KR20040106339A - Flame retardant coatings - Google Patents

Abstract

The present invention provides a flame retardant coating composition and at least one compound selected from the group consisting of the coating (A) and the hindered nitroxyl stabilizer (a), the hindered hydroxylamine stabilizer (b) and the hindered alkoxyamine stabilizer (c) ) And a mixture of one or more conventional flame retardants (ii) selected from the group consisting of organic halogen flame retardants (d), organic phosphorus flame retardants (e), isocyanurate flame retardants (f) and melamine-based flame retardants (g) A product coated with a flame retardant coating composition, comprising a flame retardant coating composition, comprising an effective amount. In flame retardant coating compositions comprising at least one ethylenically unsaturated polymerizable monomer comprising sterically hindered amine residues, conventional flame retardants are optional components. Coating products are, for example, iron, steel, stainless steel, aluminum and other nonferrous metals, wood, plywood, paper, cardboard, resin plywood, fine cardboard, plastic, thermoplastic, epoxy, neoprene, rubber, composites, fiberglass Reinforcing composites, polyesters, polymeric foams, masonry, fibers or fabrics, optical fibers, wire and cable structures, and circuit boards.

Description

Flame retardant coatings

The present invention relates to a flame retardant coating comprising at least one sterically hindered nitroxyl, hydroxylamine or alkoxyamine compound and at least one conventional flame retardant. In flame retardant coating compositions comprising at least one ethylenically unsaturated polymerizable monomer comprising sterically hindered amine residues, conventional flame retardants are optional components.

Background of the Invention

US Pat. No. 5,096,950 describes the joint use of Sb ₂ O ₃ containing flame retardants brominated in propylene with certain NOR (N-alkoxy) hindered amines.

US Pat. No. 5,393,812 describes polyolefin compositions wherein the flame retardant is prepared by a combination of a halogenated hydrocarbyl phosphate or phosphonate ester flame retardant with an alkoxyamine functionally hindered amine.

U. S. Patent 5,844, 026 describes polyolefin compositions comprising certain NOR hindered amines and certain conventional flame retardants.

US 6,117,995 describes that certain N-alkoxy hindered amines can be used as flame retardants for organic polymers.

US Pat. No. 6,271,377 describes polyolefin compositions comprising N-hydroxyalkoxy hindered amines and halogenated flame retardants.

In US Pat. No. 6,309,987 and the corresponding WO 99/54530, flame retardant polyolefin nonwovens comprising N-alkoxyamines are described.

Revolutionary UV Stability Flame Retardant Systems for Polyolefins-see R. Srinivasan, A. Gupta and D. Horsey, Int. Conf. Ad d. Polyolefins 1998, 69-830 describe polyolefins comprising certain NOR hindered amines and conventional flame retardants containing halogens and phosphorus.

Advances in Revolutionary Flame Retardant Systems for Polyolefins-R. Srinivasan, B. ROTZINGER, Polyolefins 2000, Int. Conf. Polyolefins 2000, 571-581 describe polyolefins comprising certain NOR hindered amines and brominated and phosphorus containing flame retardants.

See N. Kaprini D. and R. King, in an abstract posted on the Society of Plastics Engineers website, posted Sep. 2001, describes the use of NOR hindered amines as flame retardants in polyolefins. This summary is for polymer Modifiers and additive division subsection to be presented at the polyolefins 2002 conference in Houston, TX, Feb.

EP 0 792 911 A2 describes polyolefin compositions comprising alkoxyamine functionally hindered amines and tris (trialogenenopentyl) phosphate flame retardants.

International Publication No. 99/00450 filed co-pending with US Patent Application No. 09 / 502,239, filed November 3, 1999 and US Patent Application No. 09 / 714,717, filed November 16, 2000, The use of certain N-alkoxy hindered amines as flame retardants is described.

Flame retardant coatings are described in European Patent 568 354, US Patent 6,084,008 and US Patent 5,723,515.

Ethylenically unsaturated polymerizable monomers comprising sterically hindered amine residues are described, for example, in US Pat. Nos. 4,983,737, 5,047,489 and 5,077,340.

The flame retardant (FR) market today consists of products that function in the chemical and / or physical sense to interfere with the combustion process. Mechanically, such FRs have been proposed to function in the gas phase, condensation phase or both during the combustion of the product. Organohalogens have been proposed to generate halogen species (eg HX) that interfere with free radical organic "fuel" from the polymer substrate in the gas phase. Synergy has been suggested to produce additional chemical species that react with HX to interfere with combustion in the gas phase, such as by reacting antimony oxide with HX to produce antimony halides and water vapor. Antimony compounds, such as antimony trioxide, also act as radical scavengers to produce antimony halides. Therefore, antimony compound can suppress a fire spreading.

Although antimony compounds are efficient in terms of cost performance, this has caused concern because of the toxicity of by-products produced during combustion in the presence of halogenated flame retardants in recent years. Annimon oxide often contains trace amounts of arsenic compounds that are believed to be carcinogens. Because of these ecological concerns, there is a move to replace antimony trioxide in current flame retardant applications. However, it is very difficult to identify effective synergies that are environmentally beneficial and efficient as cost performance concerns are.

Another reason for adding flame retardant additives is to prevent dripping during the application of the fire. During combustion, portions of the polymer separate from the matrix in droplet form. Frequently, drops are combusted and pose a dreadful danger from the spread of fire. As a negative consequence for mechanical properties, it is common to add large amounts of fillers such as talc to the polymer. Other fillers used occasionally are calcium carbonate, magnesium carbonate, zinc borate, silicates, silicon, glass fibers, glass spheres, asbestos, kaolin, mica, barium sulfate, calcium sulfate, metal oxides, hydrates and hydroxides such as zinc oxide Manganese hydroxide, alumina trihydrate, silica, calcium silicate and magnesium silicate.

It has been found that a good flame retardant coating is prepared when it comprises at least one compound selected from the group consisting of sterically hindered nitroxyl, hydroxylamine and alkoxyamine additives and at least one particular conventional flame retardant. The coating having excellent flame retardancy is further prepared from a coating composition comprising at least one compound (i) selected from the group consisting of ethylenically unsaturated polymerizable monomers comprising sterically hindered amine moieties and at least one particular conventional flame retardant (ii). Turned out. When using such flame retardant additives, antimony compounds and fillers can be greatly reduced or replaced. Since the sterically hindered amine additive acts as a stabilizer, the coating composition of the present invention is efficiently protected from the deleterious effects of light, oxygen and / or heat.

details

The present invention

Coating (A) and

Steric hindrance nitroxyl stabilizer (a),

Steric hindrance hydroxylamine stabilizers (b) and

At least one compound (i) selected from the group consisting of sterically hindered alkoxyamine stabilizers (c) and

Organic halogen flame retardant (d),

Organic phosphorus flame retardant (e),

Isocyanurate flame retardant (f) and

A flame retardant coating composition comprising an effective amount of flame retardant mixture (B) with one or more conventional flame retardants (ii) selected from the group consisting of melamine-based flame retardants (g).

The invention also

Resin binder (A) and

Optionally one or more ethylenically unsaturated polymerizable monomers (i) comprising sterically hindered nitroxyl, hydroxylamine or alkoxyamine residues

Organic halogen flame retardant (a),

Organic phosphorus flame retardant (b),

Isocyanurate flame retardant (c) and

A flame retardant coating composition comprising an effective amount of flame retardant mixture (B) with one or more conventional flame retardants (ii) selected from the group consisting of melamine-based flame retardants (d).

The additive combination of component (i) and component (ii) synergizes to provide flame retardancy to the coating.

jacket

The coating component (A) of this invention is a coating layer. This is for example a cured paint, varnish, adhesive layer or sealant layer. Alternatively, it is a thin film plastic layer, for example an extruded thermoplastic coating as further described herein.

Paint or varnish formulations include resins, solvents, pigments, fillers, surfactants and other typical ingredients.

The flame retardant coatings are used in construction, transport, telecommunications, utilities, marine, chemical, petroleum, manufacturing and military, sanitation, medical, textile and clothing industries, automotive exteriors, packaging, pharmaceuticals, electrical engineering, electronics and household applications. Suitable for

Suitable substrates for the coating include, for example, iron, steel, stainless steel, aluminum and other nonferrous metals, wood, plywood, paper, cardboard, resin plywood, particulate cardboard, plastic, PVC (polyvinyl chloride), thermoplastics, Thermoplastic polyolefins, epoxy, neoprene, rubber, composites and the like.

The coating material can be used on most substrates in harsh climate and environmental conditions where heat, light, oxygen and humidity are potential degradants. This coating is suitable for interiors and exteriors of homes, roofs, factories, commercial buildings, airplanes, cars, ships, boats, yachts, etc.

Plastics and composites are suitable substrates according to the invention, such as fiber glass reinforced composites, polyesters, polymerizable foams and thermoplastics such as polyolefins and thermoplastic polyolefins (TPOs).

The coating of the present invention is suitable for use in thermoplastic olefin structures of painted automobiles.

The coatings are advantageously used in marine applications such as barriers, docks, docks, cabin penetration barriers, cables, conduits, cargo areas, cabins and decks, and offshore drilling applications.

The coating may be used for transportation applications, such as automobiles, buses, trucks, cargo ships and airplanes, automotive landing gears, exhaust systems, gas tanks, firewalls, engine rooms, catalytic converters, hoods, cargo ship patches, airport loading bridges, etc. Can be used for

Such coatings may be used in telecommunications, computers, utilities, petroleum and chemical industries, such as cable and conduit packaging, fiber optic coatings, grease filled wires and cables, telecommunication towers, fire permeation barriers, seals, pipeline packaging, storage tanks, It is advantageously used in reactors, ovens, distillation tubes, furnaces and the like.

The coating of the present invention is suitable as a coating for a circuit board, for example, a radiation curable coating for a circuit board.

The coatings are suitable as cable coatings and can be used as fire retardant fillers for cables categorized together for electrical, control and communication cables, such as cable trays and channels, junction boxes, cable trenches and similar applications.

Suitable fiber optic coatings are described, for example, in US Pat. Nos. 6,187,835, 6,350,790, 6,197,422, and 6,362,249, which are incorporated herein by reference in their entirety.

Ethylenically Unsaturated Coating Composition (B)

The coating composition is, for example, a curable paint, varnish, an adhesive or a sealant composition. The composition is, for example, heat or radiation (ultraviolet light, UV) curable. Alternatively, the composition is a curable film composition, eg, a thermoplastic coating composition for extruded films as further described herein.

Paint or varnish formulations include resins, solvents, pigments, fillers, surfactants and other typical ingredients.

Flame retardant coating compositions of the present invention include construction, transportation, telecommunications, utilities, marine, chemical, petroleum, manufacturing and military, sanitary, medical, textile and clothing industries, automotive exteriors, packaging, pharmaceuticals, electrical engineering, electronics and Suitable for coatings in the field of home appliances.

Suitable substrates for the coating composition are, for example, iron, steel, stainless steel, aluminum and other nonferrous metals, wood, plywood, paper, cardboard, resin plywood, particulate cardboard, plastic, PVC (polyvinyl chloride), thermoplastic resins. Thermoplastic polyolefin, epoxy, neoprene, rubber, composite, glass, glass fiber, plastic fiber and the like.

The coating composition can be used on most substrates in harsh climate and environmental conditions where heat, light, oxygen and humidity are potential degradants. This coating is suitable for interiors and exteriors of homes, roofs, factories, commercial buildings, airplanes, cars, ships, boats, yachts, etc.

Plastics and composites are suitable substrates according to the invention, such as fiber glass reinforced composites, polyesters, polymerizable foams and thermoplastics such as polyolefins and thermoplastic polyolefins (TPOs).

The coating composition of the present invention is suitable for use in thermoplastic olefin structures of painted automobiles.

The coating compositions are advantageously used in marine applications such as barrier walls, docks, docks, cabin permeation barriers, cables, conduits, cargo areas, cabins and decks, and offshore drilling applications.

The coating composition may be used for transportation purposes, such as automobiles, buses, trucks, cargo ships and airplanes, automobile landing gears, exhaust systems, gas tanks, firewalls, engine rooms, catalytic converters, hoods, cargo ship patches, airport loading bridges, and the like. Can be used for coating.

The coating compositions are used in telecommunications, computers, utilities, petroleum and chemical industries, such as cable and conduit packaging, fiber optic coatings, grease filled wires and cables, telecommunication towers, fire permeation barriers, seals, transport packaging, storage tanks. It is advantageously used in reactors, ovens, distillation tubes, furnaces and the like.

The coating composition of the present invention is suitable as a coating for a circuit board, for example, a radiation curable coating for a circuit board.

The coating compositions are suitable as cable coatings and can be used as fire protection fillers for cables categorized together for electrical, control and communication cables, such as cable trays and channels, junction boxes, cable trenches and similar applications.

General purpose

The coating / coating compositions of the invention are suitable as architectural paints, for example matte, low gloss, semi gloss or high gloss finishes, for example priming or finishing coatings.

The coating composition can be advantageously applied to outdoor sliding, internal structures, roofing materials, automobile garages, ceiling panels, permeation barriers, PVC wraps and the like. The coating composition can be wallpaper, plank material, plasterboard, wallboard, sheet material, truss, flooring material and flooring, gongs, architectural carpentry and windows, tiles, outdoor decking, ceiling tiles, kitchen cabinets, kitchen hoods, carpet backing It can be used in private homes, hotels and offices, as applied to materials, interior walls, doors, filing cabinets, office furniture, safes, barriers and the like.

The coating compositions of the present invention may be applied to structural steels, columns, beams, steel deck materials, bar joints, suspended ceiling materials in commercial buildings, towering office buildings and apartment complexes, bridges and tunnels, and the like.

With regard to steel and other metal substrates, such substrates include beams and columns of primary metals, structural steels, aluminum, metal alloys, structural steels, coil cladding substrates, steel honeycomb structures of junction boxes, insulated steels, stainless steel pipe materials, It can be a ship and a tank.

The coating composition of the present invention is suitable for the application of masonry such as bricks, concrete, cement blocks and plates.

Suitable wood substrates are, for example, parallax plates, plywood, fine cardboard, OOSB cardboard, unfinished indoor wood, plywood acoustic plates, insulation plates, cellulose plates, fiberboard, large rice (wood wool), wood shavers, cedar shakes, unfacing Shingles, shakes, planks, telephone poles, posts, paper, cardboard, cardboard, and corrugated cardboard.

The flame retardant additive can be applied to wood as a stain component, as a sand sealing component, as part of an envelope, by pressure or vacuum impregnation, or as a saturating agent. The flame retardant additive of the present invention applied to wood can be mixed with preservatives; It may be incorporated into the wood composite product by pressure impregnation during manufacture, or may be applied as part of a paint or surface coating.

The flame retardant additive of the present invention applied to paper may be dispensed on the wet end of the papermaking machine, added into a size press or bucket on the dry end, or applied to a coater or multi-station press.

The coating compositions of the present invention are for example foaming agents, blowing agents, carbonizing and binders, trophies, foam agents, as described in US Pat. No. 5,723,515, which is incorporated herein by reference in its entirety. ), Dipentaerythritol, and other additives.

The fibers are suitable coated substrates according to the invention, for example fiber backing coatings, welding curtains, canopies, dividers, awnings, tents, nylon ropes, net fabrics, carpet backing materials, wall coverings, decorative products, natural fibers, synthetics Fibers, furniture, carpet materials, drapery, stage curtains, mattresses, hospital fibers, and woven and nonwoven fabrics.

The coating composition of the present invention comprises a fiber structure and a polyolefin film coating and / or extrusion coating as described in US Pat. No. 6,235,658, which is incorporated herein by reference in its entirety. A coating that is part of the structure can be formed. The coating of the invention may be a polyolefin coating, as described in US Pat. No. 6,251,995, which is incorporated herein by reference in its entirety.

The fibrous fabric may be a woven, knit or nonwoven based on polyethylene, polypropylene, polyethylene terephthalate, polyamide, cellulose or cotton. The thickness of the polyolefin film or the extruded film is, for example, about 3 to about 200 μm.

The invention also relates to wear resistant coating compositions suitable for coating on polycarbonate. Such coatings as described in US Pat. No. 5,214,085 include silyl acrylates, water soluble colloidal silicas, photoinitiators and optionally polyfunctional acrylates as well as UV absorbers. In addition to flame retardancy, these coatings of the present invention provide degradation resistance after prolonged outdoor exposure to sunlight, moisture and heat. Resistance to sulfidation, delamination and formation of microcracks, and reduced transparency is also provided.

Sealants and adhesive compositions, such as sealants and adhesive layer compositions, also fall within the definition of the present invention of "flame retardant coating compositions".

For example, mastic, latex adhesive, binder, caulk, putty, mortar and sealant may be mentioned.

Adhesive compositions are, for example, laminated adhesives, pressure sensitive adhesives (PSAs) and structural adhesives. UV (ultraviolet light) curable adhesives are also subject of the present invention. UV curable adhesives are, for example, photomagnetic adhesives such as cables, connectors, amplifiers, tape bonders, and the like. Photonic adhesives belong to the group of structural adhesives.

The coating composition of the present invention can be used to form layers of laminated articles as film and / or adhesive layers. For example, coatings and layers as described in US Pat. Nos. 6,187,845, 6,191,199 and 6,268,415, which are incorporated by reference in their entirety. Such coatings, films and adhesive layers are, for example, solar control films, films and glazings, UV absorbing glass and glass coatings, windshields, retroreflective sheets and signals, sun reflectors, optical films and the like.

The coating composition of the present invention can be used to form transparent or colored coatings. It may be a water mediated system, a solvent mediated system, or may be a powder coating composition or a gel coating formulation.

The coating composition of the present invention may be ambient cured, radiation cured (eg under the influence of a photoinitiator), oven cured or cured (crosslinked) with the aid of a catalyst such as an acid catalyst.

When using a photoinitiator, the said coating composition can mention mono- or bisacylphosphine oxide photoinitiator or (alpha)-hydroxy ketone photoinitiator, for example. Such photoinitiators are described in US Pat. No. 5,942,290, which is incorporated herein by reference in its entirety.

The coating composition of the present invention is an alkyd resin; Chlorinated alkyd resins; Polyurethane resins; Thermoplastic acrylic resins; Acrylic alkyl; Acrylic resins; Latex emulsions; Acrylic alkyd or polyester resins; Acrylic alkyd or polyester resins optionally modified with silicone, isocyanates, ketimines or oxazolidines; Phenol-formaldehyde resins; Resorcinol-formaldehyde resins; Epoxy resins; Epoxide resins crosslinked with carboxylic acids, anhydrides, polyamines or mercaptans; It is based on acrylic or polyester resin systems modified with reactive groups in their backbones and crosslinked with epoxides. For example, the coating based on vinyl acetate-acrylate copolymer emulsion resin, the vinyltoluene-2-ethylhexyl acrylate copolymer solution, and a polyurethane is mentioned.

Epoxy binders are widely used in coating compositions and are suitable for the present invention. It is, for example, aliphatic, aromatic, cyclic, acyclic, cycloaliphatic or heterocyclic. Such resins include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, trimethylol Polyglycidyl ethers derived from such polyhydric alcohols such as propane, bisphenol-A and bisphenol-F. Epoxide resins also include polyglycidyl ethers of polycarboxylic acids, such as epoxy compounds (e.g. epichlorohydrin), to aliphatic or aromatic polycarboxylic acids (e.g. oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2, 6-naphthalene dicarboxylic acid and dimerized linoleic acid).

Epoxy resins also derive from the epoxidation of olefinically unsaturated alicyclic materials. Among these are epoxy alicyclic ethers and esters which are well known in the art. Epoxy resins also include materials containing oxyalkylene groups. Such groups can be pendant from the backbone of the epoxide resin or can be included as part of the attack. The proportion of oxyalkylene groups in the epoxy resin depends on a number of factors, including the size of the oxyalkylene groups and the properties of the epoxy resin.

In addition, the epoxy resins include epoxy novolac resins. Such resins are prepared by reacting epihalohydrin with condensation products of aldehydes with monohydric or polyhydric phenols. One example is the reaction product of epichlorohydrin with phenol-formaldehyde condensates. Mixtures of epoxy resins can also be used herein.

Materials such as epoxidized soybean oil, dimeric acid based materials such as EMPOL 1010 resin sold by Emery Chemicals, and rubber modified polyepoxide resins such as polyglycidyl of bisphenol A Products made from ethers such as EPON 828 manufactured by Shell Chemical, and acid functional polybutadienes.

Crosslinkable polyurethanes, polyesters, polyvinyls, polysulfides, ureas and formaldehydes are examples of resins suitable for the present invention.

The invention also relates to radiation curable (UV curable) coating systems comprising ethylenically unsaturated acrylic resins, polyurethane acrylates, epoxy acrylates, polyester acrylates, unsaturated polyester / styrene resins and silyl acrylates. The ethylenically unsaturated copolymerizable compound may also include one or more olefinic double bonds. It may be a low molecular weight (monomer) or high molecular weight (oligomeric) compound. Radiation cured coatings are described, for example, in US Pat. No. 6,376,584, filed February 27, 2001, which is incorporated herein by reference. Unsaturated monomers are typically alkyl- or hydroxyalkyl acrylates or methacrylates, styrene, ethylene glycol diacrylates, propylene glycol diacrylates, neopentyl glycol diacrylates, hexamethylene glycol diacrylates or bisphenol A diacrylates. Latex, 4,4'-bis (2-acryloyloxymethoxy) dipentylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, styrene, hexamethylene glycol or bisphenol A diacrylic Latex, 4,4'-bis (2-acryloyloxymethoxy) dipentylpropane or trimethylolpropane triacrylate. Oligomeric polyunsaturated compounds are, for example, polyester acrylates or unsaturated polyester resins prepared from maleic acid, fumaric acid, phthalic acid and one or more diols and typically having a molecular weight of about 500 to 3,000. Unsaturated carboxylic acids are, for example, acrylic acid and methacrylic acid.

The powder coating composition comprises, for example, glycidyl methacrylate with the selected alcohol component.

The coating composition of the present invention is, for example, a high solid content enamel composition based on crosslinkable acrylic resins, polyester resins, urethane resins, or alkyd resins that can be cured with additional acid catalysts. Such acid catalyzed stoving lacquers are based on, for example, acrylic resins, polyester resins, polyurethane resins, polyamide resins or alkyd resins that are capable of high temperature crosslinking.

The coating composition of the present invention is suitable for multilayer systems, for example, the flame retardant additive combinations of the present invention may be present in one or more layers of the multilayer coating system.

The coating composition of the present invention may be applied to the substrate in any conventional manner, such as by brush, roller, spraying, dipping, electrostatic attachment, extrusion / coextrusion, trawling (mastic), and the like.

The coating composition of the present invention may be expanded or unexpanded.

The coating composition of the present invention is of course used to form a thin layer. The thickness of this thin layer is, for example, about 5 μm to about 10 mils, for example about 10 μm to about 7 mils or about 1 to about 5 mils. The thickness of the thin layer is, for example, about 10 μm, or about 1, 2, 3, 4, 5 or 6 mils. Also included are thin layer thicknesses of 26 μm / mil.

The coating composition of the present invention provides a coating which is itself a flame retardant and imparts flame retardancy to the entire product which forms one part (for example a coated plastic part).

Sterically hindered compound of component (i)

Steric hindrance stabilizers of component (i) of the present invention are well known in the art, for example, [Wherein G ₁ and G ₂ are independently alkyl having 1 to 8 carbon atoms, they are pentamethylene together, Z ₁ and Z ₂ are each methyl, or Z ₁ and Z ₂ together are ester, ether, amide, To form a binding moiety that may be further substituted with an amino, carboxy or urethane group, E is oxyl, hydroxyl, alkoxy, cycloalkoxy, aralkoxy, aryloxy, -O-CO-OZ ₃ , -0-Si ( Z ₄ ) ₃ , -O-PO (OZ ₅ ) ₂ or -O-CH ₂ -OZ ₆ , wherein Z ₃ , Z ₄ , Z ₅ and Z ₆ are groups consisting of hydrogen, aliphatic, araliphatic and aromatic moieties Or E is -0-T- (OH) _b (wherein T is linear or branched alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms and cycloalkenylene having 5 to 18 carbon atoms). Or 1 to 4 carbon atoms substituted with phenyl or substituted with phenyl substituted with 1 or 2 alkyl groups of 1 to 4 carbon atoms Straight or branched alkylene, b is 1, 2 or 3, provided that b cannot exceed the carbon number of T, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atom of T )].

E is, for example, oxyl, hydroxyl, alkoxy, cycloalkoxy or aralkoxy. For example, E is methoxy, propoxy, cyclohexyloxy or octyloxy.

Steric hindrance stabilizers of component (i) of the present invention are, for example, formulas (A) to (R):

In the above formulas (A) to (R),

E is oxyl, hydroxyl, alkoxy having 1 to 18 carbon atoms, cycloalkoxy having 5 to 12 carbon atoms or araloxy having 7 to 15 carbon atoms, or E is -0-T- (OH) _b , wherein T is 1 to C carbon atoms Straight or branched chain alkylene of 18, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, or phenyl substituted by phenyl or substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms Straight chain or branched alkylene of 1 to 4, b is 1, 2 or 3, provided that b cannot exceed the carbon number of T, and when b is 2 or 3, each hydroxyl group is a different carbon of T Attached to an atom),

R is hydrogen or methyl,

m is 1 to 4,

when m is 1, R ₂ is hydrogen, C ₁ -C ₁₈ alkyl or by one or more oxygen atoms, optionally block C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₀ aryl, C _7- C ₁₈ aralkyl, glycidyl, or monovalent acyl radicals of aliphatic, cycloaliphatic or aromatic carboxylic acids or carbamic acids, for example aliphatic carboxylic acids having 2 to 18 carbon atoms, alicyclic carboxylic acids having 5 to 12 carbon atoms or carbon atoms Acyl radical of the aromatic carboxylic acid of 7 to 15, or chemical formula (Where x is 0 or 1) or a formula (Where y is 2 to 4),

when m is 2, R ₂ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylene, or a divalent acyl radical of aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or dicarbamic acid, for example For example, an acyl radical of an aliphatic dicarboxylic acid having 2 to 18 carbon atoms, an alicyclic or aromatic dicarboxylic acid having 8 to 14 carbon atoms, or an aliphatic, alicyclic or aromatic dicarboxylic acid having 8 to 14 carbon atoms, or a chemical formula , Chemical formula Or chemical formula Wherein D ₁ and D ₂ are independently hydrogen, an alkyl radical containing up to 8 carbon atoms, or an aryl or aralkyl radical comprising 3,5-di-t-butyl-4-hydroxybenzyl radical, D ₃ is hydrogen or an alkyl or alkenyl radical containing 18 or fewer carbon atoms, d is 0 to 20),

when m is 3, R ₂ is a trivalent acyl radical of aliphatic, unsaturated aliphatic, cycloaliphatic or aromatic tricarboxylic acid,

when m is 4, R ₂ is 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-ene-tetracarboxylic acid, 1,2,3,5-pentanetetracarboxylic acid and Tetravalent acyl radicals of saturated or unsaturated aliphatic or aromatic tetracarboxylic acids comprising 1,2,4,5-pentanepetracarboxylic acid,

p is 1, 2 or 3,

R ₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₉ aralkyl, C ₂ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl or benzoyl,

When p is 1, R ₄ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₈ alkenyl, aryl unsubstituted or substituted with cyano, carbonyl or carbamide groups Or aralkyl, or glycidyl, a group of the formula -CH ₂ -CH (OH) -Z, a formula -CO-Z or a formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl, or a formula Or chemical formula Is a group of where h is 0 or 1,

when p is 1, R ₃ and R ₄ together are alkylene or 2-oxo-polyalkylene having 4 to 6 carbon atoms, or a cyclic acyl radical of aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid; ,

When p is 2, R ₄ is a direct bond, C ₁ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylene, -CH ₂ CH (OH) -CH ₂ group or -CH ₂ -CH (OH ) -CH ₂ -OXO-CH ₂ -CH (OH) -CH ₂ -group, wherein X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene Provided that R ₃ is not alkanoyl, alkenoyl or benzoyl, and R ₄ may also be a divalent acyl radical of aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or may be a group -CO-;

R ₄ is (Wherein T ₈ and T ₉ are independently hydrogen or alkyl of 1 to 8 carbon atoms, or T ₈ and T ₉ together are alkylene or 3-oxapentamethylene of 4 to 6 carbon atoms, for example, T ₈ and T ₉ together are 3-oxapentamethylene),

when p is 3, R ₄ is 2,4,6-triazinyl, n is 1 or 2,

When n is 1, R ₅ and R ' ₅ are independently C ₁ -C ₁₂ allyl, C ₂ -C ₁₂ alkenyl or C ₇ -C ₁₂ aralkyl, or R ₅ is also hydrogen, or R ₅ and R ' ₅ together are C ₂ -C ₈ alkylene, hydroxyalkylene or C ₄ -C ₂₂ acyloxyalkylene;

When n is 2, R ₅ and R ' ₅ together are (-CH ₂ ) ₂ C (CH _2- ) ₂ and R ₆ is hydrogen, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C ₂ -C ₆ alkoxyalkyl;

when n is 1, R ₇ is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl , C ₂ -C ₆ alkoxyalkyl, C ₆ -C ₁₀ aryl, glycidyl, a group of the formula-(CH ₂ ) _t -COO-Q or a group of the formula-(CH ₂ ) _t -O-CO-Q, wherein t is 1 or 2 and Q is C ₁ -C ₄ alkyl or phenyl;

When n is 2, R ₇ is C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, -CH ₂ CH (OH) -CH ₂ -OXO-CH ₂ -CH (OH) -CH ₂ -group Wherein X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene, or -CH ₂ CH (OZ ') CH _2- (OCH ₂ -CH (OZ ') CH ₂ ) ₂ -group wherein Z' is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl;

Q ₁ is -N (R ₈ )-or -O-; E ₇ is a C ₁ -C ₃ alkylene, -CH ₂ -CH (R ₉ ) -O- group, wherein R ₉ is hydrogen, methyl or phenyl,-(CH ₂ ) ₃ -NH- group or directly Is a bond;

R ₁₀ is hydrogen or C ₁ -C ₁₈ alkyl, R ₈ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₁₂ aralkyl, cyanoethyl, C ₆ -C ₁₀ Aryl, —CH ₂ —CH (R ₉ ) —OH group, wherein R ₉ is as defined above; Chemical formula Group or chemical formula of In which G ₄ is C ₂ -C ₆ alkylene or C ₆ -C ₁₂ arylene; R ₈ is —E ₇ -CO-NH-CH ₂ -OR ₁₀ group;

Formula F is a repeating structural unit of a polymer, wherein T ₃ is ethylene or 1,2-propylene and repeating structural units derived from α-olefin copolymers with alkyl acrylates or methacrylates, such as ethylene Copolymer with ethyl acrylate, k being 2 to 100);

T ₄ has the same meaning as R ₄ when p is 1 or 2,

T ₅ is methyl,

T ₆ is methyl or ethyl, or T ₅ and T ₆ together are tetramethylene or pentamethylene, for example T5 and T6 are each methyl,

M and Y are independently methylene or carbonyl and T ₄ is ethylene when ethylene n is 2;

T ₇ is the same as R _7, and T ₇ is, for example, octamethylene when n is 2;

T ₁₀ and T ₁₁ are independently alkylene having 2 to 12 carbon atoms, or T ₁₁ is a chemical formula ego,

T ₁₂ is piperazinyl, formula -NR11- (CH2) d-NR11- or formula Wherein R ₁₁ is the same as R ₃ or A, b and c are independently 2 or 3, f is 0 or 1, for example a and c are 3, b is 2 and f is 1),

e is 2, 3 or 4, for example 4;

T ₁₃ is the same as R ₂ , except that T ₁₃ cannot be hydrogen when n is 1;

E ₁ and E ₂ are different and each is -CO- or -N (E ₅ )-, wherein E ₅ is hydrogen, C ₁ -C ₁₂ alkyl or C ₄ -C ₂₂ alkoxycarbonylalkyl, for example E ₁ is -CO- and E ₂ is -N (E ₅ )-,

E ₃ is hydrogen, alkyl of 1 to 30 carbon atoms, or phenyl or naphthyl substituted by chlorine or alkyl of 1 to 4 carbon atoms, phenylalkyl of 7 to 12 carbon atoms or phenylalkyl of 1 to 4 carbon atoms,

E ₄ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or

E ₃ and E ₄ together are polymethylene having 4 to 17 carbon atoms or polymethylene substituted with 4 or less alkyl groups having 1 to 4 carbon atoms, for example methyl,

E ₆ is an aliphatic or aromatic trivalent radical,

R ₂ in formula (N) is the same as previously defined when m is 1,

G ₁ is a direct bond, C ₁ -C ₁₂ alkylene, phenylene or —NH-G′-NH, wherein G ′ is C ₁ -C ₁₂ alkylene;

The hindered amine compound is a compound of Formulas I, II, III, IV, V, VI, VII, VIII, IX, X or XI:

In the above formulas (I) to (XI),

E ₁ , E ₂ , E ₃ and E ₄ are independently alkyl of 1 to 4 carbon atoms, E ₁ and E ₂ are independently alkyl of 1 to 4 carbon atoms, E ₃ and E ₄ together are pentamethylene, or E ₁ and E ₂ and E ₃ and E ₄ together form pentamethylene,

R ₁ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, acyclic or tricyclic hydrocarbon radical of 7 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl or 6 to 10 carbon atoms Aryl substituted with 1 to 3 alkyl of 1 to 18,

R ₂ is hydrogen or straight or branched chain alkyl of 1 to 12 carbon atoms,

R ₃ is alkylene having 1 to 8 carbon atoms, R ₃ is —CO—, —CO—R ₄ —, —CONR ₂ — or —CO—NR ₂ —R ₄ —,

R ₄ is alkylene having 1 to 8 carbon atoms,

R ₅ is hydrogen, straight or branched chain alkyl of 1 to 12 carbon atoms, or Or when R ₄ is ethylene, the two R ₅ methyl substituents are bonded directly such that the triazine bridge group -N (R ₅ ) -R ₄ -N (R ₅ )-is a piperazine-1,4-diyl residue Can be combined by

R ₆ is alkylene having 2 to 8 carbon atoms, or R ₆ is Provided that Y is not —OH when R ₆ is the above-mentioned structure,

A is -O- or -NR _7- , wherein R ₇ is hydrogen or straight or branched chain alkyl of 1 to 12 carbon atoms, or

R ₇ is a chemical formula Or

T is phenoxy, phenoxy substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms or -N (R ₂ ) ₂ , provided that R ₂ is not hydrogen or T is ego,

X is -NH ₂ , -NCO, -OH, -O-glycidyl or -NHNH ₂ ,

Y is -OH, -NH ₂ , -NHR ₂ , wherein R ₂ is not hydrogen; Y is -NCO, -COOH, oxiranyl, -O- glycidyl or -Si (OR ₂ ) ₃ ; The compound of formula R ₃ -Y- is -CH ₂ CH (OH) R ₂ , wherein R ₂ is alkyl or alkyl blocked with 1 to 4 oxygen atoms or the compound of formula R ₃ -Y- is -CH ₂ OR ₂ ;

The hindered amine compound is N, N ', N "'-tris {2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino]- mixture of s-triazin-6-yl} -3,3'-ethylenediimidodipropylamine; N, N ', N "-tris {2,4-bis [(1-hydrocarbyloxy-2,2 , 6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, and Formulas 1, 2, 2a and 3 A bridge derivative as represented by

R ₁ NH-CH ₂ CH ₂ CH ₂ NR ₂ CH ₂ CH ₂ NR ₃ CH ₂ CH ₂ CH ₂ NHR ₄

TE ₁ -T ₁

TE ₁

GE ₁ -G ₁ -E ₁ -G ₂

In the tetraamine of Formula 1 above,

R ₁ and R ₂ are s-triazine residues E, one of R ₃ and R ₄ is s-triazine residue E and the remainder of R ₃ or R ₄ is hydrogen,

E is a chemical formula ego,

R is methyl, propyl, cyclohexyl or octyl, for example cyclohexyl,

R ₅ is alkyl having 1 to 12 carbons, for example N-butyl,

When R is propyl, cyclohexyl or octyl, in the compound of formula 2 or formula 2a,

T and T ₁ are each tetraamine substituted by R ₁ to R ₄ as defined for Formula 1,

(1) one of the s-triazine residues E in each tetraamine is replaced by a group E ₁ forming a bridge between two tetraamines T and T ₁ , wherein E ₁ is Or

(2) group E ₁ may have two ends in the same tetraamine T as in Formula 2a, when two of the E residues of the tetraamine are replaced with one E ₁ group, or

(3) the three s-triazine substituents of tetraamine T can be E ₁ , such that all one E ₁ is bonded to T and T ₁ and another E ₁ has two ends in tetraamine T, and L is Propanediyl, cyclohexanediyl or octanediyl,

In the compound of Formula 3,

G, G ₁ and G ₂ are each tetraamine substituted by R ₁ to R ₄ as defined for Formula 1, wherein G and G ₂ each replace one of the s-triazine residues E with E ₁ , G ₁ by replacing two of the triazine moieties E in E _1, a bridge exists between G and G ₁ and a second bridge between G ₁ and G ₂ exists, and;

2 to 4 equivalents of 2,4-bis [(L-hydrocarbyl-oxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine are N Reacting with one equivalent of, N'-bis (3-aminopropyl) ethylenediamine to prepare a mixture;

The hindered amine is a compound of formula 3b,

In Formula 3b above,

Index n is 1 to 15,

R ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene-di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene), or 1,4-piperazindiyl, -O- or> NX ₁ where X ₁ Is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or is interrupted with one of the meanings of R ₁₄ described below but excluding hydrogen) or C ₄ -C ₁₂ alkylene;

R ₁₂ is a group of Formula 1b 'or Formula 1c';

In Formula 1b 'or Formula 1c' above,

when m is 2 or 3, X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Or C ₇ -C ₉ phenylalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl;

The radicals X ₃ are independently of each other C ₂ -C ₁₂ alkylene;

R ₁₃ , R ₁₄ and R ₁₅ are the same or different and are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₁₈ alkenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl phenyl; Tetrahydrofurfuryl or C ₂ -C ₄ alkyl, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula 1e 'wherein the 2, 3 or 4 position is substituted with OH;

In Formula 1e 'above,

Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ .

-N (R ₁₄ ) (R ₁₅ ) is further a group of formula 1e ';

The radicals A, independently of one another, are —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or a group of formula 3d;

In Formula 3d above,

X is —O— or> NR ₁₆ where R ₁₆ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl C ₅ -C ₁₂ cycloalkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; tetrahydrofurfuryl, a group of formula 3f or 2, 3 or Position 4 is C ₂ -C ₄ alkyl substituted by —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula 1e ′;

R ₁₁ has one of the meanings defined for R ₁₆ ;

The radicals B have one of the meanings defined for A independently of one another.

When R ₂ is a monovalent acyl radical of carboxylic acid, it is, for example, acyl radical of acetic acid, stearic acid, salicylic acid, benzoic acid or β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid.

When R ₂ is a divalent acyl radical of dicarboxylic acid, for example, oxalic acid, adipic acid, succinic acid, suberic acid, sebacic acid, dibutyl malonic acid, dibenzyl malonic acid, butyl- (3,5) -Di-t-butyl-4-hydroxybenzyl) -malonic acid or bicycloheptanedicarboxylic acid, with succinate, sebacate, phthalate and isophthalate being particularly preferred.

When R ₂ is a divalent acyl radical of dicarbamic acid, for example, it is an acyl radical of hexamethylenedicarbamic acid or 2,4-toluylenedicarbamic acid.

Hindered alkoxyamine stabilizers of component (c) are well known in the art and are also known as N-alkoxy hindered amines, NOR hindered amines, NOR hindered amine light stabilizers or NOR HALS.

This is described, for example, in U.S. Pat. 5,021,481, 6,117,995, 6,271,377, and US Patent Application No. 09 / 505,529, filed February 17, 2000, and US Patent Application No. 09 / 794,710, filed February 27, 2001. , US Patent Application No. 09 / 714,717, filed November 16, 2000, US Patent Application No. 09 / 502,239, filed November 3, 1999, and US Patent Application No. 15, 2001 60 / 312,517. Relevant content of this patent and application is incorporated herein by reference.

U.S. Patent No. 6,271,377, and U.S. Patent Application Serial No. 09 / 505,529, filed Feb. 17, 2000, and U.S. Patent Application Serial No. 09 / 794,710, filed February 27, 2001, include the above-mentioned disabled hydroxy. Alkoxyamine stabilizers are described. For the purposes of the present invention, hindered hydroxyalkoxyamine stabilizers are considered to be a subgroup of hindered alkoxyamine stabilizers and are part of the component (c). Hindered hydroxyalkoxyamine stabilizers are also known as N-hydroxyalkoxy hindered amines or NOR HALS.

Typical nitroxy of component (a) is bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1-oxyl-2,2,6 , 6-tetramethylpiperidine, 4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxyl-2,2,6,6-tetra Methylpiperidine, 4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl -2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2, 6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2, 2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-t-butyl-benzoate, bis ( 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adi Fate, bis (1-oxyl- 2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl ) Terephthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) adipamide, N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) caprolactam, N- (1-oxyl -2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6-tris- [N-butyl-N- (1-oxyl-2,2,6 , 6-tetramethylpiperidin-4-yl)]-S-triazine, 4,4'-ethylenebis (1-oxyl-2,2,6,6-tetramethylpiperazin-3-one), 2-oxyl-1,1,3,3-tetramethyl-2-isobenzazole, 1-oxyl-2,2,5,5-tetramethylpyrrolidine, and N, N-bis- (1,1 , 3,3-tetramethylbutyl) nitroxide.

Nitroxyl stabilizers of component (a) are, for example, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1-oxyl- 2,2,6,6-tetramethylpiperidine, 4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxyl-2,2, 6,6-tetramethylpiperidine, 4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperi Din, and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one.

Certain embodiments provide that the nitroxy stabilizer of component (a) is a bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and 4-hydroxy-1-oxyl-2, 2,6,6-tetramethylpiperidine.

The hydroxylamine stabilizers of component (b) are described, for example, in U.S. Pat. 5,064,883.

Specific examples of suitable compounds of component (i) of the present invention include the following:

(a) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N'- Reaction product with bis (3-aminopropyl) ethylenediamine) [CAS Reg. No. 191680-81-6;

(b) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;

(c) bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

(d) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s Triazine;

(E) bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate;

(h) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-S-triazine;

(i) 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine;

(J) 1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine;

(k) 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;

(I) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

(m) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate;

(n) 2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino } -6- (2-hydroxyethylamino) -s-triazine; And

(o) chemical formula Of a compound wherein n is 1 to 15; or

End capped with 4,4'-hexamethylene-bis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine Oligomeric compounds which are condensation products with 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) butylamino] -s-triazine; or

End capped with 4,4'-hexamethylene-bis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine Oligomeric as condensation product with 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) butylamino] -s-triazine compound.

Compound (o) is described in Example 2 of US Pat. No. 6,117,995.

Steric hindered alkoxyamines or hydroxyalkoxyamines are, for example, 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6 -Chloro-S-triazine and the reaction product of N, N'-bis (3-aminopropyl) ethylenediamine) [CAS Reg. No. 191680-81-6; Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; Compound (i), compound (J), compound (k) or compound (o); Or a mixture of hindered alkoxyamines and hydroxyalkoxyamines.

Polymerizable hindered compound of component (i)

Ethylenically unsaturated polymerizable monomers containing sterically hindered amine moieties are described, for example, in US Pat. Nos. 4,983,737, 5,047,489 and 5,077,340, the disclosures of which are incorporated herein by reference.

Chemical formula of the present invention Or chemical formula H amine moieties having independently H ₂ , wherein L ₁ , L ₁ ′, L ₂ and L ₂ ′ are independently alkyl having 1 to 4 carbon atoms, or L ₁ and L ₂ or L ₁ ′ and L ₂ ′ together are penta Methylene) is substituted with a 1-N atom with an oxyl, hydroxyl or hydrocarbyloxy group,

The monomer is selected from the group consisting of:

In the above formula,

E is independently a hindered nitroxyl, hydroxylamine or alkoxyamine moiety,

R ₁ is oxyl, hydroxyl, straight or branched alkoxy having 1 to 36 carbon atoms, straight or branched chain alkenyloxy having 2 to 18 carbon atoms, straight or branched chain alkynyloxy having 2 to 18 carbon atoms, alkoxy having 7 to 15 carbon atoms, Substituted by cycloalkoxy having 5 to 12 carbon atoms, cycloalkenyloxy having 5 to 12 carbon atoms, saturated or unsaturated acyclic or tricyclic hydrocarbyloxy radical having 7 to 12 carbon atoms, aryloxy having 6 to 10 carbon atoms, or alkyl Aryloxy, or

R ₁ is -0-T- (OH) _b ,

R ₁ ′ is independently defined as for R ₁ ,

T is a linear or branched alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms, cycloalkenylene having 5 to 18 carbon atoms, or phenyl substituted with 1 or 2 alkyl groups having 1 to 4 carbon atoms. Linear or branched alkylene having 1 to 4 carbon atoms,

b is 1, 2 or 3, provided that b cannot exceed the number of carbon atoms of T, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atom of T,

X is a direct bond, -O (polyoxyalkyleneO)-, -O-, -NH- or -NG- with 2 to 12 carbon atoms, wherein G is alkyl having 1 to 8 carbon atoms,

X ₁ is a direct bond or -O-,

n is 1 or 2,

T ₁ , T ₂ and T ₄ are independently hydrogen, halogen, alkyl of 1 to 18 carbon atoms or aryl of 6 to 10 carbon atoms,

T ₃ is hydrogen or methyl,

R ₂ is hydrogen or alkyl of 1 to 12 carbon atoms,

R ₂ ′ is hydrogen, alkyl of 1 to 12 carbon atoms or cyano,

R ₃ and R ₄ are independently hydrogen, alkyl of 1 to 12 carbon atoms, -COOH or -COOG ₁ , wherein G ₁ is straight or branched alkyl of 1 to 12 carbon atoms,

R ₅ is straight or branched chain alkyl of 1 to 8 carbon atoms,

R ₅ ′ is independently defined as for R ₅ .

R ₁ and R ₁ ′ are, for example, oxyl, hydroxyl, alkoxy, cycloalkoxy or aralkoxy. For example, R ₁ is methoxy, propoxy, cyclohexyloxy or octyloxy.

For example, L ₁ , L ₂ , L ₁ ′ and L ₂ ′ are each methyl.

For example, R ₁ and R ₁ ′ are alkoxy having 1 to 18 carbon atoms, alkenyloxy, propargyloxy, benzyloxy or cyclohexyloxy having 2 to 3 carbon atoms.

G is alkyl having 1 to 4 carbons, for example.

For example, T ₁ and T ₂ are both hydrogen.

For example, T ₃ is hydrogen.

For example, R ₂ , R ₃ and R ₄ are each hydrogen or R ₃ and R ₄ are hydrogen and R ₂ and R ₂ ′ are methyl.

When R ₁ and R ₁ ′ are alkoxy, for example, methoxy, ethoxy, butoxy, amyloxy, octyloxy, nonyloxy, dodecyloxy, tetradecyloxy, octadecyloxy, eicosyloxy , Tricosyloxy, tricontyloxy or 2-hydroxy-2-methylpropoxy.

When R ₁ and R ₁ ′ are alkenyloxy, for example, vinyloxy, allyloxy, octenyloxy or oleyloxy.

When R ₁ and R ₁ ′ are alkynyloxy, for example, propargyloxy.

When R ₁ and R ₁ ′ are cycloalkoxy, it is, for example, cyclopentyloxy, cyclohexyloxy, cyclooctyloxy, cyclododecyloxy or 1-hydroxycyclohexyloxydi.

The polymerizable monomers of the present invention each comprise ethylenically unsaturated groups which provide monomers for polymerization using free radical initiation, photoinitiation, group transfer polymerization, graft polymerization, cationic polymerization or anionic polymerization. do. One or more monomers of the present invention may be used together.

The steric hindered piperidine ring system of the present invention may also be substituted, for example, with hindered piperazine, piperazinone, morpholinone, oxazolidine ring systems, and the like.

There are several synthetic procedures that can be used to prepare the polymerizable monomers of the invention comprising sterically hindered amine residues.

This includes:

(a) transesterification using 4-hydroxy-2,2,6,6-tetramethylpiperidine and lower alkyl esters of unsaturated acids such as acrylic acid, fumaric acid, muconic acid, and the like;

(b) esterification with 4-hydroxy-2,2,6,6-tetramethylpiperidine and acid chlorides such as acryloyl or methacryloyl chloride;

(c) amidation with 4-amino-2,2,6,6-tetramethylpiperidine and acid chlorides such as acryloyl or methacryloylchloride;

(d) ring closure of intermediate maleamic acid after imidization with cyclic anhydrides such as 4-amino-2,2,6,6-tetramethylpiperidine and maleic anhydride;

(e) halide substitutions with alkali metal alcoholates of unsaturated benzyl or allyl halides and 4-hydroxy-2,2,6,6-tetramethylpiperidine; And

(f) Catalytic oxidation of 4-acyloxyloxy-2,2,6,6-tetramethylpiperidine and t-butyl hydroperoxide or hydrogen peroxide preformed in the presence of a molybdenum trioxide catalyst and a hydrocarbon solvent.

Intermediates required to prepare the compounds of the present invention are predominantly conventional terms or may be prepared by conventional methods known in the art.

Polymerizable monomers comprising sterically hindered amine moieties of the invention include:

In the above example, -OR ₁ ′ may also be independently oxyl, hydroxyl, 2-hydroxy-2-methylpropoxy, 1-hydroxycyclohexyloxy, cyclohexyloxy or propoxy.

The ethylenically unsaturated polymerizable monomers of the present invention comprising sterically hindered amine moieties are for example selected from the group consisting of formulas (i) to (v).

In the formulas (i) to (v) above,

R ₂ is hydrogen or methyl.

The composition of the present invention may further advantageously comprise a hydrocarbyloxy hindered amine compound that is not an ethylenically unsaturated monomer.

Specific examples of suitable further hindered amine compounds further include compounds a to o above:

End capped with 4,4'-hexamethylene-bis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine An oligomeric compound that is a condensation product of 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) butylamino] -s-triazine

End capped with 4,4'-hexamethylene-bis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine Oligomeric as a condensation product of 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) butylamino] -s-triazine compound.

Such further hindered amine compounds are described, for example, in US Pat. Nos. 6,472,456 and 6,117,995, the disclosures of which are incorporated herein by reference. The final named compound is described, for example, in US Pat. No. 6,117,995.

Alkyl is straight or branched, for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, N-octyl, 2-ethylhexyl, n-nonyl, n- Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Cycloalkyl groups, for example, consist of 5 to 7 carbon atoms and include cyclopentyl and cyclohexyl; Cycloalkenyl groups usually include cyclohexenyl.

Aralkyl groups include, for example, benzyl, α-methyl-benzyl, α, α-dimethylbenzyl or phenethyl.

Aryl is, for example, phenyl, naphthyl and biphenyl.

Alkoxy, aryloxy and cycloalkoxy groups are defined as for the alkyl, aryl and cycloalkyl groups of the present invention.

Halogens are, for example, chloro and bromo.

Conventional flame retardant

Organic halogen flame retardants are, for example, as follows:

Chloroalkyl phosphate esters [ANTIBLAZEE ^R AB-100, Alright &WILSON; FYROL ^R FR-2, Akzo Nobel],

Tris (2-chloroethyl) phosphate,

Dibrominated diphenyl oxide [DE-60F, Great Lakes Corp.],

Decabromodiphenyl oxide (DBDPO; SAYTEX # 102E),

Tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate (PB 370 ^R , FMC Corp.),

Tris (2,3-dibromopropyl) phosphate

Tris (2,3-dichloropropyl) phosphate,

Chloric Acid,

Tetrachlorophthalic acid,

Tetrabromophthalic acid,

Bis- (N, N'-hydroxyethyl) tetrachlorphenylene diamine,

Poly-β-chloroethyl triphosphonate mixture,

Bis (2,3-dibromopropyl ether) of bisphenol A (PE68),

Brominated epoxy resin,

Ethylene-bis (tetrabromophthalimide) (SAYTEX ^R BT-93),

Bis (hexachlorocyclopentadieno) cyclooctane (DECLORANE PLUS ^R ),

Chlorinated paraffin,

Octabromodiphenyl ether,

Hexachlorocyclopentadiene derivatives,

1,2-bis (tribromophenoxy) ethane (FF680),

Tetrabromo-bisphenol A (SAYTEX ^R RB100),

Ethylene bis- (dibromo-norbornanedicarboxyimide) (SAYTEX ^R BN-451),

Bis- (hexachlorocyclopentadieno) cyclooctane,

PTFE

Tris- (2,3-dibromopropyl) -isocyanurate and

Ethylene-bis-tetrabromophthalimide.

Organic phosphorus flame retardants are, for example, as follows:

Tetraphenyl resorcinol diphosphite (FYROLFLEX ^R , Akzo Nobel),

Triphenyl phosphate,

Trioctyl phosphate,

Tricresyl Phosphate,

Tetrakis (hydroxymethyl) phosphonium sulfide,

Diethyl-N, N-bis (2-hydroxyethyl) -aminomethyl phosphonate,

Hydroxyalkyl esters of phosphoric acid,

Ammonium polyphosphate (APP) or (HOSTAFLAM ^R AP750),

Resorcinol diphosphate oligomer (RDP),

Phosphazene flame retardants and

Ethylenediamine diphosphate (EDAP).

Isocyanurate flame retardants include polyisocyanurate, esters of isocyanuric acid and isocyanurate. For example, hydroxyalkyl isocyanurate, for example tris- (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, tris (3-hydroxy-n- Propyl) isocyanurate or triglycidyl isocyanurate.

Melamine series flame retardants are, for example, melamine cyanurate, melamine borate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate.

Boric acid may be included as a flame retardant.

Particularly preferred conventional flame retardants are chloroalkyl phosphate esters, dibrominated diphenyl oxides, decabromodiphenyl oxides, tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate, bis (2) of bisphenol A , 3-dibromopropyl ether), brominated epoxy resin, ethylene-bis (tetrabromophthalimide), bis (hexachlorocyclopentadieno) cyclooctane, chlorinated paraffin, 1,2-bis (tribromo Phenoxy) ethane, tetrabromo-bisphenol A, ethylene bis- (dibromo-norbornanedicarboxyimide), bis- (hexachlorocyclopentadieno) cyclooctane, tris- (2,3-dibromo Propyl) -isocyanurate, ethylene-bis-tetrabromophthalimide, tris- (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, tris (3-hydroxy -N-propyl) isocyanurate, Wrigley isocyanurate, melamine is cyano click rate, melamine borate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate.

Halogenated flame retardants useful in the present invention include organic aromatic halogenated compounds such as halogenated benzenes, biphenyls, phenols, ethers or esters thereof, bisphenols, diphenyloxides, aromatic carboxylic acids or polyacids, anhydrides, amides or imides thereof; Organic alicyclic or polyalicyclic halogenated compounds; And organic aliphatic halogenated compounds such as halogenated paraffins, oligomers or polymers, alkylphosphates or alkylisocyanurates. Such components are mainly known in the art and described in US Pat. Nos. 4,579,906 (e.g. col. 3, lines 30-41), 5,393,812; see also Plastics Aditives Handbook, Ed. by H. Zweifel, 5TH ED., Hanser PUBL., Munich 2001, pp. 681-698.

Phosphene flame retardants are well known in the art. This is, for example, European Patent No. 1 104 766, Japanese Patent JP 07 292 233, German Patent DE 19 828 541, DE 19 88 536, Alborn Patent JP 11 263 885, US Patent 4,107,108, 4,108,805, 4,079,035 and 6,265,599. Related contents of US patents are incorporated herein by reference.

PTFE, polytetrafluoroethylene (e.g., Teflon ^R 6C; EI Du Pont) is viewed as a further flame retardant, as described in US Patent Application No. 60 / 312,517, filed August 15, 2001. It can be advantageously added to the composition of the invention.

Advantageously, the compositions of the present invention may comprise only trace amounts of antimony compounds, such as SB ₂ O ₃ , for example less than about 1 weight percent of component (A), for example less than about 0.1 weight percent; For example, the composition of the present invention does not necessarily contain antimony.

Flame retardant fillers are not required to improve flame retardant properties and achieve high ratings in UL-94 combustion tests (infrared). As a result, the compositions of the present invention may comprise only trace amounts of flame retardant fillers, for example less than about 3 weight percent of component (A), for example less than about 1 weight percent, for example less than about 0.1 weight percent. For example, the composition of the present invention does not necessarily contain antimony.

Flame retardant fillers are known in the art and are selected from the group consisting of magnesium hydroxide, alumina trihydrate and zinc borate. The coating may comprise a flame retardant filler, for example vermiculite or portland cement. Flame retardant fillers are inorganic compounds used for flame retardant properties and "fillers" are considered at sufficiently high levels.

When conventional fillers such as talc, calcium carbonate and the like are generally used to reduce the rate of burning droplets, for example in flow properties, such conventional fillers can also be used with the compositions of the present invention. Can be reduced. For example, the compositions of the present invention comprise only trace amounts of conventional fillers, eg, less than about 3 weight percent, such as less than 1 weight percent, such as less than about 0.1 weight percent of component (A). For example, the composition of the present invention does not necessarily include conventional fillers.

In addition, the present invention allows conventional fillers to replace more expensive flame retardant fillers.

The compositions of the present invention may more advantageously comprise nanoscale fillers. Nano scale fillers are also referred to as "nano clays" and are described in US Pat. Nos. 5,853,886 and 6,020,419, the disclosures of which are incorporated herein by reference.

Nanoscale fillers of the invention are, for example, phyllosilicates or smectite clays, for example lipophilic phyllosilicates, natural phyllosilicates, synthetic phyllosilicates or mixtures of such phyllosilicates. Nanoscale fillers of the invention are, for example, montmorillonite, bentonite, Weidelite, hectorite, saponite or Stevensite.

The resulting stabilizing composition of the present invention optionally also contains from about 0.01 to about 10 weight percent of component (A) such as various conventional additives, such as the materials described below or mixtures thereof, for example from about 0.025 to about 4 weight percent, for example, from about 0.1 to about 2 weight percent.

1. Antioxidant

1.1 alkylated monophenols such as 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4, 6-dimethylphenol, 2,6-di-t-butyl-4-ethyl Phenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (A-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4 -Meth-oxymethylphenols, linear or branched nonylphenols such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1 '-Yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) Phenols and mixtures thereof.

1.2 alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6 Ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-t-butyl-4-methoxy-phenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydro Quinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di -t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis- (3, 5-di-t-butyl-4-hydroxyphenyl) adi Fate.

1.4. Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thionyl ethers such as 2,2'-thiobis (6-t-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'- Thiobis (6-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di- sec-amylphenol), 4,4-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example, methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2-methylenebis [ 4-methyl-6- (A-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4- Methylphenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2,2-ethylidenebis (4,6-di-t-butylphenol), 2,2-ethylidene Bis (6-t-butyl-4-isobutylphenol), 2,2-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2-methylenebis [6- (α, α -Dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis- (2,6-di-t-butylphenol), 4,4-methylenebis (6-t-butyl-2-methylphenol) , 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methyl -Phenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-cy-2-methyl-phenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-t- Tyl-4'-hydroxyphenyl) butyrate, bis (3-t-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'- Hydroxy-5'-methylbenzyl) -6-t-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-t-butyl-4-hydroxy2-methylphenyl) -4-N-dodecylmercaptobutane, 1,1,5,5-tetra- (5-t-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy -3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-t-butylbenzyl mercaptoacetate, tris (3,5-di-t-butyl-4-hydroxybenzyl ) Amine, bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxy-benzyl) sulfide, iso Octyl-3,5-di-t-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis- (3,5-di-t-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3 -t-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di-t-butyl-4-hydroxybenzyl) Nates, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris- (3,5-di-t-butyl-4-hydroxy-benzyl) -2,4,6-trimethyl benzene, 1,4- Bis (3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-t-butyl-4 Hydroxybenzyl) phenol.

1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-t-butyl-4-hydroxy-anilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris- (3,5-di-t-butyl-4-hydroxy Oxyphenoxy) -1, 2,3-triazine, 1,3,5-tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2,4,6-tris- (3,5-di-t-butyl-4-hydroxy Phenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxy-phenylpropionyl) -hexahydro-1,3,5- Triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) iso-cyanurate.

1.11. Benzylphosphonates such as dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphospho , Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5 Calcium salt of monoethyl ester of di-t-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols such as 4-hydroxystealide, 4-hydroxystealide, octyl N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

1.13. β (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Cyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- Ester of 2,6,7-oxabicyclo [2.2.2] octane.

1.14. β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Cyanurate, N, N'-bis- (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-1-phospha- Ester of 2,6,7-oxabicyclo [2.2.2] octane.

1.15. 3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol , Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N & -bis (hydr Oxyethyl) oxamide, 3-thiaoundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6, 7-oxabicyclo [2.2. 2] ester of octane.

1.16. 3,5-di-t-butyl-4-hydroxyphenyl acetic acid and monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonane Diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (Hydroxyethyl) oxamide, 3-thiaundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-oxabicyclo [ 2.2.2] ester of octane.

1.17. Amides of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropy Onyl) hexamethylenediamide, N, N'-bis (3,5-di-t-butyl-4-hydroxy-phenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di -t-butyl-4-hydroxyphenylpropionyl) -hydrazide, N, N'-bis [2- (3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyloxy ) Ethyl] oxamide [Nau-gard ^R XL-1 manufactured by Uniroyal].

1.18. Ascorbic acid (vitamin C)

1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -P- Phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-P-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylene Diamine, N-isopropyl-N'-phenyl-P-phenylenediamine, N- (1,3-dimethylbutyl) -N'-P-phenylenediamine, N- (1-methylheptyl) -N'- Phenyl-P-phenylenediamine, N-cyclohexyl-N'-phenyl-P-phenylenediamine, 4- (P-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di -sec-butyl-P-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-t-octylphenyl ) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example P, P'-di-t-octyldiphenylamine, 4-n-butylami Phenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-t -Butyl-4-dimethylaminomethylphenol, 2,4'-diaminoylmethane, 4,4'-diaminoylmethane, N, N, N ', N'-tetramethyl-4,4'-diamino Nylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethyl Butyl) phenyl] amine, t-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated t-butyl / t-octyldiphenylamine, mixture of mono- and dialkylated nonylylamine, mono -And mixtures of dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated t-butyldiphenylamines, 2,3-dihydro-3, 3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono- and dialkylated t-butyl / t-octylphenothiazine , Mixtures of mono- and dialkylated t-octyl-phenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di-t- Butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1 , 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3 '-t-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-t-butyl-2'-hydroxyphenyl) Benzotriazole, 2- (2'-hydroxy-4-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2 -(3 ', 5'-bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2-3'-t-butyl-2'-hydroxy-5'-(2 -Octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-5 '[2- (2-ethylhexyloxy) -carbonylethyl] -2'- Hydroxyphenyl) -5-chloro-benzot Azole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl -2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-(2-octyloxycarbo Nylethyl) phenyl) benzotriazole, 2- (3'-t-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2 (3'-dodecyl-2-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl ) Phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3'-t Transesterification product of -butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO-CH ₂ CH _2- (where R is 3'-t-butyl-4'-hydroxy-5'-2H-benzotriazol-2-2ylphenyl, 2- [2'-hydroxy-3 '-( α, α-dimethylbene ) -5 '- (1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole; 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) -phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4' -Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids such as 4-tbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-t-butylbenzoyl) rezo Lecinol, benzoyl resorcinol, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxy Oxybenzoate, octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxy Oxybenzoate.

2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α- Cyano-β-methyl-β-methoxy-cinnamate, butyl α-cyano-β-methyl-β-methoxy-cinnamate, methyl α-carbomethoxy-β-methoxycinnamate and N- ( β-carbomethoxy-β-cyanovinyl) -2-methylindolin.

2.5. 2,2'-thio-bis- [4- (1,1,3 with or without additional ligands such as nickel compounds, for example n-butylamine, triethanolamine or N-cyclohexyl diethanolamine , 3-tetramethyl-butyl) phenol] (eg 1: 1 or 1: 2 complex), nickel dibutyldithiocarbamate, monoalkyl ester (eg methyl or ethyl ester) or 4-hydroxy Nickel salt of -3,5-di-t-butylbenzylphosphonic acid, nickel complex of ketoxime, for example nickel complex of 2-hydroxy-4-methylphenyl undecylketoxim, with or without additional ligand 1 Nickel complex of -phenyl-4-lauroyl-5-hydroxypyrazole.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate Nate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-t-butyl-4-hydroxybenzylmalonate, 1- (2 -Hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N, N'-bis (2,2,6,6-tetramethyl-4 Linear or cyclic condensation products of -piperidyl) hexamethylenediamine with 4-t-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl -4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetra-methyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-te Lamethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n- Butyl-2- (2-hydroxy-3,5-di-t-butylbenzyl) -malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza Spiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6 Tetramethylpiperidyl) succinate, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro Linear or cyclic condensation product with -1,3,5-triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1 Condensation products of 3,5-triazine with 1,2-bis (3-aminopropylamino) -ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2, Condensation product of 6,6-pentamethylpiperidyl) -1,3,5-triazine with 1,2-bis- (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7 , 9,9- Tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrroli Dean-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy A mixture of cy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa Condensation product of methylenediamine with 4-cyclohexylamino-2, 6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro- Condensation products with 1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl ) -N-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 7 , 7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4,5] decane with epichlorohydrin, product 1,1 -Bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N ' -Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxy-methylene-malonic acid and 1,2,2,6,6-pentamethyl-4-hydroxy Diesters of cipiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-olefin-copolymer and 2, Reaction product with 2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butoxa Nilide, 2,2'-didodecyloxy-5, 5'-di-t-butoxanilide, 2-ethoxy-2'-ethyloxanide, N, N'-bis (3-dimethyl Aminopropyl) oxamide, mixtures with 2-ethoxy-5-t-butyl-2'-ethoxanilide and 2-ethoxy-2'-ethyl-5,4'-di-t-butoxanilide , mixtures of o- and p-methoxy-disubstituted oxanilides, mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-tri Azine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyl-oxyphenyl) -6- (2, 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tri Decyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-pro Foxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy ) Phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy -2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl-phenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3, 5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- (2 -Hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1- Oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators such as N, N'-diphenyloxamide, N-salicyl-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N ' Bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydride, Oxanilide, isophthaloyl dihydride, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydride, N, N'-bis (salicyloyl) oxalyl dihydride, N , N'-bis (salicyloyl) thiopropionyl dihydride.

4. phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol Diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-t-butyl-6- Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (t-butyl-phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-t-butyl -Phenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-t-butyl- 12H-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-t-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-t -Butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-t-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxa Phosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) Pite], 2-ethylhexyl (3,3 ', 5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl- 2- (2,4,6-tri-t-butylphenoxy) -1, 3,2-dioxaphosphyran.

Specific examples are the following phosphides:

Tris (2,4-di-t-butylphenyl) phosphite [Irgafos ^R 168, Ciba-Geigy], tris (nonylphenyl) phosphite,

(A) , (B) ,

(C) ,

(D)

(E) ,

(F) And (G)

5. hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetedecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl -N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated fatty amine.

6. Nitrons such as N-benzyl-α-phenyl-nitron, N-ethyl-α-methyl-nitron, N-octyl-α-heptyl-nitron, N-lauryl-α-unde Sil-nitrone, N-tetradecyl-α-tridecyl-nitron, N-hexadecyl-α-pentadecyl-nitron, N-octadecyl-α-heptadecyl-nitron, N-hexadecyl-α From -heptadecyl-nitron, N-octadecyl-α-pentadecyl-nitron, N-heptadecyl-α-heptadecyl-nitron, N-octadecyl-α-hexadecyl-nitron, hydrogenated fatty amines Nitron derived from derived N, N-dialkylhydroxylamine.

7. Thio synergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers such as esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazoles or zinc salts thereof, zinc dibutyl Dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.

9. Copper salts and divalent manganese salts in combination with polyamide stabilizers such as iodides and / or phosphorus compounds.

10. Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, higher fatty acids such as calcium stearate Alkali metal salts and alkaline earth metal salts of late, zinc stearate, manganese behenate, magnesium stearate, sodium ricinolate, potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate)

11. Nucleating agents such as inorganic materials such as talc, metal oxides such as titanium dioxide or manganese oxides, such as phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds such as mono or polycarboxylic acids and salts thereof (eg 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate); Polymeric compounds such as ionic copolymers (ionomers). Specific examples include 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol and 1,3: 2,4 Di (benzylidene) sorbitol.

12. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, and other wood powder (s) ) Or fiber, synthetic fiber.

13. Other additives such as plasticizers, lubricants, emulsions, pigments, flow additives, catalysts, flow control agents, fluorescent brighteners, flame retardants, flame retardants, antistatic agents and blowing agents.

14. Benzofuranone and indolinones, for example, US Pat. No. 4,325,863; No. 4,338,244; 5,175,312; 5,175,312; 5,216,052; 5,216,052; 5,252,643; 5,252,643; German Patent Application Publication No. EP-A 4 316 611; EP-A 4 316 622; EP-A 4 316 876; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxymethoxy) -phenyl] -5, 7-di-t-butyl-benzofuran-2- On, 5,7-di-t-butyl-3- [4- (2-stearoyloxymethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-t -Butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-t-butyl-3- (4-ethoxyphenyl) benzofuran-2- On, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-t-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxy Phenyl) -5,7-di-t-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-t-butyl-benzofuran-2-one, 3- (2,3-di-methylphenyl) -5,7-di-t-butyl-benzofuran-2-one.

15. Amine oxides such as amine oxide derivatives, didecyl methyl amine oxide, tridecyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide as described in US Pat. Nos. 5,844,029 and 5,880,191, for example. . U.S. Patents 5,844,029 and 5,880,191 describe the use of saturated hydrocarbon amine oxides to stabilize thermoplastic resins. It is described that the thermoplastic resin composition may further include stabilizer mixtures selected from stabilizers or phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organophosphorus compounds, alkali metal salts of fatty acids and thio synergists.

Specific examples of additives are phenolic antioxidants (item 1 of the list), additionally hindered amines (item 2.6 of the list), benzotriazole and / or hydroxyphenyltriazole group light stabilizers (items 2.1 and 2.8 of the list). , Phosphites and phosphonites (item 4 in the list), and peroxide-decomposing compounds (item 5) and the like.

Further particular examples of additives (stabilizers) are benzofuran-2-ones, for example as described in US Pat. Nos. 4,325,863, 4,338,244 or 5,175,312.

The composition of the present invention may further comprise another UV absorber selected from the group consisting of s-triazine, oxanilide, hydroxybenzophenone, benzoate and α-cyanoacrylate. In particular, the present invention further provides one or more other 2-hydroxyphenyl-2H-benzotriazole; Another tris-aryl-s-triazine; Or an effective stabilization amount of the hindered amine or mixtures thereof. For example, additional components may include additional light stabilizers, metal surface stabilizers, metal oxides, such as pigments, dyes, plasticizers, antioxidants, thixotropes, leveling aids, basic co-stabilizers, UV absorbers and / or sterically hindered amines, Organophosphorus compounds, hydroxylamines and mixtures thereof, in particular pigments, phenolic antioxidants, calcium stearate, zinc stearate, 2- (2'-hydroxyphenyl) benzotriazole and 2- (2-hydroxyphenyl) UV absorbers of the -1,3,5-triazine group, and sterically hindered amines.

The composition of the present invention may also comprise a foaming agent. Examples include tris (2-hydroxylethyl) isocyanurate and ammonium polyphosphate, melamine, methylolated melamine, hexamethoxymethyl melamine, melamine monophosphate, melamine biphosphate, melamine polyphosphate, melamine pyrophosphate, urea, Dimethylurea, dicyandiamide, gluaniurea phosphate, glycine or amine phosphate. It releases nitrogen gas when it decomposes upon exposure to heating. Compounds that release carbon dioxide or water vapor can be used when exposed to heating.

The composition of the present invention is a carbonized material (polyhydro compound), for example, pentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritol polyurethane, phenol triethylene glycol, resorcinol, inositol, sorbitol, Dextrin and starch.

The composition of the present invention may comprise silica.

The additives and optional additional components of the present invention may be added to the coating composition individually or together with one another. If desired, the individual components may be mixed with one another, for example before incorporation into the coating in dry mixing, compression or melt.

Component (i) is advantageously from about 0.1 to about 10 weight percent, such as from about 0.25 to about 8 weight percent, for example from about 0.5 to about 3 weight percent, based on coating component (A). It may be contained in the composition of the present invention in the amount of. For example, component (i) is present in an amount of about 0.25 to about 10 weight percent or about 0.5 to about 10 weight percent based on component (A). For example, component (i) is present at about 0.1 to about 8 weight percent or about 0.1 to about 3 weight percent based on component (A).

Component (ii) advantageously comprises from about 0.5 to about 45 weight percent of coating (A), for example from about 3 to about 40 weight percent, such as from about 5 to about 35 weight percent of component (A). It is contained in the composition of this invention in the quantity. For example, component (ii) may contain about 0.5 to about 10 weight percent, about 1 to about 10 weight percent, about 3 to about 10 weight percent, or about 5 to about 10 weight, based on the weight of the polymeric substrate. Used as For example, component (ii) may contain from about 0.5 to about 8 weight percent, from about 0.5 to about 6 weight percent, from about 0.51 to about 5, based on the weight of the polymeric substrate (e.g., resin binder (A)). Weight percent or from about 0.5 to about 3 weight.

The ratio (weight ratio) of component (i) to component (ii) may be, for example, from about 1: 5 to about 1: 200, for example from about 1: 50 to about 1: 100, or from about 1: 10 to About 1:25. For example, the ratio of component (i) to component (ii) may be about 1: 10 to about 1: 200, about 1: 25 to about 1: 200, about 1: 50 to about 1: 200 or about 1: 100. To about 1: 200. For example, the weight ratio of component (i) to component (ii) may be about 1: 5 to about 1: 100, about 1: 5 to about 1: 50, about 1: 5 to about 1: 25, or about 1: 5 to about 1: 10.

The amount of any conventional flame retardant used depends on the effectiveness of the particular compound (s), the particular coating and the type of application, for example as an amount of 30 to 45% by weight of the compound decabromodiphenyl oxide in the flame retardancy of the final composition. May be valid. Isocyanurate flame retardants are typically used at from about 1 to about 10 weight percent, for example from about 3 to about 6 weight percent, based on component (A).

The coating compositions of the present invention are themselves flame retardants and likewise impart flame retardancy to the substrates and articles to which they are coated. Thus, a further subject matter of the invention is

Coating (A) and

Steric hindrance nitroxyl stabilizer (a),

Steric hindrance hydroxylamine stabilizers (b) and

At least one compound (i) selected from the group consisting of sterically hindered alkoxyamine stabilizers (c) and

Organic halogen flame retardant (d),

Organic phosphorus flame retardant (e),

Isocyanurate flame retardant (f) and

A flame retardant coated article comprising a flame retardant effective amount of a mixture (B) with one or more conventional flame retardants (ii) selected from the group consisting of melamine-based flame retardants (g).

Further subject matter of the present invention

Resin binder (A) and

Optionally one or more ethylenically unsaturated polymerizable monomers (i) comprising sterically hindered nitroxyl, hydroxylamine or alkoxyamine residues

Organic halogen flame retardant (a),

Organic phosphorus flame retardant (b),

Isocyanurate flame retardant (c) and

A flame retardant coating article comprising a substrate coated with a flame retardant coating composition comprising a mixture (B) a flame retardant effective amount of at least one conventional flame retardant (ii) selected from the group consisting of melamine-based flame retardants (d).

The effective amount of flame retardant of component (B) is necessary to show the flame retardant efficiency, which is established as one of the standard methods used to evaluate flame retardancy. This is described in NFPA 701 Standard Methods of Fire Tests for Flame-Resistant Textiles and Films, 1989 and 1996 editions; the UL 94 Test for Flammability of Plastic Materials for Parts in Devices and Appliances, Edition, October 29, 1996; Limiting Oxygen Index (LOI), ASTM D-2863; and Cone Calorimetry, ASTM E-1354. The rating according to the UL 94 V test is as follows:

Rating Time after printing Combustion drip Clamping After Combustion V-0 <10 seconds none none V-1 <30 seconds none none V-2 <30 seconds has exist none failure <30 seconds has exist failure > 30 seconds none

Application tests include:

ASTM F1173 Fiber Glass Pipe and Assembly (Offshore / Marine)

UL 94 and 746C tests for flammability of plastic materials in parts in equipment and installations

UL 723

IEEE-45-Recommended Practice for Insulation on Ships

IEEE-383-Criteria for Test Types of IE Electrical Cables, Electric Field Junctions, and Coupling Groups for Nuclear Power Generation Points

ASTM-D-1360-Flame Retardant of Paint (Cabinet Method)

ASTM-E-84-Testing Surface Combustion Properties of Building Materials

ASTM-E-119-Fire Test of Building Structural Materials

ASTM-E-162-Surface Flammability of Materials Using Radiant Thermal Energy Sources

ASTM F 84

FAA 14-25. 853 ,. 855 ,. 856 ,. 867-Aviation and Rainfall (Fireproof)

Paper Substrate (Saturator) [Michelman]: ASTM E-162, ASTM E-662, NFPA 701, TAPPI 461

Corrugated w / FR coating (Michel only): ASTM E-162 / 662, FMR heat release, NFPA 30, ASTM E-84, NFPA 703, UL723

NFPA 703: Flame Retardant Impregnated Wood and Flame Retardant Coatings for Building Materials

NFPA 255, fire resistance test of building structural materials

Military details DOD-En 24607A and DOD-R-21417A (SH)

Concurrent additives found to be particularly useful for use of the compounds of the present invention in flame retardant compositions are:

UV absorbers:

2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole, [TINUVI ^R 234, Ciba Specialty Chemicals Corp .;

2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, (TINUVINO ^R P, Ciba Specialty Chemicals Corporation);

5-chloro-2- (2-hydroxy-3,5-di-t-butylphenyl) -2H-benzotriazole, (TINUVIN ^R 327, Ciba Specialty Chemicals Corporation);

2- (2-hydroxy-3,5-di-t-amylphenyl) -2H-benzotriazole, (TINUVIN ^R 328, Ciba Specialty Chemicals Corporation);

2- (2-hydroxy-3-α-cumyl-5-t-octylphenyl) -2H-benzotriazole, (TINUVIN ^R 928, Ciba Specialty Chemicals Corporation);

2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, (TINUVIN ^R 120, Ciba Specialty Chemicals Corporation);

2-hydroxy-4-n-octyloxybenzophenone, (CHIMASSORB ^R 81, Ciba Specialty Chemicals Corporation);

2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -S-triazine, [CYASORBO ^R 1164, Cytec].

The following examples are for illustrative purposes only and should not be construed as limiting the scope of the invention in any way whatsoever. In the description, the range of room temperature means 20 to 25 ° C. Percentages are based on weight of the coated substrate, unless otherwise noted.

Test Methods

NFPA 701 Standard Method for Fire Testing Fire Retardant Fibers and Films, 1989 and 1996 editions;

UL 94 test for flammability of plastic materials in parts in equipment and installations, October 29, 1996, 5th edition;

Limiting oxygen index (LOI), ASTM D-2863;

Conical calorimeter, ASTM E-1 or ASTM E 1354;

ASTM D 2633-82, Combustion Test.

Example 1 Coatings on TPO

Molded test pieces are injection molded to form thermoplastic, olefin (TPO) pellets containing pigments, phosphites, phenolic antioxidants or hydroxylamines, metal stearates, ultraviolet light absorbers or hindered amine stabilizers, or UV absorbers and hindered amine stabilizers. Manufacture.

The pigmented TPO pellets were mixed by mixing the components in a Superior / MPM 1 "single screw extruder at 400 ° F. (200 ° C.) from a purified pigment or pigment concentration, simultaneous additives and commercially available TPO with a conventional multi-purpose screw (24: 1 / LD). Prepared, cooled in a water bath and pelletized The resulting pellets are molded to a frame size of 2 "x 2" at 60 mils (0.006 inch) at about 375 ° F. (190 ° C.) with a BOY 30M injection molding machine.

Colored TPO formulations are formulated with a rubber modifier, such as ethylidene norbornene stabilized with a basic stabilization system consisting of N, N-dialkylhydroxylamine or hindered phenolic antioxidants in the presence or absence of an organic phosphorus compound. In the case of a copolymer or a mixed product reacted in situ containing a copolymer of propylene and ethylene in the presence or absence of powder, it is composed of polypropylene mixed with a rubber modifier.

All additive and pigment concentrations in the final formulations are expressed in weight percent based on resin.

The formulation comprises a thermoplastic olefin pellet and one or more of the following ingredients:

Pigment 0.0-2.0%,

Talc 0.0-50.0%,

Phosphite 0.0-0.1%,

Phenolic antioxidant 0.0-1.25%,

Hydroxylamine 0.0-0.1%,

Calcium stearate 0.05 to 0.10,

UV absorber 0.0-1.25% and

Hindered amine stabilizer 0.0-1.25%.

The above ingredients are dry mixed in a tumble dryer before extrusion and molding.

Polymer substrates are based in Akron, Ohio. Commercially available polyolefin mixture POLYTROPE ^R manufactured by A. Schulman Inc.

Light stable formulations are applied in one-pack paint systems and test for TPO / paint interaction and flame retardancy. Prior to application, the specimens are washed according to GM998-4801 and dried at 200 ° F. (94 ° C.) for 15 minutes. An adhesion promoter is applied to the dry film thickness of 0.2 to 0.4 miles. The sample is dried for 5 minutes before applying a 1K basecoat to a film thickness of 1.2 to 1.4 miles. The applied panel is dried for 3 minutes, then the clear coat is applied to a dry film thickness of 1.2 to 1.5 miles, then flash dried for 10 minutes and oven baked at 250 ° F. (121 ° C.) for 30 minutes.

One or more coating formulations comprise additives selected from compounds (a)-(o) of the present invention and flame retardants of the conventional organohalogen, organophosphorus, isocyanurate or melamine series.

Further coating formulations include additives selected from compounds (i) to (v) of the present invention and optionally flame retardants of the conventional organohalogen, organophosphorus, isocyanate or melamine series.

Paint adhesion is measured by Aggressive Adhesion Testing (proprietary test procedure conducted by Technical Finishing, INC.) And Taber Scuff. The applied panel is considered to be acceptable if it retains more than 80% of the paint finish. After an active adhesion test, samples with less than 5% paint loss are considered acceptable.

The coated product of the present invention is excellent in coating adhesion and flame retardancy. Additives (a) to (o) or (i) to (v) combined with conventional flame retardants may be present in some or all of the coating layers.

Example 2 Varnishes for Waterborne Wood

Aqueous coatings include coatings in significantly increasing proportions when used in a variety of applications, including automotive basecoats, industrial coatings, and trade coatings. Such coatings may be colored or transparent.

Test stabilizers (a) to (o) and (i) to (v) and conventional organohalogen, organophosphorus, isocyanate or melamine based flame retardants are predissolved in the cosolvent mixture and incorporated into the aqueous dispersion. Aqueous dispersions are commercially available acrylic / urethane hybrid resins. Cosolvent mixtures include TEXANOL ^R [2,2,4-trimethyl-1,3-pentanediol, Texaco] and ARCOSOLVE ^R TPM [tripropylene glycol methyl ether, Atlantic Richfield ( Atlantic Richfield).

0.45 g of each of the test stabilizers (a) to (o) and (i) to (v) and an appropriate amount of a conventional flame retardant are predissolved in 10 g of the cosolvent mixture and incorporated into the following composition:

ppw

FLEXTHANE ^R 630 [Air Products] 100.0

Foamaster VF 0.1

Water 10.0

TEXANOL / ARCOSOLVE / impaired amine 10.5

UV absorbers (TINUVINE ^R 1130, Ciba) 1.2

BYK 346 0.5

MICHEMLUBE ^R 162 2.0

Each coating is brush applied onto a 6 "x 6" piece of cedar and pine board. The coating weight applied is controlled by weighing the coating and brush before and after application and ensuring that the same weight of coating is applied to each piece.

The cladding strips are dried for 2 weeks at ambient temperature and then evaluated for flame retardancy. Cardboard is flame retardant.

Example 3 Fiber Optic Coatings

The radiation curable fiber optic coating was formulated as follows:

weight%

Wurpan acrylate oligomer 37

Bisphenol A Epoxy Diacrylate 28

Tetraethylene Glycol Diacrylate 21

Triethylene Glycol Diacrylate 4

Trimethylolpropane triacrylate 6

Benzophenone 1.5

2,2-dimethoxy-2-phenylacetophenone 0.7

Benzyl 0.5

Diethylamine 0.6

Phenothiazine 0.01

2-hydroxy-4-n-octoxybenzophenone 0.01

Silicon 0.2

N-[(2-vinylbenoamino) -ethyl] -3- 0.2

Aminopropyltrimethoxysilane (40% in MeOH)

The coating formulation further includes the additive selected from (a) to (o) and a conventional flame retardant. Other photoinitiators are suitable, for example, phosphine oxide photoinitiators. Cured coatings are excellent in flame retardancy.

Example 4 Fiber Optic Coatings

The radiation curable optical fiber coating is formulated as follows:

weight%

Urethane Acrylate Oligomer 20

Ethoxylated Bisphenol A Diacrylate 20

Propoxylated trimethylol propane triacrylate 32

Di-trimethylolpropane tetraacrylate 25

The formulation may further comprise an antiblocking agent, a silane additive or a phenolic antioxidant.

The formulation can be formulated with one or more photoinitiators, such as bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide [Irgacure ^R 819], bis (2,6-dimethoxybenzoyl) isooctyl phosph Pin oxide, [[4- (ethyl-methyl-amino) -phenyl]-(2,4,6-trimethyl-benzoyl) -phosphinoyl]-(2,4,6-trimethyl-phenyl) -methanone, [(4-Dimethylamino-phenyl)-(2,4,6-trimethyl-benzoyl) -phosphinoyl]-(2,4,6-trimethyl-phenyl) -methanone, 2,4,6-trimethylbenzoyl Diphenyl phosphine oxide, [benzyl- (4-methylsulfanyl-phenyl) -phosphinoyl]-(2,4,6-trimethyl-phenyl) -methanone and 1-hydroxycyclohexyl phenyl ketone (irga Cure ^R 184).

The coating formulation further comprises the additive selected from (i) to (v) and any conventional flame retardant. Cured coatings are excellent in flame retardancy.

Excellent results are also achieved when combining additives (a) to (o) or (i) to (v) with one of the conventional flame retardants described above in the following application systems:

Urethane Transparent Film

Coil coating

Kerosene phenolic varnish

Aromatic Urethane Varnish

Abrasion Resistant Coating Composition

Polyester urethane coating on polycarbonate

Glycidyl Methacrylate Powder Clear Film

Oil Modified Urethane Alkyd For Wood Coating

Preformed Film for Lamination on Plastic Parts

Coextrusion on PVC

Coextrusion on Polycarbonate

Multilayer polymer on ABS

Photocurable White Pigment Film

Photocurable Transparent Film

Photocurable white powder film

Photocurable White Gel Film

Intumescent Mastic Fire Resistant Coating

Film on fiberglass

Fiber composite

Claims (19)

Coating (A) and Steric hindrance nitroxyl stabilizer (a), Steric hindrance hydroxylamine stabilizers (b) and At least one compound (i) selected from the group consisting of sterically hindered alkoxyamine stabilizers (c) and Organic halogen flame retardant (d), Organic phosphorus flame retardant (e), Isocyanurate flame retardant (f) and A flame retardant coating composition comprising a flame retardant effective amount of a mixture (B) with one or more conventional flame retardants (ii) selected from the group consisting of melamine-based flame retardants (g). Resin binder (A) and Optionally one or more ethylenically unsaturated polymerizable monomers (i) comprising sterically hindered nitroxyl, hydroxylamine or alkoxyamine residues Organic halogen flame retardant (a), Organic phosphorus flame retardant (b), Isocyanurate flame retardant (c) and A flame retardant coating composition comprising a flame retardant effective amount of a mixture (B) with one or more conventional flame retardants (ii) selected from the group consisting of melamine-based flame retardants (d). 3. The sterically hindered nitroxyl, hydroxylamine or alkoxyamine moiety of claim 2 independently Or chemical formula Wherein L ₁ , L ₁ ′, L ₂ and L ₂ ′ are independently alkyl having 1 to 4 carbon atoms, or L ₁ and L ₂ or L ₁ ′ and L ₂ ′ together are pentamethylene; Formula A group consisting of: wherein E is independently a hindered nitoxyl, hydroxylamine or alkoxyamine moiety, R ₁ is oxyl, hydroxyl, straight or branched chain alkoxy having 1 to 36 carbon atoms, straight or branched chain having 2 to 18 carbon atoms Alkenyloxy, straight or branched alkynyloxy having 2 to 18 carbon atoms, aralkoxy having 7 to 15 carbon atoms, cycloalkoxy having 5 to 12 carbon atoms, cycloalkenyloxy having 5 to 12 carbon atoms, saturated or unsaturated carbon atoms Acyclic or tricyclic hydrocarbyloxy radicals, aryloxy having 6 to 10 carbon atoms, or aryloxy substituted with alkyl, or R ₁ is -0-T- (OH) _b , preferably oxyl, hydroxyl, methoxy, propoxy, cyclohexyloxy and octyloxy, 2-hydroxy-2-methyl-propoxy, or 1-hydroxy-cyclohexyl-oxy, R ₁ 'is R ₁ as with respect to the stand T is a straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms, cycloalkenylene having 5 to 18 carbon atoms, substituted with phenyl, or 1 or 2 alkyl groups having 1 to 4 carbon atoms. Straight or branched alkylene having 1 to 4 carbon atoms substituted with phenyl substituted with b, b is 1, 2 or 3 provided that b cannot exceed the number of carbon atoms in T and b is 2 or 3 And each hydroxyl group is attached to a different carbon atom of T, X is a direct bond, -O (polyoxyalkyleneO)-, -O-, -NH- or -NG-, having from 2 to 12 carbon atoms , G is alkyl of 1 to 8 carbon atoms, X ₁ is a direct bond or -O-, n is 1 or 2, T ₁ , T ₂ and T ₄ are independently hydrogen, halogen, 1 to 18 carbon atoms alkyl or aryl having 6 to 10, T ₃ is hydrogen or methyl, R ₂ is hydrogen or a 1 to 12 carbon atoms Kill and, R ₂ 'is hydrogen, alkyl or cyano group having 1 to 12 carbon atoms, R ₃ and R ₄ are independently hydrogen, C 1 -C 12 alkyl, -COOH or -COOG ₁ (wherein, G ₁ is a carbon number 1 to 12 straight or branched alkyl, R ₅ is straight or branched alkyl having 1 to 8 carbon atoms, and R ₅ ′ is independently defined as with respect to R ₅ . The compound of claim 3 wherein the monomer is of formula Wherein the ethylenically unsaturated polymerizable monomer comprising a sterically hindered nitroxyl, hydroxylamine or alkoxyamine moiety is selected from formulas i through: wherein R ₂ ′ is hydrogen or methyl and R ₃ and R ₄ are hydrogen. A composition selected from the group consisting of formula v. Formula i Formula ii Formula iii Formula iv Chemical formula v The method of claim 1 or 2, containing no antimony compound, or less than about 1% by weight, based on the weight of component (A), containing no fillers, A composition containing by weight less than about 3% by weight. The compound according to claim 1 or 2, wherein component (A) is an alkyd resin; Chlorinated alkyd resins; Polyurethane resins; Thermoplastic acrylic resins; Acrylic alkyl; Acrylic resins; Latex emulsions; Acrylic alkyd or polyester resins; Acrylic alkyd or polyester resins modified with silicone, isocyanates, ketimines or oxazolidines; Phenol-formaldehyde resins; Resorcinol-formaldehyde resins; Epoxy resins; Epoxide resins crosslinked with carboxylic acids, anhydrides, polyamines or mercaptans; And acrylic or polyester resin systems modified with reactive groups in the backbone thereof and crosslinked with epoxides; In particular a resin binder selected from epoxy resins. The composition of claim 1 wherein the coating is a thermoplastic layer, in particular a polypropylene layer. The method according to claim 1 or 2, which is waterborne or solvent borne, powder coating composition or gel coating formulation, mastic, adhesive, binder, cork, putty, mortar or sealing formulation, ambient curing, A radiation cured, oven cured or catalytic cured composition, which is a transparent or colored composition. 3. Foaming agents, blowing agents, carbonizing agents and binders, thixotropes, foaming agents and carbonizing agents, pigments, dyes, plasticizers, phenolic antioxidants, leveling aids, basic aids according to claim 1 or 2 A composition further comprising a component selected from stabilizers, nitron stabilizers, amine oxide stabilizers, benzofuranone stabilizers, UV absorbers, hindered amines, metal surface stabilizers, metal oxides, organophosphorus compounds, hydroxylamines, and mixtures thereof. The compound of claim 1, wherein the compound of component (i) is [Wherein G ₁ and G ₂ are independently alkyl having 1 to 8 carbon atoms, they are together pentamethylene, Z ₁ and Z ₂ are each methyl, or Z ₁ and Z ₂ together are ester, ether, amide, amino, Forms a binding moiety that may be further substituted with a carboxy or urethane group, E is oxyl, hydroxyl, alkoxy, cycloalkoxy, aralkoxy, aryloxy, -O-CO-OZ ₃ , -0-Si (Z ₄ ) ₃ , -O-PO (OZ ₅ ) ₂ or -O-CH ₂ -OZ ₆ , wherein Z ₃ , Z ₄ , Z ₅ and Z ₆ are selected from the group consisting of hydrogen, aliphatic, araliphatic and aromatic moieties Or E is -0-T- (OH) _b (wherein T is linear or branched alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms, cycloalkenylene having 5 to 18 carbon atoms, or Straight chains having 1 to 4 carbon atoms substituted with phenyl or substituted with phenyl substituted with 1 or 2 alkyl groups of 1 to 4 carbon atoms, or Is branched alkylene, b is 1, 2 or 3, provided that b cannot exceed the carbon number of T, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atom of T) It is composed of; The compound of claim 1 wherein the compound of component (i) (a) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N'- Reaction products with bis (3-aminopropyl) ethylenediamine); (b) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; (c) bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; (d) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s Triazine; (e) bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; (h) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-S-triazine; (i) 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine; (j) 1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine; (k) 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; (l) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate; (m) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate; (n) 2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino } -6- (2-hydroxyethylamino) -s-triazine; And (o) chemical formula Of a compound wherein n is 1 to 15 and a compound (i) , Compound (ii) , Compound (iii) , Compound (iv) And compound (v) As well as a composition selected from the group consisting of mixtures thereof. The composition of claim 1 or 2, wherein the flame retardant of component (ii) is selected from the group consisting of: Chloroalkyl phosphate esters, Tris (2-chloroethyl) phosphate, Dibrominated diphenyl oxide, Decabromodiphenyl oxide, Tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate, Tris (2,3-dibromopropyl) phosphate Tris (2,3-dichloropropyl) phosphate, Chloric Acid, Tetrachlorophthalic acid, Tetrabromophthalic acid, Bis- (N, N'-hydroxyethyl) tetrachlorphenylene diamine, Poly-β-chloroethyl triphosphonate mixture, Bis (2,3-dibromopropyl ether) of bisphenol A, Brominated epoxy resin, Ethylene-bis (tetrabromophthalimide), Bis (hexachlorocyclopentadieno) cyclooctane, Chlorinated paraffin, Octabromodiphenyl ether, Hexachlorocyclopentadiene derivatives, 1,2-bis (tribromophenoxy) ethane, Tetrabromo-bisphenol A, Ethylene bis- (dibromo-norbornanedicarboxyimide), Bis- (hexachlorocyclopentadieno) cyclooctane, PTFE Tris- (2,3-dibromopropyl) -isocyanurate, Ethylene-bis-tetrabromophthalimide, Tetraphenyl resorcinol diphosphite, Triphenyl phosphate, Trioctyl phosphate, Tricresyl Phosphate, Tetrakis (hydroxymethyl) phosphonium sulfide, Diethyl-N, N-bis (2-hydroxyethyl) -aminomethyl phosphonate, Hydroxyalkyl esters of phosphoric acid, Ammonium polyphosphate, Resorcinol diphosphate oligomer, Phosphazene flame retardants, Ethylenediamine diphosphate, Polyisocyanurate, Esters of isocyanuric acid, Isocyanurate, Hydroxyalkyl isocyanurate, Melamine cyanurate, Melamine borate, Melamine phosphate, Melamine polyphosphate and Melamine pyrophosphate. The method according to claim 1 or 2, wherein component (i) is present at about 0.1 to about 10% by weight, based on component (A), and the flame retardant of component (ii) is selected from the resin binder (A). And from about 0.5 to about 45 weight percent, based on weight. Coating (A) and Steric hindrance nitroxyl stabilizer (a), Steric hindrance hydroxylamine stabilizers (b) and At least one compound (i) selected from the group consisting of sterically hindered alkoxyamine stabilizers (c) and Organic halogen flame retardant (d), Organic phosphorus flame retardant (e), Isocyanurate flame retardant (f) and A flame-retardant coating article comprising a substrate coated with a flame-retardant coating composition comprising a mixture (B) a flame-retardant effective amount of at least one conventional flame retardant (ii) selected from the group consisting of melamine-based flame retardants (g). Resin binder (A) and Optionally one or more ethylenically unsaturated polymerizable monomers (i) comprising sterically hindered nitroxyl, hydroxylamine or alkoxyamine residues Organic halogen flame retardant (a), Organic phosphorus flame retardant (b), Isocyanurate flame retardant (c) and A flame-retardant coating article comprising a substrate coated with a flame-retardant coating composition comprising a mixture (B) a flame-retardant effective amount of at least one conventional flame retardant (ii) selected from the group consisting of melamine-based flame retardants (d). The method of claim 14 or 15, wherein the substrate is made of iron, steel, stainless steel, aluminum and other nonferrous metals, wood, plywood, paper, cardboard, resin plywood, particulate cardboard, plastic, thermoplastic, epoxy, neoprene, rubber, A coating product selected from the group consisting of composites, fiber glass reinforced composites, polyesters, polymeric foams, masonry, fibers or fabrics, wire and cable structures and circuit boards. The process of claim 14 or 15, wherein the substrate is polyvinyl chloride, polycarbonate, polyolefin, thermoplastic polyolefin, ABS or polyester, or woven, knitted or nonwoven and is polyethylene, polypropylene, polyethylene terephthalate, polyamide, cellulose or A coated product selected from the group consisting of cotton-based fibers or fabrics. 16. The coated article according to claim 14 or 15, which is an automotive thermoplastic olefin structure, a coextruded plastic article or a coated optical fiber. 16. The coated article according to claim 14 or 15, wherein the coating is extruded plastic.