5-methylphenyl) benzotriazole CAS 2440-22-4.

[0228] The well-blended formulation was dried in a vacuum oven at 80°C for 3 hours before melt compounding in a Collin ZK25×42D twin-screw extruder under nitrogen at a set temperature of 220°C and 160 rpm. The pelletized samples were dried at 80°C for 3 hours and compression molded into 2 mm thick molding plates (50×75 mm) by pressing at 220°C for 3 minutes.

[0229] The molding plates were exposed to the UV-C aging device described in Example 1. The molding plates were tested for color change (Delta E) with increasing exposure time using a Datacolor 800 spectrophotometer (20 mm aperture) according to DIN EN ISO / CIE 11664-4. The Delta E values after 12 hours and 18 hours of exposure are summarized in Table 2.

[0230]

Table 2

[0231] This data indicated that Samples B - E stabilized the polymer better against degradation caused by artificial UV - C light compared to Sample A.

[0232] Example 3: LDPE blown film Density 0.922 g / cm 3 (ISO 1183) and 0.25 g / 10 min melt index at 190 °C / 2.16 kg (ISO 1133) of low - density polyethylene Riblene FC 30 was compounded with 1000 ppm of an oligomeric hindered amine light stabilizer (polymer having butanedioic acid, dimethyl ester, 4 - hydroxy - 2,2,6,6 - tetramethyl - 1 - piperidineethanol, CAS 65447 - 77 - 0) and the additives listed in Table 3.

[0233] The amounts of addition are expressed by weight in ppm (parts per million) based on the weight of the polymer. All formulations further contained 2000 ppm of erucamide (Crodamide ER - MB - GD) and a blend of 1000 ppm of 80% tris(2,4 - di - tert - butylphenyl) phosphite and 20% octadecyl - 3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) - propionate as antioxidants.

[0234] The additives were blended with the polymer powder pulverized in a high - speed mixer. The well - blended formulation was melt - compounded at a maximum of 200 °C and 160 rpm under nitrogen in a Berstorff ZE25A×47D twin - screw extruder. The pelletized samples were processed into a 100 - micron - thick single - layer film using a 100 - mm die and a laboratory blown - film line (Dolci) with a set temperature of 180 °C.

[0235] The film samples were exposed to the UVC aging device described in Example 1.

[0236] The oxidation damage of the polyethylene film sample was measured using the change in the intensity of the C=O absorption (carbonyl absorption) in the IR spectrum. The spectrum was measured at 1721 cm -1 using the FT-IR spectrometer Nicolet iN10MX from Thermo Fisher Scientific Inc. The time to reach a carbonyl value of 0.1 is reported in Table 3.

[0237]

Table 3

[0238] This data showed that samples C and D with a low amount of compound (8) stabilized the polymer better against degradation caused by artificial UV-C light compared to samples A and B with a high amount of compound (8).

[0239] Example 4: LDPE blown film Low-density polyethylene (density 0.922 g / cm 3 (ISO 1183) and melt index of 0.25 g / 10 min at 190 °C / 2.16 kg (ISO 1133), Riblene FC 30) was compounded with 3000 ppm of a blocked oligomeric hindered amine light stabilizer (1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer and the reaction product of 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, CAS 192268-64-7) and the additives listed in Table 4.

[0240] The addition amounts are expressed in ppm (parts per million) by weight based on the weight of the polymer.

[0241] The additive was blended with the polymer powder pulverized by a high-speed mixer. The well-blended formulation was melt compounded at a maximum temperature of 200 °C and 160 rpm under nitrogen using a Berstorff ZE25A×47D twin-screw extruder. The pelletized samples were processed into 5-layer 100-micron-thick films (30 / 5 / 30 / 5 / 30) using an 80-mm die and a laboratory blow film line (Collin BL) with a set temperature of 210 °C.

[0242] The film samples were exposed to the UV-C aging device described in Example 1.

[0243] The oxidative damage of the polyethylene film samples was measured using the change in the intensity of the C=O absorption (carbonyl absorption) in the IR spectrum. The spectrum was measured at 1721 cm -1 using an FT-IR spectrophotometer Nicolet iN10MX from Thermo Fisher Scientific Inc. The time to reach a carbonyl value of 0.1 is reported in Table 4.

[0244]

Table 4

[0245] This data showed that Samples B, C, D, and F stabilized the polymer better against degradation caused by artificial UV-C light compared to Sample A.

[0246] This data showed that Sample E, which has a lower amount of compound (7), stabilized the polymer better against degradation caused by artificial UV-C light compared to Samples A and D, which have a higher amount of compound (7).

[0247] This data showed that Sample G, which has a lower amount of compound (5), stabilized the polymer better against degradation caused by artificial UV-C light compared to Samples A and F, which have a higher amount of compound (5).

[0248] Example 5: Polypropylene Compression Molding Plate Polypropylene homopolymer (Moplen HP500N) was compounded with 0.1% of 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% of tris(2,4-di-tert.-butylphenyl) phosphite, 0.145 of 1,6-hexanediamine, a polymer with N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction product (CAS 192268-64-7) and 0.07% of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, CAS 124172-53-8 and the additives listed in Table 5.

[0249] The listed formulation components were premixed in a high-speed mixer. The well-blended formulation was melt compounded in a Collin ZK25×42D twin-screw extruder under nitrogen at a set temperature of 230 °C and 160 rpm. The pelletized sample was injection molded into a 1 mm thick plate (90×85 mm) using an Arburg 320 S injection molding machine at 230 °C.

[0250] The molded plate was exposed to the UV-C aging device described in Example 1.

[0251] The oxidative damage of the polyethylene film sample was measured using the change in the intensity of the C=O absorption (carbonyl absorption) in the IR spectrum. The spectrum was measured at 1721 cm -1 using a Nicolet iN10MX FT-IR spectrophotometer from Thermo Fisher Scientific Inc. The time to reach a carbonyl value of 0.1 is reported in Table 5.

[0252]

Table 5

[0253] This data showed that Samples B and C (both with low amounts of compound (8)) better stabilized the polymer against degradation caused by artificial UV-C light compared to Sample A with a high amount of compound (8).

[0254] Example 6: PMMA Solution Cast Film Film preparation was carried out according to the following procedure: 10 g of amorphous thermoplastic polymethyl methacrylate (Plexiglas® 7N) was dissolved in 40 g of methylene chloride together with 0.1 g of 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)polymer and the reaction product of 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (CAS 192268-64-7) (as a base stabilizer for the integrity of the prepared film) and 0.103 g of the compound listed in Table 6.

[0255] The film was drawn out with the assistance of an automatic Blade (Erichsen) at a blade speed of 12 mm / sec and a height gap of 120 mm.

[0256] The film was exposed to the UV-C aging device described in Example 1. The time until the film became brittle (in hours) is shown in Table 6.

[0257] [Table 6]

[0258] This data showed that Samples A, C, E and G stabilized the polymer against degradation caused by artificial UV-C light.

[0259] This data also showed that samples B, D, F, and H (all with low amounts of the first additive) better stabilized the polymer against degradation caused by artificial UV-C light compared to samples A, C, E, and G, respectively, which had high amounts of the first additive.

[0260] Example 7: TPU Molding Plate The aromatic thermoplastic polyurethane TPU (Desmopan® 385S from Covestro) was compounded with 0.27% ethylene bis(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% dimethyl butanedioate, a polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (CAS 65447-77-0), and the additives listed in Table 7.

[0261] This polymer was dried under a nitrogen blanket and at 80 °C under vacuum until the water content was less than 0.05%. The listed formulation components were premixed in a high-speed mixer. The well-blended formulation was directly melt-compounded in a Berstorff ZE25A×47D twin-screw extruder under nitrogen at a set temperature of 210 °C and 160 rpm. The pelletized samples were air-dried at 80 °C for 4 hours (water content less than 0.03%) and injection-molded into 2-mm-thick molding plates (44×68 mm) at 210 °C using an Engel e-mac 100 injection molding machine.

[0262] The molding plates were exposed to the UV-C aging device described in Example 1. The time until the ΔE value of the molding plates reached 12 is shown in Table 7.

[0263]

Table 7

[0264] This data indicated that Sample B better stabilized the polymer against degradation caused by artificial UV-C light compared to Sample A.

[0265] This data indicated that Sample C better stabilized the polymer against degradation caused by artificial UV-C light compared to Sample A.

[0266] Example 8: TPU Molding Plate Aromatic TPU (Elastollan® 1185 A 10000 from BASF) was compounded with 1.0% dimethyl butanedioate, a polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (CAS 65447-77-0), and the additives listed in Table 8.

[0267] This polymer was dried under a nitrogen blanket and at 80 °C under vacuum to a moisture content of less than 0.02% 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×47D twin-screw extruder under nitrogen at a set temperature of 205 °C and 160 rpm. The pelletized samples were air-dried at 80 °C for 4 hours (moisture content less than 0.02%) and injection molded into 2 mm thick molding plates (44×68 mm) at 210 °C using an Engel e-mac 100 injection molding machine.

[0268] The molding plates were exposed to the UV-C aging device described in Example 1. The time until the delta E value of the molding plate reached 12 is shown in Table 8.

[0269]

Table 8

[0270] This data indicated that Sample A stabilized the polymer against degradation caused by artificial UV-C light.

[0271] This data showed that samples B, C, and D (all with low amounts of compound (2)) stabilized the polymer better against degradation caused by artificial UV-C light compared to sample A with a high amount of compound (2).

Claims

1. For stabilizing a molded polymer article against degradation caused by artificial UV-C light, Compound (1) 【Chemical 1】 Compound (2) 【Chemical Formula 2】 Compound (3) [Chemical Formula 3] Compound (4) 【Chemical Formula 4】 Compound (5) 【Chemical Formula 5】 Compound (6) 【Chemical Formula 6】 Compound (7) 【Chemical Formula 7】 Compound (8) 【Chemical Formula 8】 and a mixture with a hydroxyphenyltriazine selected from compound (10), (11) or (12), or [Chemical Formula 9] a mixture of compound (9) and a hydroxyphenyltriazine selected from compound (10), (11) or (12) 【Chemical Formula 10】 Use of a stabilizer selected from the group consisting of

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

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

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

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

6. The use according to any one of claims 1 to 5, wherein said molded polymer article contains each of said stabilizers in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

7. The use according to any one of claims 1 to 6, wherein said molded polymer article is made of a synthetic polymer, preferably polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, 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 said compound (8) or compound (9) to said hydroxyphenyltriazine selected from 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 said degradation by UV-C light is caused by UV-C sterilization of microorganisms on said molded polymer article.

10.

11. At least 100 μW·s / cm within 24 hours ２ The use according to any one of claims 1 to 9, wherein a dose of is received at the surface of the molded polymer article. The use according to any one of claims 1 to 10, wherein said molded polymer article is a film, foil, fiber, cloth, plate or device.

12. ​ Use according to any one of claims 1 to 11, wherein the non-porous surface of the molded polymer article is stabilized against said deterioration. **Claim 13** Use according to any one of claims 1 to 12, wherein the opaque surface of the molded polymer article is stabilized against said deterioration. **Claim 14** A method for stabilizing a molded polymer article against deterioration caused by artificial UV-C light, the method comprising incorporating into the molded polymer article according to any one of claims 1 to 13 a stabilizer selected from the stabilizers according to claim 1.

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