CN1646615A - Flame retardant coatings - Google Patents
Flame retardant coatings Download PDFInfo
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- CN1646615A CN1646615A CNA03808015XA CN03808015A CN1646615A CN 1646615 A CN1646615 A CN 1646615A CN A03808015X A CNA03808015X A CN A03808015XA CN 03808015 A CN03808015 A CN 03808015A CN 1646615 A CN1646615 A CN 1646615A
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- fire retardant
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
Abstract
Provided are flame retardant coating compositions and articles coated therewith, which compositions comprise (A) a coating and (B) an effective flame retarding amount of a mixture of (i) at least one compound selected from the group consisting of the (a) sterically hindered nitroxyl stabilizers, (b) sterically hindered hydroxylamine stabilizers and (c) sterically hindered alkoxyamine stabilizers and (ii) at least one conventional flame retardant selected from the group consisting of (d) organohalogen flame retardants, (e) organophosphorous flame retardants, (f) isocyanurate flame retardants and (g) melamine based flame retardants. In flame retardant coating compositions that comprise at least one ethylenically unsaturated, polymerizable monomer, which monomer contains a sterically hindered amine moiety, the conventional flame retardant is an optional component. The coated articles are for example iron, steel, stainless steel, aluminum and other non-ferrous metals, wood, plywood, paper, cardboard, chip board, particle board, plastics, thermoplastics, epoxies, neoprene, rubber, composites, fiberglass reinforced composites, polyesters, polymeric foam, masonry, fabric or textiles, optical fibers, wire and cable constructions and circuit boards.
Description
The present invention relates to comprise at least a sterically hindered nitroxyl, the anti-flaming dope of oxyamine or alkoxylamine compound and at least a conventional flame retardants.In comprising at least a ethylenic unsaturated polymerizable monomer fire retardant coating compositions of (described monomer comprises sterically hindered amine moiety), described conventional flame retardants is dispensable component.
Background of the present invention
U.S.Pat.No.5,096,950 discloses the Sb that contains of some NOR (N-alkoxyl group) bulky amine and bromination
2O
3Fire retardant shared in polypropylene.
U.S.Pat.No.5,393,812 disclose by halogenation alkyl phosphate or phosphonate fire retardant and alkoxylamine official can bulky amine combine the polyolefin compositions that becomes fire-retardant.
U.S.Pat.No.5,844,026 disclose the polyolefin compositions that comprises some NOR bulky amine and some conventional flame retardants.
U.S.Pat.No.6,117,995 disclose the fire retardant that some N-alkoxyl group bulky amine can be used as organic polymer.
U.S.Pat.No.6,271,377 disclose the polyolefin compositions that comprises N-hydroxy alkoxy base bulky amine and halogenated fire-retardants.
U.S.Pat.No.6,309,987 and convertible WO 99/54530 propose to comprise the polyolefine nonwoven fire retardant fabric of N-alkoxylamine.
Be used for the stable fire retardant systems-R.Srinivasan of polyolefinic revolutionary UV, A.Gupta and D.Horsey, Int.Conf.Addit.Polyolefins 1998, and the 69-83 proposition comprises the polyolefine of the conventional flame retardants of some NOR bulky amine and halogen-containing and phosphorus.
Progress-the R.Srinivasan that is used for polyolefinic revolutionary fire retardant systems, B.Rotzinger, Polyolefins 2000, and Int.Conf.Polyolefins 2000, and 571-581 proposes to comprise the polyolefine of some NOR bulky amine and bromination and phosphonium flame retardant.
N.Kaprinidis and R.King have discussed the NOR bulky amine as the application of fire retardant in polyolefine in the summary of the plastic engineer institute website of announcement in September calendar year 2001.This summary is the paper that is submitted to polymer modifiers and branch of additive branch, is used for Polyolefins 2002 meetings (Houston, TX) upward introduction on February 24th, 2002.The website is www.PMAD.org.
EP 0792911 A2 discloses the polyolefin compositions that comprises alkoxylamine official energy bulky amine and three (three halogen amyl groups) phosphate flame retardant.
WO 99/00450 (common unsettled U.S. application Nos.09/502 submitted on November 3rd, 239,1999 and on November 16th, 09/714,717,2000 submitted) discloses the purposes of some N-alkoxyl group bulky amine as fire retardant.
EP 568354, U.S.Pat.No.6, and 084,008 and U.S.Pat.No.5,723,515 have described refractory paint.
The ethylenic unsaturated polymerizable monomer that comprises sterically hindered amine moiety for example is disclosed in U.S.Pat.Nos.4, and 983,737,5,047,489 and 5,077,340.
Fire retardant (FR) market comprises the product that is used to disturb combustion processes by chemistry and/or physics mode at present.On the mechanism, these FRs have been suggested in the goods combustion processes in gas phase, and condensation plays a role mutually or among both.Organic halogen is considered to produce halogen species (as HX) to disturb from the free radical of polymeric substrate organic " fuel " in gas phase.Synergistic agent is considered to form other chemical substance to disturb the burning in the gas phase with the HX reaction, forms antimony halides and water vapour as weisspiessglanz and HX reaction.Antimony compounds such as ANTIMONY TRIOXIDE SB 203 99.8 PCT are also as the free-radical scavengers that forms antimony halides.Therefore, they can suppress the propagation of fire.
Although antimony compounds on cost is implemented effectively, they recently since when in the presence of halogenated fire-retardants, burning the By-product Toxicology of formation go wrong.It is carcinogenic arsenic compound that weisspiessglanz comprises the trace quilt doubtful usually.Because these ecological problems, trend substitutes ANTIMONY TRIOXIDE SB 203 99.8 PCT in present commercial fire retardant is used.But be very difficult to find a kind of environment friendliness and with regard to cost is implemented effective synergistic agent.
Another reason that adds flame retardant additives is to being to prevent with the drippage in the fiery process.In combustion processes, partial polymer separates from matrix with droplet profile.Usually, drop is incendiary and fire is spread the generation great risk.Usually in polymkeric substance, add mass filler such as talcum, but mechanical property is had a negative impact.Sometimes other filler of Shi Yonging comprises lime carbonate, magnesiumcarbonate, zinc borate, silicate, siloxanes, glass fibre, glass sphere, asbestos, kaolin, mica, barium sulfate, calcium sulfate, metal oxide, hydrate and oxyhydroxide such as zinc oxide, magnesium hydroxide, alumina trihydrate, silica, Calucium Silicate powder, Magnesium Silicate q-agent.
Have been found that if coating comprises at least a sterically hindered nitroxyl that is selected from; the compound of oxyamine and alkoxylamine additive and at least a reliable conventional flame retardants; just prepare coating with good flame retardancy; further find; good flame-retardance can coating by comprising (i) at least a compound that is selected from the ethylenic unsaturated polymerizable monomer, described monomer comprise sterically hindered amine moiety and optionally (ii) the coating composition of at least a reliable conventional flame retardants make.By using these flame retardant additives, antimony compounds and filler can be greatly reduced or substitute.Because present sterically hindered amines additive is an effective stabilizer, coating composition of the present invention is protected not to be subjected to light effectively, the harmful effect of oxygen and/or heat.
Detailed disclosure
The present invention relates to fire retardant coating compositions, comprise
(A) coating and
(B) the following mixture of flame-retardant effective amount
(i) at least aly be selected from following compound
(a) sterically hindered nitroxyl stablizer,
(b) sterically hindered oxyamine stablizer and
(c) sterically hindered alkoxylamine stablizer and
(ii) at least aly be selected from following conventional flame retardants
(d) organic halogen fire retardant,
(e) organophosphorous fire retardant,
(f) the isocyanuric acid ester fire retardant and
(g) melamine based flameproofing.
The invention further relates to fire retardant coating compositions, comprise
(A) resin glue and
(B) flame-retardant effective amount
(i) at least a ethylenic unsaturated polymerizable monomer, described monomer comprises sterically hindered nitroxyl, oxyamine or alkoxylamine part and
Optionally
(ii) at least aly be selected from following conventional flame retardants
(a) organic halogen fire retardant,
(b) organophosphorous fire retardant,
(c) the isocyanuric acid ester fire retardant and
(d) melamine based flameproofing.
Component (i) and additive combination (ii) are for providing flame retardant resistance to have synergy to coating.
Coating
Coating composition of the present invention (A) is a coating.It is for example to solidify paint, varnish, tackiness agent or sealant layer.In addition, it is thin ductile bed, and example is the extruded thermoplastic coating as further described herein.
Paint or lacquer formulation comprise resin, solvent, pigment, filler, tensio-active agent and other typical component.
This anti-flaming dope for example is applicable to following field: building, and transportation, telecommunication, public utilities, the ocean, chemistry, oil is made and military affairs, hygiene department, medical sector, weaving and Clothing industry, automobile is used, packing, pharmacy, electric works, electronics and family expenses occasion.
The base material that is applicable to this coating is an iron for example, steel, stainless steel, aluminium and other non-ferrous metal, timber, multi-ply wood, paper, cardboard, chipboard, particle board, plastics, PVC (polyvinyl chloride), thermoplastics, TPO, epoxide, chloroprene rubber, rubber, matrix material and analogue.
This coating can be used for most of base materials and is used for harsh weather and envrionment conditions, and wherein hot, light, oxygen and moisture are possible degradation agentss.This coating is applicable to the interior and outer of house, roof, factory, commercial building, aircraft, vehicle, boats and ships, canoe, sailing boat and analogue.
Plastics and matrix material are according to suitable substrates of the present invention, fiberglass reinforced composite for example, polyester, polymer foams and thermoplastic resin such as polyolefine and TPO (TPO).
Coating of the present invention is applicable to painted tide of motorism plasticity alkene structures.
This coating is advantageously used in ocean occasion such as bulkhead, harbour, dock, cabin infiltration isolation layer, cable, conduit, cargo area, cabin and floor and offshore boring occasion.
This coating can be used for transporting occasion, for example at automobile, and bus, truck, freighter and aircraft are used to be coated with vehicle chassis, the waste gas system, gas tank, firewall, engine compartment, catalytic converter, cupboard, the cargo liner cover plate, the airport loading bridge, etc.
This coating is advantageously used in telecommunication, computer, public utilities, oil and chemical industry for example are used for cable and catheter jacket, optical fiber coating, the electric wire and cable that lubricating grease is filled, communications tower, fire infiltration isolation layer, sealing, pipeline overcoat, hold-up vessel, reactor, baking oven, distillation column, stove and analogue.
Coating of the present invention is suitable for the coating of making circuit card, for example is used for the radiation-curable coating of circuit card.
This coating is suitable for makes cable coating with as electric, control and communication cable, and for example at hank of cable and raceway, tapping box, the flame retardant bed of the cable that makes up together in cable trench and the similar applications.
Suitable optical fiber coating for example is disclosed in U.S.Pat.Nos.6, and 187,835,6,350,790,6,197,422 and 6,362,249, its disclosure is incorporated the present invention into as a reference at this.
The coating composition that comprises ethylenic unsaturated (B)
This coating composition is for example curable paint, varnish, tackiness agent or encapsulant composition.This composition be for example heat or radiation (UV-light, UV) curable.In addition, it is the curable film composition, and example is used for the thermoplastic paint composition of extruded films as further described herein.
Paint or lacquer formulation comprise resin, solvent, pigment, filler, tensio-active agent and other typical component.
This fire retardant coating compositions is applicable to for example building, transportation, telecommunication, public utilities, ocean, chemistry, oil is made and military field, hygiene department, medical sector, weaving and Clothing industry, automobile is used, packing, pharmacy, electric works, the coating of electronics and family expenses device.
The suitable substrates that is used for this coating composition is an iron for example, steel, stainless steel, aluminium and other non-ferrous metal, timber, multi-ply wood, paper, cardboard, chipboard, particle board, plastics, PVC (polyvinyl chloride), thermoplastics, TPO, epoxide, chloroprene rubber, rubber, matrix material, glass, glass fibre, plastic optical fibre and analogue.
This coating composition can be used for most of base materials and uses under harsh weather and envrionment conditions, and wherein hot, light, oxygen and moisture are possible degradation agentss.This coating is applicable to inside and outside the family, roof, factory, commercial building, aircraft, vehicle, boats and ships, canoe, sailing boat and analogue.
Plastics and matrix material are according to suitable substrate of the present invention, fiberglass reinforced composite for example, polyester, polymer foams and thermoplastic resin such as polyolefine and TPO (TPO).
The coating composition of the present invention tide of motorism plasticity alkene structures that is used to suitably paint.
This coating composition is advantageously used in ocean occasion such as bulkhead, harbour, dock, cabin infiltration isolation layer, cable, conduit, cargo area, cabin and floor and offshore boring occasion.
This coating composition can be used for transporting occasion, for example at automobile, and bus, truck, freighter and aircraft are used to be coated with vehicle chassis, the waste gas system, gas tank, firewall, engine compartment, catalytic converter, cupboard, the cargo liner cover plate, the airport loading bridge, etc.
This coating composition is advantageously used in telecommunication, computer, public utilities, oil and chemical industry for example are used for cable and catheter jacket, optical fiber coating, the electric wire and cable that lubricating oil is filled, communications tower, fire infiltration isolation layer, sealing, pipeline overcoat, hold-up vessel, reactor, baking oven, distillation column, stove and analogue.
Coating composition of the present invention is suitable for the coating of making circuit card, for example is used for the radiation-curable coating of circuit card.
This coating composition is suitable for makes cable coating with as electric, control and communication cable, and for example at hank of cable and raceway, tapping box, the coating of the cable that makes up together in cable trench and the similar applications.
The general application
Coating/coating composition of the present invention is applicable to architectural paints, and is for example smooth, low, half or the high gloss final lacquer, and for example as priming paint or final coating.
This coating composition can advantageously be applied to outer side, inner structure, roof, garage, top ceiling, infiltration isolation layer, PVC lapping and analogue.They can be used for private home, and hotel and office for example are applied to wallpaper, plate, dry wall, wallboard, dado, crane span structure, floor and carcass-flooring, peg, building machinery workpiece and decoration, watt, outer deck, smallpox pan tile, kitchen cabinet, kitchen cupboard, the carpet backing, inwall, door, file cabinet, office furniture, safety locker, isolation layer and analogue.
This coating composition can be applicable to structure iron, post, bundle, steel deck-plate, lever bracket beam, the furred ceiling in commercial building, work in high level chamber building and the mansion, bridge and tunnel and analogue.
About steel and other metal base, these base materials can be underlying metals, structure iron, aluminium, metal alloy, structure iron bundle and post, coiled material coated substrate, the steel honeycomb structure in the tapping box, insulation steel, stainless steel pipes, container and jar.
Coating composition of the present invention is applicable to masonry such as brick, concrete, cement brick and sheet material.
Suitable wood substrates is for example size saw lumber, multi-ply wood, particle board, OOSB plate, the interior timber of using of ornamenting not, multi-ply wood insulating board, insulcrete, cellulose plate, fiberboard, wood wool (wooden suede), wood chip, cdear shingle, no sheath plate, shingle, side, call box, mark post, paper, cardboard, card board kai, corrugated sheet, etc.
This flame retardant additives can be used as the dyeing component, as mixing husky coating composition, as the part of finishing coat, is applied to timber by pressure or vacuum impregnation or as penetrant.This flame retardant additives that is applied to timber can combine with sanitas; They can be introduced in the wood composite material product by pressure impregnation in manufacturing processed, or can be used as paint or the part of top coat and use.
This flame retardant additives that is applied to paper can or can add at the sizing applicator or the water tank place of dry end in the spraying of the green end of paper machine; Or available spreader or apply with the multi-work-station printing press.
This coating composition can further comprise pore forming material, whipping agent, and carbonized agent and binding agent, thixotropic agent, foaming agent, Dipentaerythritol and for example be disclosed in U.S.Pat.No.5, other additive of 723,515, its disclosure is incorporated the present invention as a reference into.
Textiles is according to suitable coated substrate of the present invention, textiles back coating for example, bonding curtain, canopy, dividers, canopy, tent, nylon rope, net, carpet backing, wall coverture, ornament, natural fiber, synthon, decoration, carpet, cloth, stage curtain, mattress, hospital's fabric and system of knitting and nonwoven fabric.
This coating composition can form as the composite structure with textiles character, the coating of a part that for example comprises the structure of textile fabric and polyolefin film coating and/or extruding coating, for example in U.S.Pat.No.6,235,658 is disclosed, and its disclosure is incorporated the present invention as a reference into.This coating can be for example to be disclosed in U.S.Pat.No.6,251,995 polyolefin coatings, and its disclosure is incorporated the present invention into as a reference at this.
Fabric can be based on polyethylene, polypropylene, polyethylene terephthalate, polymeric amide, Mierocrystalline cellulose or the cotton system of knitting, braiding or nonwoven fabric.Polyolefin film or extruding coating are for example about 3 to about 200 micron thickness.
The invention still further relates to and be applicable to the wear-resistant paint composite that is coated on the polycarbonate.For example be described in U.S. patent No.5, this class coating of 214,085 comprises the silyl acrylate, aqueous, colloidal silica, light trigger and polyfunctional acrylic ester optionally and UV absorption agent.Except flame retardant resistance, these coating are provided at long-term outdoor exposure in sunlight, the degradation resistant after moisture and the heat.The patience that delamination and microfracture form and transparency descends is provided at jaundice.
Sealing agent and binder composition, for example sealing agent and binder layer composition also drop in the definition of this paper to " fire retardant coating compositions ".For example, as mastic coatings, latex adhesive, binding agent, putty, putty, clay and sealing agent.
Binder composition is a laminating adhesive for example, pressure sensitive adhesive (PSA) and construction adhesive.UV (UV-light) curable adhesive also is a theme of the present invention.The UV curable adhesive is for example photochemical tackiness agent, and the latter for example is used for cable, junctor, and amplifier, joint, etc.Photochemical tackiness agent falls in the construction adhesive scope.
This coating composition can be used as film and/or is used to form the layer of laminated product as binder layer.For example, be disclosed in U.S.Pat.Nos.6,187,845,6,191,199 and 6,268,415 coating and layer, its disclosure is incorporated the present invention as a reference into.These coatings, film and binder layer are solar control films for example, film and glaze, UV heat absorbing glass and glass paint, windscreen, back reflection sheet and signboard, solar reflector, blooming and analogue.
This coating composition can be used for forming Clear coating or colored film. they can be aqueous based systems or solvent based maybe can be powder paint compositions or gel coating prescription.
But this coating composition ambient cure, radiation curing (for example under the influence of light trigger), baker solidify or utilize catalyzer, for example acid catalyst and solidify (crosslinked).
If the use light trigger, they are for example single-or diacyl phosphine oxide photoinitiator or alpha-alcohol ketone photoinitiator.These light triggers for example are described in U.S. patent No.5, and 942,290, be introduced in that this is for reference.
This coating composition is based on for example Synolac; Chlorinated alkyd; Urethane resin; Thermoplastic acrylic resin; Acrylic acid alkyl; Acrylic resin; Latex emulsion; Vinylformic acid alkyd or vibrin are optionally used the silicon modification, isocyanic ester, ketoimine Huo oxazolidine; Phenol-formaldehyde resin; Resorcinol-formaldehyde resin; Resins, epoxy; Use carboxylic acid, acid anhydrides, the epoxide resin that polyamine or mercaptan are crosslinked; Or in its main chain with the reactive group modification with epoxy crosslinked vinylformic acid and vibrin system.For example, based on the coating of vinyl-acetic ester-acrylate copolymer emulsion, the solution of Vinyl toluene-2-EHA multipolymer and urethane.
Epoxy adhesive is widely used in coating composition and is applicable to the present invention.Epoxide is for example aliphatic, aromatics, and ring-type, acyclic, alicyclic or heterocyclic.These resins can be derived from polyvalent alcohol such as ethylene glycol, Diethylene Glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerine, TriMethylolPropane(TMP), the polyglycidyl ether of bisphenol-A and bisphenol-f.The also polycarboxylic polyglycidyl ether of epoxide resin, for example by epoxy compounds such as Epicholorohydrin and aliphatic series or aromatic multi-carboxy acid such as oxalic acid, succsinic acid, pentanedioic acid, terephthalic acid, 2, the reaction of 6-naphthalene dicarboxylic acids and linoleic acid dimer and the material made.
Resins, epoxy is also derived from the epoxidation of ethylenic unsaturated cycloaliphatic material.Epoxy alicyclic ethers and ester that wherein capable territory is known.Resins, epoxy also comprises those that comprise oxyalkylene group.These groups can be used as the sidepiece of main chain of epoxide resin or the part that they can be used as main chain.The ratio of oxyalkylene group in Resins, epoxy depends on many factors, comprising the size of oxyalkylene group and the character of Resins, epoxy.
In addition, Resins, epoxy comprises epoxy-Novolak resin.These resins are by making the condensation product reaction of epihalohydrins and aldehyde and monobasic or multi-phenol.An example is the reaction product of Epicholorohydrin and P-F condenses.Also can use the mixture of Resins, epoxy at this.
Material such as epoxidised soybean oil, the dimeracid sill, as EMPOL 1010 resins available from Emery Chemicals, poly-epoxide resin with modified rubber, as the product of making by the polyglycidyl ether of dihydroxyphenyl propane, can polyhutadiene as EPON 828 and sour official from Shell Chemical.
Crosslinkable urethane, polyester, polyvinyl, polysulphide, urea and formaldehyde are the examples that is applicable to resin of the present invention.
The invention still further relates to and comprise the unsaturated acrylic resin of ethylenic, urethane acrylate, epoxy acrylate, polyester acrylate, radiation-curable (UV-the is curable) coating system of unsaturated polyester/styrene resin and silyl acrylate.Ethylenic unsaturated polymerizable compound can comprise one or more olefinic double bonds.They can be low molecule (monomer) or polymer (oligomeric) compound.Radiation curable coating is for example to be described in the U.S.Pat.No.6 that submits February 27 calendar year 2001,376,584, and it incorporates the present invention as a reference into.Unsaturated monomer is alkyl-or hydroxyalkyl acrylates or methacrylic ester normally, vinylbenzene, glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, six methylene omega-diol diacrylate or bisphenol a diacrylates, 4,4 '-two (2-acryloyl-oxy base oxethyl) diphenyl propane, Viscoat 295, pentaerythritol triacrylate or tetraacrylate, vinylbenzene, six methylene glycol or bisphenol a diacrylates, 4,4 '-two (2-acryloyl-oxy base oxethyl) diphenyl propane or Viscoat 295.Oligomeric polyunsaturated compounds is for example by toxilic acid, and fumaric acid, phthalic acid and one or more glycol are made and had about 500 to 3000 polyester acrylate of molecular weight or unsaturated polyester resin usually.Unsaturated carboxylic acid is for example vinylformic acid and methacrylic acid.
Powder paint compositions for example comprises the glycidyl methacrylate with selected alkoxide component.
This coating composition is for example to have highly filled enamel composition, based on crosslinkable vinylformic acid, and polyester, urethanum, or available other acid catalyst solidified Synolac.These acid catalysis stoving lacquers are based on for example hot crosslinkable vinylformic acid, polyester, urethane, polymeric amide or Synolac.
This coating composition is applicable to multilayer system, and flame retardant additives composition for example of the present invention can be present in the one or more layer of multilayer coating system.
This coating composition can pass through any usual manner, for example by brush, and roller, spraying, dipping, electrostatic precipitation, extrusion molding/co-extrusion, trowel is coated with (thick slurry) and similar fashion is administered on the base material.
This coating composition can be expansion or unexpansive.
This coating composition can be used for forming thin layer certainly.These layers are for example about 5 microns, and extremely about 10mil is thick, and for example about 10 microns extremely about 7mil is thick, or about 1mil is thick to about 5mil.They are for example about 10 microns, or about 1,2,3,4,5 or 6mil thick.Every mil has 26 microns.
This coating composition provides self to be the coating of fire retardant and to be that the whole goods of an one parts (for example applying plastic parts) provide flame retardant resistance to them.
The sterically hindered compound of component (i)
The sterically hindered stablizer of basis of component (i) is well known in the art and for example has structural formula
G wherein
1And G
2Be the alkyl of 1 to 8 carbon atom independently or be pentamethylene together,
Z
1And Z
2Be respectively methyl, or Z
1And Z
2Common formation can be in addition by ester, ether, acid amides, amino, the connection portion that carboxyl or urethane ester group replace and
E is the oxygen base, hydroxyl, alkoxyl group, cycloalkyloxy, aralkoxy, aryloxy ,-O-CO-OZ
3,-O-Si (Z
4)
3,-O-PO (OZ
5)
2Or-O-CH
2-OZ
6, Z wherein
3, Z
4, Z
5And Z
6Be selected from hydrogen, aliphatic series, araliphatic and aromatics part; Or E is-O-T-(OH)
b,
T is the straight or branched alkylidene of 1 to 18 carbon atom, the ring alkylidene group of 5 to 18 carbon atoms, the ring alkylene group of 5 to 18 carbon atoms, the straight or branched alkylidene of 1 to 4 carbon atom, the latter is replaced by phenyl or the phenyl that replaced by the alkyl by one or two 1 to 4 carbon atom;
B is 1,2 or 3, if prerequisite is that carbonatoms and the b that b can not surpass among the T is 2 or 3, each hydroxyl is connected on the different carbon atoms of T.
E is for example oxygen base, hydroxyl, alkoxyl group, cycloalkyloxy or aralkoxy.For example, E is a methoxyl group, propoxy-, cyclohexyl oxygen base or octyloxy.
The sterically hindered stablizer of basis of component (i) for example has structural formula A-R
Wherein
E is the oxygen base, hydroxyl, and the alkoxyl group of 1 to 18 carbon atom, the aralkoxy of the cycloalkyloxy of 5 to 12 carbon atoms or 7 to 15 carbon atoms, or E is-O-T-(OH)
b,
T is the straight or branched alkylidene of 1 to 18 carbon atom, the ring alkylidene group of 5 to 18 carbon atoms, the ring alkylene group of 5 to 18 carbon atoms, the straight or branched alkylidene of 1 to 4 carbon atom, the latter is replaced by phenyl or the phenyl that replaced by the alkyl by one or two 1 to 4 carbon atom;
B is 1,2 or 3, if prerequisite is that carbonatoms and the b that b can not surpass among the T is 2 or 3, each hydroxyl is connected on the different carbon atoms of T;
R is hydrogen or methyl,
M is 1 to 4,
If m is 1,
R
2Be hydrogen, C
1-C
18Alkyl or described alkyl optionally are interrupted C by one or more Sauerstoffatom
2-C
12Alkenyl, C
6-C
10Aryl, C
7-C
18Aralkyl, glycidyl, aliphatic series; cyclic aliphatic or aromatic carboxylic acid, or carbamic unit price carboxyl groups for example have the aliphatic carboxylic acid of 2-18 C atom; have 5-12 C atom cycloaliphatic carboxylic acid or have the aromatic carboxylic acid's of 7-15 C atom carboxyl groups, or
Wherein x is 0 or 1,
Wherein y is 2-4;
If m is 2,
R
2Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, xylylene, aliphatic series, cyclic aliphatic, the divalence carboxyl groups of araliphatic or aromatic dicarboxylic acid or diamino acid for example has the aliphatic dicarboxylic acid of 2-18 C atom, has the cyclic aliphatic or the aromatic dicarboxylic acid of 8-14 C atom, or has the aliphatic series of 8-14 C atom, the carboxyl groups of cyclic aliphatic or aromatics diamino acid;
Or
D wherein
1And D
2Be hydrogen independently, comprise the alkyl group of the highest 8 carbon atoms, comprise 3, the aryl or aralkyl group of 5-two-tertiary butyl-4-hydroxy benzyl group, D
3Be hydrogen, or to comprise the alkyl of the highest 18 carbon atoms or kiki alkenyl group and d be 0-20;
If m is 3, R
2Be aliphatic series, unsaturated aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid's trivalent carboxyl groups;
If m is 4, R
2Be to comprise 1,2,3,4-butanetetra-carboxylic acid, 1,2,3,4-but-2-ene-tetracarboxylic acid and 1,2,3,5-and 1,2,4, the saturated or unsaturated aliphatic of 5-penta tetracarboxylic acid or aromatic acid's tetravalence carboxyl groups;
P is 1,2 or 3,
R
3Be hydrogen, C
1-C
12Alkyl, C
5-C
7Cycloalkyl, C
7-C
9Aralkyl, C
2-C
18Alkyloyl, C
3-C
5Enoyl-or benzoyl; If p is 1,
R
4Be hydrogen, C
1-C
18Alkyl, C
5-C
7Cycloalkyl, C
2-C
8Alkenyl (unsubstituted or by cyano group, carbonyl or carbonamido replace), aryl, aralkyl, or it is glycidyl, has formula-CH
2-CH (OH)-Z or have formula-CO-Z or-group of CONH-Z, wherein Z is a hydrogen, methyl or phenyl; Or following formula group
Or
Wherein h is 0 or 1,
R
3And R
4Jointly, if p is 1, can be the alkylidene group or the 2-oxo-polyalkylene of 4 to 6 carbon atoms, aliphatic series or aromatics 1,2-or 1, the ring carboxyl groups of 3-dicarboxylic acid,
If p is 2,
R
4Be direct key or C
1-C
12Alkylidene group, C
6-C
12Arylidene, xylylene ,-CH
2CH (OH)-CH
2Group or group-CH
2-CH (OH)-CH
2-O-X-O-CH
2-CH (OH)-CH
2-wherein X is C
2-C
10Alkylidene group, C
6-C
15Arylidene or C
6-C
12The ring alkylidene group; Or, if R
3Not alkyloyl, enoyl-or benzoyl, R
4Also aliphatic, the divalence carboxyl groups of cyclic aliphatic or aromatic dicarboxylic acid or diamino acid maybe can be group-CO-; Or
R
4Be
T wherein
8And T
9Be hydrogen independently, the alkyl of 1 to 18 carbon atom, or T
8And T
9Be alkylidene group or 3-oxa-pentamethylene, for example T of 4 to 6 carbon atoms together
8And T
9Be 3-oxa-pentamethylene together;
If p is 3,
R
4Be 2,4, the 6-triazinyl,
N is 1 or 2,
If n is 1,
R
5And R '
5Be C independently
1-C
12Alkyl, C
2-C
12Alkenyl, C
7-C
12Aralkyl, or R
5Also be hydrogen, or R
5And R '
5Be C together
2-C
8Alkylidene group or hydroxy alkylidene or C
4-C
22The acyloxy alkylidene group;
If n is 2,
R
5And R '
5Be (CH together
2)
2C (CH
2-)
2
R
6Be hydrogen, C
1-C
12Alkyl, allyl group, benzyl, glycidyl or C
2-C
6Alkoxyalkyl;
If n is 1,
R
7Be hydrogen, C
1-C
12Alkyl, C
3-C
5Alkenyl, C
7-C
9Aralkyl, C
5-C
7Cycloalkyl, C
2-C
4Hydroxyalkyl, C
2-C
6Alkoxyalkyl, C
6-C
10Aryl, glycidyl has formula-(CH
2)
t-COO-Q or have formula-(CH
2)
tThe group of-O-CO-Q, wherein t be 1 or 2 and Q be C
1-C
4Alkyl or phenyl; Or
If n is 2,
R
7Be C
2-C
12Alkylidene group, C
6-C
12Arylidene, group-CH
2CH (OH)-CH
2-O-X-O-CH
2-CH (OH) CH
2-, wherein X is C
2-C
10Alkylidene group, C
6-C
15Arylidene or C
6-C
12Ring alkylidene group, or group CH
2CH (OZ ') CH
2-(OCH
2-CH (OZ ') CH
2)
2-, wherein Z ' is a hydrogen, C
1-C
18Alkyl, allyl group, benzyl, C
2-C
12Alkyloyl or benzoyl;
Q
1Be-N (R
8)-or-O-; E
7Be C
1-C
3Alkylidene group, group-CH
2-CH (R
9)-O-, wherein R
9Be hydrogen, methyl or phenyl, group-(CH
2)
3-NH-or direct key;
R
10Be hydrogen or C
1-C
18Alkyl, R
8Be hydrogen, C
1-C
18Alkyl, C
5-C
7Cycloalkyl, C
7-C
12Aralkyl, cyano ethyl, C
6-C
10Aryl, group-CH
2-CH (R
9)-OH, wherein R
9Implication with above definition; The following formula group
Or following formula group
G wherein
4Be C
2-C
6Alkylidene group or C
6-C
12Arylidene; Or R
8Be group-E
7-CO-NH-CH
2-OR
10
Structural formula F represents the repeated structural unit of polymkeric substance, wherein T
3Be ethylidene or propylene, be derived from the alpha-olefin copolymer of alkyl acrylate or methacrylic ester; For example the repeated structural unit of the multipolymer of ethene and ethyl propenoate and wherein k be 2 to 100;
T
4Have and R
4Identical implication, if p is 1 or 2,
T
5Be methyl,
T
6Be methyl or ethyl, or T
5And T
6Be tetramethylene or pentamethylene, for example T together
5And T
6Be respectively methyl,
M and Y are methylene radical or carbonyl independently, and T
4Be ethylidene, wherein n is 2;
T
7With R
7Identical, and T
7Be eight methylene radical for example, wherein n is 2,
T
10And T
11Be the alkylidene group of 2 to 12 carbon atoms independently, or T
11Be
T
12Be piperazinyl,
-NR
11-(CH
2)
d-NR
11-or
R wherein
11With R
3Identical or also be
A, b and c be independently 2 or 3 and f be 0 or 1, for example a and c are respectively 3, b be 2 and f be 1; With e be 2,3 or 4, for example 4;
T
13With R
2Identical, prerequisite is T
13Can not be hydrogen, if n is 1;
E
1And E
2, be different, be respectively-CO-or-N (E
5)-, be E wherein
5Be hydrogen, C1-C
12Alkyl or C
4-C
22Alkoxycarbonyl alkyl, for example E
1Be-CO-and E
2Be-N (E
5)-,
E
3Be hydrogen, the alkyl of 1 to 30 carbon atom, phenyl, naphthyl, by chlorine or by the described phenyl or the described naphthyl of the replacement of the alkyl of 1 to 4 carbon atom, or the phenylalkyl of 7 to 12 carbon atoms, or by the described phenylalkyl of the alkyl of 1 to 4 carbon atom replacement,
E
4Be hydrogen, the alkyl of 1 to 30 carbon atom, phenyl, the naphthyl or the phenylalkyl of 7 to 12 carbon atoms, or
E
3And E
4Be the polymethylene of 4 to 17 carbon atoms together, or by the alkyl of the highest four 1 to 4 carbon atoms, for example methyl substituted described polymethylene,
E
6Be aliphatic series or aromatics quaternary groups,
The R of structural formula (N)
2Define as above, if m is 1;
G
1Be direct key, C
1-C
12Alkylidene group, phenylene or-NH-G '-NH, wherein G ' is C
1-C
12Alkylidene group; Or
Wherein the bulky amine compound is to have structural formula I, II, III, IV, V, VI, VII, VIII, IX, the compound of X or XI
E wherein
1, E
2, E
3And E
4Be the alkyl of 1 to 4 carbon atom independently, or E
1And E
2Be the alkyl and the E of 1 to 4 carbon atom independently
3And E
4Be pentamethylene jointly, or E
1And E
2And E
3And E
4Be respectively pentamethylene jointly,
R
1Be the alkyl of 1 to 18 carbon atom, the cycloalkyl of 5 to 12 carbon atoms, the dicyclo of 7 to 12 carbon atoms or tricyclic hydrocarbon base, the phenylalkyl of 7 to 15 carbon atoms, the aryl of 6 to 10 carbon atoms or the described aryl that is replaced by the alkyl of 1-3 1 to 8 carbon atom,
R
2Be the straight or branched alkyl of hydrogen or 1 to 12 carbon atom,
R
3Be the alkylidene group of 1 to 8 carbon atom, or R
3Be-CO--CO-R
4-,-CONR
2-, or-CO-NR
2-R
4-,
R
4Be the alkylidene group of 1 to 8 carbon atom,
R
5Be hydrogen, the straight or branched alkyl of 1 to 12 carbon atom, or
If or R
4Be ethylidene, two R then
5Methyl substituents can be by direct key keyed jointing, triazine bridge joint group-N (R like this
5)-R
4-N (R
5)-be piperazine-1,4-two base section,
R
6Be the alkylidene group or the R of 2 to 8 carbon atoms
6Be
Prerequisite is that Y is not-OH, if R
6Be the above structure of describing,
A is-O-or-NR
7-, R wherein
7Be hydrogen, the straight or branched-chain alkyl of 1 to 12 carbon atom, or R
7Be
T is a phenoxy group, by the alkyl of one or two 1 to 4 carbon atom, the alkoxyl group of 1 to 8 carbon atom or-N (R
2)
2The phenoxy group that replaces, prerequisite is R
2Be not hydrogen, or T is
X is-NH
2,-NCO ,-OH ,-O-glycidyl, or-NHNH
2And
Y is-OH-NH
2,-NHR
2, R wherein
2Not hydrogen; Or Y is-NCO ,-COOH, and Oxyranyle ,-O-glycidyl, or-Si (OR
2)
3Or composition R
3-Y-is-CH
2CH (OH) R
2, R wherein
2Be alkyl or the described alkyl that is interrupted by 1-4 Sauerstoffatom, or R
3-Y-is-CH
2OR
2Or
Wherein the bulky amine compound is N, N ', N " '-three { 2,4-two [(1--oxyl-2,2,6,6-tetramethyl piperidine-4-yl) alkylamino]-s-triazine-6-yl }-3,3 '-ethylene imino-dipropylamine; N, N ', N " three { 2,4-two [(1--oxyl-2,2,6,6-tetramethyl piperidine-4-yl) alkylamino]-s-triazine-6-yl }-3,3 '-ethylene imino-dipropylamine and for example be described as formula I, II, the mixture of the bridge joint derivative of IIA and III
R
1NH-CH
2CH
2CH
2NR
2CH
2CH
2NR
3CH
2CH
2CH
2NHR
4??????(I)
T-E
1-T
1???(II)
T-E
1????(IIA)
G-E
1-G
1-E
1-G
2(III) wherein have in the tetramine of formula I
R
1And R
2Be s-triazine part E; And R
3And R
4One of be s-triazine part E and other R
3Or R
4Be hydrogen, E is
R is a methyl, propyl group, and cyclohexyl or octyl group, cyclohexyl for example,
R
5Be the alkyl of 1 to 12 carbon atom, for example normal-butyl wherein has in the compound of formula II or IIA, if R is a propyl group, and cyclohexyl or octyl group, then
T and T
1Be respectively by R
1-R
4The tetramine that replaces, R
1-R
4As wherein defined to formula I
(1) one of s-triazine part E in each tetramine is by group E
1Substitute, the latter is at two tetramine T and T
1Between form bridge,
E
1Be
Or (2) group E
1Can have two ends in the tetramine T identical with formula IIA, wherein two of tetramine E parts are by an E
1Group substitutes, or
(3) three all s-triazine substituting groups of tetramine T can be E
1, make an E
1Keyed jointing T and T
1And the 2nd E
1In tetramine T, have two ends,
L is propane two bases, hexanaphthene two bases or octane two bases;
Wherein have in the compound of formula III
G, G
1And G
2Be respectively by as to the defined R of formula I
1-R
4The tetramine that replaces, just G and G
2Has one respectively by E
1Alternate s-triazine part E, and G
1Have two by E
1Alternate triazine part E is like this at G and G
1Between have a bridge and at G
1And G
2Between have second bridge;
Described mixture is by with 2-4 equivalent 2,4-two [(1--oxyl-2,2,6,6-piperidin-4-yl) butyl amino]-6-chloro-s-triazine and 1 equivalent N, N '-two (3-aminopropyl) reacting ethylenediamine and making; Or this bulky amine is the compound with structural formula II Ib
Indicate that wherein n is 1 to 15;
R
12Be C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
5-C
7The ring alkylidene group, C
5-C
7Ring alkylidene group-two (C
1-C
4Alkylidene group), C
1-C
4Alkylidene group two (C
5-C
7The ring alkylidene group), phenylene two (C
1-C
4Alkylidene group) or by 1,4-piperazine two bases ,-O-or＞N-X
1The C that is interrupted
4-C
12Alkylidene group, wherein X
1Be C
1-C
12Acyl group or (C
1-C
12Alkoxyl group) carbonyl or have the following R that provides
14One of definition (eliminating hydrogen); Or R
12It is group with structural formula (Ib ') or (Ic ');
Wherein m is 2 or 3,
X
2Be C
1-C
18Alkyl, unsubstituted or by 1,2 or 3 C
1-C
4The C that alkyl replaces
5-C
12Cycloalkyl; Unsubstituted or by 1,2 or 3 C
1-C
4Alkyl or C
1-C
4The phenyl that alkoxyl group replaces; Unsubstituted or replace on phenyl by 1,2 or 3 C
1-C
4The C that alkyl replaces
7-C
9Phenylalkyl; And radicals X
3Be C independently of each other
2-C
12Alkylidene group;
R
13, R
14And R
15Being identical or different, is hydrogen, C
1-C
18Alkyl, unsubstituted or by 1,2 or 3 C
1-C
4The C that alkyl replaces
5-C
12Cycloalkyl; C
3-C
18Alkenyl, unsubstituted or by 1,2 or 3 C
1-C
4Alkyl or C
1-C
4The phenyl that alkoxyl group replaces; Unsubstituted or on phenyl by 1,2 or 3 C
1-C
4The C that alkyl replaces
7-C
9Phenylalkyl; Tetrahydrofurfuryl or at 2,3 or 4 quilt-OH, C
1-C
8Alkoxyl group, two (C
1-C
4Alkyl) the amino C that replaces
2-C
4Alkyl or have the group of structural formula (Ie ');
Wherein Y is-O-,-CH
2-,-CH
2CH
2-or＞N-CH
3,
Or-N (R
14) (R
15) be group in addition with structural formula (Ie '); Group A is-OR independently of each other
13,-N (R
14) (R
15) or have the group of structural formula (IIId);
X is-O-or＞N-R
16
R
16Be hydrogen, C
1-C
18Alkyl, C
3-C
18Alkenyl, unsubstituted or by 1,2 or 3 C
1-C
4The C that alkyl replaces
5-C
12Cycloalkyl; Unsubstituted or on phenyl by 1,2 or 3 C
1-C
4The C that alkyl replaces
7-C
9Phenylalkyl; Tetrahydrofurfuryl has the group of structural formula (IIIf),
Or at 2,3 or 4 quilt-OH, C
1-C
8Alkoxyl group, two (C
1-C
4Alkyl) the amino C that replaces
2-C
4Alkyl or have the group of structural formula (Ie ');
R
11Have and be R
16One of definition that provides; Has one of definition that provides for A independently of each other with group B.
If R
2Be the unit price carboxyl groups of carboxylic acid, it is an acetate for example, stearic acid, Whitfield's ointment, the carboxyl groups of phenylformic acid or β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid.
If R
2Be the divalence carboxyl groups of dicarboxylic acid, it is an oxalic acid for example, hexanodioic acid; succsinic acid; suberic acid, sebacic acid, phthalic acid dibutyl propanedioic acid; dibenzyl propanedioic acid or butyl-(3; 5-two-tertiary butyl-4-hydroxy benzyl)-propanedioic acid, or the carboxyl groups of double-heptene dicarboxylic acid, wherein succinate; sebate, phthalic ester and isophthalic acid ester are object lessons.
If R
2Be the divalence carboxyl groups of diamino acid, it is a hexa-methylene diamino formic acid or 2 for example, the carboxyl groups of 4-methylene phenyl diamino acid.
The steric hindrance alkoxylamine stablizer of component (c) is well known in the art, also is called N-alkoxyl group bulky amine and NOR bulky amine or NOR hindered amine light stabilizer or NOR HALS.
They for example are disclosed in U.S.Pat.Nos.5,004,770,5,204,473,5,096,950,5,300,544,5,112,890,5,124,378,5,145,893,5,216,156,5,844,026,5,439,958,5,021,481,6,117,995,6,271,377 and U.S. application Ser.Nos.09/505,529 (on February 17th, 2000 submitted), 09/794,710 (submit February 27 calendar year 2001), 09/714,717 (on November 16th, 2000 submitted), 09/502,239 (on November 3rd, 1999 submitted) and 60/312,517 (submit August 15 calendar year 2001).The relevant disclosure of these patents and application is incorporated the present invention as a reference into.
U.S.Pat.No.6 cited above, 271,377 and U.S. application Ser.Nos.09/505,529 (on February 17th, 2000 submitted) and 09/794,710 (submit February 27 calendar year 2001) disclose steric hindrance hydroxy alkoxy base amine stabiliser.For the present invention, steric hindrance hydroxy alkoxy base amine stabiliser is considered to the subclass of steric hindrance alkoxylamine stablizer and is the part of this component (c).The agent of steric hindrance hydroxy alkoxy base amine-stabilized also is called N-hydroxy alkoxy base bulky amine, or NORolHALS.
The typical nitroxyl of component (a) comprises sebacic acid two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, 4-hydroxyl-1-oxygen base-2,2; 6,6-tetramethyl piperidine, 4-oxyethyl group-1-oxygen base-2; 2,6, the 6-tetramethyl piperidine; 4-propoxy--1-oxygen base-2,2,6; the 6-tetramethyl piperidine, 4-acetylaminohydroxyphenylarsonic acid 1-oxygen base-2,2; 6,6-tetramethyl piperidine, 1-oxygen base-2; 2,6, the 6-tetramethyl piperidine; 1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-ketone, 1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-yl acetate, 2 ethyl hexanoic acid 1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-base ester; stearic acid 1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-base ester, phenylformic acid 1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-base ester, the 4-tertiary butyl-phenylformic acid 1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-base ester; succsinic acid two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, hexanodioic acid two (1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-yl) ester, n-butylmalonic acid two (1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) ester; phthalic acid two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, m-phthalic acid two (1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-yl) ester, terephthalic acid two (1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) ester; six hydrogen terephthalic acids two (1-oxygen base-2,2,6; 6-tetramethyl piperidine-4-yl) ester, N, N '-two (1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) hexanamide; N-(1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) hexanolactam; N-(1-oxygen base-2; 2,6,6-tetramethyl piperidine-4-yl) the dodecyl succinimide; 2; 4,6-three-[N-butyl-N-(1-oxygen base-2,2; 6; 6-tetramethyl piperidine-4-yl)]-the s-triazine, 4,4 '-ethylene (1-oxygen base-2; 2; 6,6-tetramethyl-piperazine-3-ketone), the 2-Oxy-1; 1; 3,3-tetramethyl--2-isoindole, 1-oxygen base-2; 2; 5,5-tetramethylpyrrolidi-e, and N; N-two-(1; 1,3, the 3-tetramethyl butyl) nitro oxide.
The nitroxyl stablizer of component (a) is two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate for example, 4-hydroxyl-1-oxygen base-2; 2,6,6-tetramethyl piperidine, 4-oxyethyl group-1-oxygen base-2,2; 6,6-tetramethyl piperidine, 4-propoxy--1-oxygen base-2,2,6; the 6-tetramethyl piperidine, 4-acetylaminohydroxyphenylarsonic acid 1-oxygen base-2,2,6,6-tetramethyl piperidine; 1-oxygen base-2,2,6, the 6-tetramethyl piperidine; with 1-oxygen base-2,2,6,6-tetramethyl piperidine-4-ketone.
A particular is that wherein the nitroxyl stablizer of component (a) is two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate and 4-hydroxyl-1-oxygen bases-2,2,6, the 6-tetramethyl piperidine.
The oxyamine stablizer of component (b) is for example to be disclosed in U.S. patent Nos.4,831,134,4,590,231,4,668,721,4,691,015,4,831,134,5,006,577 and 5,064, and those of 883, its relevant portion is incorporated the present invention as a reference into.
The object lesson of the suitable combination thing of this component (i) comprising:
(a) 2,4-two [(1-cyclohexyl oxygen base-2,2,6,6-piperidin-4-yl) butyl amino]-6-chloro-s-triazine and N, N '-two (3-aminopropyl) quadrol) reaction product [CASReg.No.191680-81-6];
(b) 1-cyclohexyl oxygen base-2,2,6,6-tetramethyl--4-octadecyl amino piperidine;
(c) sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) ester;
(d) 2,4-two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-6-(2-hydroxyethyl amino-s-triazine;
(e) hexanodioic acid two (1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) ester;
(h) 2,4-two [(1-cyclohexyl oxygen base-2,2,6,6-piperidin-4-yl) butyl amino]-6-chloro-s-triazine;
(i) 1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine;
(j) 1-(2-hydroxy-2-methyl propoxy-)-4-oxo-2,2,6, the 6-tetramethyl piperidine;
(k) 1-(2-hydroxy-2-methyl propoxy-)-4-stearoyl oxygen base-2,2,6, the 6-tetramethyl piperidine;
(l) sebacic acid two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) ester;
(m) hexanodioic acid two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) ester;
(n) 2,4-two N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-N-butyl amino }-6-(2-hydroxyethyl amino)-s-triazine; With
(o) following formula: compound
Wherein n is 1 to 15;
Or as 4,4 '-hexa-methylene two (amino-2,2,6, the 6-tetramethyl piperidine) with by 2-chloro-4,6-two (dibutylamino)-s-triazine is end capped 2,4-two chloro-6-[(1-octyl group oxygen bases-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-oligomeric compound of the condensation product of s-triazine; Or
As 4,4 '-hexa-methylene two (amino-2,2,6, the 6-tetramethyl piperidine) with by 2-chloro-4,6-two (dibutylamino)-s-triazine is end capped 2,4-two chloro-6-[(1-cyclohexyl oxygen bases-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-oligomeric compound of the condensation product of s-triazine.
Compound (o) is disclosed in U.S. patent No.6,117,995 embodiment 2.
Sterically hindered alkoxylamine or hydroxy alkoxy base amine are for example 2,4-two [(1-cyclohexyl oxygen base-2,2,6, the 6-piperidin-4-yl) butyl amino]-6-chloro-s-triazine and N, N '-two (3-aminopropyl) quadrol) reaction product [CAS Reg.No.191680-81-6]; Sebacic acid two (1-octyl group oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) ester; Or compound (i), (j), (k) or (o); Or the mixture of described steric hindrance alkoxylamine and hydroxy alkoxy base amine.
The polymerizable sterically hindered compound of component (i)
This ethylenic unsaturated polymerizable monomer that comprises sterically hindered amine moiety for example is disclosed in U.S.Pat.Nos.4, and 983,737,5,047,489 and 5,077,340, its relevant disclosure is incorporated the present invention as a reference into.
By the oxygen base, hydroxyl or alkyl oxygen base group replace this steric hindrance amine moiety on the 1-N atom, and described part has structural formula independently
Or
Wherein
L
1, L
1', L
2And L
2' be the alkyl of 1 to 4 carbon atom independently, or L
1And L
2Or L
1' and L
2' be that pentamethylene and described monomer are selected from the following formula group jointly
Wherein
E is sterically hindered nitroxyl independently, oxyamine or alkoxylamine part,
R
1It is the oxygen base, hydroxyl, straight or the branched alkoxy of 1 to 36 carbon atom, the straight or branched alkenyl oxygen base of 2 to 18 carbon atoms, the straight or side chain alkynyloxy base of 2 to 18 carbon atoms, the aralkoxy of 7 to 15 carbon atoms, the cycloalkyloxy of 5 to 12 carbon atoms, the cycloalkenyl oxygen base of 5 to 12 carbon atoms, the group of the saturated or unsaturated dicyclo of 7 to 12 carbon atoms or tricyclic hydrocarbon base oxygen base, or the aryloxy of 6 to 10 carbon atoms or the described aryloxy that replaced by alkyl
Or R
1Be-O-T-(OH)
b,
R
1' define as R independently
1,
T is the straight or branched alkylidene of 1 to 18 carbon atom, the ring alkylidene group of 5 to 18 carbon atoms, the ring alkylene group of 5 to 18 carbon atoms, the straight or branched alkylidene of 1 to 4 carbon atom, the latter replaces by phenyl or by the phenyl that the alkyl of 1 or 21 to 4 carbon atom replaces;
B is 1,2 or 3, if prerequisite is that carbonatoms and the b that b can not surpass among the T is 2 or 3, each hydroxyl is connected on the different carbon atoms of T,
X is direct key, 2 to 12 carbon atoms-O (polyoxy alkylidene group O)-,-O-,-NH-or-NG-, wherein G is the alkyl of 1 to 8 carbon atom,
X
1Be direct key or-O-,
N is 1 or 2,
T
1, T
2And T
4Be hydrogen independently, halogen, the aryl of the alkyl of 1 to 18 carbon atom or 6 to 10 carbon atoms,
T
3Be hydrogen or methyl and
R
2Be the alkyl of hydrogen or 1 to 12 carbon atom,
R
2' be hydrogen, the alkyl or the cyano group of 1 to 12 carbon atom,
R
3And R
4Be hydrogen independently, the alkyl of 1 to 12 carbon atom ,-COOH, or-COOG
1, G wherein
1Be the straight or branched-chain alkyl of 1 to 12 carbon atom,
R
5Be 1 to 8 carbon atom straight or branched-chain alkyl and
R
5' define as R independently
5
R
1And R
1' be for example oxygen base, hydroxyl, alkoxyl group, cycloalkyloxy or aralkoxy.For example, R
1Be methoxyl group, propoxy-, cyclohexyl oxygen base or octyl group oxygen base.
For example, L
1, L
2, L
1' and L
2' be respectively methyl.
For example, R
1And R
1' be the alkoxyl group of 1 to 18 carbon atom, the alkenyl oxy of 2 to 3 carbon atoms, propargyloxy, benzyl oxygen base or cyclohexyl oxygen base.
G is the alkyl of 1 to 4 carbon atom for example.
For example, T
1And T
2All be hydrogen.
For example, T
3Be hydrogen.
For example, R
2, R
3And R
4Be respectively hydrogen or R
3And R
4Be hydrogen and R
2And R
2' be methyl.
If R
1And R
1' be alkoxyl group, they for example are, methoxyl group, oxyethyl group, butoxy, pentyloxy, octyloxy, the ninth of the ten Heavenly Stems oxygen base, dodecyl oxygen base, tetradecyl oxygen base, octadecyl oxygen base, eicosyl oxygen base, tricosyl oxygen base, tritriacontyl oxygen base or 2-hydroxy-2-methyl propoxy-.
If R
1And R
1' be alkenyl oxy, they for example are, vinyl oxygen base, allyl group oxygen base, octenyl oxygen base or oil base oxygen base.
If R
1And R
1' be the alkynyloxy base, they are propargyloxy for example.
If R
1And R
1' be cycloalkyloxy, they for example are, cyclopentyloxy, cyclohexyl oxygen base, ring octyl group oxygen base, cyclo-dodecyl oxygen base or 1-hydroxy-cyclohexyl oxygen base.
This polymerisable monomer comprises the ethylenic unsaturated group respectively makes this monomer can use free radical to cause, light-initiated, group transfer polymerization, graft polymerization, or positively charged ion or anionoid polymerization and polymerization.More than one this monomer can use jointly.
This sterically hindered piperidine ring system also can be for example by the steric hindrance piperazine, piperazine ketone, and morpholone mai ， oxazolidine member ring systems and analogue replace.
There are several synthesis steps to can be used for preparing this polymerisable monomer that comprises sterically hindered amine moiety.
These comprise:
(a) use 4-hydroxyl-2,2,6,6-tetramethyl piperidine and unsaturated acid such as vinylformic acid, fumaric acid, the transesterification reaction of the lower alkyl esters of muconic acid or analogue;
(b) use 4-hydroxyl-2,2,6, the esterification of 6-tetramethyl piperidine and acyl chlorides such as acryl or methacrylic chloride;
(c) use 4-amino-2,2,6, the amidation of 6-tetramethyl piperidine and acyl chlorides such as acryl or methacrylic chloride;
(d) use 4-amino-2,2,6, cyclisation by the intermediate maleinamic acid is followed in the inferior amidation of 6-tetramethyl piperidine and cyclic acid anhydride such as maleic anhydride;
(e) use unsaturated benzyl or allyl halide and 4-hydroxyl-2,2,6, the halogenide displacement of the alkali metal alcoholates of 6-tetramethyl piperidine; With
(f) preformed 4-acyloxy-2,2,6,6-tetramethyl piperidine and t-butyl hydroperoxide or the hydrogen peroxide catalyzed oxidation in the presence of molybdenum trioxide catalyst and varsol.
Preparing the required intermediate of this compound mainly is that items in commerce maybe can be made by ordinary method known in the art.
The polymerisable monomer that comprises the sterically hindered amine moiety of the present invention comprises following:
R????????????R
1′???????????X????????????????R
2′
H allyl group O H
H allyl group NH methyl
H cyclohexyl O methyl
H methyl O H
H methyl N (normal-butyl) H
Methyl Octyl O H
H methyl N H H
H methyl N H methyl
H hexyl N (normal-butyl) methyl
H cyclohexyl NH methyl
H octadecyl O methyl
H benzyl O H
H octyl group O methyl
Methyl Octyl O methyl
H octyl group NH H
H octyl group N (normal-butyl) methyl
H octyl group NH methyl
R????????????????R
1′???????????????R
2
The H cyclohexyl methyl
H methyl H
The H methyl
H cyclohexyl H
H octyl group H
H octyl group methyl
The Methyl Octyl methyl
H allyl group H
The H allyl methyl
H octadecyl H
The H octadecyl methyl
R????????????R
1′???????????T
1??????????T
2
H methyl H H
H cyclohexyl H dodecyl
H methyl H dodecyl
H octyl group H H
H octyl group methyl
The Methyl Octyl methyl
H octyl group H dodecyl
H allyl group H H
H allyl group H methyl
H octadecyl H H
R????????????????R
1′
The H methyl
The H cyclohexyl
The H octyl group
The H octadecyl
Methyl Octyl
The H allyl group
R????????????R
1′???????????N?????????????X
H cyclohexyl 1 O
H cyclohexyl 2 O
H methyl 1 O
Methyl Octyl 1 O
Methyl Octyl 2 O
H octyl group 1 O
H octyl group 2 O
H allyl group 1 O
H octadecyl 1 O
H cyclohexyl 1 NH
H cyclohexyl 1 N (normal-butyl)
H methyl 1 NH
H methyl 1 N (normal-butyl)
H octyl group 1 NH
H octyl group 1 N (normal-butyl)
H allyl group 1 N (normal-butyl)
H octadecyl 1 N (normal-butyl)
In above example ,-OR
1' also can be the oxygen base independently, hydroxyl, 2-hydroxy-2-methyl propoxy-, 1-hydroxy-cyclohexyl oxygen base, cyclohexyl oxygen base or propoxy-.
This ethylenic unsaturated polymerizable monomer that comprises sterically hindered amine moiety for example is selected from
R wherein
2Be hydrogen or methyl.
The present composition can further advantageously comprise the alkyl oxygen base bulky amine compound that is not ethylenically unsaturated monomers.
The object lesson of the bulky amine compound of suitable other comprises above more preceding compound (a)-(o);
As 4,4 '-hexa-methylene-two (amino-2,2,6, the 6-tetramethyl piperidine) with by 2-chloro-4,6-two (dibutylamino)-s-triazine is end capped 2,4-two chloro-6-[(1-octyl group oxygen bases-2,2,6,6-tetramethyl--piperidin-4-yl) butyl amino]-oligomeric compound of the condensation product of s-triazine; With
As 4,4 '-hexa-methylene-two (amino-2,2,6, the 6-tetramethyl piperidine) and by 2-chloro-4,6-two (dibutylamino)-s-triazine end capped 2,4-two chloro-6-[(1-cyclohexyl oxygen bases-2,2,6,6-four-methyl piperidine-4-yl) butyl amino]-oligomeric compound of the condensation product of s-triazine.
These other bulky amine compound for example is disclosed in U.S.Pat.No.6, and 472,456 and 6,117,995, its relevant disclosure is incorporated the present invention as a reference into.The compound of mentioning at last is disclosed in U.S. patent No.6,117,995 embodiment 2.
Alkyl is straight or side chain and be methyl for example, ethyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-hexadecyl or Octadecane base.
Group of naphthene base for example has 5 to 7 carbon atoms and comprises cyclopentyl and cyclohexyl; Typical cycloalkenyl group comprises cyclohexenyl.
Aromatic alkyl group comprises for example benzyl, Alpha-Methyl-benzyl, α, α-Er Jiajibianji or styroyl.
Aryl is for example phenyl, naphthyl and xenyl.
Alkoxyl group, aryloxy and cycloalkyloxy group definition such as this alkyl, aryl and group of naphthene base.
Halogen is for example chlorine and bromine.
Conventional flame retardants
The organic halogen fire retardant for example is:
Chlorine alkyl phosphate (ANTIBLAZE AB-100, Albright﹠amp; Wilson; FYROL FR-2, Akzo Nobel),
Tricresyl phosphate (2-chloroethyl) ester
Poly-brominated diphenyl base oxide (DE-60F, Great Lakes Corp.),
Decabrominated dipheny base oxide (DBDPO; SAYTEX 102E),
Tricresyl phosphate [3-bromo-2,2-two (brooethyl) propyl group] ester (PB370 , FMC Corp.),
Tricresyl phosphate (2, the 3-dibromopropyl) ester
Tricresyl phosphate (2,3-two chloropropyls) ester,
Chlorendic acid,
Tetrachlorophthalic acid,
Tetrabromophthalate,
Two-(N, N '-hydroxyethyl) tetrachloro phenylenediamines,
Poly--β-chloroethyl tri methylene phosphonic acid ester mixture
Two (2,3-dibromopropyl ether) of dihydroxyphenyl propane (PE68),
Brominated epoxy resin,
Ethylidene-two (tetrabromo phthalimide) (SAYTEX BT-93),
Two (hexachlorocyclopentadiene base) cyclooctane (DECLORANE PLUS ),
Clorafin,
Octabromodiphenyl base ether,
The hexachlorocyclopentadiene derivative,
1,2-two (tribromophenoxy) ethane (FF680),
Tetrabromo-dihydroxyphenyl propane (SAYTEX RB100),
Ethylene-(two bromo-norbornanes, two carbimides) (SAYTEX BN-451),
Two-(hexachlorocyclopentadiene base) cyclooctane,
PTFE，
Three-(2, the 3-dibromopropyl)-isocyanuric acid ester and
Ethylidene-two-tetrabromo phthalimide.
Organophosphorous fire retardant for example is:
Tetraphenyl Resorcinol diphosphites (FYROLFLEX RDP, Akzo Nobel),
Triphenylphosphate,
Tricresyl phosphate octyl group ester,
Tritolyl Phosphate,
Four (hydroxymethyl) phosphoric sulfide,
Phosphonic acids diethyl-N, N-two (2-hydroxyethyl)-amino methyl ester,
The hydroxyalkyl acrylate of phosphoric acid,
Ammonium polyphosphate (APP) or (HOSTAFLAM AP750),
Resorcinol diphosphate oligopolymer (RDP),
Phosphonitrile fire retardant and
Quadrol bisphosphate (EDAP).
The isocyanuric acid ester fire retardant comprises poly-isocyanurate, the ester of isocyanuric acid and isocyanuric acid ester.For example, the hydroxyalkyl isocyanuric acid ester is as three-(2-hydroxyethyl) isocyanuric acid esters, three (hydroxymethyl) isocyanuric acid ester, three (3-hydroxyl-n-propyl) isocyanuric acid ester or triglycidyl group isocyanuric acid esters.
The melamine based flameproofing for example is:
Melamine cyanurate,
The melamine boric acid ester,
The melamine phosphoric acid ester,
The melamine poly phosphate and
The melamine pyrophosphate.
Boric acid can be used as fire retardant and is comprised.
Especially preferred conventional flame retardants is
The chlorine alkyl phosphate,
Poly-brominated diphenyl base oxide,
The decabrominated dipheny base oxide,
Tricresyl phosphate [3-bromo-2,2-two (brooethyl) propyl group] ester,
Two (2,3-dibromopropyl ether) of dihydroxyphenyl propane,
Brominated epoxy resin,
Ethylidene-two (tetrabromo phthalimide),
Two (hexachlorocyclopentadiene base) cyclooctane,
Clorafin,
1,2-two (tribromophenoxy) ethane,
Tetrabromo-dihydroxyphenyl propane,
Ethylene-(two bromo-norbornanes, two carbimides),
Two-(hexachlorocyclopentadiene base) cyclooctane,
Three-(2, the 3-dibromopropyl)-isocyanuric acid ester,
Ethylidene-two-tetrabromo phthalimide,
Three-(2-hydroxyethyl) isocyanuric acid esters,
Three (hydroxymethyl) isocyanuric acid ester,
Three (3-hydroxyl-n-propyl) isocyanuric acid ester,
The triglycidyl group isocyanuric acid ester,
Melamine cyanurate,
The melamine boric acid ester,
The melamine phosphoric acid ester,
The melamine poly phosphate and
The melamine pyrophosphate.
It is optional from organic aromatics halogenated compound such as benzene halide to be used for halogenated fire-retardants of the present invention, biphenyl, phenols, its ether or ester, bis-phenol, phenylbenzene oxidation thing, aromatic carboxylic acid or polyacid, acid anhydrides, its acid amides or imide; Organic cyclic aliphatic or poly-cyclic aliphatic halogenated compound; With organic aliphatic halogenated compound such as halogenated paraffin, oligomeric-or polymkeric substance, alkyl phosphate or alkyl isocyanide urea acid esters.These components are known in the art mostly, referring to as US patent Nos.4, and 579,906 (as hurdle 3,30-41 is capable), 5,393,812; In addition referring to the plastics additive handbook (H.Zweifel edits, 5
ThEd., Hanser Publ., Munich 2001, pp.681-698).
Phosphonitrile fire retardant is well known in the art.They for example are disclosed in EP1104766, JP07292233, DE19828541, DE1988536, JP11263885, U.S.Pat.Nos.4,107,108,4,108,805 and 4,079,035 and 6,265, the relevant disclosure of 599. these U.S. patents is incorporated the present invention as a reference into.
PTFE, tetrafluoroethylene (Teflon 6C for example; E.I.Du Pont) can advantageously be added in this composition, for example be disclosed in U.S. application 60/312,517 (submit August 15 calendar year 2001) as other fire retardant.
Advantageously, this composition can comprise only a spot of antimony compounds such as Sb
2O
3, as be lower than the about 1% of component (A), for example be lower than about 0.1% weight; For example, this composition does not have antimony basically.
Fire-retardant filler for improve flame retardant properties and, optional as realization higher level in UL-94 combustion test (following description).Therefore, the present composition can comprise only a spot of fire-retardant filler, as is lower than the about 3% of component (A), for example is lower than approximately 1%, for example is lower than about 0.1% weight; For example, this composition does not have fire-retardant filler basically.
Fire-retardant filler is known in the art and is selected from magnesium hydroxide, alumina trihydrate and zinc borate.Coating can comprise fire-retardant filler such as vermiculite or silicate cement.Fire-retardant filler is to be used for the mineral compound of flame retardant properties and to be considered to " filler " under sufficiently high content.
If conventional fillers such as talcum, lime carbonate and analogue for example are used for flowing property routinely to reduce the propagation of burning drop (is not fire-retardant) itself, these conventional fillers also can reduce by using this composition.For example, this composition can comprise only a spot of conventional fillers, for example is lower than the about 3% of component (A), for example is lower than 1%, for example is lower than about 0.1% weight; For example, this composition does not have conventional fillers basically.
In addition, the present invention allows to substitute more expensive fire-retardant filler with conventional fillers.
The present composition can further advantageously comprise nano-sized filler.Nano-sized filler is also referred to as " nanoclay ", for example is disclosed in U.S.Pat.Nos.5, and 853,886 and 6,020,419, its relevant disclosure is incorporated the present invention as a reference into.
Nano-sized filler of the present invention is for example leaf silicate or smectite clay, for example organophilic leaf silicate, naturally occurring leaf silicate, the mixture of synthetic leaf silicate or these leaf silicate.This nano-sized filler is for example montmorillonite, wilkinite, beidellite, hectorite, talcum powder or rich magnesium montmorillonite.
Gained stable composition of the present invention can optionally also comprise various conventional additives, for example account for component (A) about 0.01 to about 10%, for example about 0.025 to about 4%, for example about 0.1 to about 2% weight as the following material of enumerating, or its mixture.
1. antioxidant
1.1. the single phenols of alkylation, for example 2,6-two-tertiary butyl-4-methylphenol, the 2-tertiary butyl-4,6-two-methylphenol, 2,6-two-tertiary butyl-4-ethylphenol, 2,6-two-tertiary butyl-4-normal-butyl phenol, 2,6-two-tertiary butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(methylcyclohexyl)-4,6-dimethyl-phenol, 2,6-two (octadecyl)-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-two-tertiary butyl-4-methoxymethyl phenol is a nonylphenol class linear or branching in side chain, for example, 2,6-two-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methyl, 11-1 '-yl) phenol, 2,4-dimethyl-6-(1 '-methyl 17-1 '-yl) phenol, 2,4-dimethyl-6-(1 '-methyl 13-1 '-yl) phenol and its mixture.
1.2. alkylthiomethyl phenols, for example 2,4-dioctyl sulphomethyl-6-tert.-butyl phenol, 2,4-dioctyl-sulphomethyl-6-methylphenol, 2,4-dioctyl sulphomethyl-6-ethylphenol, 2,6-two-dodecyl sulphomethyl-4-nonylphenol.
1.3. Resorcinol and alkylated hydroquinone, for example 2,6-two-tertiary butyl-4-methoxyl group-phenol, 2,5-two-Tert. Butyl Hydroquinone, 2,5-two-tert-pentyl Resorcinol, 2,6-phenylbenzene-4-18 oxygen base phenol, 2,6-two-Tert. Butyl Hydroquinone, 2,5-two-tertiary butyl-4-hydroxy phenylmethylether, 3,5-two-tertiary butyl-4-hydroxy phenylmethylether, stearic acid 3,5-two-tert-butyl-hydroxy phenyl ester, hexanodioic acid two-(3,5-two-tert-butyl-hydroxy phenyl) ester.
1.4. tocopherol, alpha-tocopherol for example, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and its mixture (vitamin-E).
1.5. hydroxylation sulfo-diphenyl ether, for example 2,2 '-thiobis (the 6-tertiary butyl-4-methylphenol), 2,2 '-thiobis (4-octyl phenol), 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (the 6-tertiary butyl-2-methylphenol), 4,4 '-thiobis-(3,6-two-sec.-amyl sec-pentyl secondary amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulphide.
1.6. alkylidene bisphenolsFor example 2,2 '-methylene-bis (uncle's 6-fourth double-basis-4-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(methylcyclohexyl)-phenol], 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-nonyl-4-methylphenol), 2,2 '-methylene-bis (4,6-two-tert.-butyl phenol), 2,2 '-ethylenebis (4,6-two-tert.-butyl phenol), 2,2 '-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Jibianji)-4-nonylphenol], 2,2 '-methylene-bis [6-(α, α-Er Jiajibianji)-the 4-nonylphenol], 4,4 '-methylene-bis-(2,6-two-tert.-butyl phenol), 4,4 '-methylene-bis (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methyl-phenol of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-methyl-phenyl)-3-dodecyl sulfydryl butane of 1-, ethylene glycol bis (3,3-pair (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric ester), two (3-tertiary butyl-4-hydroxy-5-methyl-phenyl) Dicyclopentadiene (DCPD), two [2-(3 '-tertiary butyl-2 '-hydroxy-5-methyl base the benzyl)-6-tertiary butyl-4-aminomethyl phenyl] terephthalate, 1, two (3, the 5-dimethyl-2-hydroxy phenyl) butane of 1-, 2,2-two-(3,5-two-tert-butyl-hydroxy phenyl) propane, 2,2-two-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-n-dodecyl sulfydryl butane, 1,1,5,5-four-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.
1.7.O-, N-and S-benzyl compounds, for example 3,5,3 ', 5 '-four-tertiary butyl-4,4 '-dihydroxyl two-benzylic ether, Thiovanic acid octadecyl-4-hydroxyl-3,5-dimethyl benzyl ester, tridecyl-4-hydroxyl-3,5-two-tertiary butyl benzyl mercaptoacetate, three (3,5-two-tertiary butyl-4-hydroxy benzyl) amine, two (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) esters of dithio terephthalic acid, two (3,5-two-tertiary butyl-4-hydroxy benzyl) sulfide, Thiovanic acid iso-octyl-3,5-two-tertiary butyl-4-hydroxy benzyl ester.
1.8. hydroxybenzyl malonic ester, propanedioic acid two-octadecyl-2 for example, 2-two-(3,5-two-tertiary butyl-2-hydroxybenzyl) ester, propanedioic acid two-octadecyl-2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) ester, propanedioic acid two-dodecyl mercaptoethyl-2,2-two-(3,5-two-tertiary butyl-4-hydroxy benzyl) ester, propanedioic acid is two, and [4-(1,1,3, the 3-tetramethyl butyl) phenyl]-2, two (3, the 5-two-tertiary butyl-4-hydroxy benzyl) esters of 2-.
1.9. aromatic hydroxy benzyl compounds, for example 1,3,5-three-(3,5-two-tertiary butyl-4-hydroxy-benzyl)-2,4,6-Three methyl Benzene, 1, two (3,5-two-tertiary butyl-4-hydroxy benzyl)-2,3,5 of 4-, 6-tetramethyl-benzene, 2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) phenol.
1.10. triaizine compounds, for example 2, two (octyl group the sulfydryl)-6-(3,5-two-tertiary butyl-4-hydroxy-anilino)-1 of 4-; 3, the 5-triazine, 2-octyl group sulfydryl-4,6-two (3; 5-two-tertiary butyl-4-hydroxy anilino)-and 1,3,5-triazines, 2-octyl group sulfydryl-4; two (3,5-two-tertiary butyl-4-hydroxy phenoxy group)-1,3,5-triazines of 6-; 2,4,6-three-(3,5-two-tertiary butyl-4-hydroxy phenoxy group)-1; 2,3-triazine, 1,3; 5-three-(3,5-two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 2,4; 6-three-(3,5-two-tert-butyl-hydroxy phenyl ethyl)-1,3,5-triazines; 1,3,5-three (3,5-two-tertiary butyl-4-hydroxy-phenyl propionyl)-six hydrogen-1; 3,5-triazine, 1; 3,5-three (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.
1.11. benzylphosphonic acid esterDimethyl-2 for example, 5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester, diethyl-3,5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester, two-octadecyl 3,5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester, two-octadecyl-5-tertiary butyl-4-hydroxy-3-methyl-benzyl phosphonic acid ester, 3, the calcium salt of single ethyl ester of 5-two-tertiary butyl-4-hydroxy benzylphosphonic acid.
1.12. acyl amino phenols, 4-hydroxyl gold anilide for example, 4-hydroxyl stearanilide, N-(3,5-two-tert-butyl-hydroxy phenyl) carboxylamine octyl group ester.
1.13. β-(3,5-two-tert-butyl-hydroxy phenyl propionic acid and list-or polyvalent alcohol, as with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propane diol, neopentyl glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-undecyl alcohol, 3-thiophene pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.14. β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and list-or polyvalent alcohol, as with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two-(hydroxyethyl) oxamide, 3-sulfo-undecyl alcohol, 3 one thiophene pentadecanols, the own urea glycol of trimethylammonium, trimethyl propane, 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.15. β-(3,5-dicyclohexyl-4-hydroxy phenyl) propionic acid and list-or polyvalent alcohol, as with methyl alcohol, ethanol, octanol, stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-undecyl alcohol, 3-thiophene pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.16.3,5-two-tert-butyl-hydroxy phenyl acetate and list-or polyvalent alcohol, as with methyl alcohol, ethanol, octanol, stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thio-diethylene glycol, Diethylene Glycol, triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-undecyl alcohol, 3-thiophene pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.17. the acid amides of β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acidAs N; N '-two (3,5-two-tert-butyl-hydroxy phenyl propionyl) hexa-methylene diamide, N; N '-two (3; 5-two-tertiary butyl-4-hydroxy-phenyl propionyl) trimethylene diamide, N, N '-two (3; 5-two-tert-butyl-hydroxy phenyl propionyl) hydrazides; N, and N '-two [2-(3-[3,5-two-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxamide (by the Naugard XL-1 of Uniroyal supply).
1.18. xitix(vitamins C)
1.19. amine antioxidantsN for example; N '-two-sec.-propyl-P-pHENYLENE dI AMINE; N; N '-two-sec-butyl-Ursol D; N; N '-two (1; 4-dimethyl amyl group)-Ursol D; N; N '-two (1-ethyl-3-methyl amyl)-Ursol D; N; N '-two (1-methylheptyl)-Ursol D; N; N '-dicyclohexyl-Ursol D; N; N '-phenylbenzene-Ursol D, N, N '-two (2-naphthyl)-Ursol D; N-sec.-propyl-N '-phenyl-Ursol D; N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D, N-(1-methylheptyl)-N '-phenyl-Ursol D; N-cyclohexyl-N '-phenyl-Ursol D; 4-(to the amino toluene alkylsulfonyl) diphenylamine, N, N '-dimethyl-N; N '-two-sec-butyl-Ursol D; diphenylamine, N-allyl group diphenylamine, 4-isopropoxy diphenylamine; the N-phenyl-1-naphthylamine; N-(uncle's 4-octyl phenyl)-1-ALPHA-NAPHTHYL AMINE, N-phenyl-2-ALPHA-NAPHTHYL AMINE, octyl group diphenylamine; for example right; right '-two-uncle octyldiphenylamine, 4-normal-butyl amino-phenol, 4-butyryl radicals amino-phenol; 4-nonanoyl amino-phenol; 4-lauroyl amino-phenol, 4-stearoyl amino-phenol, two (4-p-methoxy-phenyl) amine; 2; 6-two-tertiary butyl-4-dimethylaminomethyl phenol, 2,4 '-diaminodiphenyl-methane; 4; 4 '-diaminodiphenyl-methane, N, N; N '; N '-tetramethyl--4,4 '-diaminodiphenyl-methane, 1; two [(2-aminomethyl phenyl) amino] ethane of 2-; 1, two (phenyl amino) propane of 2-, (o-tolyl) biguanides; two [4-(1 '; 3 '-dimethylbutyl) phenyl] amine, uncle's octyl group N-phenyl-1-naphthylamine, single-and the mixture of the dialkyl group tertiary butyl/uncle's octyldiphenylamine; single-and the mixture of dialkyl group nonyl diphenylamine; single-and the mixture of dialkyl group dodecyl diphenylamine, single-and the mixture of dialkyl group sec.-propyl/isohexyl diphenylamine, single-and the mixture of dialkyl group tert-butyl diphenyl amine; 2; 3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine; thiodiphenylamine; single-and the mixture of the dialkyl group tertiary butyl/uncle's octyl group thiodiphenylamine, single-and the mixture of dialkyl group uncle octyl group-thiodiphenylamine, N-allyl group thiodiphenylamine; N; N, N ', N '-tetraphenyl-1; 4-diamino but-2-ene; N, N-two (2,2; 6; 6-tetramethyl--piperidin-4-yl-hexamethylene-diamine, sebacic acid two (2,2; 6; 6-tetramethyl piperidine-4-yl) ester, 2,2; 6; 6-tetramethyl piperidine-4-ketone, 2,2; 6,6-tetramethyl piperidine-4-alcohol.
2.UV absorption agent and photostabilizer
2.1.2-(2 '-hydroxy phenyl) benzotriazoleFor example 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-benzotriazole, 2-(3 ', 5 '-two-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole phenyl), 2-(3 ', 5 '-two-tertiary butyl-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chloro-benzotriazole, 2-(3 '-sec-butyl-5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyl group oxygen base phenyl) benzotriazole, 2-(3 ', 5 '-two-tert-pentyl-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two-(α, α-Er Jiajibianji)-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-octyl group oxygen base carbonyl ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethylhexyl-oxygen base)-carbonyl ethyl]-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methyl-oxygen base carbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-octyl group oxygen base carbonyl-ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethylhexyl oxygen base) carbonyl ethyl]-2 '-hydroxyl-phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-iso-octyl oxygen base carbonyl ethyl) phenyl benzotriazole, 2,2 '-methylene radical-two (4-(1,1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol); 2-(3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl)-product of transesterification reaction of 2H-benzotriazole and Liquid Macrogol;
Wherein R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base phenyl, 2-[2 '-hydroxyl-3 '-(α, α-Er Jiajibianji)-5 '-(1,1,3, the 3-tetramethyl butyl)-phenyl]-benzotriazole; 2-[2 '-hydroxyl-3 '-(1,1,3, the 3-tetramethyl butyl)-5 '-(α, α-Er Jiajibianji)-phenyl] benzotriazole.
2.2.2-hydroxy benzophenone, 4-hydroxyl for example, the 4-methoxyl group, 4-octyl group oxygen base, 4-decyl oxygen base, 4-dodecyl oxygen base, 4-benzyl oxygen base, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-the dimethoxy derivative.
2.3. that replace and unsubstituted benzoic ester, the 4-tertiary butyl-phenyl salicylic acid esters for example, phenyl salicylic acid esters; the octyl phenyl salicylate, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol; the benzoyl Resorcinol, 2,4-two-tert-butyl-phenyl 3; 5-two-tertiary butyl-4-hydroxy benzoic ether, hexadecyl 3,5-two-tertiary butyl-4-hydroxy benzoic ether; octadecyl 3,5-two-tertiary butyl-4-hydroxy benzoic ether, 2-methyl-4; 6-two-tert-butyl-phenyl 3,5-two-tertiary butyl-4-hydroxy benzoic ether.
2.4. acrylateEthyl alpha-cyano-β for example, β-diphenylacrylate ester, iso-octyl alpha-cyano-β, β-diphenylacrylate ester, methyl α-methoxycarbonyl laurate, methyl alpha-cyano-Beta-methyl-to methoxyl group-laurate, butyl alpha-cyano-Beta-methyl-to methoxyl group-laurate, methyl α-methoxycarbonyl-p-methoxycinnamic acid ester and N-(beta-methoxy-carbonyl-beta-cyano vinyl)-2-methyl indoline.
2.5. nickel compoundFor example 2; 2 '-sulfo--two-[4-(1; 1; 3; 3-tetramethyl--butyl) phenol]) nickel complex (be with or without other part such as n-butylamine as 1: 1 or 1: 2 title complex; trolamine or N-cyclohexyl diethanolamine); nickel dibutyl dithiocaarbamate ester, 4-hydroxyl-3, the mono alkyl ester of 5-two-tertiary butyl benzylphosphonic acid; nickel salt as methyl or ethyl ester; ketoxime, as the nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketoxime, the 1-phenyl-4-lauroyl-nickel complex of 5-hydroxypyrazoles when being with or without other part.
2.6. sterically hindered amines, for example sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, succsinic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester, two (the 1-octyl group oxygen bases-2 of sebacic acid, 2,6,6-tetramethyl--4-piperidyl) ester, propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) normal-butyl-3,5-two-tertiary butyl-4-hydroxy benzyl ester, 1-(2-hydroxyethyl)-2,2,6, the condenses of 6-tetramethyl--4-hydroxy piperidine and succsinic acid, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and uncle's 4-octyl group amino-2, the linearity or the ring-shaped condensate of 6-two chloro-1,3,5-triazines, nitrilotriacetic acid(NTA) three (2,2,6,6-tetramethyl--4-piperidyl) ester, 1,2,3,4-butane-tetracarboxylic acid four (2,2,6,6-four-methyl-4-piperidyl) ester, 1,1 '-(1,2-second two bases)-two (3,3,5,5-tetramethyl-piperazine ketone), 4-benzoyl-2,2,6, the 6-tetramethyl piperidine, 4-stearyl oxygen base-2,2,6, the 6-tetramethyl piperidine, propanedioic acid two (1,2,2,6,6-pentamethyl-piperidyl)-2-normal-butyl-2-(2-hydroxyl-3,5-two-tertiary butyl benzyl) ester, 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2,4-diketone, two (the 1-octyl group oxygen bases-2 of sebacic acid, 2,6, the 6-tetramethyl-piperidyl) ester, two (the 1-octyl group oxygen bases-2 of succsinic acid, 2,6, the 6-tetramethyl-piperidyl) ester, N, N '-two-(2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2, the linearity or the ring-shaped condensate of 6-two chloro-1,3,5-triazines, 2-chloro-4,6-two (4-normal-butyl amino-2,2,6, the 6-tetramethyl-piperidyl)-1,3,5-triazine and 1, the condenses of two (3-the amino propyl amino)-ethane of 2-, 2-chloro-4,6-two-(4-normal-butyl amino-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazines and 1, the condenses of 2-pair-(3-amino propyl amino) ethane, 8-ethanoyl-3-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2,4-diketone, 3-dodecyl-1-(2,2,6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone, 3-dodecyl-1-(1,2,2,6,6-pentamethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone, 4-hexadecyl oxygen base-and 4-stearyl oxygen base-2,2,6, the mixture of 6-tetramethyl piperidine, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-cyclohexyl amino-2,6-two chloro-1,3, the condensation product of 5-triazine, 1, two (3-amino propyl amino) ethane and 2 of 2-, 4,6-three chloro-1,3, the condensation product of 5-triazine and 4-butyl amino-2,2,6, the 6-tetramethyl piperidine (CAS Reg.No.[136504-96-6]); N-(2,2,6,6-tetramethyl--4-piperidyl)-dodecyl succinimide; N-(1,2,2,6; 6-pentamethyl--4-piperidyl)-and the dodecyl succinimide, 2-undecyl-7,7,9; 9-tetramethyl--1-oxa--3,8-diaza-4-oxo-spiral shell [4,5] decane, 7; 7,9,9-tetramethyl--2-encircles 11-1-oxa--3,8-diaza-4-oxo spiral shell [4; 5] reaction product of decane and Epicholorohydrin, 1,1-two (1,2; 2,6,6-pentamethyl--4-piperidyl oxygen base carbonyl)-2-(4-p-methoxy-phenyl) ethene, N; N '-two-formyl radical-N, N '-two (2,2,6; 6-tetramethyl--4-piperidyl) hexamethylene-diamine, 4-methoxyl group-methylene radical-propanedioic acid and 1,2; 2,6, the diester of 6-pentamethyl--4-hydroxy piperidine; poly-[methyl-propyl-3-oxygen base-4-(2,2,6; 6-tetramethyl--4-piperidyl)] siloxanes, maleic anhydride-alpha-olefin-multipolymer and 2,2; 6,6-tetramethyl--4-amino piperidine or 1,2; 2,6, the reaction product of 6-pentamethyl--4-amino piperidine.
2.7. oxamideFor example 4,4 '-dioctyl oxygen base oxanilide, 2,2 '-the diethoxy oxanilide, 2,2 '-dioctyl oxygen base-5,5 '-two-uncle butyranilide, 2,2 '-docosyl oxygen base-5,5 '-two-uncle butyranilide, 2-oxyethyl group-2 '-the ethyl oxanilide, N, N '-two (3-dimethylaminopropyl) oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-Acetanilide and itself and 2-oxyethyl group-2 '-ethyl-5, the mixture of 4 '-two-uncle butyranilide, adjacent and to the mixture of methoxyl group-dibasic oxanilide and adjacent and to the mixture of oxyethyl group-dibasic oxanilide.
(2.8.2-2-hydroxy phenyl)-1,3,5-triazines, for example 2,4,6-three (2-hydroxyl-4-octyl group oxygen base phenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-octyl group oxygen base phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3, the 5-triazine, 2-(2, the 4-dihydroxy phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3, the 5-triazine, 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2 of 4-, the 4-3,5-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxyl-4-octyl group oxygen base phenyl)-4, two (the 4-aminomethyl phenyls)-1 of 6-, 3,5-triazine, 2-(2-hydroxyl-4-dodecyl oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-tridecyl oxygen base phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1,3 of 6-, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butyl oxygen base-propoxy-) phenyl]-4, two (2, the 4-dimethyl)-1 of 6-, 3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyl group oxygen base-propyl group oxygen base) phenyl]-4,6-two (2, the 4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyl oxygen base/tridecyl oxygen base-2-hydroxyl propoxy-)-2-hydroxyl-phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyl oxygen base-propoxy-) phenyl]-4, two (2,4-dimethyl-phenyl)-1,3 of 6-, the 5-triazine, 2-(2-hydroxyl-4-hexyl oxygen base) phenyl-4,6-phenylbenzene-1,3, the 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3, the 5-triazine, 2,4,6-three [2-hydroxyl-4-(3-butoxy-2-hydroxyl-propoxy-) phenyl]-1,3, the 5-triazine, 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3, the 5-triazine, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen base)-2-hydroxypropyl oxygen base] phenyl }-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3, the 5-triazine.
3. metal deactivator, N for example, N '-phenylbenzene oxamide; N-salicyl-N '-salicyloyl hydrazine, N, N '-two (salicyloyl) hydrazine; N; N '-two (3,5-two-tert-butyl-hydroxy phenyl propionyl) hydrazine, 3-salicyloyl amino-1; 2; the 4-triazole, two (benzylidene) oxalyl group two hydrazides, oxanilide; isophthaloyl two hydrazides; the sebacoyl biphenyl hydrazine, N, N '-diacetyl adipyl two hydrazides; N; N '-two (salicyloyl) oxalyl group two hydrazides, N, N '-two (salicyloyl) sulfo-propionyl two hydrazides.
4. phosphorous acid ester and phosphinate, triphenyl phosphite for example, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite Lauryl Ester, tricresyl phosphite-stearyl, distearyl pentaerythrityl diphosphite, tricresyl phosphite (2,4-two-tert-butyl-phenyl) ester, the diiso decyl pentaerythritol diphosphites, two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-two-tertiary butyl-4-aminomethyl phenyl)-pentaerythritol diphosphites, diiso decyl oxygen base pentaerythritol diphosphites, two (2,4-two-tertiary butyl-6-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-three (tertiary butyl-phenyl) pentaerythritol diphosphites, three stearyl sorbyl alcohol GW-540s, two phosphonous acid four (2,4-two-tertiary butyl-phenyl) 4,4 '-the biphenylene ester, 6-iso-octyl oxygen base-2,4,8,10-four-tertiary butyl-12H-dibenzo-[d, g]-1,3,2-two oxa-phosphocin, two (2, the 4-two-tertiary butyl-6-aminomethyl phenyl) methyl ester of phosphorous acid, phosphorous acid two (2,4-two-tertiary butyl-6-aminomethyl phenyl) ethyl ester, 6-fluoro-2,4,8,10-four-tertiary butyl-12-methyl-dibenzo [d, g]-1,3,2-two oxa-phosphocin, 2,2 ', 2 " nitrilo [triethyl three (3; 3 '; 5,5 '-four-tertiary butyl-1,1 '-biphenyl-2; 2 '-two bases) phosphorous acid ester]; phosphorous acid 2-ethylhexyl (3,3 ', 5; 5 '-four-tertiary butyl-1,1 '-biphenyl-2,2 '-two bases) ester, 5-butyl-5-ethyl-2-(2,4,6-three-tertiary butyl phenoxy group)-1,3,2-two oxa-phosphirane.
Object lesson is following phosphorous acid ester:
Three (2,4-two-tert-butyl-phenyl) phosphorous acid ester (Irgafos 168, Ciba-Geigy), tricresyl phosphite (nonyl phenyl) ester,
5. oxyamine, for example, N, N-dibenzyl oxyamine, N, N-diethyl oxyamine, N, N-dioctyl oxyamine, N, N-dilauryl oxyamine, N, N-two-tetradecyl oxyamine, N, N-two-hexadecyl oxyamine, N, N-two-octadecyl oxyamine, N-hexadecyl-N-octadecyl hydroxyl base amine, N-heptadecyl-N-octadecyl oxyamine, derived from the N of hydrogenated butter amine, N-dialkyl group oxyamine.
6. nitroneFor example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-Alpha-Methyl-nitrone, N-octyl group-α-heptyl-nitrone, N-lauryl-α-undecyl-nitrone, N-tetradecyl-α-tridecyl-nitrone, N-hexadecyl-α-pentadecyl-nitrone, N-octadecyl-α-heptadecyl-nitrone, N-hexadecyl-α-heptadecyl-nitrone, N-octadecyl-α-pentadecyl-nitrone, N-heptadecyl-α-heptadecyl-nitrone, N-octadecyl-α-hexadecyl-nitrone, derived from the N of hydrogenated butter amine, N-dialkyl group oxyamine institute deutero-nitrone.
7. sulfo-synergistic agent, for example, thiodipropionate dilauryl or thio-2 acid distearyl ester.
8. peroxide scavenger, for example ester of β-thio-2 acid, for example lauryl, stearyl, myristyl or tridecyl ester, the zinc salt of mercaptobenzimidazole or 2-sulfydryl-benzoglyoxaline, zinc dibutyl dithiocarbamate, two-octadecyl disulphide, tetramethylolmethane four (β-dodecyl sulfydryl) propionic ester.
9. polymeric amide stablizer, for example, mantoquita combines with the salt of iodide and/or phosphorus compound and bivalent manganese.
10. alkaline co-stabilizer, for example, melamine, Polyvinylpyrolidone (PVP), Dyhard RU 100, triallylcyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, an alkali metal salt of higher fatty acid and alkaline earth salt be calcium stearate for example, Zinic stearas ， docosoic magnesium, Magnesium Stearate, sodium ricinoleate and potassium palmitate, pyrocatechol antimony or pyrocatechol zinc.
11. nucleator, for example, inorganic substance such as talcum, metal oxides such as titanium dioxide or magnesium oxide, the phosphoric acid salt of alkaline-earth metal for example, carbonate or vitriol; Organic compound is as single-or poly carboxylic acid and its salt, as the 4-p t butylbenzoic acid, and hexanodioic acid, diphenyl acetic acid, sodium succinate or Sodium Benzoate; Polymkeric substance such as ionic copolymer (ionomer).Object lesson is 1,3:2,4-pair (3 ', 4 '-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-two (to the methyl dibenzylidene) sorbyl alcohol and 1,3:2,4-two (benzylidene) sorbyl alcohol.
12. filler and toughener, for example, lime carbonate, silicate, glass fibre, glass sphere, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, the powder or the fiber of wood powder and other natural product, synthon.
13. other additive, for example, softening agent, lubricant, emulsifying agent, pigment, rheologic additive, catalyzer, flow control agent, white dyes, fire retardant, static inhibitor and whipping agent.
14. benzofuranone and indolinone, for example be disclosed in U.S.4,325,863; U.S.4,338,244; U.S.5,175,312; U.S.5,216,052; U.S.5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; Those of EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5; 7-two-tertiary butyl-benzofuran-2-ones; 5; 7-two-tertiary butyl-3-[4-(2-stearyl-oxygen base oxethyl) phenyl] benzofuran-2-ones; 3,3 '-two [5,7-two-tertiary butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones]; 5; 7-two-tertiary butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones, 3-(4-acetoxy-3,5-3,5-dimethylphenyl)-5; 7-two-tertiary butyl-benzofuran-2-ones; 3-(3,5-dimethyl-4-new pentane acyloxy phenyl)-5,7-two-tertiary butyl-benzofuran-2-ones; 3-(3; the 4-3,5-dimethylphenyl)-5,7-two-tertiary butyl-benzofuran-2-ones, 3-(2; 3-two-aminomethyl phenyl)-5,7-two-tertiary butyl-benzofuran-2-ones.
15. amine oxide, for example be disclosed in U.S. patent Nos.5,844,029 and 5,880,191 amine oxide derivative, didecyl methyl oxidation amine, three decyl amine oxides, three-dodecyl amine oxide and three-hexadecyl amine oxide.U.S. patent Nos.5,844,029 and 5,880,191 disclose the purposes of stable hydrocarbon amine oxide for the stabilising thermoplastic resin.Wherein open, thermoplastic compounds can further comprise and is selected from phenol antioxidant, hindered amine light stabilizer, ultraviolet absorbers, organo phosphorous compounds, the stablizer or the stabilizer blend of the alkaline metal salt of lipid acid and sulfo-synergistic agent.
The object lesson of additive is phenol antioxidant (project of enumerating 1), other sterically hindered amines (project of enumerating 2.6), benzotriazole and/or o-hydroxy-phenyl triazines as light stabilizer (project of enumerating 2.1 and 2.8), phosphorous acid ester and phosphinate (project of enumerating 4) and superoxide-destruction compound (project of enumerating 5).
The object lesson of other of additive (stablizer) is a benzofuran-2-ones, for example is described in US-A-4,325,863, and US-A-4,338,244 or US-A-5,175,312.
This composition can comprise in addition and is selected from the s-triazine, oxanilide, hydroxy benzophenone, another UV absorption agent of benzoic ether and α-Qing Jibingxisuanzhi.Especially, this composition can comprise at least a other 2-hydroxy phenyl-2H-benzotriazole of effective stable quantity in addition; Another three-aryl-s-triazine; Or bulky amine or its mixture.For example, other component is selected from pigment, dyestuff, softening agent, antioxidant, thixotropic agent, leveling auxiliary agent, alkaline co-stabilizer, other photostabilizer such as UV absorption agent and/or sterically hindered amines, metal passivator, metal oxide, organo phosphorous compounds, oxyamine and its mixture, pigment especially, phenol antioxidant, calcium stearate, Zinic stearas, 2-(2 '-hydroxy phenyl) benzotriazole and 2-(2-hydroxy phenyl)-1,3,5-triazines UV absorption agent, and sterically hindered amines.
This composition also can comprise foaming agent.Example is the combination of three (2-hydroxyethyl) isocyanuric acid esters and ammonium polyphosphate, melamine, methylolation melamine, hexamethoxy methyl cyanuramide, the melamine phosplate, melamine bisphosphate, melamine poly phosphate, the melamine pyrophosphate, urea, dimethyl urea, Dyhard RU 100, miaow base urea phosphoric acid ester, glycine or phosphamide.When decomposing being exposed to heat, aforementioned substances discharges nitrogen.Also can adopt at the compound that is exposed to release of carbon dioxide when hot or water vapour.
This composition can comprise carbonific material (many hydrogen compounds) as tetramethylolmethane, Dipentaerythritol, tripentaerythritol, tetramethylolmethane urethane, phenol triethylene glycol, Resorcinol, inositol, sorbyl alcohol, dextrin and starch.
This composition can comprise silica.
Additive of the present invention and other optional component can separately or be added in the formulation for coating material mutual the mixing.If desired, each component can for example be mixed by doing before introducing coating, compacting or mix mutually with melt form.
The content of component (i) in the present composition advantageously coating based component (A) about 0.1% to about 10% weight; For example about 0.25% to about 8% weight; For example about 0.5% to about 3% weight.For example, the amount of component (i) based on (A) about 0.25% to about 10% or about 0.5% to about 10% weight.For example, the amount of component (i) be based on (A) about 0.1% to about 8% or about 0.1% to about 3% weight.
Component (ii) the content in the present composition advantageously coating (A) about 0.5% to about 45% weight; For example about 3% to about 40%; For example about 5% component (A) to about 35% weight.For example, component consumption (ii) be based on polymeric substrate weight about 0.5% to about 10% weight, about 1% to about 10%, about 3% to about 10% or about 5% to about 10% weight.For example, component consumption (ii) is based on polymeric substrate, as the weight of resin glue (A) about 0.5% to about 8%, about 0.5% to about 6%, about 0.5% to about 5%, or about 0.5% to about 3% weight.
Component (i) is for example about 1: 5 to about 1: 200 with component ratio (weight part) (ii), for example about 1: 50 to about 1: 100, or for example component (i) and component ratio (ii) were about 1: 10 to about 1: 200 in about 1: 10 to about 1: 25., about 1: 25 to about 1: 200, about 1: 50 to about 1: 200 or about 1: 100 to about 1: 200. are for example, component (i) is about 1: 5 to about 1: 100 with component weight ratio (ii), about 1: 5 to about 1: 50, about 1: 5 to about 1: 25, or about 1: 5 to about 1: 10.
The consumption of optional conventional flame retardants also depends on the effectiveness of specific compound, specific coating and use type; For example, the compound tricresyl phosphate of the amount of 5 to 15% weight [3-bromo-2,2-two (brooethyl) propyl group] ester can with the compound decabrominated dipheny base oxide of the amount of 30 to 45% weight effective equally aspect the flame retardant resistance of final composition.The consumption of isocyanuric acid ester fire retardant normally based on (A) about 1 to about 10% weight, for example about 3 to about 6% weight.
Coating composition of the present invention self is fire-retardant and provides flame retardant resistance to their coated base materials and goods equally.Therefore, another theme of the present invention is a kind of fire retardant coated article, comprises
(A) coating and
(B) the following mixture of flame-retardant effective amount
(i) at least aly be selected from following mixture
(a) sterically hindered nitroxyl stablizer,
(b) sterically hindered oxyamine stablizer and
(c) sterically hindered alkoxylamine stablizer and
(ii) at least aly be selected from following conventional flame retardants
(d) organic halogen fire retardant,
(e) organophosphorous fire retardant
(f) the isocyanuric acid ester fire retardant and
(g) melamine based flameproofing.
Another theme of the present invention is a kind of fire retardant coated article, comprises
Scribble the base material of the fire retardant coating compositions that comprises following material
(A) resin glue and
(B) flame-retardant effective amount
(i) at least a ethylenic unsaturated polymerizable monomer, described monomer comprises sterically hindered nitroxyl, oxyamine or alkoxylamine part and optional
(ii) at least aly be selected from following conventional flame retardants
(a) organic halogen fire retardant,
(b) organophosphorous fire retardant,
(c) the isocyanuric acid ester fire retardant and
(d) melamine based flameproofing.
The component of flame-retardant effective amount (B) is that to show the fire-retardant effectiveness that one of standard method of being used for evaluation of flame retardancy determined required.These methods comprise that NFPA 701 is used for the standard method (1989 and 1996 editions) of the fire test of flame retardant textiles and film; Be used for flammable UL 94 test (the 5th edition, on October 29th, 1996) of plastic material of the parts of equipment and device; Limited oxygen index (LOI), ASTM D-2863; With the awl calorimetry, ASTM E-1354. is summarized in following table according to the grade of UL 94 V test:
| Grade | The residual flame time | The burning drop | Burning is to fixed |
| V-0 | ＜10s | Do not have | Do not have |
| V-1 | ＜30s | Do not have | Do not have |
| V-2 | ＜30s | Have | Do not have |
| Failure | ＜30s | Have | |
| Failure | ＞30s | Do not have |
Applicable test comprises:
ASTM F1173 fiberglass pipe and equipment (coastal waters/sea)
Be used for the flammable UL 94 of plastic material and the 746C test of the parts of equipment and device
UL??723
The IEEE-45-recommendation is used for the electric installation on the ship
IEEE-383-is used for the IE level cable of Nuclear power plants, the standard of open-air joint and the typical test that is connected
The flame retardant resistance (cabinet method) of ASTM-D-1360-paint
ASTM-E-84-is used for the test of the surface burning characteristics of material of construction
The fire test of ASTM-E-119-building structural materials
ASTM-E-162-uses the surface combustibility of the material of radiation thermal energy source
ASTM?F84
FAA14-25.853 .855 .856 .867-aviation and space (fire protection)
Paper base material (penetrant) is (Michelman): ASTM E-162, and ASTM E-662, NFPA701, TAPPI 461
Corrugated material w/FR coating (Michelman): ASTM E-162/662, FMR heat discharges, and NFPA 30, ASTM E-84, NFPA 703, UL723
NFPA 703: be used for flame-retardant impregnating timber and the standard that is used for the anti-flaming dope of material of construction
NFPA 255, the fire testing of building structural materials
Military specification book DOD-En 24607A and DOD-R-21417A (SH)
Having found especially can be as follows with the common additive that this compound uses in flame retardant composition:
The UV absorption agent:
2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-2H-benzotriazole, (TINUVIN 234, Ciba Specialty Chemicals Corp.);
2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, (TINUVIN P, CibaSpecialty Chemicals Corp.);
5-chloro-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole, (TINUVIN 327, Ciba Specialty Chemicals Corp.);
2-(2-hydroxyl-3,5-two-tert-pentyl phenyl)-2H-benzotriazole, (TINUVIN 328, Ciba Specialty Chemicals Corp.);
2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole, (TINUVIN 928, Ciba Specialty Chemicals Corp.);
2,4-two-tert-butyl-phenyl 3,5-two-tertiary butyl-4-hydroxy benzoic ether, (TINUVIN 120, Ciba Specialty Chemicals Corp.);
2-hydroxyl-4-n-octyl oxygen base benzophenone, (CHIMASSORB 81, Ciba SpecialtyChemicals Corp.);
2, two (2, the 4-the 3,5-dimethylphenyl)-6-(2-hydroxyl-4-octyl group oxygen base phenyl) of 4--s-triazine, (CYASORB 1164, Cytec).
Following examples only are used for explanation and do not constitute limiting scope of the present invention by any way.Given room temperature is meant temperature 20-25 degree centigrade.Unless refer else, percentage ratio is in the weight of coated substrate.
Test method
Be used for NFPA 701 standard methods (1989 and 1996 editions) of the fire test of flame retardant textiles and film;
Be used for flammable UL 94 test (the 5th edition, on October 29th, 1996) of plastic material of the parts of equipment and device;
Limited oxygen index (LOI), ASTM D-2863;
The awl calorimetry, ASTM E-1 or ASTM E 1354;
ASTM D 2633-82, combustion test.
Embodiment 1
Coating on TPO
The molded test sample is by the injection-molded pigment that comprises, phosphorous acid ester, phenol antioxidant or oxyamine, Metallic stearates, thermoplastic olefin (TPO) pellet of the mixture of ultraviolet absorbers or sterically hindered amine stabilizer or UV absorption agent and sterically hindered amine stabilizer and making.
Painted TPO pellet is by pure pigment or condensed pigment, altogether additive and commercially available TPO are by " single screw extrusion machine mixes down at 400 °F (200 degrees centigrade), cooling and granulation in water-bath and make at the Superior/MPM 1 with general Universal screw rod (24: 1 L/D) with these components.The gained pellet is molded as 2 " x2 " plate of 60mil (0.006 inch) on BOY 30M injection moulding machine under about 375 °F (190 degrees centigrade).
Use by N by the painted TPO prescription that polypropylene and rubber modifier blend are formed, the base fixed system that N-dialkyl group oxyamine or hindered phenolic antioxidants (being with or without organo phosphorous compounds) are formed is stable, and wherein rubber modifier is multipolymer or the blended product that comprises the real-world effectiveness of propylene and ethylene copolymer (being with or without ternary component such as ethylidene norbornene).
All additives in the end formulation and pigment concentration are expressed as the % weight based on resin.
Prescription comprises thermoplastic olefin pellet and one or more following components:
0.0 to 2.0% pigment,
0.0 to 50.0% talcum,
0.0 to 0.1% phosphorous acid ester,
0.0 to 1.25% phenol antioxidant,
0.0 to 0.1% oxyamine
0.05 to 0.10 calcium stearate,
0.0 to the 1.25%UV absorption agent and
0.0 to 1.25% sterically hindered amine stabilizer.
Each component is dried mixed in the tumble dry device before extrusion molding and the molding.
Polymeric substrate is commercially available polyolefin blends POLYTROPE TPP 518-01 (by A.Schulman Inc.Akron, Ohio supplies with)
The light stabilized formulations packs the paint systems japanning with list and test TPO/ paint interacts and flame retardant resistance.Before japanning, test sample is at first washed according to GM998-4801 and was descended dry 15 minutes at 200 °F (94 degrees centigrade).Adhesiving reinforcing agent is applied to build 0.2-0.4mil.Sample drying 5 minutes is applied to film thickness 1.2-1.4mil with the 1K undercoat then.With dry 3 minutes of painted plate, subsequently with clear coat application to build 1.2-1.5mil, expansion drying 10 minutes and in 250 (121 degrees centigrade) baking oven baking 30 minutes down subsequently.
One or more formulation for coating material comprise additive and conventional organic halogen, organophosphorus, isocyanuric acid ester or the melamine based flameproofing that is selected from this compound (a)-(o).
Other formulation for coating material comprises and is selected from this compound (i)-(additive v) and optional conventional organic halogen, organophosphorus, isocyanuric acid ester or melamine based flameproofing.
Paint adhesion is measured by aggressiveness adhesiveness test (at Technical Finishing, the special-purpose testing sequence that Inc. carries out) and Taber Scuff.Reservation is considered to and can accepts greater than the lacquered board of 80% paint final lacquer.After the aggressiveness adhesiveness test, the sample that is lower than 5% paint loss is considered to and can accepts.
This painting products has excellent paint adhesion and flame retardant resistance.With conventional flame retardants bonded additive (a)-(o) or (i)-(v) can in any or all coating, exist.
Embodiment 2
Water base wood varnish
Water-based paint comprises the coating that is used for various occasions significant and the increase ratio, comprises the automobile bottom, industrial coating and retail coating.These coating can be colored or be transparent.
Test stablizer (a)-(o) and (i)-(v) with conventional organic halogen, organophosphorus, isocyanuric acid ester or melamine based flameproofing are introduced into aqueous based dispersions by predissolve in the cosolvent adulterant.Aqueous based dispersions is a kind of commercially available vinylformic acid/urethanum hybrid resin.The cosolvent adulterant be TEXANOL (2,2,4-trimethylammonium-1, the 3-pentanediol, Texaco) and 1: 1 mixture of ARCOSOLVE TPM (tripropylene glycol methyl ether, Atlantic Richfield).
0.45 every kind of test stablizer (a)-(o) and (i) of gram-(v) and the predissolve in 10g cosolvent adulterant of the conventional flame retardants of appropriate amount, join subsequently in the following composition:
ppw
FLEXTHANE630(Air?Products)??????????????????100.0
Foamaster?VF??????????????????????????????????0.1
Water 10.0
TEXANOL/ARCOSOLVE/ bulky amine 10.5
UV absorption agent (TINUVIN 1130, Ciba) 1.2
BYK?346???????????????????????????????????????0.5
MICHEMLUBE162???????????????????????????????2.0
Each coating is brushed in 6 " * 6 " section of cdear and deal board.Coating that the weight of the coating of being used applies front and back by weighing and brushing are regulated and are guaranteed that the coating of identical weight is applied in each section.
Coated board section dry at ambient temperature 2 weeks, evaluation of flame retardancy subsequently.Plate shows excellent flame.
Embodiment 3
Optical fiber coating
The radiation-curable optical fiber coating is formulated as follows:
% weight
Urethanum origoester acrylate 37
Bisphenol-A epoxy diacrylate 28
Viscoat 335HP 21
Triethylene glycol diacrylate 4
Viscoat 295 6
Benzophenone 1.5
2,2-dimethoxy-2-phenyl methyl phenyl ketone 0.7
Benzil 0.5
Diethylamide 0.6
Thiodiphenylamine 0.01
2-hydroxyl-4-n-octyloxy benzophenone 0.01
Silicon 0.2
N-[(2-vinyl benzene amino)-ethyl]-3-aminopropyl trimethoxy 0.2
Base silane (40%, in MeOH)
Formulation for coating material comprises this additive and the conventional flame retardants that is selected from (a)-(o) in addition.Other light trigger is suitable, for example phosphine oxide photoinitiator.This coating material solidified excellent flame that demonstrates.
Embodiment 4
Optical fiber coating
The radiation-curable optical fiber coating is formulated as follows:
% weight
Urethanum origoester acrylate 20
Ethoxylated bisphenol a diacrylate 20
Propoxylation Viscoat 295 32
Two-trimethylolpropane tetra-acrylate 25
This prescription can comprise antiblocking agent or silane additives or phenol antioxidant in addition.
This prescription comprises one or more light triggers; for example one or more are selected from two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure 819), two (2,6-dimethoxy benzoyl) iso-octyl phosphine oxide; [[4-(ethyl-methyl-amino)-phenyl]-(2; 4,6-trimethylammonium-benzoyl)-phosphino-]-(2,4; 6-trimethylammonium-phenyl)-ketone; [(4-dimethylamino-phenyl)-(2,4,6-trimethylammonium-benzoyl)-phosphino-]-(2; 4; 6-trimethylammonium-phenyl)-and ketone, 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide; the light trigger of [benzyl-(4-methyl sulfahydantoin-phenyl)-phosphino-]-(2,4,6-trimethylammonium-phenyl)-ketone and 1-hydroxycyclohexylphenylketone (Irgacure 184).
Formulation for coating material comprises in addition and is selected from (i)-(this additive v) and optional conventional flame retardants.This coating material solidified excellent flame that demonstrates.
Good result also when additive (a)-(o) or (i)-(realize when v) in following application system, combining with one of above conventional flame retardants of enumerating:
Carbamate Clear coating on steel
Coil coating
Tung oil phenols varnish
Aromatic urethanes varnish
Wear-resistant paint composite
Polyester urethane coating on polycarbonate
Glycidyl methacrylate based powders Clear paint
The oily modified amido manthanoate alkyd that is used for timber
Be used to be laminated to the preformed film of plastic components
Co-extrusion on PVC
Co-extrusion on polycarbonate
Co-extrusion on ABS
Multilayer polymer structure
The photocuring white coating
The photocuring Clear coating
Photocuring white powder coating
Photocuring white gels coating
Expansion coating
The coating that is used for the construction of cable of lubricating grease filling
The thick slurry refractory paint of expansible
Coating on fiberglass
Textile material composites
Claims (19)
1. a fire retardant coating compositions comprises
(A) coating and
(B) the following mixture of flame-retardant effective amount
(i) at least aly be selected from following compound
(a) sterically hindered nitroxyl stablizer,
(b) sterically hindered oxyamine stablizer and
(c) sterically hindered alkoxylamine stablizer and
(ii) at least aly be selected from following conventional flame retardants
(d) organic halogen fire retardant,
(e) organophosphorous fire retardant,
(f) the isocyanuric acid ester fire retardant and
(g) melamine based flameproofing.
2. a fire retardant coating compositions comprises
(A) resin glue and
(B) flame-retardant effective amount
(i) at least a ethylenic unsaturated polymerizable monomer, described monomer comprises sterically hindered nitroxyl, oxyamine or alkoxylamine part and
Randomly
(ii) at least aly be selected from following conventional flame retardants
(a) organic halogen fire retardant,
(b) organophosphorous fire retardant,
(c) the isocyanuric acid ester fire retardant and
(d) melamine based flameproofing.
3. according to the composition of claim 2, wherein sterically hindered nitroxyl, oxyamine or alkoxylamine part have structural formula independently
Or
Wherein
L
1, L
1', L
2And L
2' be the alkyl of 1 to 4 carbon atom independently, or L
1And L
2Or L
1' and L
2' be together pentamethylene and
Described monomer is selected from down various
Wherein
E is sterically hindered nitroxyl independently, oxyamine or alkoxylamine part,
R
1It is the oxygen base, hydroxyl, straight or the branched alkoxy of 1 to 36 carbon atom, the straight or branched alkenyl oxygen base of 2 to 18 carbon atoms, the straight or side chain alkynyloxy base of 2 to 18 carbon atoms, the aralkoxy of 7 to 15 carbon atoms, the cycloalkyloxy of 5 to 12 carbon atoms, the cycloalkenyl oxygen base of 5 to 12 carbon atoms, the group of the saturated or unsaturated dicyclo of 7 to 12 carbon atoms or tricyclic hydrocarbon base oxygen base, or the aryloxy of 6 to 10 carbon atoms or the described aryloxy that replaced by alkyl
Or R
1Be-O-T-(OH)
b, R
1Oxygen base preferably, hydroxyl, methoxyl group, propoxy-, cyclohexyloxy, octyloxy, 2-hydroxy-2-methyl propoxy-or 1-hydroxyl cyclohexyloxy,
R
1' define as R independently
1,
T is the straight or branched alkylidene of 1 to 18 carbon atom, the ring alkylidene group of 5 to 18 carbon atoms, the ring alkylene group of 5 to 18 carbon atoms, the straight or branched alkylidene of 1 to 4 carbon atom, the latter replaces by phenyl or by the phenyl that the alkyl of 1 or 21 to 4 carbon atom replaces;
B is 1,2 or 3, if prerequisite is that carbonatoms and the b that b can not surpass among the T is 2 or 3, each hydroxyl is connected on the different carbon atoms of T,
X is direct key, 2 to 12 carbon atoms-O (polyoxy alkylidene group O)-,-O-,-NH-or-NG-, wherein G is the alkyl of 1 to 8 carbon atom,
X
1Be direct key or-O-,
N is 1 or 2,
T
1, T
2And T
4Be hydrogen independently, halogen, the aryl of the alkyl of 1 to 18 carbon atom or 6 to 10 carbon atoms,
T
3Be hydrogen or methyl and
R
2Be the alkyl of hydrogen or 1 to 12 carbon atom,
R
2' be hydrogen, the alkyl or the cyano group of 1 to 12 carbon atom,
R
3And R
4Be hydrogen independently, the alkyl of 1 to 12 carbon atom ,-COOH, or-COOG
1, G wherein
1Be the straight or branched-chain alkyl of 1 to 12 carbon atom,
R
5Be 1 to 8 carbon atom straight or branched-chain alkyl and
R
5' define as R independently
5
4. according to the composition of claim 3, wherein said monomer has structural formula
R wherein
2' be hydrogen or methyl and R
3And R
4Be hydrogen, or wherein comprise sterically hindered nitroxyl that the described ethylenic unsaturated polymerizable monomer of oxyamine or alkoxylamine part is selected from
With
5. according to the composition of claim 1 or 2, antimony containing compounds or comprise the antimony compounds that is lower than based on about 1% weight of component (A) weight not; Do not contain filler or comprise the filler that is lower than based on about 3% weight of component (A) weight.
6. according to the composition of claim 1 or 2, wherein component (A) is a resin glue, is selected from Synolac; Chlorinated alkyd; Urethane resin; Thermoplastic acrylic resin; Acrylic acid alkyl; Acrylic resin; Latex emulsion; Vinylformic acid alkyd or vibrin; With the vinylformic acid alkyd or the vibrin of silicon modification, isocyanic ester, ketoimine Huo oxazolidine; Phenol-formaldehyde resin; Resorcinol-formaldehyde resin; Resins, epoxy; Use carboxylic acid, acid anhydrides, the epoxide resin that polyamine or mercaptan are crosslinked; With in its main chain with the reactive group modification with epoxy crosslinked vinylformic acid or vibrin system; Especially Resins, epoxy.
7. according to the composition of claim 1, its floating coat is the thermoplastic layer, especially polypropylene layer.
8. according to the composition of claim 1 or 2, it is water base or solvent based powder paint compositions or gel coating prescription, thick slurry, tackiness agent, binding agent, putty, putty, mortar or sealant dispensing, ambient cure, radiation curing, baker solidifies or the catalyzer cured compositions, and it is transparent or painted.
9. according to the composition of claim 1 or 2, further comprise and be selected from pore forming material, whipping agent, coking agent, binding agent, thixotropic agent, foaming agent and carbonific material, pigment, dyestuff, softening agent, phenol antioxidant, thixotropic agent, leveling auxiliary agent, alkaline co-stabilizer, nitrone stablizer, amine oxide stabilizer, the benzofuranone stabilization agent, UV absorption agent, sterically hindered amines, metal passivator, metal oxide, organo phosphorous compounds, the component of oxyamine and its mixture.
10. according to the composition of claim 1, wherein the compound of component (i) has structural formula
G wherein
1And G
2Be the alkyl of 1 to 8 carbon atom independently or be pentamethylene together,
Z
1And Z
2Be respectively methyl, or Z
1And Z
2Forming together can be in addition by ester, ether, acid amides, amino, the connection portion that carboxyl or carbamate groups replace and
E is the oxygen base, hydroxyl, alkoxyl group, cycloalkyloxy, aralkoxy, aryloxy ,-O-CO-OZ
3,-O-Si (Z
4)
3,-O-PO (OZ
5)
2Or-O-CH
2-OZ
6, Z wherein
3, Z
4, Z
5And Z
6Be selected from hydrogen, aliphatic series, araliphatic and aromatics part; Or E is-O-T-(OH)
b,
T is the straight or branched alkylidene of 1 to 18 carbon atom, the ring alkylidene group of 5 to 18 carbon atoms, the ring alkylene group of 5 to 18 carbon atoms, the straight or branched alkylidene of 1 to 4 carbon atom, the latter is replaced by phenyl or the phenyl that replaced by the alkyl by one or two 1 to 4 carbon atom; With
B is 1,2 or 3, if prerequisite is that carbonatoms and the b that b can not surpass among the T is 2 or 3, each hydroxyl is connected on the different carbon atoms of T.
11. according to the composition of claim 1, wherein the compound of component (i) is selected from
(a) 2, two [(1-cyclohexyl oxygen base-2,2,6,6-piperidin-4-yl) butyl amino]-6-chloro-s-triazine and the N of 4-, N '-two (3-aminopropyl) quadrol) reaction product;
(b) 1-cyclohexyl oxygen base-2,2,6,6-tetramethyl--4-octadecyl amino piperidine;
(c) two (1-octyl group oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) esters of sebacic acid;
(d) 2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-6-(the 2-hydroxyethyl amino-s-triazine of 4-;
(e) two (1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) esters of hexanodioic acid;
(h) 2, two [(1-cyclohexyl oxygen base-2,2,6,6-piperidin-4-yl) butyl the amino]-6-chloro-s-triazines of 4-;
(i) 1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine;
(j) 1-(2-hydroxy-2-methyl propoxy-)-4-oxo-2,2,6, the 6-tetramethyl piperidine;
(k) 1-(2-hydroxy-2-methyl propoxy-)-4-stearoyl oxygen base-2,2,6, the 6-tetramethyl piperidine;
(l) two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) esters of sebacic acid;
(m) two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) esters of hexanodioic acid;
(n) 2,4-pair (N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-N-butyl amino }-6-(2-hydroxyethyl amino)-s-triazine; With
(o) following formula: compound
Wherein n is 1 to 15, and compound
With
With and composition thereof.
12. according to the composition of claim 1 or 2, wherein component fire retardant (ii) is selected from
The chlorine alkyl phosphate,
Tricresyl phosphate (2-chloroethyl) ester,
Poly-brominated diphenyl base oxide,
The decabrominated dipheny base oxide,
Tricresyl phosphate [3-bromo-2,2-two (brooethyl) propyl group] ester,
Tricresyl phosphate (2, the 3-dibromopropyl) ester,
Tricresyl phosphate (2,3-two chloropropyls) ester,
Chlorendic acid,
Tetrachlorophthalic acid,
Tetrabromophthalate,
It is two-(N, N '-hydroxyethyl) four ammonia phenylenediamines,
It is poly--β-chloroethyl tri methylene phosphonic acid ester mixture,
Two (2,3-dibromopropyl ether) of dihydroxyphenyl propane,
Brominated epoxy resin,
Ethylidene-two (tetrabromo phthalimide),
Two (hexachlorocyclopentadiene base) cyclooctane,
Clorafin,
Octabromodiphenyl base ether,
The hexachlorocyclopentadiene derivative,
1, two (tribromophenoxy) ethane of 2-,
Tetrabromo-dihydroxyphenyl propane,
Ethylenebis-(two bromo-norbornanes, two carbimides),
It is two-(hexachlorocyclopentadiene base) cyclooctane,
PTFE
Three-(2, the 3-dibromopropyl)-isocyanuric acid ester and
Ethylidene-two-tetrabromo phthalimide,
Tetraphenyl Resorcinol diphosphites,
Triphenylphosphate,
Tricresyl phosphate octyl group ester,
Tripotassium phosphate phenolic group ester,
Four (hydroxymethyl) phosphoric sulfide,
Phosphonic acids diethyl-N, two (2-the hydroxyethyl)-amino methyl esters of N-,
The hydroxyalkyl acrylate of phosphoric acid,
Ammonium polyphosphate,
The resorcinol diphosphate oligopolymer,
Phosphonitrile fire retardant,
The quadrol bisphosphate,
Poly-isocyanurate,
The ester of isocyanuric acid,
Isocyanuric acid ester,
The hydroxyalkyl isocyanuric acid ester,
Melamine cyanurate,
The melamine boric acid ester,
The melamine phosphoric acid ester,
The melamine poly phosphate and
The melamine pyrophosphate.
13. according to the composition of claim 1 or 2, wherein the amount of component (i) about 0.1 the amount that is based on component (A) to about 10% weight and component fire retardant (ii) be based on resin glue (A) weight about 0.5 to about 45% weight.
14. a fire retardant coated article comprises
Scribble the base material of the fire retardant coating compositions that comprises following material
(A) coating and
(B) the following mixture of flame-retardant effective amount
(i) at least aly be selected from following compound
(a) sterically hindered nitroxyl stablizer,
(b) sterically hindered oxyamine stablizer and
(c) sterically hindered alkoxylamine stablizer and
(ii) at least a conventional flame retardants is selected from
(d) organic halogen fire retardant,
(e) organophosphorous fire retardant,
(f) the isocyanuric acid ester fire retardant and
(g) melamine based flameproofing.
15. a fire retardant coated article comprises
Scribble the base material of the fire retardant coating compositions that comprises following material
(A) resin glue and
(B) flame-retardant effective amount
(i) at least a ethylenic unsaturated polymerizable monomer, described monomer comprises sterically hindered nitroxyl, oxyamine or alkoxylamine part and
Optional
(ii) at least a conventional flame retardants is selected from
(a) organic halogen fire retardant,
(b) organophosphorous fire retardant,
(c) the isocyanuric acid ester fire retardant and
(d) melamine based flameproofing.
16. according to the coated article of claim 14 or 15, base material chosen from Fe wherein, steel, stainless steel, aluminium and other non-ferrous metal, timber, multi-ply wood, paper, cardboard, chipboard, particle board, plastics, thermoplastics, epoxide, chloroprene rubber, rubber, matrix material, fiberglass reinforced composite, polyester, polymer foams, masonry, fabric or textiles, electric wire and cable structure and circuit card.
17. coated article according to claim 14 or 15, wherein base material is selected from polyvinyl chloride, polycarbonate, polyolefine, TPO, ABS or polyester, or knit system, braiding or nonwoven and based on polyethylene, polypropylene, polyethylene terephthalate, polymeric amide, Mierocrystalline cellulose or cotton fabric or textiles.
18. according to the coated article of claim 14 or 15, it is tide of motorism plasticity alkene structures or coextrusion plastics or applies optical fiber.
19. according to the coated article of claim 14 or 15, described coating is an extrusion plastic.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37135502P | 2002-04-10 | 2002-04-10 | |
| US60/371,355 | 2002-04-10 | ||
| US41693302P | 2002-10-08 | 2002-10-08 | |
| US60/416,933 | 2002-10-08 | ||
| US42644502P | 2002-11-14 | 2002-11-14 | |
| US60/426,445 | 2002-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1646615A true CN1646615A (en) | 2005-07-27 |
Family
ID=28795012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA03808015XA Pending CN1646615A (en) | 2002-04-10 | 2003-04-03 | Flame retardant coatings |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1492840A1 (en) |
| JP (1) | JP2005522532A (en) |
| KR (1) | KR20040106339A (en) |
| CN (1) | CN1646615A (en) |
| AU (1) | AU2003224035A1 (en) |
| BR (1) | BR0309237A (en) |
| CA (1) | CA2479946A1 (en) |
| MX (1) | MXPA04009834A (en) |
| WO (1) | WO2003085039A1 (en) |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN1178978C (en) * | 1997-06-30 | 2004-12-08 | 西巴特殊化学品控股有限公司 | Flame retardant compositions |
-
2003
- 2003-04-03 CN CNA03808015XA patent/CN1646615A/en active Pending
- 2003-04-03 JP JP2003582223A patent/JP2005522532A/en not_active Withdrawn
- 2003-04-03 AU AU2003224035A patent/AU2003224035A1/en not_active Abandoned
- 2003-04-03 MX MXPA04009834A patent/MXPA04009834A/en unknown
- 2003-04-03 CA CA002479946A patent/CA2479946A1/en not_active Abandoned
- 2003-04-03 EP EP03720419A patent/EP1492840A1/en not_active Withdrawn
- 2003-04-03 BR BR0309237-2A patent/BR0309237A/en not_active IP Right Cessation
- 2003-04-03 WO PCT/EP2003/003492 patent/WO2003085039A1/en not_active Application Discontinuation
- 2003-04-03 KR KR10-2004-7016133A patent/KR20040106339A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2003085039A1 (en) | 2003-10-16 |
| MXPA04009834A (en) | 2004-12-07 |
| JP2005522532A (en) | 2005-07-28 |
| AU2003224035A1 (en) | 2003-10-20 |
| EP1492840A1 (en) | 2005-01-05 |
| KR20040106339A (en) | 2004-12-17 |
| CA2479946A1 (en) | 2003-10-16 |
| BR0309237A (en) | 2005-02-09 |
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