CN101268144B

CN101268144B - Scratch resistant polymer and coating compositions

Info

Publication number: CN101268144B
Application number: CN2006800350051A
Authority: CN
Inventors: A·H·沙马; P·S·索尔拉; S·R·卡斯帕斯
Original assignee: Ciba Spezialitaetenchemie Holding AG
Current assignee: BASF Schweiz AG
Priority date: 2005-09-22
Filing date: 2006-09-13
Publication date: 2011-08-03
Anticipated expiration: 2026-09-13
Also published as: WO2007039421A1; EP1926777A1; CA2621186A1; KR20080049057A; TW200724624A; CN101268144A; BRPI0616087A2; JP2009509016A

Abstract

Polymer substrates, for example ABS, PBT, PVC, PET, nylon 6, nylon 6'6, ABS/PBT, PC/ABS or ionomers; and coating compositions, for example oil or water based coatings with alkyd, acrylic, acrylic alkyd, polyester, phenolic, melamine, epoxy or polyurethane resins, are made scratch resistant by the incorporation therein of an additive combination of b) a carboxylic acid reagent functionalized olefin polymer or copolymer and c) a primary or secondary fatty acid amide. The present polymers and coatings exhibit good weatherability, scratch resistance, good processability, good mechanical strength, good gloss retention and are non-sticky. The carboxylic acid reagent functionalized olefin polymer is for example maleic anhydride grafted polypropylene or polyethylene, or is a reaction product of maleic anhydride and an alpha-olefin, or is a tallow alcohol ester of said maleic anhydride products. The fatty acid amide is for example oleyl palmitamide or stearyl erucamide.

Description

Scratch resistant polymer and coating composition

The present invention relates to a kind of scratch resistant polymer and coating composition.The invention still further relates to and a kind ofly give the method for anti-zoned property to polymkeric substance and coating composition by introducing specific anti-zoned property additive.Polymer composition is for example nylon, ABS, polycarbonate, polyester, polyvinyl chloride or its blend.Molded parts is used for for example automobile application.Coating composition is for example Synolac, acrylic resin, vinylformic acid Synolac, vibrin, crosslinked Resins, epoxy or based on the resin of urethane.Described coating is covered with paint, lacquer, colour wash, etc. as for example building coating or as automobile.

The functionalized maleic anhydride inoculated polypropylene of long-chain alcohol is disclosed in Polyolefins 2003, TheInternational Conference of Polyolefins, and 24-February 26 February, Houston, Texas is as polyolefinic processing aid.

US 6,048, and 942 disclose Themoplastic olefin compositions, and it contains anti-zoned additive, are selected from polysiloxane, Metallic stearates, unsaturated fatty acid amide and unsaturated fatty acids acid amides.

JP-A-2002338778 has instructed the graft copolymer composition that contains fatty acid amide.

US 5,731, and 376 disclose polypropylene block copolymer, have improved anti-zoned property by comprising organopolysiloxane.These compositions can further comprise fatty acid amide.

US 5,585, and 420 disclose anti-zoned property polyolefin compositions, and it contains flaky inorganic filler.These compositions can further contain high rubber ethylene-propylene copolymer, fatty acid amide, organopolysiloxane or Resins, epoxy.

JP-A-2002003692 discloses the acrylic resin that contains fatty acid amide.

JP-A-62072739 relates to the moulded parts that is used for trolley part, is mixed with by the mica with specified particle diameter with specific polyolefine and rubber material and specified quantitative.This polyolefine contains specific polypropylene and by for example maleic anhydride modified polyolefine of unsaturated carboxylic acid (acid anhydrides).

JP-A-63017947 relates to anti-zoned property prolylene polymer composition.

JP-A-20021261902 relates to polypropylene resin composite, with the moulding material that acts on the preparation interior finish.

US-A-2003/0004245 has described polyolefine and polyolefine and α, the blend of the reaction product of beta-unsaturated carboxylic acid ester, carboxylic acid or acid anhydrides.

Poly-anhydride resin is described among the CPChem Specialty Chemicals data sheet in 2004.

So, the invention provides polymkeric substance and coating composition with improved anti-zoned property and light stability, it comprises:

A) polymeric matrix or binder for film formation,

B) functionalized olefin polymer of carboxylic acid reagent or multipolymer and

C) uncle or secondary fatty acid amide;

Prerequisite is the polyolefine that polymeric matrix not only comprises polyolefine or modified rubber.

The present invention also provides a kind of and gives the method for anti-zoned property to polymeric matrix and the coating composition that comprises film for additive, and this method comprises the additive combination that comprises following component of introducing significant quantity in described polymkeric substance or coating composition:

B) functionalized olefin polymer of carboxylic acid reagent or multipolymer and

C) uncle or secondary fatty acid amide,

The polyolefine of modified rubber is also referred to as TPO (TPO).TPO for example is disclosed in US 6,048, in 942.The polyolefine of polyolefine and modified rubber can be not only the polymeric matrix of the present composition.Do not get rid of as polymeric matrix be the multipolymer of polyolefine and other polymer formation, or the blend of polyolefine and other following polymer formation.

The polymeric matrix of giving anti-zoned performance for example is:

1. polystyrene, poly-p-methylstyrene, poly alpha methylstyrene, high-impact polystyrene.

2. the aromatic homopolymers of derived from ethylene base aromatic monomer and multipolymer, vi-ny l aromatic monomers comprises all isomer (particularly right-Vinyl toluene) of vinylbenzene, alpha-methyl styrene, Vinyl toluene, all isomer, propylstyrene, vinyl biphenyl, vinyl naphthalene and the vinyl anthracene of ethyl styrene, and their mixture.

Homopolymer and multipolymer can have any three-dimensional arrangement, comprise being equal to upright structure, syndiotaxy, half-syndiotaxy or atactic.In stereoblock polymer is also included within.

2a. comprise above-mentioned vi-ny l aromatic monomers and the multipolymer that is selected from following comonomer: ethene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl-acetic ester and vinylchlorid or acrylic acid derivative and their mixture, for example phenylethylene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymer), styrene/methacrylic acid alkyl ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; The styrol copolymer of high impact and other mixture of polymers, for example polyacrylic ester, diene polymer or ethylene/propylene/diene ter-polymers; And cinnamic segmented copolymer, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

2b. the hydrogenant aromatic(based)polymer is derived from 2.) described in the hydrogenation of polymkeric substance, the poly-cyclohexyl ethene (PCHE) particularly including by the preparation of hydrogenation random isotactic polystyrene is commonly referred to polyvinyl eyclohexane (PVCH).

2c. the hydrogenant aromatic(based)polymer is derived from 2a.) described in the hydrogenation of polymkeric substance.

3. the graft copolymer of vi-ny l aromatic monomers, for example vinylbenzene or alpha-methyl styrene, the graft copolymer of vinylbenzene on polyhutadiene for example, the graft copolymer of vinylbenzene on polyhutadiene/vinylbenzene or polybutadiene/acrylonitrile; Vinylbenzene and vinyl cyanide (or methacrylonitrile) graft copolymer on polyhutadiene; Vinylbenzene, vinyl cyanide and the methyl methacrylate graft copolymer on polyhutadiene; Vinylbenzene and the maleic anhydride graft copolymer on polyhutadiene; Vinylbenzene, vinyl cyanide and the maleic anhydride graft copolymer on polyhutadiene; Vinylbenzene and the maleimide graft copolymer on polyhutadiene; Vinylbenzene and alkyl acrylate or the alkyl methacrylate graft copolymer on polyhutadiene; Vinylbenzene and the vinyl cyanide graft copolymer on the ethylene/propylene/diene ter-polymers; Vinylbenzene and the vinyl cyanide graft copolymer on polyalkyl acrylate or polyalkyl methacrylate; Vinylbenzene and the vinyl cyanide graft copolymer on acrylate/butadiene copolymers, and their mixture with 6) described in the mixture of multipolymer, for example be called the copolymer mixture of ABS, MBS, ASA or AES polymkeric substance.

4. halogen-containing polymkeric substance, sovprene for example, chlorinated rubber, the chlorination of isobutylene-isoprene and brominated copolymer (halobutyl rubber), chlorination or sulfo group chlorating polyethylene, the multipolymer of ethene and ethylene chloride, Epicholorohydrin homopolymer and multipolymer; The polymkeric substance of halogen-containing vinyl compound particularly, for example polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride), and their multipolymer, for example vinylchlorid/vinylidene chloride, vinylchlorid/vinyl-acetic ester or vinylidene fluoride/vinyl acetate copolymer.

5. derived from alpha, the polymkeric substance of beta-unsaturated acid and derivative thereof, for example polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and polyacrylonitrile carry out impact modified with butyl acrylate.

6. following 9) described in monomer each other or the multipolymer that forms with other unsaturated monomer, for example acrylonitrile/butadiene multipolymer, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate multipolymer or vinyl cyanide/vinyl halides multipolymer, or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.

7. derived from the polymkeric substance of unsaturated alkohol and amine or its acyl derivative or acetal, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, polyvinyl butyral, poly-O-phthalic allyl propionate or polyene propyl group melamine; And they and above-mentioned 1) described in the multipolymer of alkene.

8. the homopolymer of cyclic ethers and multipolymer, for example multipolymer of polyalkylene glycol, polyethylene oxide, polyoxytrimethylene or itself and diglycidylether.

9. polyacetal, for example polyoxymethylene and contain the polyoxymethylene of oxyethane as comonomer; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.

10. polyphenylene oxide and polyphenylene sulfide, and the mixture of polyphenylene oxide and styrene polymer or polymeric amide.

11. urethane, derived from hydroxy-end capped polyethers, polyester or polyhutadiene and aliphatic series or aromatic polyisocyanate, and their precursor.

12. polymeric amide and copolyamide, derived from diamines and dicarboxylic acid and/or derived from aminocarboxylic acid or corresponding lactam, for example polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12 are from m-xylene diamine and hexanodioic acid deutero-aromatic poly; Polymeric amide from hexamethylene-diamine and m-phthalic acid or terephthalic acid preparation is with or without the elastomerics as properties-correcting agent, for example gathers 2,4,4-tri-methyl hexamethylene terephthalamide or poly-isophthaloyl metaphenylene amine; And the segmented copolymer of above-mentioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding or the formation of grafted elastomerics, or and polyethers, for example with polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; And with the polymeric amide or the copolyamide of EPDM or ABS modification; And the polymeric amide of condensation during processing (RIM polymeric amide system).

13. polyureas, polyimide, polyamide-imide, polyetherimide, polyester-imide, poly-glycolylurea and polybenzimidazole.

14. derived from dicarboxylic acid and glycol and/or derived from the polyester of hydroxycarboxylic acid or corresponding lactone, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-hydroxymethyl-cyclohexane terephthalate, poly-alkylene naphthalate (PAN) and poly-hydroxybenzoate, and from hydroxy-end capped polyethers deutero-block cyclic ethers ester; And with the polyester of polycarbonate or MBS modification.

15. polycarbonate (PC) and polyestercarbonate.

16. polyketone.

17. polysulfones, polyethersulfone and polyetherketone.

18. on the one hand derived from aldehyde with on the other hand derived from the cross-linked polymer of phenol, urea and melamine, for example phenol/formaldehyde resins, urea/formaldehyde resin and melamine/formaldehyde resin.

19. unsaturated polyester resin is derived from saturated and unsaturated dicarboxylic acid and polyvalent alcohol with as the copolyesters of the vinyl compound of linking agent, with and have a halogen-containing modified form of low combustible.

20. the blend of above-mentioned polymkeric substance (poly-blend), for example polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrylate, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/AB S or PBT/PET/PC.

21. ethylene/alkyl acrylate copolymer, the ethylene/methacrylic acid alkyl ester copolymer, ethylene, or ethylene/acrylic acid copolymer, and the mixture of their salt (ionomer) and these multipolymers and other multipolymer, for example LDPE/ vinyl-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA, with alternately or random polyalkylene/carbon monoxide multipolymer, and they and other polymkeric substance mixture of polymeric amide for example.

For example, polymeric matrix of the present invention is acrylonitrile/butadiene/styrene multipolymer (ABS), styrene/butadiene/styrene copolymers (SBS), styrene/acrylonitrile copolymer (SAN), vinyl cyanide/styrene/acrylonitrile copolymer (ASA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), unsaturated polyester (UPES), polyamide (PA), thermoplastic polyurethane (TPU), polystyrene (PS), high-impact polystyrene (HIPS), polycarbonate (PC), the PC/ABS blend, the ABS/PBT blend, polyvinyl chloride (PVC); PVC blend, for example PVC/ABS, PVC/ASA or PVC/ acrylate or ionomer.

For example, polymeric matrix of the present invention is ABS, PBT, PVC, PET, nylon 6, nylon 6,6, ABS/PBT, PC/ABS or ionomer.

Binder for film formation can be industrial any tackiness agent commonly used in principle, for example at Ullmann ' s Encycopedia of Industrial Chemistry, and the 5th edition, the A18 volume, the 368-426 page or leaf, VCH, Weinheim 1991 is open.Usually, this is based on the binder for film formation of thermoplasticity or thermosetting resin, mainly based on thermosetting resin.Example is Synolac, acrylic resin, vinylformic acid Synolac, phenol resins, melamine resin, Resins, epoxy and urethane resin and their mixture.

But component can be cold-curing or heat-setting tackiness agent a); It can be favourable adding curing catalysts.The suitable tackiness agent solidified catalyzer that can promote for example is described in Ullmann ' sEncycopedia of Industrial Chemistry, the A18 volume, and 469 pages, VCHVerlagsgesellschaft, Weinheim 1991.

Coating of the present invention is for example as the finish paint of automobile or as wood coating.

Preferably wherein component is the coating composition that contains the tackiness agent of functional acrylic resins and linking agent a).

The example that contains the coating composition of special adhesive is:

1. paint based on can cold crosslinked or Synolac, acrylate, polyester, Resins, epoxy or the melamine resin of thermally cross-linkable or the mixture of these resins, adds curing catalysts if necessary.

2. two component polyurethane paints, based on acrylate, polyester or polyether resin and aliphatic series or aromatic isocyanate, isocyanuric acid ester or the polyisocyanates of hydroxyl.

3. mono-component polyurethane paints, and based on end capped isocyanic ester, isocyanuric acid ester or polyisocyanates, they take off end-blocking during toasting, and add melamine resin if necessary.

4. mono-component polyurethane paints, based on the resin of triazine crosslinked dose of tri-alkoxy carbonyl and hydroxyl, for example acrylate, polyester or polyether resin.

5. mono-component polyurethane paints, based on the aliphatic series that in the urethane structure, has free amine group or aromatic urethanes acrylate or urethane acrylate, and melamine resin or polyether resin, words are used curing catalysts if desired.

6. two-pack is painted, based on (gathering) ketoimine and aliphatic series or aromatic isocyanate, isocyanuric acid ester or polyisocyanates,

7. two-pack is painted, based on (gathering) ketoimine and unsaturated acrylate resin or poly-ethanoyl acetate resins or methacrylamido glycolic acid methyl esters.

8. two-pack is painted, based on containing carboxyl or containing amino polyacrylic ester and polyepoxide.

9. two-pack is painted, based on the acrylate resin that contains anhydride group with based on poly-hydroxy or polyamino component.

10. two-pack is painted, based on acid anhydrides that contains acrylate and polyepoxide.

11. two-pack paint is based on (gathering)

Azoles quinoline and the acrylate resin that contains anhydride group, or unsaturated acrylate resin, or aliphatic series or aromatic isocyanate, isocyanuric acid ester or polyisocyanates,

12. two-pack paint is based on unsaturated polyester acrylate and poly-malonic ester.

13. thermoplastic polypropylene acid esters paint is based on the acrylate resin and the etherification melamine resin of thermoplastic acrylic resin or external crosslinking.

14. paint systems is based on acrylate resin silicone-modified or the fluorine modification.

What paid close attention to is to have the coating composition that improves anti-zoned property, and wherein binder for film formation is Synolac, acrylic resin or vinylformic acid Synolac, preferred acrylic resins.

In addition, coating composition of the present invention can contain the photostabilizer of bulky amine type, 2-(2-hydroxy phenyl)-1,3,5-triazines and/or 2-hydroxy phenyl-2H-benzotriazole type.

For example, photostabilizer is:

2-(2-hydroxy phenyl)-2H-benzotriazole compound, for example known disclosed benzotriazole compound: Nos.3 in hydroxy phenyl-2H-benzotriazole category and the following United States Patent (USP), 004,896 of being purchased; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905,4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987,5,977,219 and 6,166,218,2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole for example, 2-(3,5-di-t-butyl-2-hydroxy phenyl)-the 2H-benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-t-butyl-2-hydroxy phenyl)-the 2H-benzotriazole, 5-chloro-2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, 2-(the 3-sec-butyl-5-tertiary butyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(2-hydroxyl-4-octyl group oxygen base phenyl)-2H-benzotriazole, 2-(3,5-two tert-pentyls-2-hydroxy phenyl)-the 2H-benzotriazole, 2-(3,5-pair-α-cumyl-2-hydroxy phenyl)-the 2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-(ω-hydroxyl-eight-(ethyleneoxy group) carbonyl-ethyl)-, phenyl)-the 2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-octyl group oxygen base carbonyl) ethylphenyl)-2H-benzotriazole, the 2-of dodecylization (2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-octyl group oxygen base carbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole, 2-(the 3-tertiary butyl-5-(2-(2-ethylhexyl oxygen base)-carbonyl ethyl)-2-hydroxy phenyl)-5-chloro-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-methoxycarbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-methoxycarbonyl ethyl) phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-5-(2-(2-ethylhexyl oxygen base) carbonyl ethyl)-2-hydroxy phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-iso-octyl oxygen base carbonyl ethyl) phenyl-2H-benzotriazole, 2,2 '-methylene radical-two (uncle's 4-octyl groups-(6-2H-benzotriazole-2-yl) phenol), 2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole, 2-(2-hydroxyl-uncle's 3-octyl group-5-α-cumyl phenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-the 2H-benzotriazole, 5-chloro-2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-the 2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-iso-octyl-oxygen base carbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxyl-uncle's 5-octyl phenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxyl-3,5-two uncle's octyl phenyls)-the 2H-benzotriazole, 3-(5-trifluoromethyl-2H-benzotriazole-2-y1)-5-tertiary butyl-4-hydroxy hydrogen cinnamic acid methyl ester, 5-butyl alkylsulfonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--5-tert-butyl-phenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-the 2H-benzotriazole, 5-butyl alkylsulfonyl-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole and 5-phenyl sulfonyl-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole;

Sterically hindered amine stabilizer, for example 4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-allyl group-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine, 1-benzyl-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (2,2,6,6-tetramethyl--4-piperidyl) succinate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1-octyl group oxygen bases-2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) normal-butyl-3,5-two-tertiary butyl-4-hydroxy benzyl malonic acid 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 straight chain or the ring-shaped condensate of 6-two chloro-1,3,5-triazines, three (2,2,6,6-tetramethyl--4-piperidyl) nitrilotriacetate, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, 1,1 ' (1,2-second two bases)-two (3,3,5,5-tetramethyl-piperazine ketone), 4-benzoyl-2,2,6,6-tetramethyl piperidine, 4-stearyl oxygen base-2,2,6,6-tetramethyl piperidine, two (1,2,2,6,6-pentamethyl-piperidyl)-2-normal-butyl-2-(2-hydroxyl-3,5-two-tertiary butyl benzyl) malonic ester, 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone, two (1-octyl group oxygen bases-2,2,6, the 6-tetramethyl-piperidyl) sebate, two (1-octyl group oxygen bases-2,2,6, the 6-tetramethyl-piperidyl) succinate, N, N '-two-(2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholinyl-2, the straight chain 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-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-two-(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 mixture of 5-triazine, 1, two (3-amino propyl amino) ethane and 2 of 2-, 4,6-three chloro-1,3,5-triazine and 4-butyl amino-2,2,6, the condensation product of 6-tetramethyl piperidine (CAS Reg.No.[136504-96-6]); N-(2,2,6,6-tetramethyl--4-piperidyl)-and the dodecyl succinimide, N-(1,2,2,6,6-pentamethyl--4-piperidyl)-the dodecyl succinimide, 2-undecyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxa--spiral shell [4,5] decane, 7,7,9,9-tetramethyl--2-encircles undecyl-1-oxa--3, the reaction product of 8-diaza-4-oxaspiro [4,5] 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 '-diformyl-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 that 6-pentamethyl--4-hydroxy piperidine forms, poly-[methyl-propyl-3-oxygen base-4-(2,2,6,6-tetramethyl--4-piperidyl)] siloxanes, maleic anhydride-alpha-olefin-multipolymer and 2,2,6, the reaction product of 6-tetramethyl--4-amino piperidine, 1,2,2,6,6-pentamethyl--4-amino piperidine or two-(1,2,2,6,6-pentamethyl-piperidin-4-yl) p-methoxyl group toluenyl malonic ester (CAS#147783-69-5);

Bulky amine also can be a United States Patent (USP) 5,980, one of compound of describing in 783, this is component I-a), I-b), I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or compound I-1), particularly at United States Patent (USP) 5, photostabilizer 1-a-1,1-a-2,1-b-1,1-C-1,1-C-2,1-d-1,1-d-2,1-d-3,1-e-1,1-f-1,1-g-1,1-g-2 or 1-k-1 that 980,783 64-72 hurdles are listed;

Bulky amine also can be a United States Patent (USP) 6,046, one of compound of describing in 304 and 6,297,299, for example claim 10 or 38 or the compound described in embodiment 1-12 or D-1 to D-5;

The bulky amine that alkoxyl group replaced that on nitrogen-atoms, is replaced, for example compound 1-(2-hydroxy-2-methyl propoxy-)-4-octadecanoyl oxygen base-2,2 by hydroxyl, 6,6-tetramethyl piperidine, 1-(2-hydroxy-2-methyl propoxy-)-4-hexadecanoyl oxygen base-2,2,6,6-four-methyl piperidine, 1-oxygen base-4-hydroxyl-2,2,6,6-tetramethyl piperidine and reaction product, 1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2 from the carbon-based group of tert-pentyl alcohol, 2,6,6-tetramethyl piperidine, 1-(2-hydroxy-2-methyl propoxy-)-4-oxa--2,2,6,6-tetramethyl piperidine, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) succinate, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) glutarate, 2, two { the N-[1-(2-hydroxy-2-methyl propoxy-)-2 of 4-, 2,6,6-tetramethyl piperidine-4-yl]-normal-butyl amino }-6-(2-hydroxyethyl amino)-s-triazine; Or

Triaryl-o-hydroxy-phenyl-s-triazine, for example known triazine of describing in three-aryl-o-hydroxy phenyl-s-triazine and the following United States Patent (USP) that is purchased: 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309; 5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543; 6,242,598 and 6,255,483, for example 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2-hydroxyl-4-octyl group oxygen base phenyl)-s-triazine, Cyasorb

1164, Cytec Corp, 4,6-two (2, the 4-3,5-dimethylphenyl)-2-(2, the 4-dihydroxy phenyl)-the s-triazine, 2,4-two (2, the 4-dihydroxy phenyl)-6-(4-chloro-phenyl-)-s-triazine, 2,4-two [2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(4-chloro-phenyl-)-s-triazine, 2,4-two [2-hydroxyl-4-(2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-6-(2, the 4-3,5-dimethylphenyl)-the s-triazine, 2,4-two [2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-two [2-hydroxyl-4-(2-acetoxyethoxy) phenyl]-6-(4-chloro-phenyl-)-s-triazine, 2,4-two (2, the 4-dihydroxy phenyl)-6-(2, the 4-3,5-dimethylphenyl)-the s-triazine, 2,4-two (4-xenyl)-6-(2-hydroxyl-4-octyl group oxygen base carbonyl ethyleneoxy group phenyl)-s-triazine, 2-phenyl-4-[2-hydroxyl-4-(3-sec-butyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-6-[2-hydroxyl-4-(3-the second month in a season-amyl group oxygen base-2-hydroxypropyl oxygen base) phenyl]-the s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-benzyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-the s-triazine, 2,4-two (2-hydroxyl-4-normal-butyl oxygen base phenyl)-6-(2,4-di-n-butyl oxygen base phenyl)-the s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-oxygen in ninth of the ten Heavenly Stems base *-2-hydroxypropyl oxygen base)-5-α-cumyl phenyl]-(* represents octyl group oxygen base to the s-triazine, the ninth of the ten Heavenly Stems oxygen base and the last of the ten Heavenly stems oxygen base mixture), methylene radical two-{ 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-butyl oxygen base-2-hydroxyl propoxy-) phenyl]-the s-triazine }, methylene bridged dimer mixture, wherein 3: 5 ', 5: 5 ' and 3: 3 ' the position according to 5: 4: 1 ratio bridge joint, 2,4,6-three (2-hydroxyl-4-iso-octyl oxygen base carbonyl isopropylidene-oxygen base phenyl)-s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-hexyl oxygen base-5-α-cumyl phenyl)-s-triazine, 2-(2,4, the 6-trimethylphenyl)-4,6-two [2-hydroxyl-4-(3-butyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-s-triazine, 2,4,6-three [2-hydroxyl-4-(3-sec-butyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-s-triazine, 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2-hydroxyl-4-(3-dodecyl oxygen base-2-hydroxyl propoxy-)-phenyl)-s-triazine and 4,6-two-(2, the 4-3,5-dimethylphenyl)-and the mixture of 2-(2-hydroxyl-4-(3-tridecyl oxygen base-2-hydroxyl propoxy-)-phenyl)-s-triazine, Tinuvin

400, Ciba Specialty Chemicals Corp., 4,6-two-(2, the 4-3,5-dimethylphenyl)-and 2-(2-hydroxyl-4-(3-(2-ethylhexyl oxygen base)-2-hydroxyl propoxy-)-phenyl)-s-triazine and 4,6-phenylbenzene-2-(4-hexyl oxygen base-2-hydroxy phenyl)-s-triazine.

Coating composition can also contain other component, for example solvent, pigment, dyestuff, softening agent, stablizer, thixotropic agent, dry catalyst and/or flow agent.The example of possible component is described in Ullmann ' s Encycopedia of Industrial Chemistry, and the 5th edition, Vol.A18, pp.429-471, VCH, Weinheim 1991.

Possible dry catalyst or curing catalysts are organometallic compounds for example, and amine contains amino resin, and/or phosphine.The example of organometallic compound is a metal carboxylate, particularly the carboxylate salt of metal Pb, Mn, Co, Zn, Zr or Cu; Or metallo-chelate, the particularly inner complex of metal A l, Ti or Zr; Or organometallic compound, for example organo-tin compound.

The example of metal carboxylate is the stearate of Pb, Mn or Zn, the octylate of Co, Zn or Cu, the naphthenate of Mn and Co, or corresponding linoleate, resinate or resinate.

The example of metallo-chelate is aluminium, titanium or the zirconium chelate of methyl ethyl diketone, methyl aceto acetate, salicylic aldehyde, bigcatkin willow oxime, orthohydroxy-acetophenone or trifluoroacetyl group ethyl acetate, and the alkoxide of these metals.

The example of organo-tin compound is dibutyl tin oxide, dibutyl tin dilaurate or two sad two fourth tin.

The example of amine is tertiary amine particularly, for example tributylamine, trolamine, N methyldiethanol amine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclo octane (triethylenediamine) and their salt.Other example is a quaternary ammonium salt, for example trimethyl benzyl ammonia chloride.

Containing amino resin is tackiness agent and curing catalysts simultaneously.Its example is to contain amino acrylate copolymer.

Used curing catalysts also can be phosphine, for example triphenylphosphine.

Coating composition also can be the coating composition of radiation-hardenable.In this case, tackiness agent contains the monomer or the oligomeric compound of ethylenic unsaturated bond substantially, and they promptly are converted to crosslinked high molecular form using the back by actinic radiation curing.When system was UV curing, it also contained light trigger usually.Corresponding system is described in above-mentioned document Ullmann ' sEncycopedia of Industrial Chemistry, and the 5th edition, Vol.A18 is in the 451-453 page or leaf.

Coating composition of the present invention can be applied on any required matrix, for example metal, timber, plastics or stupalith.They for example are used as finish paint in automobile is covered with paint, lacquer, colour wash, etc.

Also openly coating composition of the present invention is used to protect the purposes of wood surface, for example by with components b of the present invention) and c) introduce in varnish, paint, dyestuff or the impregnant on the timber.So the invention still further relates to a kind ofly provides the method for mar-resistance to wood surface, this method is included in and uses coating composition of the present invention, particularly varnish, paint, dyestuff or impregnant on the timber.Components b) and c) can be used as the part of dyestuff or impregnant or use as the part of finish paint.

At wood coating is under the situation of dyestuff or impregnant, and preferred used solvent is selected from for example aliphatic hydrocrbon, alicyclic hydrocarbon, aromatic hydrocarbons, alcohol, ether, ester, ketone, glycol, glycol ethers, diol ester, polyglycol or their mixture.In this case, preferred adhesive is selected from the Synolac of Synolac, modification, automatically cross-linked or non-automatic crosslinked acrylic resin, vibrin, dry oil, phenol resins, Nitrocellulose or their mixture.

Useful additive such as sterilant or sterilant are operable.Useful sterilant is for example tributyltin oxide, phenyl mercuric salt, copper naphthenate, 1-chloronaphthalene or pentachlorophenol.Useful sterilant is that for example DDT, Dieldrin-attapulgite mixture, lindane (lindane), azaconazol, Cypermethrin, benzene are pricked hydrochloride (benzalkoniumhydrochloride), Wocosin 50TK or thiophos.

Any coating composition that applies timber that is applicable to can be used as finish paint.Usually contain tackiness agent, dissolve or be dispersed in the organic solvent or in the water or in the mixture of water and solvent.Tackiness agent can be normally at the air-dry or surfaces hardened coating resins of room temperature energy.The example of these tackiness agents is Nitrocellulose, polyvinyl acetate, polyvinyl chloride, unsaturated polyester resin, polyacrylic ester, urethane, Resins, epoxy, phenol resins, particularly Synolac.Tackiness agent also can be the mixture of different surfaces coating resins.If tackiness agent is curable tackiness agent, then they use with stiffening agent and/or promotor usually.

Finish paint also can be the radiation-hardenable of photopolymerization compound and not solvent-laden batching.Example is the mixture of acrylate or methacrylic ester, unsaturated polyester/styrene mixture, or the mixture of other ethylenically unsaturated monomer or oligomer.

Finish paint can contain soluble dye and/or pigment and/or filler.Pigment can be organic and inorganic or metallic pigment.Pigment can be opaque or transparent, for example transparent ferric oxide.Filler is kaolin, lime carbonate or pure aluminium silicate normally.Preferred finish paint is a transparent varnish, does not promptly contain undissolved component.

The present invention is used in particular for following application: domestic applications, for example furniture, timber floor, cardboard or wood working; Outdoor application, for example fence, building element, the wooden shop front, window frame etc.

Coating composition of the present invention can be administered on the base material by ordinary method, for example by brush, spray, topple over, dipping or electrophoresis; Referring to Ullmann ' s Encycopedia ofIndustrialChemistry, the 5th edition, Vol.A18,491-500 page or leaf.

According to adhesive composition, coating can be in room temperature or by being heating and curing.Coating can be for example 50-150 ℃ temperature-curable, and under the situation of powder coating or coil coating in higher temperature-curable.

Coating composition can contain the organic solvent or the solvent mixture of energy dissolved adhesive.Coating composition can be the aqueous solution or aqueous dispersions.Medium also can be the mixture of organic solvent and water.Coating composition can be the paint of high solids content, maybe can be not solvent-laden (for example powder coating material).Powder coating for example is described in Ullmann ' s Encycopedia of IndustrialChemistry, the 5th edition, Vol.A18,438-444 page or leaf.The powder coating material also can have the form (powder is the dispersion liquid in water preferably) of powder slurry.

Pigment can be the pigment of inorganic, organic or metal.Coating composition of the present invention can not contain pigment and be used as Clear coating.

Polymkeric substance or copolymer component b as functional olefines), olefin polymer or multipolymer for example are homopolymer polypropylene and multipolymer, and Natene and multipolymer.For example, polypropylene, high density polyethylene(HDPE) (HDPE), linear low density polyethylene (LLDPE), polypropylene is random and anti-impact (heterogeneous) multipolymer, propylene/ethylene copolymer, or ethene-alpha-olefin copolymer.

What paid close attention to is polymkeric substance and the coating composition with improved anti-zoned property and light stability, wherein component (b) is by α, beta-unsaturated carboxylic acid reagent grafted olefin polymer or multipolymer, preferably wherein component (b) is selected from following α, beta-unsaturated carboxylic acid reagent grafted olefin polymer or multipolymer: vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, methacrylic acid 2-hydroxypropyl acrylate, butyl acrylate and maleic anhydride.

What paid close attention to is polymkeric substance and the coating composition with improved anti-zoned property and light stability, and wherein component (b) is by the polypropylene of maleic anhydride graft or polyethylene.

Functionalized olefin polymer or multipolymer are for example to be disclosed in (on January 2nd, 2003 is open) in the U.S. Patent application 2003/0004245).

Functionalized olefin polymer or multipolymer are for example at least a polyolefine and at least a α, the reaction product of beta-unsaturated carboxylic acid reagent (for example acid, ester or acid anhydrides).

What paid close attention to is polymkeric substance and the coating composition with improved anti-zoned property and light stability, wherein component (b) is alpha-olefin and α, the reaction product of beta-unsaturated carboxylic acid reagent, α wherein, beta-unsaturated carboxylic acid reagent is selected from vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, methacrylic acid 2-hydroxypropyl acrylate, butyl acrylate and maleic anhydride; C preferably ₁₈-C ₂₆The reaction product of-alpha-olefin and maleic anhydride.

In one embodiment, the polyolefinic number-average molecular weight of using in this component can be 2000-10,000.These polymkeric substance have the melt flow of 8-40 or 10-35 or 15-30g/10min usually.With the amount of the carboxylic acid reagent of polyolefine reaction be 0.5-30% or 1-20% or 2-15% or 4-10%, by weight.

α, beta-unsaturated carboxylic acid reagent can be monocarboxylic acid or dicarboxylic acid reagent.Carboxylic acid reagent comprises carboxylic acid, ester and salt.The α of monobasic, beta-unsaturated carboxylic acid reagent comprise vinylformic acid, methacrylic acid, annamic acid, Ba Dousuan and their ester, for example have the ester of 1-20 carbon atom, and salt, for example sodium salt, calcium salt or magnesium salts.The example of dicarboxylic acid reagent comprises toxilic acid, maleic anhydride, fumaric acid, methylfumaric acid, norbornene dicarboxylic anhydride, methylene-succinic acid, citraconic acid, itaconic anhydride, citraconic anhydride, monomethyl maleate, toxilic acid list sodium etc.Particularly preferred α, beta-unsaturated carboxylic acid reagent are vinylformic acid, methacrylic acid, acrylate, methacrylic ester and maleic anhydride.

Reaction between carboxylic acid reagent and olefin polymer or the multipolymer can be undertaken by well known to a person skilled in the art mode.For example, reaction can be undertaken by carry out melt technology in the presence of radical initiator in solution.Radical initiator is superoxide or various organic azo-compound normally.The consumption of initiator is 0.01-5 weight % normally, based on the gross weight meter of polyolefine and carboxylic acid reagent.

Reaction between carboxylic acid reagent and olefin polymer or the multipolymer is called " grafting ".For example, functionalized olefin polymer of the present invention or multipolymer are by the olefin polymer or the multipolymer of vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, methacrylic acid 2-hydroxypropyl acrylate, butyl acrylate or maleic anhydride graft.Under the situation of for example using maleic anhydride graft, be called " maleation ".

The polyolefinic example of acroleic acid esterification is the POLYBOND polymkeric substance, can obtain from UniroyalChemical Company.Useful especially polymkeric substance is POLYBOND 1002, and it has the melt flow of 15-25g/10min and the acrylic acid content of 5.5-7.0 weight %.Commercially available toxilic acid grafted polypropylene for example is an Epolene E-43 wax, from Eastman ChemicalProducts, Inc.Epolene E-43 has 47 acid number and about 4500 number-average molecular weight.Epolene C-16 and C-18 wax are toxilic acid grafted polyethylene, have about 8000 and 4000 molecular weight respectively.The maleation ethylene-propylene elastomeric also is useful, and these elastomericss can obtain with affirmation 99-10,99-14 and 99-26 from Exxon Chemical Company.These multipolymers contain 77%, 64% and 43% ethene respectively, and the maleation product contains 0.76%, 0.56% and 0.35% toxilic acid or maleic anhydride respectively.

The polyolefinic example of other commercially available maleic anhydride graft comprises the KratonFG1901X from Shell, is commonly referred to maleation selective hydration SEBS multipolymer; Ter-polymers can be from CdF Chimie with trade(brand)name for example Lotader 3200 (from the preparation of the mixture of 88 weight % ethene, 9 weight % butyl acrylate cores and 3% maleic anhydride), Lotader 6600 (70% ethene, 27% acrylate and 3% maleic anhydride) etc.; Can be obtained from Quantum Chemical Corp by the ethylene of maleic anhydride graft (EVA-MAH).

Perhaps, as components b) functionalized olefin polymer or multipolymer be alpha-olefin and above-mentioned α, the reaction product of beta-unsaturated carboxylic acid reagent.This reaction is carried out by means commonly known in the art.For example, reaction can be undertaken by carry out melt technology in the presence of radical initiator.Radical initiator for example is superoxide or organic azo-compound.Equally, unsaturated carboxylic reagent is for example vinylformic acid, methacrylic acid, acrylate, methacrylic ester or maleic anhydride.

For example, alpha-olefin is from C ₃To about C ₃₃, for example alpha-olefin is C ₈-C ₂₆Alpha-olefin, for example C ₂₂-C ₂₆Alpha-olefin or C ₁₈Alpha-olefin.

For example, functional olefines is the maleation alpha-olefin, just the reaction product of alpha-olefin and maleic anhydride.For example the maleation alpha-olefin has formula I:

Wherein R is C ₁₆-C ₂₄Alkyl, n be integer so that molecular-weight average 20,000-50 is in 000 the scope.

Functionalized olefin polymer of the present invention or multipolymer can further react with long-chain alcohol or long-chain amine.

That is to say that functionalized olefin polymer or multipolymer can form ester or acid amides or imide product with long-chain alcohol or long-chain amine reaction.

These additives are called long-chain ester, acid amides or the imide of functionalized olefin polymer or multipolymer.Long-chain ester, acid amides or imide are equally also in the range of definition of the present invention's olefin polymer functionalized for carboxylic acid reagent or multipolymer.

The carbochain of long-chain alcohol or long-chain amine is straight chain or branching, can be saturated or undersaturated.Amine is primary amine or secondary amine.

For example, functionalized olefin polymer of the present invention or multipolymer can further form ester, partial ester or half ester product with the long-chain alcohol reaction, form acid amides, inclined to one side acid amides or imide product with long-chain primary amine or secondary amine reaction.Imide can be by the preparation of heating half amide.Functionalized olefin polymer of the present invention or multipolymer can further react the mixture that forms ester and acid amides.

Half ester or partial ester derivative can form under the condition that water is not removed from reaction mixture by alcohol being added dropwise in the functionalized olefin polymer that stirring or the acid catalysis solution of multipolymer in suitable solvent making.

Suitable solvent is a methyl iso-butyl ketone (MIBK) for example.Suitable acid catalyst comprises sulfuric acid, methylsulfonic acid and tosic acid.Diester uses excessive alcohol preparation and removes and anhydrate to drive reaction to complete esterification development.

For example, long-chain ester of the present invention is the ester or the half ester of the maleation alpha-olefin of formula II:

Wherein R is C ₁₆-C ₂₄Alkyl;

R ₁And R ₂Be hydrogen independently, C ₁-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl, wherein R ₁And R ₂In at least one be C ₁₂-C ₂₂Alkyl or C ₁₂-C ₂₂Alkenyl, n be integer so that molecular-weight average 20,000-50 is in 000 scope.

For example, the acid amides of the long-chain acid amides of the present invention maleation alpha-olefin that is formula III:

Wherein R is C ₁₆-C ₂₄Alkyl;

R ₁, R ₂, R ₃And R ₄Be hydrogen or C independently ₁-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl, wherein R ₁, R ₂, R ₃And R ₄In at least one be C ₁₂-C ₂₂Alkyl or C ₁₂-C ₂₂Alkenyl, n be integer so that molecular-weight average 20,000-50 is in 000 scope.

For example, the imide of the long-chain imide of the present invention maleation alpha-olefin that is formula IV:

Wherein R is C ₁₆-C ₂₄Alkyl;

R ₁Be C ₁₂-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl and

N be integer so that molecular-weight average 20,000-50 is in 000 scope.

For example R is C ₁₆Alkyl or C ₂₀-C ₂₄Alkyl.

For example, the long-chain ester of functionalized olefin polymer of the present invention or multipolymer is half ester or the ester that forms with tallow fatty alcohol, castor-oil plant alcohol [CAS#540-11-4] or oil base alcohol.

For example, the long-chain ester of functionalized olefin polymer of the present invention or multipolymer is the half ester or the ester reaction product of maleation olefin polymer or multipolymer and long-chain alcohol.

For example, long-chain ester of the present invention is the half ester or the ester reaction product of maleation alpha-olefin and long-chain alcohol.

For example, long-chain acid amides of the present invention is the amide reaction product of maleation alpha-olefinic polymer or multipolymer or maleation alpha-olefin and oleylamide, erucicamide, stearylamide, docosane acid amides, oleyl palmitamide, stearyl erucicamide, ethene-distearyl acid amides or ethene-two oleylamide, or with the corresponding imide reaction product of oleylamide, erucicamide, stearylamide or docosane acid amides.That is to say the acid amides of maleation alpha-olefinic polymer or multipolymer or maleation alpha-olefin and long-chain amine or imide reaction product.

For example, functionalized olefin polymer of the present invention or multipolymer are long-chain ester, long-chain half ester, long-chain acid amides, the inclined to one side acid amides of long-chain or long-chain imide, wherein said ester, half ester, acid amides, inclined to one side acid amides or imide through type R ₁The long-chain alcohol of OH or formula R ₁R ₂The long-chain of NH uncle or secondary amine with by α, beta-unsaturated carboxylic acid reagent grafted olefin polymer or copolymer reaction formation, wherein R ₁Be C ₁₂-C ₂₂Alkyl or C ₁₂-C ₂₂Alkenyl, R ₂Be hydrogen, C ₁-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl; Or with alpha-olefin and α, the reaction of beta-unsaturated carboxylic acid reagent forms.

Preferably, component (b) is maleation polypropylene, maleation polyethylene or maleation C ₁₈-C ₂₆Half ester or ester that alpha-olefin and tallow fatty alcohol, castor-oil plant alcohol or oleyl alcohol form.

Uncle or secondary fatty acid amide be for example wherein the fat group of lipid acid be C ₁₁-C ₂₁Alkyl or C ₁₁-C ₂₁Alkenyl.

Uncle or secondary fatty acid amide are for example at least a following compounds that is selected from: oleylamide, erucicamide, stearylamide, docosane acid amides, oleyl palmitamide, stearyl erucicamide, ethene-distearyl acid amides and ethene-two oleylamide.

Particularly, fatty acid amide of the present invention is secondary fatty acid amide, for example stearyl erucicamide or oleyl palmitamide.

The suitable fatty acids acid amides for example is disclosed in US 6,228, in 915.

Alkyl is a straight or branched, is methyl for example, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, 2-ethyl-butyl, n-pentyl, isopentyl, the 1-methyl amyl, 1,3-dimethylbutyl, n-hexyl, 1-methyl hexyl, n-heptyl, different heptyl, 1,1,3, the 3-tetramethyl butyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylammonium hexyl, 1,1,3,3-tetramethyl-amyl group, nonyl, decyl, undecyl, 1-methyl undecyl, dodecyl, 1,1,3,3,5,5-hexamethyl hexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.

Alkenyl is the undersaturated alkyl of olefinic, for example allyl group.

Functionalized olefin polymer or copolymer additives are for example 20: 1 to 1: 20 to the weight ratio of uncle or secondary fatty acid amide, 10: 1 to 1: 10, and 1: 1 to 20: 1, for example 1: 1 to 15: 1,1: 1 to 10: 1,1: 1 to 7: 1, or 1: 1 to 5: 1.For example, functionalized maleation alpha-olefin is 1.5: 1,2: 1,3: 1 or 4: 1 to the weight ratio of uncle or secondary fatty acid amide.

Introduce functionalized olefin polymer or multipolymer b in the polymeric matrix) and uncle or secondary fatty acid amide additive c) total amount of combination is 1-15 weight % for example, based on the weight meter of polymeric matrix.For example, the amount of described additive combination is 1-10 weight %, and 3-7 weight %, or 3-5 weight % are based on the weight meter of polymeric matrix.For example, the amount of additive combination of the present invention is 1-3 weight %, and 1-5 weight %, or 1-7 weight % are based on the weight meter of polymeric matrix.

Introduce functionalized olefin polymer or multipolymer b in the coating composition) and uncle or secondary fatty acid amide additive c) total amount of combination is 0.1-15 weight % for example, based on the weight meter of binder for film formation.For example, the amount of described additive combination is 0.1-10 weight %, and 0.3-0.7 weight %, or 0.3-5 weight % are based on the weight meter of binder for film formation.For example, the amount of additive combination of the present invention is 0.1-3 weight %, and 0.1-5 weight %, or 0.1-7 weight % are based on the weight meter of binder for film formation.

Additive of the present invention can separately or be mixed with each other and add in the polymeric matrix.If desired, each component is mixed with each other before can be in introducing polymkeric substance, for example mixes by doing, compacting or carry out in melt.

The introducing of additive of the present invention is undertaken by known method, for example do to mix with form of powder, or with the form wet mixing of for example solution in inert solvent, water or oil, dispersion liquid or suspension.Additive of the present invention can for example be introduced before or after molding, or by dissolving or dispersive additive or additive agent mixture are coated onto on the polymer materials and carry out, needed or do not need evaporating solvent or suspension/dispersion reagent subsequently.They also can directly add (for example forcing machine, internal mixer etc.) in the processing unit, for example as dry mixture or powder, or as solution or dispersion liquid or suspension or melt adding.

Introducing operates in any heatable container that is equipped with agitator to be carried out, for example at airtight equipment for example in kneader, mixing tank or the stirred vessel.Introducing operation preferably carries out in forcing machine or kneader.Processing still is not to be important in the presence of oxygen in inert atmosphere.

Adding additive to polymeric matrix can carry out in all conventional hybrid machines, wherein polymer melt and mix with additive.Suitable machine is well known to those skilled in the art.They mainly are mixing tank, kneader and forcing machine.

Processing comprise extrude, mediate altogether, squeeze draw that (pultrusion), compression moulding, sheet material are extruded, thermoforming, injection moulding or rotational molding.This optimal process is undertaken by introduce additive during processing in forcing machine.

Particularly preferred processing machine is single screw extrusion machine, reverse rotation and homodromal twin screw extruder, rotational molding equipment, planetary gear forcing machine, ring type forcing machine or common kneader.Also processing machine can be used, wherein vacuum can be applied with at least one deaerating chamber.

Suitable forcing machine and kneader are described in for example Handbuch derKunststoffextrusion, the 1st volume Grundlagen, editor F.Hensen, W.Knappe, H.Potente, 1989, the 3-7 page or leaf, ISBN:3-446-14339-4 (the 2nd volume Extrusionsanlagen1986, ISBN 3-446-14329-7).

For example, spiro rod length is a 1-60 screw diameter, preferred 35-48 screw diameter.The speed of rotation of screw rod is 10-600 rev/min of (rpm), very particularly preferably 25-300rpm preferably.

Maximum production depends on screw diameter, speed of rotation and motivating force.The inventive method also can be carried out in the level lower than maximum production, by changing the machine of weighing of above-mentioned parameter or use conveying and metering.

If add a plurality of components, these components can be pre-mixed or add separately.

Additive of the present invention also can spray on the polymer materials.They can dilute other additive (for example Ren Xuan conventional additives) or their melt, so that they can spray on the polymer materials with these additives.It is particularly advantageous adding by spraying between the deactivation period of polyalcohol catalyst, and in this case, the water vapour that is produced can be used for the passivation of catalyzer.

Additive of the present invention and optional other additive also can add with the form of masterbatch (enriched material) in the polymkeric substance, and it contains concentration and is each component in the introducing polymkeric substance of for example 1-40 weight %, preferred 2-20 weight %.Polymkeric substance be not must be when wherein finally adding additive polymer phase with.In these operations, polymkeric substance can use with the form of powder, particle, solution, suspension or with the form of latex.

Introduce operation can before the forming operation or during carry out, by will dissolve or the dispersive compound administration to polymkeric substance, be with or without evaporating solvent subsequently.Another kind of possible the mode that additive of the present invention is introduced polymeric matrix be with they before the corresponding monomeric polymerization, during or afterwards directly or adding before crosslinked.In this respect, additive of the present invention can former state add or the form adding (for example in wax, oil or polymkeric substance) to seal.

The described here polymkeric substance that contains additive of the present invention can be used to produce moulded work, rotation molded articles, injection-molded item, blow-molded article, section bar etc.

Polymkeric substance of the present invention can randomly also contain the various conventional additives of 0.01-5 weight %, preferred 0.025-2 weight %, particularly 0.1-1 weight %, for example following material, or their mixture.

1. antioxidant

1.1. the alkylation monohydric phenol, for example 2,6-two-tertiary butyl-4-methylphenol, the 2-tertiary butyl-4,6-xylenol, 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-(Alpha-Methyl cyclohexyl)-4,6-xylenol, 2, the two octadecyls of 6--4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-two-tertiary butyl-4-methoxymethyl phenol, straight chain or in side chain the nonylphenol of branching, for example 2,6-two-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methyl undecane-1-yl) phenol, 2,4-dimethyl-6-(1-methyl heptadecane-1-yl) phenol, 2,4-dimethyl-6-(1-methyl tridecane-1-yl) phenol and their mixture.

1.2. the alkyl sulfide methylphenol, for example 2,4-dioctyl thiomethyl-6-tert.-butyl phenol, 2,4-dioctyl thiomethyl-6-methylphenol, 2,4-dioctyl thiomethyl-6-ethylphenol, 2,6-two-dodecyl thiomethyl-4-nonylphenol.

1.3. quinhydrones and alkylation quinhydrones, for example 2,6-two-tertiary butyl-4-methoxyl group-phenol, 2,5-two-tertiary butylated hydroquinone, 2,5-two-amyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2,6-two-tertiary butylated hydroquinone, 2,5-two-tertiary butyl-4-hydroxy phenylmethylether, 3,5-two-tertiary butyl-4-hydroxy phenylmethylether, 3,5-two-tert-butyl-hydroxy phenyl stearate, two-(3,5-two-tert-butyl-hydroxy phenyl) adipic acid ester.

1.4. tocopherol, for example alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and their 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, two-second month in a season of 6--amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulfide.

1.6. alkylidene bisphenols, for example 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl)-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-two (3-tert-butyl-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 benzyl)-the 6-tertiary butyl-4-aminomethyl phenyl] terephthalate, 1,1-pair-(3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two-(3,5-two-tert-butyl-hydroxy phenyl) propane, 2,2-pair-(5-tertiary butyl-4-hydroxy 2-aminomethyl phenyl)-4-dodecyl sulfydryl butane, 1,1,5,5-four-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.

1.7. benzyl compounds, for example 3,5,3 ', 5 '-four-tertiary butyl-4,4 '-the dihydroxyl dibenzyl ether, octadecyl-4-hydroxyl-3,5-dimethyl benzyl mercaptoacetate, tridecyl-4-hydroxyl-3,5-two-tertiary butyl-benzyl mercaptoacetate, three (3,5-two-tertiary butyl-4-hydroxy benzyl) amine, 1,3,5-three-(3,5-two-tertiary butyl-4-hydroxy benzyl)-2,4, the 6-Three methyl Benzene, two-(3,5-two-tertiary butyl-4-hydroxy benzyl) thioethers, 3,5-two-tertiary butyl-4-hydroxy benzyl-sulfydryl-acetate isooctyl acrylate, two-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) dithio 1 terephthalate, 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, 3, the two stearyl and 3 of 5-two-tertiary butyl-4-hydroxy benzyl-phosphoric acid, 5-two-tertiary butyl-4-hydroxy benzyl-mono phosphoric acid ester ethyl ester, calcium salt.

1.8. the hydroxybenzyl malonic ester, for example two octadecyls-2,2-two-(3,5-two-tertiary butyl-2-hydroxybenzyl)-and malonic ester, two-octadecyl-2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl)-malonic ester, two-dodecyl mercaptoethyl-2,2-two-(3,5-two-tertiary butyl-4-hydroxy benzyl) malonic ester, it is two that [4-(1,1,3, the 3-tetramethyl butyl) phenyl]-2, two (3, the 5-two-tertiary butyl-4-hydroxy benzyl) malonic esters of 2-.

1.9. the aromatic hydroxy benzyl compounds, for example 1,3,5-three-(3,5-two-tertiary butyl-4-hydroxy-benzyl)-2,4, the 6-Three methyl Benzene, 1, two (3,5-two-tertiary butyl-4-hydroxy benzyl)-2,3,5 of 4-, the 6-tetramethyl-benzene, 2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) phenol.

1.10. triaizine compounds, for example 2,4-two (octyl group sulfydryl)-6-(3,5-two-tertiary butyl-4-hydroxy anilino)-1; 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; 6-two (3,5-two-tertiary butyl-4-hydroxy phenoxy group)-1,3,5-triazines; 2,4,6-three (3; 5-two-tertiary butyl-4-hydroxy phenoxy group)-1,2, the 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-triazine, 1; 3,5-three (3,5-two-tert-butyl-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 ester, dimethyl-2 for example, 5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester, diethyl-3,5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester, two octadecyls 3,5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester, two octadecyls-S-the tertiary butyl-hydroxyl-S-methyl-benzyl phosphonic acid ester, 3, the calcium salt of single ethyl ester of 5--two-tertiary butyl-4-hydroxy benzylphosphonic acid.

1.12. the acyl aminophenols class, 4-hydroxyl-lauric acid N-anilide for example, 4-hydroxyl-stearic acid N-anilide; 2; 4-two-octyl group sulfydryl-6-(3,5-tertiary butyl-4-hydroxy anilino)-s-triazine and octyl group-N-(3,5-two-tert-butyl-hydroxy phenyl)-carbamate.

1.13. β-(3,5-two-tert-butyl-hydroxy phenyl) ester of propionic acid and monohydroxy-alcohol or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, the triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.

1.14. the ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, the triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.

1.15. β-(3,5-dicyclohexyl-4-hydroxy phenyl) ester of propionic acid and monohydroxy-alcohol or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, the triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.

1.16.3, the ester of 5-two-tert-butyl-hydroxy phenyl acetate and monohydroxy-alcohol or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, the triethylene glycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.

1.17. the acid amides of β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid, for example 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] propionyl oxygen base) ethyl] oxamide (Naugard

XL-1 is from Uniroyal).

1.18. xitix (vitamins C)

1.19. amine antioxidants; N for example; N '-two-sec.-propyl-right-phenylenediamine; N; N '-two-sec-butyl-right-phenylenediamine; N; N '-two (1; 4-dimethyl amyl group)-right-phenylenediamine; N; N '-two (1-ethyl-3-methyl amyl)-right-phenylenediamine; N; N '-two (1-methylheptyl)-right-phenylenediamine; N1N '-dicyclohexyl-right-phenylenediamine; N; N '-phenylbenzene-right-phenylenediamine; N; N '-two (2-naphthyl)-right-phenylenediamine; N-sec.-propyl-N '-phenyl-right-phenylenediamine; N-(1; the 3-dimethylbutyl)-N '-phenyl-right-phenylenediamine; N-(1-methylheptyl)-N '-phenyl-right-phenylenediamine; N-cyclohexyl-N '-phenyl-right-phenylenediamine; 4-(p-toluenesulfonyl) diphenylamine; N; N '-dimethyl-N; N '-two-sec-butyl-right-phenylenediamine, 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; the octyl group diphenylamine; p for example, p '-two-uncle octyldiphenylamine, 4-normal-butyl amino-phenol; 4-butyryl radicals amino-phenol; 4-nonanoyl amino-phenol, 4-lauroyl amino-phenol, 4-octadecanoyl 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; 2-two [(2-aminomethyl phenyl) amino] ethane, 1,2-two (phenyl-amino) propane; (neighbour-tolyl) biguanides; two [4-(1 ', 3 '-dimethylbutyl) phenyl] amine, uncle's octyl group N-phenyl-1-naphthylamine; the mixture of list and the dialkyl group tertiary butyl/uncle's octyl group phenylbenzene-amine; the mixture of list and dialkyl group nonyl diphenylamine, the mixture of list and dialkyl group dodecyl diphenylamine, the mixture of list and dialkyl group sec.-propyl/isohexyl two-phenyl amine; the mixture of list and dialkyl group tert-butyl diphenyl amine; 2,3-dihydro-3,3-dimethyl-4H-1; the 4-benzothiazine; thiodiphenylamine, the mixture of list and the dialkyl group tertiary butyl/uncle's octyl group thiodiphenylamine, the mixture of list and dialkyl group uncle octyl group-thiodiphenylamine; 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; two (2; 2,6,6-tetramethyl piperidine-4-yl) sebate; 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)-2H-benzotriazole category, for example known benzotriazole that is purchased hydroxy phenyl-2H-benzotriazole and following U.S. Patent Publication: 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905,4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5; 607; 987; 5; 977; 219 and 6; 166; 218; 2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole for example; 2-(3; 5-two-tertiary butyl-2-hydroxy phenyl)-the 2H-benzotriazole; 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole; 2-(2-hydroxyl-uncle's 5-octyl phenyl)-2H-benzotriazole; 5-chloro-2-(3; 5-two-tertiary butyl-2-hydroxy phenyl)-the 2H-benzotriazole; 5-chloro-2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-2H-benzotriazole; 2-(the 3-sec-butyl-5-tertiary butyl-2-hydroxy phenyl)-2H-benzotriazole; 2-(2-hydroxyl-4-octyl group oxygen base phenyl)-2H-benzotriazole; 2-(3; 5-two-tert-pentyl-2-hydroxy phenyl)-the 2H-benzotriazole; 2-(3; 5-pair-α-cumyl-2-hydroxy phenyl)-the 2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-(ω-hydroxyl-eight (ethyleneoxy group) carbonyl-ethyl)-; phenyl)-the 2H-benzotriazole; 2-(3-dodecyl-2-hydroxy-5-methyl base phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-octyl group oxygen base carbonyl) ethylphenyl)-2H-benzotriazole; dodecyl 2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-octyl group oxygen base carbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole; 2-(the 3-tertiary butyl-5-(2-(2-ethylhexyl oxygen base)-carbonyl ethyl)-2-hydroxy phenyl)-5-chloro-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-methoxycarbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-methoxycarbonyl ethyl) phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-5-(2-(2-ethylhexyl oxygen base) carbonyl ethyl)-2-hydroxy phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-iso-octyl oxygen base carbonyl ethyl) phenyl-2H-benzotriazole; 2; 2 '-methylene radical-two (uncle's 4-octyl group-(6-2H-benzotriazole-2-yl) phenol); 2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 2-(2-hydroxyl-3-t-octyl group-5-α-cumyl phenyl)-2H-benzotriazole; 5-fluoro-2-(2-hydroxyl-3; 5-two-α-cumyl phenyl)-the 2H-benzotriazole; 5-chloro-2-(2-hydroxyl-3; 5-two-α-cumyl phenyl)-the 2H-benzotriazole; 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-iso-octyl oxygen base carbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-uncle's 5-octyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-3; 5-two-uncle octyl phenyl)-the 2H-benzotriazole; methyl 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-tertiary butyl-4-hydroxy hydrogen laurate; 5-butyl alkylsulfonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--5-tert-butyl-phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-3; 5-two-tert-butyl-phenyl)-the 2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-3; 5-two-α-cumyl phenyl)-the 2H-benzotriazole; 5-butyl alkylsulfonyl-2-(2-hydroxyl-3; 5-two-tert-butyl-phenyl)-2H-benzotriazole and 5-phenyl sulfonyl-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole.

2.2.2-hydroxy benzophenone, for example 4-hydroxyl, 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. replace and unsubstituted benzoic ester; Whitfield's ointment 4-tert-butyl-phenyl ester for example; the Whitfield's ointment phenylester; Whitfield's ointment octyl phenyl ester; dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol; 3; 5-two-tertiary butyl-4-hydroxy phenylformic acid 2,4-two-tert-butyl-phenyl ester, 3; 5-two-tertiary butyl-4-hydroxy phenylformic acid cetyl ester; 3,5-two-tertiary butyl-4-hydroxy phenylformic acid stearyl, 3; 5-two-tertiary butyl-4-hydroxy phenylformic acid 2-methyl-4,6-two-tert-butyl-phenyl ester.

2.4. acrylate and malonic ester, alpha-cyano-β for example, β-diphenylacrylate ethyl ester or isooctyl acrylate, alpha-carbon methoxyl group-cinnamic acid methyl ester, alpha-cyano-Beta-methyl-to methoxyl group-cinnamic acid methyl ester or butyl ester, the alpha-carbon methoxyl group-to methoxyl group-cinnamic acid methyl ester, N-(β-carbon methoxyl group-beta-cyano vinyl)-2-methyl-indoles, Sanduvor

PR25, dimethyl is right-methoxyl group toluenyl malonic ester (CAS#7443-25-6), and Sanduvor

PR31, two-(1,2,2,6,6-pentamethyl-piperidin-4-yl) to methoxyl group toluenyl malonic ester (CAS#47783-69-5).

2.5. nickel compound, for example 2,2 '-sulfo--two-[4-(1,1,3,3-tetramethyl butyl) phenol] nickel complex, for example 1: 1 or 1: 2 title complex contain or do not contain extra part, for example n-butylamine, trolamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamate, the nickel salt of mono alkyl ester, for example methyl or ethyl ester, 4-hydroxyl-3,5-two-tertiary butyl benzylphosphonic acid; The nickel complex of ketone group oxime, for example nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketone group oxime; The nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazoles contains or does not contain extra part.

2.6. sterically hindered amine stabilizer, for example 4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-allyl group-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine, 1-benzyl-4-hydroxyl-2,2,6,6-tetramethyl--piperidines, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (2,2,6,6-tetramethyl--4-piperidyl) succinate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1-octyl group oxygen bases-2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) normal-butyl-3,5-two-tertiary butyl-4-hydroxy benzyl malonic acid 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 straight chain or the ring-shaped condensate of 6-two chloro-1,3,5-triazines, three (2,2,6,6-tetramethyl--4-piperidyl) nitrilotriacetate, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane-tetracarboxylic ester, 1,1 '-(1,2-ethane two bases)-two (3,3,5,5-tetramethyl-piperazine ketone), 4-benzoyl-2,2,6,6-tetramethyl piperidine, 4-stearyl oxygen base-2,2,6,6-tetramethyl piperidine, two (1,2,2,6,6-pentamethyl-piperidyl)-2-normal-butyl-2-(2-hydroxyl-3,5-two-tertiary butyl benzyl) malonic ester, 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone, two (1-octyl group oxygen bases-2,2,6, the 6-tetramethyl-piperidyl) sebate, two (1-octyl group oxygen bases-2,2,6, the 6-tetramethyl-piperidyl) succinate, N, N '-two-(2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholinyl-2, the straight chain 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-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-two-(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-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 (CASReg.No.[136504-96-6]); N-(2,2,6,6-tetramethyl--4-piperidyl)-dodecyl succinimide; N-(1,2,2,6; 6-pentamethyl--4-piperidyl)-and dodecyl-succinimide, 2-undecyl-7,7,9; 9-tetramethyl--1-oxa--3,8-diaza-4-oxa--spiral shell [4,5] decane, 7; 7,9,9-tetramethyl--2-encircles undecyl-1-oxa--3,8-diaza-4-oxa--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.

Bulky amine also can be a U.S. Patent No. 5,980, one of compound of describing in 783, just component 1-a), 1-b), 1-c), 1-d), 1-e), 1-f), 1-g), 1-h), 1-i), 1-j), 1-k) or 1-1) compound, particularly in U.S. Patent No. 5, the photostabilizer 1-a-1 that 980,783 64-72 hurdles are listed, 1-a-2,1-b-1,1-C-1,1-C-2,1-d-1,1-d-2,1-d-3,1-e-1,1-f-1,1-g-1,1-g-2 or 1-k-1.

Bulky amine also can be a United States Patent (USP) 6,046, one of compound of describing in 304 and 6,297,299, for example claim 10 or 38 or the compound described of embodiment 1-12 or D-1 to D-5.

2.7. the bulky amine that alkoxyl group replaced that on the N atom, is replaced, for example compound 1-(2-hydroxy-2-methyl propoxy-)-4-stearoyl oxygen base-2,2 by hydroxyl, 6, the 6-tetramethyl piperidine, 1-(2-hydroxy-2-methyl propoxy-)-4-hexadecanoyl oxygen base-2,2,6, the 6-tetramethyl piperidine, 1-oxygen base 1-4-hydroxyl-2,2,6,6-tetramethyl piperidine and reaction product from the carbon-based group of tertiary amyl alcohol, 1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine, 1-(2-hydroxy-2-methyl propoxy-)-4-oxa--2,2,6, the 6-tetramethyl piperidine, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester, two (1-(2-hydroxy-2-methyl-propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) succinate, two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) glutarate and 2, the two { N-[1-(2-hydroxy-2-methyl propoxy-)-2,2 of 4-, 6,6-tetramethyl piperidine-4-yl]-normal-butyl amino }-6-(2-hydroxyethyl amino)-s-triazine.

2.8. oxamide, for example 4,4 '-two octyloxy N, N '-oxalyl pentanoic, 2,2 '-diethoxy N, N '-oxalyl pentanoic, 2,2 '-dioctyl oxygen base-5,5 '-two-tertiary butyl N, N '-oxalyl pentanoic, 2,2 '-two dodecyl oxygen bases-5,5 '-two-tertiary butyl N, N '-oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl n, N '-oxalyl pentanoic, N, N '-two (3-dimethylaminopropyl) oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-second N, N '-oxalyl pentanoic and with 2-oxyethyl group-2 '-ethyl-5,4 '-two-uncle base N, the mixture of N '-oxalyl pentanoic, adjacent and to methoxyl group-dibasic N, the mixture of N '-oxalyl pentanoic, and adjacent and to oxyethyl group-dibasic N, the mixture of N '-oxalyl pentanoic.

2.9. three-aryl-o-hydroxy-phenyl-s-triazine, the triazine of describing in for example known industrial three-aryl-o-hydroxyl-phenyl-s-triazine and the following United States Patent (USP): 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309; 5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543; 6,242,598 and 6,255,483, for example 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2-hydroxyl-4-octyl group oxygen base phenyl)-s-triazine, Cyasorb

1164, Cytec Corp, 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2, the 4-dihydroxy phenyl)-the s-triazine, 2,4-two (2, the 4-dihydroxy phenyl)-6-(4-chloro-phenyl-)-s-triazine, 2,4-two [2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(4-chloro-phenyl-)-s-triazine, 2,4-two [2-hydroxyl-4-(2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-6-(2, the 4-3,5-dimethylphenyl)-the s-triazine, 2,4-two [2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-two [2-hydroxyl-4-(2-acetoxyethoxy) phenyl]-6-(4-chloro-phenyl-)-s-triazine, 2,4-two (2, the 4-dihydroxy phenyl)-6-(2, the 4-3,5-dimethylphenyl)-the s-triazine, 2,4-two (4-xenyl)-6-(2-hydroxyl-4-octyl group oxygen base carbonyl ethyleneoxy group phenyl)-s-triazine, 2-phenyl-4-[2-hydroxyl-4-(3-sec-butyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-6-[2-hydroxyl-4-(3-sec.-amyl sec-pentyl secondary amyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-the s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-benzyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-the s-triazine, 2,4-two (2-hydroxyl-4-normal-butyl oxygen base phenyl)-6-(2,4-di-n-butyl oxygen base phenyl)-the s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-nonyl oxygen base *-2-hydroxypropyl oxygen base)-5-α-cumyl phenyl]-(* represents octyl group oxygen base to the s-triazine, the mixture of nonyl oxygen base and decyl oxygen base), methylene radical two-{ 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-butyl oxygen base-2-hydroxyl propoxy-) phenyl]-the s-triazine }, methylene bridged dimer mixture (3: 5 ', 5: 5 ' and 3: 3 ' position according to 5: 4: 1 ratio bridge joint), 2,4,6-three (the inferior isopropyl phenyl of 2-hydroxyl-4-iso-octyl oxygen base carbonyl)-s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-hexyl oxygen base-5-α-cumyl phenyl)-s-triazine, 2-(2,4, the 6-trimethylphenyl)-4,6-two [2-hydroxyl-4-(3-butyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-s-triazine, 2,4,6-three [2-hydroxyl-4-(3-sec-butyl oxygen base-2-hydroxypropyl oxygen base) phenyl]-s-triazine, 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2-hydroxyl-4-(3-dodecyl oxygen base-2-hydroxyl propoxy-)-phenyl)-s-triazine and 4,6-two-(2, the 4-3,5-dimethylphenyl)-and the mixture of 2-(2-hydroxyl-4-(3-tridecyl oxygen base-2-hydroxyl propoxy-)-phenyl)-s-triazine, Tinuvin 400, Ciba Specialty Chemicals Corp., 4,6-two-(2, the 4-3,5-dimethylphenyl)-and 2-(2-hydroxyl-4-(3-(2-ethylhexyl oxygen base)-2-hydroxyl propoxy-)-phenyl)-s-triazine and 4,6-phenylbenzene-2-(4-hexyl oxygen base-2-hydroxy phenyl)-s-triazine.

3. metal passivator, 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-salicylyl amino-1; 2,4-triazole, two (benzylidene) oxalyl, two hydrazines; N; N '-oxalyl pentanoic, toluene two formyls two hydrazides, salicyloyl phenylbenzene hydrazides; 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, tricresyl phosphite phenylester for example, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite Lauryl Ester, the tricresyl phosphite stearyl, distearyl pentaerythrityl diphosphite, three (2,4-two-tert-butyl-phenyl) phosphorous acid ester, 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 (tert-butyl-phenyl) pentaerythritol diphosphites, three stearyl sorbyl alcohol GW-540s, four (2,4-two-tert-butyl-phenyl) 4,4 '-diphenylene two phosphinates, 6-iso-octyl oxygen base-2,4,8,10-four-tertiary butyl-dibenzo [d, f] [1,3,2] two oxa-phosphepin, 6-fluoro-2,4,8,10-four-tertiary butyl-12-methyl-dibenzo [d, g] [1,3,2] two oxa-phosphocin, two (2,4-two-tertiary butyl-6-aminomethyl phenyl) methyl phosphorous acid ester, two (2,4-two-tertiary butyl-6-aminomethyl phenyl) ethide phosphite ester, 2,2 ', 2 " nitrilo [triethyl three (3,3 '; 5; 5 '-four-tertiary butyl-1,1 '-phenylbenzene-2,2 '-two bases) phosphorous acid ester]; the 2-ethylhexyl (3; 3 ', 5,5 '-four-tertiary butyl-1; 1 '-phenylbenzene-2,2 '-two bases) phosphorous acid ester.

Preferred especially following phosphorous acid ester:

Tricresyl phosphite (2,4-two-tert-butyl-phenyl) ester (lrgafos 168, Ciba SpecialtyChemicals Corp.), tricresyl phosphite (nonyl phenyl) ester,

5. oxyamine, N for example, 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 oxyamine, N-heptadecyl-N-octadecyl oxyamine, N-methyl-N-octadecyl oxyamine and from hydrogenated butter amine deutero-N, N-dialkyl group oxyamine.

6. nitrone, N-benzyl-alpha-phenyl nitrone for example, 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, N-methyl-α-heptadecyl nitrone and from hydrogenated butter amine deutero-N, N-dialkyl group oxyamine deutero-nitrone.

7. amine oxide, for example United States Patent (USP) 5,844,029 and 5,880,191 disclosed amine oxide derivatives, didecyl methyl oxidation amine, three decyl amine oxides, three (dodecyl) amine oxides and three (hexadecyl) amine oxide.

8. benzofuranone and indolone, for example United States Patent (USP) 4,325; 863; 4,338,244; 5; 175,312; 5,216; 052; 5; 252,643; 5,369; 159; 5; 356,966; 5,367; 0085; 428,177 or 5,428; 162 those disclosed; or 3-[4-(2-acetoxyethoxy) phenyl]-5,7-two-tertiary butyl-benzofuran-2-ones, 5; 7-two-tertiary butyl-3-[4-(2-stearoyl keto 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-two-methyl-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-ethanoyl-5-iso-octyl phenyl)-5-iso-octyl benzofuran-2-ones and 3-(2; the 3-3,5-dimethylphenyl)-5,7-two-tertiary butyl-benzofuran-2-ones.

9. sulfo-synergist, for example dilauryl thiodipropionate or distearyl thiodipropionate.

10. peroxide scavenger, the ester of β-thio-2 acid for example, for example lauryl, stearyl, myristyl or tridecyl ester, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, two-octadecyl disulfide, tetramethylolmethane four (β-dodecyl sulfydryl) propionic ester.

11. the polymeric amide stablizer, for example combination of mantoquita and iodide and/or phosphorus compound, and manganous salt.

12. alkaline auxiliary stablizer, melamine for example, polyvinylpyrrolidone, Dyhard RU 100, triallylcyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, the an alkali metal salt of higher fatty acid and alkaline earth salt, for example calcium stearate, Zinic stearas, mountain Yu acid magnesium, Magnesium Stearate, natrium ricinoleicum and potassium palmitate, pyrocatechol antimony or pyrocatechol zinc.

13. nucleator, for example inorganic substance, for example talcum; Metal oxide, for example titanium dioxide or magnesium oxide; The phosphoric acid salt of preferred bases earth metals, carbonate or vitriol; Organic compound, for example monocarboxylic acid or poly carboxylic acid and their salt, for example 4-p t butylbenzoic acid, hexanodioic acid, diphenyl acetic acid, sodium succinate or Sodium Benzoate; Polymkeric substance, for example ionic copolymer (ionomer).

14. filler and toughener, the for example powder of lime carbonate, silicate, glass fibre, glass sphere, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, wood powder and other natural product or fiber, synthon.

15. dispersion agent, for example polyoxyethylene wax or mineral oil.

16. other additive, for example softening agent, lubricant, emulsifying agent, pigment, dyestuff, whitening agent, rheologic additive, catalyzer, flow control agent, antiseize paste, linking agent, crosslinking accelerator, halogen scavenger, smog inhibitor, fire retardant, static inhibitor, transparent base for example replace and unsubstituted Sorbitol dibenzal, benzo

Piperazine ketone UV absorption agent, for example 2,2 '-to phenylene-two (3, the 1-benzo

Piperazine-4-ketone), Cyasorb

3638 (CAS#18600-59-4), and whipping agent.

What paid close attention to is polymkeric substance and the coating composition with improved anti-zoned property and light stability, except the component (a) and (b) with (c), they contain other one or more be selected from additive in oxyamine stablizer, organophosphorus stablizer, benzofuranone stabilization agent, hindered amine light stabilizer and hydroxy phenyl benzotriazole, hydroxy phenyl-s-triazine or the benzophenone ultraviolet absorbers.

Nano level filler or nano composite material also can be used for composition of the present invention.Comprise " nanoclay ", for example be described in United States Patent (USP) 5,853,886 and 6,020,419.

Nano-sized filler is for example leaf silicate or smectic clays, the mixture of for example organic affinity leaf silicate, naturally occurring leaf silicate, synthetic leaf silicate or these leaf silicate.Nano-sized filler of the present invention is for example polynite, wilkinite, beidellite, hectorite, talcum powder or stevensite.

For example, the nano level polynite has " sheet " or strip structure.These small pieces have the thickness less than about 2nm usually.It is about 30 that small pieces or particle have about 20-usually, the mean diameter of 000nm and about 30,000: 1 to 20: 1 long-width ratio.Commercially available nano level polynite with this structure is the Nanomer that obtains from Nanocor

I.42E and the Cloisite that obtains from Southern Clay

30B.

Nano-sized filler has great surface-area and high surface energy.So the conventional micron order filler of compatible ratio between the passivation of surface energy and nano-sized filler and the polymkeric substance is more important, assembles avoiding, and reach the excellence that nano level is filled in the polymkeric substance and disperse.Nano-sized filler is similar to leaf silicate, becomes organic affinity by ion-exchange, for example carries out ion-exchange with alkylammonium salt.The organic affinity leaf of these nano levels silicate is swelling and be easier to be dispersed in the polymeric matrix better.

Nano-sized filler after the processing is also referred to as " layered clay material after the processing " or " organic clay ".

The concentration of nano-sized filler in the present composition is 0.5-10 weight %, based on the weight meter of polymkeric substance or binder for film formation, for example is 1-9 weight %, 3-7 weight % for example, and 5 weight % for example are based on the weight meter of polymkeric substance or binder for film formation.

Polymer composition of the present invention shows good weathering resistance (to the stability of heat, oxygen and light), anti-zoned property, good processibility, excellent mechanical intensity, good gloss retentivity, and is not clamminess.The polymer molding parts for example are applicable to that automobile uses, i.e. snubber panel (fascia) etc.

Polymer composition of the present invention also can be the form of a part, electric wire or cable insulation, film or the natural product matrix material of for example sheet material, multilayered structure.

Following examples illustrate in greater detail the present invention.Except as otherwise noted, all per-cents all are unit with the weight part.

Embodiment 1: the anti-zoned property of polymkeric substance and coating

Functionalized olefin polymer b of the present invention) be:

B1) C ₂₂-C ₂₆The polymkeric substance of alpha-olefin and maleic anhydride,

B2) C ₂₂-C ₂₆The tallow fatty alcohol ester of the polymkeric substance of alpha-olefin and maleic anhydride:

R wherein ₁And R ₂Be butter, R is C ₂₀-C ₂₄Alkyl, n are about 45 mean value,

B3) toxilic acid grafted polypropylene, or

B4) the polyacrylic tallow fatty alcohol ester of toxilic acid grafted.

Amount of component b of the present invention) fatty acid amide is:

C1) stearyl erucicamide, or

C2) oleyl palmitamide.

Preparation carboxylic acid reagent functionalized olefin polymer b) with uncle or secondary fatty acid amide c) 2: 1 (weight: weight) blend.Equally, 1: 1 (weight: weight) blend and 1: 2 (weight: weight) blend of preparation.

Components b) and weight percent summation c) be 3 weight %, based on polymeric matrix or binder for film formation meter.

The polymeric matrix of experiment is PC/ABS, nylon 6, nylon 6,6, PC, PVC, PET, ABS, PBT, ABS/PBT and ABS/PC.

Other additive that is used for the contrast properties evaluation is oleylamide, stearyl erucicamide and DowCorning MB 50-321 polysiloxane additives.Weight percent is based on the polymkeric substance of binder for film formation.Additive mixes in polymeric matrix.All mixing are to use the 25mm twin screw extruder to carry out under industry standard conditions.Injection molding plates uses BOY 50-M injection moulding machine to produce under standard conditions from biased sample.

Carry out several experiments to estimate before weathering and afterwards anti-zoned property and shock resistance.

Standard the five fingers scratching experiment guide (Daimler Chrysler Corporation Test NumberLP-463DD-18-1,2002-07-24)

Estimate The cut width Albefaction

The wide nothing of 1 (best)＜0.2mm

Almost cannot see

The wide nothing of 2 0.2-0.3mm

Distortion a little, in short range as seen

3 0.3-0.4mm are wide, and are clearly visible

Wide can the seeing on whole cut of 4 0.4-0.5mm turned white

5 (the poorest)＞0.5mm is wide turns white on whole cut, and can

Can be attended by defective

Blend of the present invention provides for example excellent anti-zoned property and has not been clamminess.

Result after weathering: in independent studying in great detail, display result after weathering.Xenon arc WeatherOmeter is at 0.55W/m ²Radiation (340nm), SAE J 1885-NAFTA interior automotive prototype, 89 ℃ of blackboard temperatures, drying conditions.Wish to reach 600kJ/m ²Anti-zoned property.Examination criteria the five fingers experiment grading.After the 600KJS weathering, blend of the present invention shows outstanding anti-zoned property.

The plate that only contains the stearyl erucicamide is clamminess after being exposed to 600KJS.Blend of the present invention obtains surprising synergy, and weathering is not had any disadvantageous effect.That is to say that blend of the present invention provides excellent anti-zoned property and weather-proof stability, and is not clamminess.

The coating that only contains the stearyl erucicamide is clamminess after being exposed to 600KJS.Blend of the present invention obtains surprising synergy, and weathering is not had any disadvantageous effect.That is to say that blend of the present invention provides excellent anti-zoned property and weather-proof stability, and is not clamminess.

The coating of the present invention that detects anti-zoned property is:

Be applied to the tung oil phenolic varnish on the cypress plate; Be applied to the aromatic polyurethane varnish on the cypress plate; Be sprayed onto the white bi-component polyester urethane gloss enamel paint on the steel plate, it makes base paint with epoxy polyamide priming paint; The vinylformic acid Synolac is modified enamel paint again, with the aluminium pigment coloring and be sprayed onto with Synolac priming paint and do on the steel plate of base paint; The middle oil alkyd resin enamel is with the aluminium pigment coloring and be sprayed onto with Synolac priming paint and do on the steel plate of base paint; Modify the crosslinked vinylformic acid Synolac of enamel paint again with aliphatic isocyanate is crosslinked, and be sprayed onto on the steel plate of using Synolac priming paint; Be sprayed onto with epoxy primer and do alkyd paint on the steel plate of priming paint; Be sprayed onto with Synolac and make thermoplastic acrylic varnish on the steel plate of priming paint.

Coating of the present invention also contains hindered amine light stabilizer and benzotriazole or s-triazine UV absorption agent.

Modification Tai Shi wear test range estimation guide

Estimate The cut width Relative performance

1 (best)＜50mm excellence

2 200-300mm are good

3 300-400mm are general

4 400-500mm are poor

The non-constant of 5 (the poorest)＞500mm

According to the Tai Shi wear test, blend of the present invention provides excellent abrasive.

According to the notched izod impact experiment, additive blends of the present invention provides excellent shock strength.

Embodiment 2: the anti-zoned property of multilayer polymer structure

Components b of the present invention) and c) can be used as anti-zoned additive in the polymer layer in multilayer polymer structure.The example of these polymer architectures includes but not limited to:

1.) sheet material and mark be referring to for example U.S.6, and 150,440or U.S.5,387,458;

2.) the solar control film of various structures, referring to for example U.S.3,290,203,3,681,179,3,776,805 or 4,095,013; With

3.) be used for the bed material or the liftout of coextrusion structure, the coextrusion structure is for example window sectional material, the laminating material on automobile buffer or automobile exterior panel.

The multiple layer polymer matrix material prepares by variety of way, and for example one or more polymer composition coextrusion form multilayer materials.Perhaps, polymer composition carries out compression moulding or the required polymer composites of thermoforming production.Particularly, these technology are used to produce annunciator, are generally comprised within one or more layers polymer materials on the base material (metal sheet, plastics etc.).

Claims

1. polymer composition with improved anti-zoned property and light stability, it comprises:

A) polymeric matrix,

B) functionalized olefin polymer of carboxylic acid reagent or multipolymer and

C) uncle or secondary fatty acid amide;

Prerequisite is the polyolefine that polymeric matrix not only comprises polyolefine or modified rubber;

Wherein carboxylic acid reagent functionalized olefin polymer in the polymer composition or multipolymer are long-chain ester, long-chain half ester, long-chain acid amides, the inclined to one side acid amides of long-chain or long-chain imide, wherein this ester, half ester, acid amides, inclined to one side acid amides or imide through type R ₁The long-chain alcohol of OH or formula R ₁R ₂The long-chain of NH uncle or secondary amine with by α, beta-unsaturated carboxylic acid reagent grafted olefin polymer or copolymer reaction formation, wherein R ₁Be C ₁₂-C ₂₂Alkyl or C ₁₂-C ₂₂Alkenyl, R ₂Be hydrogen, C ₁-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl; Or with alpha-olefin and α, the reaction of beta-unsaturated carboxylic acid reagent forms.

2. coating composition with improved anti-zoned property and light stability, it comprises:

A) binder for film formation,

B) functionalized olefin polymer of carboxylic acid reagent or multipolymer and

C) uncle or secondary fatty acid amide;

Wherein carboxylic acid reagent functionalized olefin polymer in the coating composition or multipolymer are long-chain ester, long-chain half ester, long-chain acid amides, the inclined to one side acid amides of long-chain or long-chain imide, wherein this ester, half ester, acid amides, inclined to one side acid amides or imide through type R ₁The long-chain alcohol of OH or formula R ₁R ₂The long-chain of NH uncle or secondary amine with by α, beta-unsaturated carboxylic acid reagent grafted olefin polymer or copolymer reaction formation, wherein R ₁Be C ₁₂-C ₂₂Alkyl or C ₁₂-C ₂₂Alkenyl, R ₂Be hydrogen, C ₁-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl; Or with alpha-olefin and α, the reaction of beta-unsaturated carboxylic acid reagent forms.

3. according to the composition of claim 2, wherein binder for film formation is selected from acrylic resin, vibrin, resol, melamine resin, Resins, epoxy and urethane resin.

4. according to the composition of claim 1 or 2, wherein functionalized olefin polymer or multipolymer are 20: 1 to 1: 20 to the weight ratio of uncle or secondary fatty acid amide additive.

5. according to the composition of claim 1 or 2, wherein the total amount of functionalized olefin polymer or multipolymer and uncle or secondary fatty acid amide additive combination is 0.1-15 weight %, based on the weight meter of polymeric matrix or binder for film formation.

6. according to the composition of claim 1 or 2, wherein said composition further contains one or more and is selected from additive in oxyamine stablizer, organophosphorus stablizer, benzofuranone stabilization agent, hindered amine light stabilizer and hydroxy phenyl benzotriazole, hydroxy phenyl-s-triazine or the benzophenone ultraviolet absorbers.

7. one kind provides the method for anti-zoned property to polymeric matrix and the coating composition that comprises binder for film formation, and this method comprises the additive combination that comprises following component of introducing significant quantity in described polymer composition or coating composition:

B) functionalized olefin polymer of carboxylic acid reagent or multipolymer and

C) uncle or secondary fatty acid amide,

Wherein carboxylic acid reagent functionalized olefin polymer in polymer composition and the coating composition or multipolymer are long-chain ester, long-chain half ester, long-chain acid amides, the inclined to one side acid amides of long-chain or long-chain imide, wherein this ester, half ester, acid amides, inclined to one side acid amides or imide through type R ₁The long-chain alcohol of OH or formula R ₁R ₂The long-chain of NH uncle or secondary amine with by α, beta-unsaturated carboxylic acid reagent grafted olefin polymer or copolymer reaction formation, wherein R ₁Be C ₁₂-C ₂₂Alkyl or C ₁₂-C ₂₂Alkenyl, R ₂Be hydrogen, C ₁-C ₂₂Alkyl or C ₂-C ₂₂Alkenyl; Or with alpha-olefin and α, the reaction of beta-unsaturated carboxylic acid reagent forms,