• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: Provided are a novel polymer article of low thickness and good transparency having enhanced stability against the effects of light, oxygen, heat and aggressive chemicals, which is also effective as a selective UV filter for agricultural applications, and some novel stabilizers suitable for this application. CONSTITUTION: The transparent polyolefin, polyester or polyamide article stabilized by addition of 0.005-0.30% by weight the polymer substrate of a hydroxyphenyl triazine UV absorber, is characterized in that the article has a thickness between 1 and 500 micron. The articles contain a compound of the formula 1 as a hydroxyphenyl triazine UV absorber. In formula 1, R1 is H or OR7; R2 and R3 independently are H, C1-C8alkyl, and OR9; R4 and R5 independently are H, C1-C8alkyl, OR10; R6 is H, C1-C8alkyl, C5-C12cycloalkyl, C7-C12phenylalkyl, C7-C12alkylphenyl, C3-C12alkenyl, halogen, OH, OR9; R8 is H; halogen; C1-C12alkoxy; C1-C12alkyl; C3-C24 alkyl interrupted by oxygen and/or substituted by OH; or is NH-CO-R14 or NH-COO-R12; R7, R9 and R10 independently are H; C1-C24alkyl; C3-C12 alkenyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is C5-C12 cycloalkyl, C7-C12phenylalkyl, C7-C12 alkylphenyl; CH2CH(OH)CH2OR11; C1-C12alkyl substituted by COOR12, CONR13R14, OCOR15, OH or halogen; or R7 is a polymeric hydrocarbon residue of 10 to 1000 carbon atoms, preferably 20 to 500 carbon atoms; and R7 also embraces a residue of formula 2.
    公开号:KR20020010530A
    申请号:KR1020010045242
    申请日:2001-07-26
    公开日:2002-02-04
    发明作者:레파드데이비드죠지；구구무스프랑소와스；보노라미켈라
    申请人:시바 스폐셜티 케미칼스 홀딩 인코포레이티드；
    IPC主号:
    专利说明:

    Transparent polymer articles of low thickness
    [5] The present invention is a novel polymeric material that has improved stability to light, oxygen, heat and active chemicals, is thin and transparent and is an effective UV filter for agricultural applications and several novel stabilizers suitable for such applications. It is about.
    [6] Several ultraviolet-containing polyolefinic materials, in the form of hydroxyphenyl triazines, are known from GB-A-2319523, EP-A-704560, WO 99/57189.
    [7] The problem to be solved by the present invention is to improve the stability to light, oxygen, heat and active chemicals, thin thickness and excellent transparency, making it a novel polymer material that is effective as an optional UV filter in agriculture and several suitable for such use. It is to provide a novel stabilizer.
    [1] Fig. 1 shows the effect of addition of the hydroxyphenyl-triazine UV absorber compound (j) in the presence of low molecular weight HALS H-2 in the PP cast film,
    [2] FIG. 2 shows the effect of addition of the hydroxyphenyl-triazine UV absorber compound (j) in the presence of a polymerizable HALS H-3, H-4 and 1 part H-3 and 1 part H-4 in a PP cast film. Indicates,
    [3] Fig. 3 shows the addition effect of the hydroxyphenyl-triazine UV absorber compound (j) in the presence of high molecular weight HALS H-5 in the PP cast film, and
    [4] Figure 4 shows the effect of addition of the hydroxyphenyl-triazine UV absorber compound (j) in the presence of 0.1% polymerizable H-3 in the PP cast film.
    [8] The present invention relates to transparent polyolefin, polyester or polyamide materials having a thickness of 1 to 500 microns, stabilized by the addition of 0.005 to 0.30% by weight of a polymer substrate of hydroxyphenyl triazine UV absorber.
    [9] Preferred materials contain a compound of formula 1 as hydroxyphenyl triazine UV absorber:
    [10]
    [11] here
    [12] R 1 is H or OR 7 ;
    [13] R 2 and R 3 are independently H, C 1 -C 8 alkyl, , OR 9 ;
    [14] R 4 and R 5 are independently H, C 1 -C 8 alkyl, OR 10 ;
    [15] R 6 is H, C 1 -C 18 , C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl, C 3 -C 12 alkenyl, halogen, OH, OR 9 ;
    [16] R 8 is H; halogen; C 1 -C 12 alkoxy; C 1 -C 12 alkyl; C 3 -C 24 alkyl substituted by interrupt and / or by OH by oxygen; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; CH 2 CH (OH) CH 2 OR 11 ; C 1 -C 12 alkyl substituted by COOR 12 , CONR 13 R 14 , OCOR 15 , OH or halogen; Or R 7 is a polymerizable hydrocarbon residue having 10 to 1000, preferably 20 to 500 carbons; And
    [17] R 7 also includes residues of formula (2).
    [18]
    [19] Wherein X is C 2 -C 24 alkylene; -CH 2 CH (OH) CH 2- ; -CH 2 CH (OH) CH 2 OD-OCH 2 CH (OH) CH 2 ; (C 1 -C 18 alkylene) -CO-OD-CO- (C 1 -C 18 alkylene); CO; CO- (C 2 -C 24 alkylene) -CO; The interrupted by oxygen C 3 -C 24 alkylene;
    [20] D is C 2 -C 12 alkylene; C 4 -C 50 alkylene interrupted by O; Phenylene; Biphenylene or phenylene-E-phenylene;
    [21] E is O, S, SO 2 ; CH 2 ; CO or —C (CH 3 ) 2 —;
    [22] R 11 is H, C 1 -C 12 alkyl; Phenyl; Phenyl substituted by 1-3 C 1 -C 4 alkyl; C 5 -C 12 cycloalkyl; C 7 -C 12 phenylalkyl; C 3 -C 12 alkenyl;
    [23] R 12 is H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 36 alkyl interrupted by oxygen and / or substituted by OH; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; Phenyl;
    [24] R 13 and R 14 are independently H, C 1 -C 18 alkyl; Phenyl; Phenyl substituted by 1-3 C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl;
    [25] R 15 is C 1 -C 12 alkyl; Phenyl; Phenyl substituted by 1-3 C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl; C 1 -C 12 alkoxy; Or NR 13 R 14 .
    [26] More preferably, in the hydroxyphenyl triazine UV absorber of the formula (1)
    [27] R 4 and R 5 are independently H or methyl;
    [28] R 6 is H;
    [29] R 8 is H; C 1 -C 8 alkoxy; C 1 -C 8 alkyl;
    [30] R 7 , R 9 are independently H; C 1 -C 18 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl substituted by interrupt and / or by OH by oxygen; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkyl, phenyl, COOR 12, OCOR 15, substituted C 1 -C 12 alkyl by OH; Or R 7 is a polymerizable hydrocarbon residue having 20 to 500 carbon atoms; And
    [31] R 7 also includes a residue of Formula 2 wherein X is C 2 -C 18 alkylene; -CH 2 CH (OH) CH 2- ; -CH 2 CH (OH) CH 2 OD-OCH 2 CH (OH) CH 2 ; (C 1 -C 4 alkylene) -CO-ODO-CO- (C 1 -C 4 alkylene); CO; CO- (C 2 -C 18 alkylene) -CO; C 3 -C 18 alkylene interrupted by oxygen; D is C 2 -C 12 alkylene;
    [32] R 12 is H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl substituted by interrupt and / or by OH by oxygen; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; Phenyl;
    [33] R 15 is C 1 -C 12 alkyl; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl;
    [34] Especially
    [35] R 1 is OR 7 ;
    [36] R 2 and R 3 are independently H, methyl, , OR 9 ;
    [37] R 4 and R 5 and R 6 are H;
    [38] R 8 is H; C 1 -C 8 alkoxy; C 1 -C 4 alkyl;
    [39] R 7 , R 9 are independently C 4 -C 18 alkyl or C 5 -C 12 cycloalkyl; And
    [40] R 7 also includes a residue of Formula 2 wherein X is C 4 -C 18 alkylene.
    [41] The most important compound is that R 1 is OR 7 ; Each of R 2 and R 3 is phenyl; R 4 , R 5 and R 6 are hydrogen; And a compound of Formula 1 wherein R 7 is C 4 -C 18 alkyl or C 5 -C 12 cycloalkyl or a residue of Formula 2 wherein X is C 4 -C 12 alkylene.
    [42] Halogen substituents are -F, -Cl, -Br or -I, preferably -F, -Cl or Br and especially -Cl.
    [43] Alkylphenyl is alkyl-substituted phenyl; C 7 -C 14 alkylphenyls are, for example, methylphenyl (toyl), dimethylphenyl (xylyl), trimethylphenyl (methyl), ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptyl Phenyl and octylphenyl.
    [44] Phenylalkyl is phenyl-substituted alkyl; C 7 -C 11 phenylalkyl includes, for example, benzyl, α-methylbenzyl, α-ethylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylpropyl, phenylbutyl and phenylpentyl.
    [45] n-alkyl or alkyl-n is an unbranched alkyl radical.
    [46] Alkyl interrupted by O, NH, NR 13, etc., may typically include one or more non-adjacent heteroatoms. Preferably, the carbon atoms of the alkyl chain are bonded to one or more heteroatoms. As alkyl substituted by COOR 12 , R 7 , R 9 and R 10 , in particular R 7, are preferably CH 2 -COOR 12 . R 12 is most preferably C 1 -C 18 alkyl, or C 6 -C 12 cycloalkyl; Cycloalkyl is most preferably cyclohexyl or cyclododecyl.
    [47] Within the scope of the described definitions, the radicals R 4 , R 5 , R 6 , R 8 , R 11 , R 12 , R 13 , R 14 , R1 5 as alkyl are branched or unbranched alkyl, for example methyl , Ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl , 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3- Trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
    [48] C 1 -C 4 alkyl is especially methyl, ethyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl or tert-butyl.
    [49] Within the scope of the described definitions, R 4 , R 5 , R 6 , R 9 , R 11 , R 12 , R 13 , R 14 , R 1 5 as alkenyl is allyl, isopropenyl, 2-butenyl, 3 -Butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-ethyl.
    [50] R 4 , R 5 and R 6 are most preferably hydrogen. R 2 and R 3 are most preferably phenyl or OR 9 , in particular phenyl. R 9 is most preferably C 1 -C 4 alkyl.
    [51] The most effective as compounds of formula 1 are illustrated below or through the following table:
    [52] 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -Octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-tri Azine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4.6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-di Phenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine , 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2- Ethoxyhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.
    [53] Table 1 : Chemical Formula Compound of
    [54]
    [55] In the above definition, n represents an alkyl straight chain.
    [56] Table 2: Compounds of Formula (k)
    [57]
    [58]
    [59] Or X is C 13 -C 24 alkylene; (C 1 -C 18 alkylene) -CO-ODO-CO- (C 1 -C 18 alkylene), where D is C 2 -C 12 ; CO- (C 13 -C 24 alkylene) -CO; Corresponding compound which is C 3 -C 24 alkylene interrupted by oxygen, in particular (C 1 -C 3 alkylene) -O- (C 1 -C 3 alkylene).
    [60] Further examples of highly effective compounds of Formula 1 include the following compounds,
    [61]
    [62]
    [63]
    [64] Several compounds of formula 1 are known, for example, from WO 96/28431, US-5591850, EP-A-434608; For example, the following compounds are known,
    [65]
    [66] (b), (f), (g) and (h) are novel compounds. They are usually prepared by methods similar to those described in these references, in particular those described in Example 18 of WO 96/28431.
    [67] A particularly useful use of the polymer films of the invention, in particular polyolefin films, is to be used as greenhouse films. Some types of crops are degraded by the ultraviolet component of the sun's radiation, which must be filtered to increase crop quality and productivity. In addition, microorganisms such as fungi, for example, Botrytis cieria, Botryrisporium, Cladosporium kucumerium, Endomyces getriquiium, Endomyces fibulinger, Spaerotheca pannosa, Eri Cife polygony, gonatobotris, cylindrocapron, fusarium, tirabiobipsis, verticillium, and viruses such as cucumo-virus, tombus-virus and the like as well as harmful pests, for example White flies, aphids, shovels or leafminers, etc., are propagated by certain ultraviolet radiation. These pests can be significantly reduced when ultraviolet light is not irradiated to the plant or less. See literature [R. Reuveni et al., Development of photoselective PE films for control of foliar pathogens in greenhouse-grown crops, Plasticulture No. 102, p. 7 (1994); Y. Antignus et al., The use of UV absorbing plastic sheets to protect crops against insects and spread of virus diseases, CIPA Congress March 1997, pp. 23-33]. On the other hand, bee activity that requires a certain band of ultraviolet irradiation is required in the greenhouse, thereby securing the fruit of flowering plants, such as tomatoes, cucumbers, pumpkins, melons, lemons, roses, strawberries, lettuce, grapes, and peppers. do.
    [68] The present hydroxyphenyl triazine UV absorbers exhibit good suitability and durability for polyolefins, polyesters or polyamides. At the same time, these UV absorbers provide excellent and selective ultraviolet shielding to inhibit the growth of microorganisms in a protected environment, while retaining the ultraviolet radiation necessary for the activity of bees and bumblebees, especially in the case of plant cultivation. Accordingly, the present invention relates to the use of transparent polyolefin films as mentioned above to inhibit microbial growth in a protected growing environment.
    [69] Examples of the polyolefins used to prepare the materials of the present invention include the following polymers:
    [70] 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and also polymers of cycloolefins For example cyclopentene or norbornene, polyethylene (which may be optionally crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW) ), Medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
    [71] Polyolefins, for example polymers of the monoolefins exemplified above, preferably polyethylene and polypropylene, can be prepared differently and in particular by the following methods:
    [72] a) radical polymerization (usually under high pressure and elevated temperature).
    [73] b) Catalytic polymerization using a catalyst, usually containing one or more metals of Group IVb, Group Vb or Group VIII of the Periodic Table. These metals are usually one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or π-bonded or σ-bonded. These metal complexes may be in free form or immobilized on a substrate, usually activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used on their own in the polymerization or additional activators, usually metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes can be used, where the metal is Group Ia, IIa on the periodic table. Group and / or group IIIa elements. The activator may be conveniently modified by additional ester, ether, amine or silyl ether groups. These catalyst systems are usually Phillips, Standard Oil Indiana, Ziegler (-Natta), TNG (Dupont), metallocene or single site It is referred to as Single site catalysts (SSC).
    [74] 2. Mixtures of the polymers mentioned in 1), eg mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and 00 mixtures of other forms of polyethylene (For example LDPE / HDPE).
    [75] 3. Polyolefin copolymers: Monoolefins and diolefins with each or other vinyl monomers thereof, for example ethylene / propylene copolymers, mixtures having linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), propylene / but- 1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / Butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and Their salts (ionomers), as well as terpolymers and dienes of ethylene and propylene, for example hexadiene, dicyclopentadiene or Ethylidene-norbornene; And their respective copolymers and copolymers with the polymers mentioned in 1), such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and mixtures thereof with polyalkylene / carbon monooxide alternating or random copolymers and other polymers, for example polyamides.
    [76] The polyesters used to prepare the materials of the invention are mainly derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4 Block copolyether esters derived from hydroxyl-terminated polyethers as well as those derived from dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoate; And polyesters modified with polycarbonate or MBS. Preferred is polyethylene terephthalate (PET).
    [77] Polyamides are usually those derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4 Aromatic polyamides disclosed from / 6, 12/12, polyamide 11, polyamide 12, m-xylene diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid with or without elastomer as modifier, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthal amides; And block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; Or block copolymers of the aforementioned polyamides with polyethers (eg, polyethylene glycol, polypropylene glycol or polytetramethylene glycol); As well as polyamides or copolyamides modified with EPDM or ABS; And polyamides condensed during the process (RIM polyamide system).
    [78] Most preferred are polyethylene, especially polyolefins such as LDPE or LLDPE or polypropylene.
    [79] Preferably, the amount of hydroxyphenyl triazine UV absorber in the transparent polymeric material of the present invention is 0.005 to 0.15% by weight, preferably 0.005 to 0.06% by weight, more preferably 0.01 to 0.06% by weight of the polymer substrate.
    [80] The transparent polyolefin, polyester or polyamide materials of the invention are usually films, fibers, ribbons or stretched tapes, in particular agricultural films. The thickness is preferably 1 to 300 µm, particularly 1 to 200 µm. The film, ribbon or tape of the present invention is not usually biaxially stretched. The transparent polyolefin, polyester or polyamide materials of the present invention are often, for example, another light stabilizer, process stabilizer, filler, clarifier, modifier, acid remover, pigment, flame retardant or other known additives. It contains at least one other component selected from. These components do not effectively block transmitted light through the present polymeric material, which is usually white incident light above 20%, in particular above 50%, more particularly above 80%. In order to sufficiently increase the transparency, the present material does not contain a crystal component in an amount that greatly impairs this property; Preferably it contains a small amount of polymer of the crystalline inorganic component or filler, eg 0-5% by weight, or no pigment and polymer at all, having a lower opacity effect than pigments (eg hydrotalcite). Examples of additional components that may be included in the polymeric material of the present invention include the following components.
    [81] 1. Antioxidant
    [82] 1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- ( α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl- 4-methoxymethylphenol, nonylphenol branched from straight or branched chain, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undes-1'- Yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptades-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltrides-1'-yl ) -Phenols and mixtures thereof.
    [83] 1.2. Alkylthiomethylphenols such as 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl- 6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
    [84] 1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di Phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy Roxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
    [85] 1.4. Tocopherol , α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
    [86] 1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'- Thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secondary Amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
    [87] 1.6. Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2 '-Methylenebis [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6 -Nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'- Methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6- Tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2 -Hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4- Hydroxy-2-methylphenyl) -3-n-dodecylmercap Tobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopenta Diene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5- Dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -propane, 2,2-bis (5-tert-butyl-4-hydroxy Oxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
    [88] 1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine , Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl- 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
    [89] 1.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tertiary- Butyl-4-hydroxy-5-methylbenzyl) malonate, dididosylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    [90] 1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3 , 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Benzyl) phenol.
    [91] 1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2- Octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy ) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4- Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3 , 5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5- Tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    [92] 1.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, 3,5-di Calcium salt of tert-butyl-4-hydroxybenzyl-phosphonic acid monoethylester.
    [93] 1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    [94] 1.13. Esters of mono- or polyhydric alcohols with β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid , such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6 -Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocy Anurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2 Ester with 6,7-trioxabicyclo [2.2.2] octane.
    [95] 1.14. Esters of mono- or polyhydric alcohols with β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid , for example methanol, ethanol, n-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Cyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- 2,6,7-trioxabicyclo- [2.2.2] octane; 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetra Ester with oxaspiro [5.5] -undecane.
    [96] 1.15. Esters of mono- or polyhydric alcohols with β- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid , for example methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6 -Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocy Anurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2 Ester with 6,7-trioxabicyclo [2.2.2] octane.
    [97] 1.16. Esters of mono- or polyhydric alcohols with 3,5-di-tert-butyl-4-hydroxyphenylacetic acid , for example methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol , 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6, Ester with 7-trioxabicyclo [2.2.2] octane.
    [98] 1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid , for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropy Onyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di- Tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] Oxamide (Naugard ™ XL-1, manufactured by Uniroyal).
    [99] 1.18. Ascorbic acid (vitamin C)
    [100] 1.19. Amine antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-secondary-butyl-p-phenylenediamine, N, N'-bis- (1,4 -Dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenyl Rendiamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine , N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N '-Phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N' -Di-tert-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2- Naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-no Nan oil aminophenol, 4-dodecane oil aminophenol, 4-octadecane oil aminophenol, bis (4-methoxyphenyl) amine, 2, 6-di- tert- butyl-4- dimethylamino methyl phenol, 2 , 4'-diaminodiphenylmethane, 4,4'-diaminophenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [ (2-methyl-phenyl) amino] ethane, 1,2-bis- (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, Tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / 3 tert-octyldiphenylamine, mono and dialkylated nonyldiphenylamine, mono- and dialkylated dodec Mixture of sildiphenylamine, mixture of mono- and dialkylated isopropyl / isohexyldiphenylamine, mixture of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl- A mixture of 4H-1,4-benzothiazine, phenothiazine, mono- and dialkylated tert-butyl / tert-octyl phenothiazine, Mixtures of mono- and dialkylated tertiary octyl phenothiazines, N-allylphenothiazines, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-enes, N, N-bis (2,2,6,6-tetramethylpiperid-4--4-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2, 6, 6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol.
    [101] 2. UV absorbers and light stabilizers
    [102] 2.1. 2- (2'-hydroxyphenyl) -benzotriazole , for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl -2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1, 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-secondarybutyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyl Mixture of oxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2' Hydroxyphenyl) -5 -Chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3 '-Tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-( 2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) Benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5 '-(2 Isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; polyethylene Transesterification product of glycol 300 with 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -2H-benzotriazole; R is 3' [R-CH 2 CH 2 -COO-CH 2 CH 2 ) 2 ], tert-butyl-4'-hydroxy-5'-2H-benzotriazol- 2 -ylphenyl 2- ; 2- [2'-hydroxy-3 '-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole; 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) phenyl] benzotriazole.
    [103] 2.2. 2-hydroxybenzophenones , for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
    [104] 2.3. Esters of unsubstituted or substituted benzoic acid , for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl-benzoyl) Resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4- Hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxy Oxybenzoate.
    [105] 2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cya No-β-methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxy-cinnamate and N- ( β-carbomethoxy-β-cyanovinyl) -2-methylindolin.
    [106] 2.5. 2,2'-thio-bis [4- (1,1,3,2) with nickel compounds , for example with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, where appropriate 3-tetramethylbutyl) phenol] (such as 1: 1 or 1: 2 complex), nickel dibutyl dithiocarbamate, 4-hydroxy-3,5-di-tert-butyl benzyl phosphonic acid monoalkyl Nickel salts of esters (eg methyl esters or ethyl esters), nickel complexes of ketoximes (eg 2-hydroxy-4-methylphenylundecyl ketoxime), 1-phenyl-4-lau with appropriate ligands where appropriate Nickel Complexes of Loyl-5-hydroxy Pyrazole.
    [107] 2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethyl-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4 Hydroxybenzyl malonate, condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2, Condensation product of 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6 , 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate , 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4 -Stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpipepe Dill) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3 , 8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2 Linear or cyclic condensation products of, 6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperi Condensation product of dill) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-bis (4-n-butylamino-1,2,2 , 6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane condensation product, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperi Dill) pyrrolidine- 2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy and Mixture of 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine And condensation reaction products of 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1 , 3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6] condensation reaction product; 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, and N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpy Condensation reaction products of ferridine (CAS Reg. No. [192268-64-7]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl ) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 7 Reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4,5] decane and epichlorohydrin, 1,1- Bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethane, N, N'-bis-formyl-N, N ' -Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperi Dean's diester, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin copolymer 2, Reaction product of 2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
    [108] 2.7. Oxamides , for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanide, 2-ethoxy-2'-ethyloxanide, N, N'-bis (3-dimethylaminopropyl) oxamide , 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p- A mixture of methoxy-disubstituted oxanilides and a mixture of o- and p-ethoxy-disubstituted oxanilides.
    [109] 3. Metal deactivators such as N, N'-diphenyloxamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N ' -Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxa Nilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N '-Bis (salicyloyl) thiopropionyl dihydrazide.
    [110] 4. Phosphites and phosphonites , for example triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diss Tearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol depot Spite, bis (2,4,6-tris-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-ratio Phenylene diphosphonite, 6-isooctyloxy-2,4,8,10-te Tri-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl Ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, 2, 2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2 Ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,11'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2- ( 2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphyran.
    [111] Particular preference is given to the following phosphites:
    [112] Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ™ 168, Ciba-Geigy), tris (nonylphenyl) phosphite,
    [113]
    [114]
    [115] 5. Hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N Ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N- Octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated animal oil amine.
    [116] 6. Nitrons such as N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl-nit Ron, N-tetradecyl-alpha-tridecyl-nitron, N-hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha-heptadecyl From nitron, N-octadecyl-alpha-pentadedecyl-nitron, N-heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, hydrogenated animal oil amine Nitron derived from derived N, N-dialkylhydroxylamine.
    [117] 7. Thio synergists, such as dilauryl thiodipropionate or distearyl thiodipropionate.
    [118] 8. Peroxide-removing agents , for example esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzoimidazole or 2-mercaptobenzimidazole, zinc di Butyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.
    [119] 9. Polyamide stabilizers such as copper salts and divalent manganese salts with iodides and / or phosphorus compounds.
    [120] 10. Basic co-stabilizers , for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids. Such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
    [121] 11. Nucleating agents , for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds such as mono- or polycarboxylic acids and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers (ionomers). Especially preferred are 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol, and 1,3: 2, 4-di (benzylidene) sorbitol.
    [122] 12. Fillers and reinforcing agents , for example calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural products, synthetic fibers Of flour or fiber.
    [123] 13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, flow aids, catalysts, flow regulators, fluorescent brighteners, flame retardants, antistatic agents and blowing agents.
    [124] 14. Benzofuranone and indolinone, US4 325 863, US4 338 244 or US5 175 312, US5 216 052, US5 252 643, DE-A-4 316 611, DE-A-4 316 622 DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di Tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] -phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxy Phenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl- 4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one.
    [125] If necessary, conventional additives are carefully used in amounts of up to 10% by weight, for example from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, based on the material to be stabilized.
    [126] Acid removers may be added, in particular, to improve the life of agricultural materials, such as greenhouse films, which are in contact with the pesticide. Components that act as acid scavengers include GB-A-2300192, 2, 2 to 4, as well as metal oxides and / or hydroxides, for example zinc, magnesium, aluminum, calcium, oxides or hydroxides of mixed salts thereof, Hydrotalcite or zeolite described up to line 22.
    [127] The thin wall material of the present invention, in particular the transparent polyolefin agricultural film, acts as an optional UV filter that enhances plant growth and grain while inhibiting the growth of harmful microorganisms. Light and distant UV regions (eg, 200-360 nm, especially 300-340 nm) of the medium required by these microorganisms are effectively blocked. At the same time, the activity of useful insects such as bees and bumblebees is not affected.
    [128] Preferably, the transparent polyolefin, polyester or polyamide materials of the present invention also contain sterically hindered amines as another stabilizer to achieve optimal light stability of the substrate. The hindered amine is usually contained in an amount of 0.01 to 6% by weight of a polyolefin, polyester or polyamide, preferably in a weight ratio of 2: 1 to 20: 1 of the hindered amine: hydroxyphenyl triazine UV absorber.
    [129] Examples of sterically hindered amines preferably contained in polyolefin, polyester or polyamide materials are shown in the above list (section 2.6). More preferred sterically hindered amines are the following compounds or mixtures thereof:
    [130] Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate;
    [131] Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate;
    [132] Condensates of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid (CAS-No. 65447-77-0);
    [133] N, N ', N ", N'"-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazine -2-yl) -4,7-diazadecan-1,10-diamine (CAS-No. 106990-43-6);
    [134]
    [135] (Chimassorb TM 2020, (CAS- No. 192268-64-7),
    [136] In the above formula, n is mainly 3 to 5.
    [137] Best results are obtained when using sterically hindered amines from the type of hydroxylamine ether. Steric hindered hydroxylamine ethers are piperidine derivatives containing one or more functional groups of the general formula:
    [138]
    [139] Wherein R and R 'are independently a chemical bond of hydrogen or methyl and an oxygen atom, optionally another chemical bond is bonded to an organic moiety and the remainder is saturated with hydrogen; Or all three chemical bonds are bonded to an organic moiety. Examples of such compounds are described in US Pat. No. 5,204,473, US Pat. No. 5,216,156 or GB-A-2,347,928.
    [140] Examples of the most preferred hydroxylamine ethers are compounds of the general formula (1 g-1):
    [141]
    [142] Where
    [143] n is 1 to 15, especially 3 to 9;
    [144] R 12 is 1,4-piperazinyl aphids one, -O- or> NX 1 (X 1 is a C 1 -C 12 acyl or (C 1 -C 12 alkoxy) carbonyl, or R 14 or below except hydrogen C 2 -C 12 alkylene, C 4 -C 12 alkenylene, C 5 -C 7 cycloalkylene, C 5 -C 7 cycloalkylene-di (C 1- ) having one of the definitions) C 4 alkylene), C 1 -C 4 alkylenedi (C 5 -C 7 cycloalkylene), phenylenedi (C 1 -C 4 alkylene) or C 4 -C 12 alkylene; or
    [145] R 12 is a group of the following general formula (Ib ′) or (Ic ′);
    [146] (1b ')
    [147] (1c ')
    [148] In the food,
    [149] m is 2 or 3,
    [150] X 2 is C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; Phenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy; C 7 -C 9 phenylalkyl unsubstituted or substituted with 1, 2 or 3 C 1 -C 4 alkyl in phenyl; In addition
    [151] The radicals X 3 independently of one another are C 2 -C 12 alkylene;
    [152] The radicals B, independently of each other, are Cl, —OR 13 , —N (R 14 ) (R 15 ) or a group of formula (3d);
    [153] (3d);
    [154] The same or different R 13 , R 14 and R 15 are hydrogen, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 3 -C 18 alkenyl, phenyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy; C 7 -C 9 phenylalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl in phenyl; Tetrahydrofurfuryl or C 2 -C 4 alkyl substituted by —OH, C 1 -C 8 alkoxy, di (C 1 -C 4 alkyl) amino or a group of formula (1e ′) at the 2, 3 or 4 position; ;
    [155] (1e ')
    [156] Y is —O—, —CH 2 —, —CH 2 CH 2 — or> N—CH 3 , or —N (R 14 ) (R 15 ) is additionally a group of formula (1e ′) above;
    [157] X is -O- or> NR 16 ;
    [158] R 16 is hydrogen, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 5 -C 12 cycloalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 7 -C 9 phenylalkyl unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl in phenyl; Tetrahydrofurfuryl, group of formula (3f)
    [159] (3f)
    [160] Or C 2 -C 4 alkyl substituted by —OH, C 1 -C 8 alkoxy, di (C 1 -C 4 alkyl) amino or a group of formula (1e ′) at the 2, 3 or 4 position;
    [161] R 11 has the definition given in R 16 .
    [162] In said compounds, the terminal group bonded to the triazine residue is for example group B or -N (R 11 ) -R 12 -B such as chlorine or the following group;
    [163]
    [164] And the end groups bound to the diamino groups are for example hydrogen or di-B-substituted triazinyl groups, such as the following groups:
    [165]
    [166] It may be advantageous to substitute the chlorine attached to the triazine with, for example, -OH or an amino group. Suitable amino groups are typically as follows: pyrrolidin-1-yl, morpholino, -NH 2 , -N (C 1 -C 8 alkyl) 2 and -NY '(C 1 -C 8 alkyl), Wherein Y 'is hydrogen or a chemical formula It is the flag of.
    [167] Among the oligomeric and polymerizable compounds described above, examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1- Methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n- Octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethyl, dodecyl, 1 , 1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, aicosyl and docosyl; Examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; An example of C 7 -C 9 phenylalkyl is benzyl; Examples of alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene. Another example of a hindered amine ether used advantageously in the polymeric materials of the present invention is a compound of the formula:
    [168]
    [169] Examples of very effective compounds of formula (1g-1) are compounds of formula (1g-2):
    [170]
    [171] Wherein n 'is the NO-n-propyl derivative of about 3 (Example 2 of GB-A-2334717, CAS # 247243-62-5, block oligomer Chimassorb R 2020 CAS # 192268-64-7 (Ciba Specialty) Manufactured by Chemicals Corp.).
    [172] Additives and optional additional components of the invention can be added individually to the polymeric material or mixed with each other. If desired, the individual components may be mixed with each other in the melt (melt blending) prior to mixing with the polymer. The incorporation of the additives and optional further components of the invention into the polymer is effected by known methods such as dry mixing in powder form or wet mixing in solution or suspension form. The additives of the present invention and any further additives may be applied to the polymeric material, for example mixed or dissolved or dispersed before or after molding, and then incorporated into the solvent, with or without evaporation. The additives and further additives may be added to the processing apparatus (eg extruders, internal mixers, etc.) directly, for example as a dry mixture or powder, or as a solution or melt.
    [173] The incorporation can be carried out in a heatable vessel with a closed device such as a stirrer, such as a kneader, a mixer or a stirring vessel. The mixing is preferably carried out in an extruder or kneader. It does not matter whether the processing is carried out in an inert atmosphere or in the presence of oxygen.
    [174] Additives of the present invention and any additional additives may be added to the polymer in the form of a masterbatch containing the component at a concentration of about 2.5 to about 25 weight percent, in which the polymer is used in powders, granules, solutions, It can be used in suspension or latis form.
    [175] The embodiments described below illustrate the present invention in detail without constituting any limitation. Parts and percentages are by weight; Examples referring to room temperature mean a temperature in the range from 20 to 25 ° C. For solvent mixtures such as chromatography, parts are by volume. These definitions apply equally unless otherwise noted. The following abbreviations are as follows:
    [176] m.p. Melting point or melting range
    [177] NMR nuclear magnetic resonance
    [178] T g glass transition temperature
    [179] h: hour
    [180] Preparation of Hydroxyphenyl Triazine UV Absorber
    [181] a)
    [182] Synthesis of 2,4-bis-biphenyl-6- [2-hydroxy-4- (2-ethyl-hexyloxy) phenyl] -1,3,5-triazine
    [183] To a dimethylformamide (30 ml) was added a yellow suspension of 2,4-bis-biphenyl-6- [2,4-dihydroxyphenyl] -1,3,5-triazine (11.2 g, 0.0227 mol) to 70 Heated under nitrogen at ° until a clear brown solution was formed. Anhydrous potassium carbonate (3.77 g, 0.0227 mol) was added and the brown suspension was heated to 80 ° C over 30 minutes. 2-ethylhexyl bromide (5.70 g, 0.0295 mol) was added dropwise over 30 minutes, after which the suspension was further heated at 110 ° C. for 3 hours. The precipitated salt was filtered off and the filtrate was cooled to 0 ° C. Methanol (20 ml) was added and the precipitated product was removed by filtration. After drying in vacuo, 2,4-bis-biphenyl-6- [2-hydroxy-4- (2-ethylhexyloxy-phenyl] -1,3,5-triazine (12.8) has a melting point of 70 ° C. g) was obtained.
    [184] h) the same amount of 2,4-bis (4-methoxy) as the free product 2,4-bis-bisphenyl-6- [2,4-dihydroxyphenyl] -1,3,5-triazine in the preparation Phenyl) -6- [2,4-dihydroxyphenyl] -1,3,5-triazine, to obtain compound h of the following structural formula:
    [185] (Melting point: 105 ° C)
    [186] The compounds shown in the table below can be obtained when the reaction (a) is repeated with the corresponding amounts of other alkylbromide or alkylene-dibromide.
    [187]
    [188]
    [189] X is C 13 -C 24 alkylene; (C 1 -C 18 alkylene) -CO-ODO-CO- (C 1 -C 18 alkylene); CO- (C 13 -C 24 alkylene) -CO; Corresponding compounds which are C 3 -C 24 alkylene comprising oxygen in the middle, in particular (C 1 -C 18 alkylene) -O- (C 1 -C 3 alkylene), are suitable alkylene-dibromide or Obtained using -CO-ODO-CO- or alkylene-dibromide comprising oxygen, or dichloride or dibromide of aliphatic C 15 -C 26 diacids.
    [190] l) Preparation of a Compound of Formula
    [191]
    [192] In a manner similar to Example 16 of WO96 / 28431, starting material 4- (4,6-bis-biphenyl-4-yl- (1,3,5) triazin-2-yl) -benzene-1,3 White powder was obtained from diol and allyl bromide.
    [193] 1 H NMR (300 MHz, CDCl 3 ): δ = 13.3 (s, 1HO, 8.7-6.2 (aromatic signal, 21H), 6.1 (m, 1H), 5.3 (m, 2H), 4.3 (m, 2H).
    [194] m) Preparation of Oligomers of Formula
    [195]
    [196] 30 g (0.056 mol) of compound of Example (l) and 30.2 g (0.320 mol) of norbornylene and 42.3 g (0.320 mol) of dicyclopentadiene and catalyst bis (tricyclopentylphosphine) dichloro (3-methyl- 0.49 g (0.6 mmol) of 2-butenylidene) ruthenium (APT Cat ASMC 716) was added to 300 ml of toluene. The mixture was reacted at 30 ° C. for 24 hours. The solution was concentrated in vacuo to yield a pale yellow solid.
    [197] Neck melting point: 168-180 ° C .;
    [198] Elemental Analysis:
    [199]
    [200] n) Preparation of Hydrogenated Oligomers of Formula
    [201]
    [202] 1.0 g of platinum / carbon (10% w / w) was added to a solution in which 92 g (0.050 mol) of the oligomer of Example (m) was dissolved in 300 ml of xylene. The mixture was poured into an autoclave and hydrogenated at 65 bar (p H2 ) and 105 ° C for 24 hours. 10 g at 80-90 ° C Purification from the catalyst was added for 2 hours and left under vigorous stirring for 2 hours. After filtration over 10 g Tonsil pad the filtered yellow liquid was concentrated in vacuo to yield a pale yellow solid.
    [203] Neck melting point range: 55-68 ° C .;
    [204]
    [205] Application Example
    [206] In some of the application examples, the following hindered amines (HALS) were used:
    [207]
    [208] H-2 bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate)
    [209] Condensate of H-3 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (CAS-No. 65447-77-0)
    [210] H-4
    [211] H-5 N, N ', N ", N"'-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) Amino) triazin-2-yl) -4,7-diazadecan-1,10-diamine (CAS-No. 106990-43-6).
    [212] Example 1 Combination of Hydroxyphenyl Triazine Compound (a) and Compound (1g-2)
    [213] In order to evaluate the UV-absorbent properties of hydroxyphenyl triazine compound (a) when mixed with commercially available thermoplastics, 0.15% by weight of the compound (a) in a typical formulation and the polymerizable system in an environment very necessary for agricultural use A thin low density polyethylene (LDPE) film was prepared containing 0.70% by weight of hindered amine ether (1 g-2) used as light stabilizer. To do this, a suitable weight of the compound is crushed LDPE (supplied by Polymer Europa, Encheme, Milan Italy) characterized by a density of 0.921 g / cm 3 and a melt flow index (190 ° C./2.16 kg) of 0.6; Mix in a turbo mixer. The mixture was extruded in an OMC R twin screw extruder at a maximum temperature of 200 ° C. The granules thus obtained were blown in a laboratory scale Formac R blown extruder at a maximum temperature of 210 ° C. to obtain a 150 μm thick membrane.
    [214] The UV-Vis spectra of the membranes thus obtained were recorded in the range of 200-800 nm using a Perkin-Elmer lambda R 20 spectrophotometer with RSA-PE-20 Labsphere R agglomerates. At 0.15% loading, compound (a) imparts strong UV absorption characteristics to the film and exhibits less than 10% light transmittance in the range 290 to 360 nm and less than 1% light transmittance in the range 300 to 340 nm. The light stability of compound (a) exposes the membrane sample to UV light at Atlas Ci 65 Xenon Arc Weather-O-meter R (WOM, 63 ° C. black panel temperature, continuous drying cycle, according to ASTM G 26-96). It is represented by. After 1500 hours of WOM exposure, the minimum light transmittance exhibited by the film is almost 1% at 320 nm.
    [215] Compound (a) is sufficiently compatible with the LDPE membrane; No blooming is observed even after 6000 hours of storage at room temperature. The same results are obtained after the membrane is kept in an oven at 60 ° C. for the same time. After exposure in the oven for the same time, no significant change in the UV-Vis absorption spectrum was observed and there was no additive loss due to high temperatures.
    [216] WOM exposure of the combination reported in this example continues to assess the light stability performance of the polymer containing Compound (a). Samples are treated with pesticides to assess their natural exposure and resistance to chemicals applicable in agriculture.
    [217] Example 2 Hydroxyphenyl Triazine Compound (c) as UV Filter in Polyethylene Agrofilm
    [218] To prepare a thin LDPE film and to evaluate the spectral characteristics imparted by the additive and its toughness, compound (c) has a density of 0.921 g / cm 3 and a melt flow index of 0.6 (190 ° C./2.16 kg). It is mixed in a turbo mixer with LDPE pellets (Riblene FF 29, Polymer Europa, Milan Italy supplied) to obtain a blend containing 0.15% by weight of an additive. The mixture was extruded in an OMC twin screw extruder at a maximum temperature of 200 ° C. The granules thus obtained were blown in a laboratory scale Formac blow extruder at a maximum temperature of 210 ° C. to obtain a 150 μm thick membrane. UV-Vis spectra were recorded in the 200-800 nm range using a Perkin-Elmer Lambda 20 spectrophotometer with RSA-PE-20 Labspher integration.
    [219] Results : The film exhibits a strong absorption band in the range from 280 to 360 nm. In particular, the light transmittance was less than 20% in the above-mentioned range and less than 5% in the 295-345 nm range.
    [220] In order to test the light stability of the additive when exposed to light, a portion of the film was subjected to Atlas Weather-O-Meter (WOM), model Ci65A (0.35 W / m 2 irradiation, according to ASTM G26-96, black panel temperature 63 ± 3). Exposure). After 1000 hours of exposure, the film showed a light transmittance of less than 40% in the range of 280 to 360 nm and a light transmittance of less than 25% in the range of 295 to 345 nm.
    [221] Example 3
    [222] Membranes containing 0.15% by weight of compound (d) were prepared as described in Example 2. The film exhibits a strong absorption band in the range from 280 to 360 nm. In particular, it exhibits a light transmittance of less than 20% in the above range and a light transmittance of less than 5% in the range of 295 to 345 nm.
    [223] After 1000 hours of exposure in the WOM (see Example 2 for details), the film retains the spectral characteristics as described above.
    [224] The other part of the membrane is exposed in a forced circulation air oven at 60 ° C. to evaluate the heat resistance of the additives in the membrane. After 1000 hours of exposure, the membrane still has initial spectral characteristics.
    [225] Example 4
    [226] A membrane containing 0.15% by weight of compound (b) was prepared as described in Example 2. The film exhibits a strong absorption band in the range from 280 to 360 nm. In particular, it exhibits a light transmittance of less than 20% in the above-mentioned range and a light transmittance of less than 5% in the range of 295-345 nm.
    [227] After 1000 hours of exposure in the WOM (see Example 2 for details), the film retains the spectral characteristics as described above.
    [228] Example 5
    [229] Membranes containing 0.15% by weight of compound (g) were prepared as described in Example 2. The film exhibits a strong absorption band in the range from 280 to 360 nm. In particular, it exhibits a light transmittance of less than 20% in the above-mentioned range and a light transmittance of less than 5% in the range of 295-345 nm.
    [230] After 1000 hours of exposure in WOM (see Example 2 for details), the membrane exhibits less than 25% light transmittance in the range 280 to 360 nm and less than 10% light transmittance in the range 295 to 345 nm.
    [231] The other part of the membrane is exposed in an oven at 60 ° C. After 1000 hours of exposure, the membrane maintains about 75% of initial absorption.
    [232] Example 6 : A membrane containing 0.15% by weight of compound (f) was prepared as described in Example 2. The film exhibits a strong absorption band in the range from 280 to 360 nm. In particular, it exhibits a light transmittance of less than 20% in the above-mentioned range and a light transmittance of less than 5% in the range of 295-345 nm.
    [233] After 1000 hours of exposure in WOM (see Example 2 for details), the membrane exhibits less than 25% light transmittance in the range 280 to 360 nm and less than 15% light transmittance in the range 295 to 345 nm.
    [234] Example 7 Light Stabilization of Polypropylene (PP) Cast Membranes
    [235] In a barrel mixer, 100 parts of polypropylene powder (melt flow index: 3.8 g / 10 min, 230 ° C./2160 g) was charged with 0.05 parts of pentaerythritol-tetrakis-3- (3,5-ditertbutyl-4-hydroxyphenyl ) Propionate, 0.05 parts tris- (2,4-ditert-butylphenyl) -phosphite, 0.1 parts Ca stearate, 0.1 parts HALS and the amount of UV absorber (compound j) shown in the figure. The mixture was then ground in an extruder at 180-220 ° C. The granules and granulated material obtained on the extruder were formed into a film in a second extruder with a flat sheet die at 220 to 260 ° C. A 60 × 25 mm sample was cut into 0.11 mm membrane and exposed at WEATHER-OMETER Ci 65 (black panel temperature 63 ± 2 ° C., no water spray).
    [236] Periodically, the samples were withdrawn from the exposure apparatus and their carbonyl content was measured with an infrared spectrophotometer. The exposure time taken to form carbonyl absorption 0.1 was measured by the stabilization efficiency of the light stabilizer. The values thus obtained are recorded in FIGS. 1, 2 and 3. The following HALS was used (0.1 parts each per 100 parts PP):
    [237] 1: low molecular weight mass HALS H-2 (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate);
    [238] 2: polymerizable HALS H-3 (CAS-No. 65447-77-0, white circle),
    [239] Polymerizable HALS H-4 (white square) and
    [240] Mixture of 1 part H-3 and 1 part H-4 (black circle)
    [241] 3: non-polymeric high molecular weight HALS H-5.
    [242] The plots of Figures 1, 2 and 3 show that small amounts of hydroxyphenyl triazine UV absorbers significantly improve the UV stability imparted by HALS.
    [243] Example 8 Light Stabilization of Polypropylene Tape
    [244] 100 parts of polypropylene powder (melt flow index 3.5 g / 10 min, 230 ° C./2160 g) was added to 0.05 parts of pentaerythritol-tetrakis-3- (3,5-ditertbutyl-4-hydroxy in a barrel mixer. Phenyl) -propionate, 0.05 parts Tris- (2,4-di-tert-butylphenyl) -phosphite, 0.1 part Ca stearate, 0.1% polymerizable HALS H-3 (1- (2-hydroxyethyl) Mixed with a condensate of -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (CAS-No. 65447-77-0) and the amount of the light stabilizer compound (j) indicated in the figure The resulting mixture was ground in an extruder at 180 to 220 ° C. The granules and granulated material obtained on the extruder were converted to a membrane in a second extruder with a flat sheet die at 220 to 260 ° C. The membrane was turned into a ribbon. The cuts were made and drawn at a draw ratio of 1: 6. The tape obtained in the process was 50 μm thick and 2.5 mm wide.
    [245] The tape was mounted on the sample holder without tension and naturally exposed in Florida (45 ° Southern, Direct, about 140 kLy / year). Periodically, the tensile strength of the exposed tape was measured. The energy (kLy) required to lose 50% initial tensile strength is a measure of the stabilization efficiency of the light stabilizer. The values obtained with polymerizable HALS and hydroxyphenyl triazine UV absorbers are listed in FIG. 4.
    [246] The results in FIG. 4 show that the action of the UV absorber on light stabilization is significant on the PP tape, which is less than half the thickness of the PP film used in Example 7.
    [247] Example 9 Photostabilization of Polypropylene Tape
    [248] 100 parts of polypropylene powder (melt flow index 3.5 g / 10 min, 230 ° C./2160 g) was added to 0.05 parts of pentaerythritol-tetrakis-3- (3,5-ditertbutyl-4-hydroxy in a barrel mixer. Phenyl) -propionate, 0.05 parts tris- (2,4-di-tert-butylphenyl) -phosphite, 0.1 part Ca stearate and the amount of light stabilizer indicated in the figure. The resulting mixture was ground in an extruder at 180-220 ° C. The granules and granulated material obtained on the extruder were converted to membranes in a second extruder with a flat sheet die at 220-260 ° C. The membrane was cut with a ribbon and drawn at a draw ratio of 1: 6. The tape obtained in this process is 50 μm thick and 2.5 mm wide.
    [249] The tape was mounted on the sample holder without tension and exposed at WEATHER-O-METER Ci65 (black panel temperature 63 ± 2 ° C., no water spray). Periodically, the tensile strength of the exposed tape was measured. The exposure time (T50) required to lose 50% initial tensile strength is a measure of the stabilization efficiency of the light stabilizer.
    [250] The obtained values are listed in the table below.
    [251] Table : Effect of different UV absorber types on the performance of HALS on PP tapes
    [252]
    [253] Compound V-1 is 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.
    [254] Compound V-2 is a chemical formula being.
    [255] Example 10 Absorption Bands and Resistance in LDPE of Compound (m)
    [256] A thin low density polyethylene (LDPE) membrane was prepared as described in Example 2 except without adding HALS. They have a thickness of 150 μm and contain 0.5% of compound m. UV-Vis spectra were recorded as described in Example 2. The film exhibits strong absorption in the range of 280 to 360 nm. A transmittance of less than 3% was observed in the range from 290 to 350 nm.
    [257] The resistance of the polymer in the LDPE membrane was evaluated as described in Example 3 after exposing the membrane in a forced circulation air oven at 60 ° C. No decrease in maximum absorption was observed even after 3000 hours at 60 ° C.
    权利要求:
    Claims (16)
    [1" claim-type="Currently amended] 1 to 500 microns thick, stabilized against the effects of light, oxygen, heat and / or active chemicals by adding 0.005 to 0.30% by weight of hydroxyphenyl triazine UV absorbers on a polyolefin, polyester or polyamide basis Transparent polyolefin, polyester or polyamide materials.
    [2" claim-type="Currently amended] The transparent polyolefin material of claim 1 having a thickness of 1 to 500 microns, stabilized against the effects of light, oxygen, heat and / or active chemicals by adding 0.005 to 0.30% by weight of hydroxyphenyl triazine UV absorbers on a polyolefin basis. .
    [3" claim-type="Currently amended] The transparent polyolefin, polyester or polyamide material according to claim 1, which contains as a further stabilizer a sterically hindered amine in an amount of 0.01 to 6% by weight, based on the polyolefin, polyester or polyamide.
    [4" claim-type="Currently amended] 4. The transparent polyolefin, polyester or polyamide material according to claim 3, wherein the weight ratio of sterically hindered amine: hydroxyphenyl triazine UV absorber is from 2: 1 to 20: 1.
    [5" claim-type="Currently amended] 4. The transparent polyolefin, polyester or polyamide material of claim 3, wherein the sterically hindered amine belongs to the hydroxylamine ether class.
    [6" claim-type="Currently amended] The transparent polyolefin, polyester or polyamide of claim 1, wherein the hydroxyphenyl triazine UV absorber is a compound of Formula 1:
    [Formula 1]
    here
    R 1 is H or OR 7 ;
    R 2 and R 3 are independently H, C 1 -C 8 alkyl, , OR 9 ;
    R 4 and R 5 are independently H, C 1 -C 8 alkyl, OR 10 ;
    R 6 is H, C 1 -C 18 , C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl, C 3 -C 12 alkenyl, halogen, OH, OR 9 ;
    R 8 is H; halogen; C 1 -C 12 alkoxy; C 1 -C 12 alkyl; C 3 -C 24 alkyl substituted by interrupt and / or by OH by oxygen; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; CH 2 CH (OH) CH 2 OR 11 ; C 1 -C 12 alkyl substituted by COOR 12 , CONR 13 R 14 , OCOR 15 , OH or halogen; Or R 7 is a polymerizable hydrocarbon residue having 10 to 1000, preferably 20 to 500 carbons; And
    R 7 also includes residues of formula (2).
    [Formula 2]
    Wherein X is C 2 -C 24 alkylene; -CH 2 CH (OH) CH 2- ; -CH 2 CH (OH) CH 2 OD-OCH 2 CH (OH) CH 2 ; (C 1 -C 18 alkylene) -CO-OD-CO- (C 1 -C 18 alkylene); CO; CO- (C 2 -C 24 alkylene) -CO; The interrupted by oxygen C 3 -C 24 alkylene;
    D is C 2 -C 12 alkylene; C 4 -C 50 alkylene interrupted by O; Phenylene; Biphenylene or phenylene-E-phenylene;
    E is O, S, SO 2 ; CH 2 ; CO or —C (CH 3 ) 2 —;
    R 11 is H, C 1 -C 12 alkyl; Phenyl; Phenyl substituted by 1-3 C 1 -C 4 alkyl; C 5 -C 12 cycloalkyl; C 7 -C 12 phenylalkyl; C 3 -C 12 alkenyl;
    R 12 is H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 36 alkyl interrupted by oxygen and / or substituted by OH; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; Phenyl;
    R 13 and R 14 are independently H, C 1 -C 18 alkyl; Phenyl; Phenyl substituted by 1-3 C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl;
    R 15 is C 1 -C 12 alkyl; Phenyl; Phenyl substituted by 1-3 C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl; C 1 -C 12 alkoxy; Or NR 13 R 14 .
    [7" claim-type="Currently amended] The hydroxyphenyl triazine UV absorber of claim 1, wherein
    R 2 and R 3 are independently H, methyl, , OR 9 ;
    R 4 and R 5 are independently H or methyl, in particular H;
    R 6 is H;
    R 8 is H; C 1 -C 8 alkoxy; C 1 -C 8 alkyl;
    R 7 , R 9 are independently H; C 1 -C 18 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl substituted by interrupt and / or by OH by oxygen; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkyl, phenyl, COOR 12, OCOR 15, substituted C 1 -C 12 alkyl by OH; Or R 7 is a polymerizable hydrocarbon residue having 20 to 500 carbon atoms; And
    R 7 also includes a residue of Formula 2 wherein X is C 2 -C 18 alkylene; -CH 2 CH (OH) CH 2- ; -CH 2 CH (OH) CH 2 OD-OCH 2 CH (OH) CH 2 ; (C 1 -C 4 alkylene) -CO-ODO-CO- (C 1 -C 4 alkylene); CO; CO- (C 2 -C 18 alkylene) -CO; C 3 -C 18 alkylene interrupted by oxygen; D is C 2 -C 12 alkylene;
    R 12 is H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl substituted by interrupt and / or by OH by oxygen; Or C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; Phenyl;
    R 15 is C 1 -C 12 alkyl; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl.
    [8" claim-type="Currently amended] Transparent polyolefin, polyester or polyamide material according to claim 1, which is a film, fiber, ribbon or elongated tape, in particular a polyolefin agricultural film.
    [9" claim-type="Currently amended] Transparent polyolefin, polyester or polyamide material according to claim 8, having a thickness of 1 to 300 microns, in particular 1 to 200 microns.
    [10" claim-type="Currently amended] The transparent polyolefin, polyester or polyamide material of claim 1, wherein the polyolefin is polyethylene or polypropylene.
    [11" claim-type="Currently amended] The transparent polyolefin according to any one of the preceding claims, further comprising a component selected from the group comprising processing stabilizers, fillers, clarifiers, modifiers, acid removers, flame retardants and in particular further light stabilizers. , Polyester or polyamide materials.
    [12" claim-type="Currently amended] A method of using the transparent polyolefin film of claim 8 to inhibit the growth of microorganisms in a protected growing environment.
    [13" claim-type="Currently amended] A method for inhibiting microbial growth in a protected environment by covering the environment protected with the polyolefin film of claim 8.
    [14" claim-type="Currently amended] The method of claim 13, wherein the protected environment is plant cultivation.
    [15" claim-type="Currently amended] A method for selectively screening sunlight and / or artificial light irradiated to crops in the greenhouse by covering the greenhouse with the polyolefin film of claim 8.
    [16" claim-type="Currently amended] A compound of any one of Formulas a, b, f, g, h or k:






    Wherein X is C 13 -C 24 alkylene; (C 1 -C 18 alkylene) -CO-ODO-CO- (C 1 -C 18 alkylene), where D is C 2 -C 12 ; CO- (C 13 -C 24 alkylene) -CO; C 3 -C 24 alkylene interrupted by oxygen, in particular (C 1 -C 3 alkylene) -O- (C 1 -C 3 alkylene).
    类似技术:
    公开号 | 公开日 | 专利标题
    JP6247378B2|2017-12-13|Use of organic oxyimides as flame retardants for plastic materials, flame retardant plastic material compositions, and molded articles produced therefrom
    JP6623217B2|2019-12-18|Use of phosphorus-containing organooxyimides as flame retardants for plastic materials and / or as stabilizers, flame retardant and / or stable plastic material compositions, methods for their production, and molded articles, paints and coatings
    KR100525173B1|2006-05-16|Hydroxyphenyltriazine
    JP5431300B2|2014-03-05|DOPO flame retardant composition
    EP1646681B1|2006-11-29|Flame retardant polylactic acid
    KR100902337B1|2009-06-12|Syngergistic composition of UV absorbers for pigmented polyolefins
    KR100943687B1|2010-02-23|-crystalline polypropylenes
    AU2003203667B2|2007-07-19|Stabilizer mixtures
    NL1019532C2|2002-09-06|Improved weather resistance of flame-resistant polyolefin.
    KR100891436B1|2009-04-03|Additive functionalized organophilic nano-scaled fillers
    US7169835B2|2007-01-30|Stabilizer mixture
    US7323502B2|2008-01-29|Flame retardant compositions
    JP5405400B2|2014-02-05|Synergistic combination of UV absorbers
    KR100611554B1|2006-08-10|Synthetic polymers comprising additive blends with enhanced effect
    JP4764632B2|2011-09-07|Flame retardant composition
    AU780925B2|2005-04-28|Synergistic mixtures of UV-absorbers in polyolefins
    US8349923B2|2013-01-08|Flame retardant compositions comprising sterically hindered amines
    AU2004275997B2|2010-07-22|Stabilization of photochromic systems
    DE19616185B4|2009-04-16|Polyethylene or ethylene copolymer film containing a stabilizer combination, process for their stabilization and their use
    US7820744B2|2010-10-26|Stabilizer mixtures
    JP4406869B2|2010-02-03|Flame retardant composition
    JP4490276B2|2010-06-23|Flame retardant composition
    EP1749051B1|2009-11-18|Flame-retardants
    US7019053B2|2006-03-28|Stabilizer mixtures
    JP4359846B2|2009-11-11|Amorphous solid modified product of bis | pentaerythritol diphosphite
    同族专利:
    公开号 | 公开日
    US20100178484A1|2010-07-15|
    CA2352708A1|2002-01-26|
    ITMI20011606D0|2001-07-25|
    US20050059758A1|2005-03-17|
    DE10135795A1|2002-04-04|
    GR20010100357A|2002-03-29|
    GR1004356B|2003-10-07|
    US20070259165A1|2007-11-08|
    JP2002114879A|2002-04-16|
    FR2812299A1|2002-02-01|
    CN1334287A|2002-02-06|
    GB2367824B|2003-04-30|
    US20030236327A1|2003-12-25|
    KR20070081460A|2007-08-16|
    CA2352708C|2011-10-18|
    US20090291289A1|2009-11-26|
    ES2208018A1|2004-06-01|
    CN1660823A|2005-08-31|
    GB0117537D0|2001-09-12|
    IL144490D0|2002-05-23|
    US20060141207A1|2006-06-29|
    SA2230B1|2009-06-01|
    KR100778769B1|2007-11-27|
    NL1018520C2|2002-06-21|
    US20090042006A1|2009-02-12|
    NL1018520A1|2002-01-29|
    GB2367824A|2002-04-17|
    US20020083641A1|2002-07-04|
    CO5231248A1|2002-12-27|
    US7166653B2|2007-01-23|
    ES2208018B1|2005-03-16|
    CN1308314C|2007-04-04|
    FR2812299B1|2007-04-27|
    ITMI20011606A1|2002-01-28|
    DE10135795B4|2015-03-19|
    US7265171B2|2007-09-04|
    BE1014316A5|2003-08-05|
    AU5596601A|2002-01-31|
    CN1198873C|2005-04-27|
    AU778032B2|2004-11-11|
    JP5489383B2|2014-05-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-07-26|Priority to EP00810666.8
    2000-07-26|Priority to EP00810666
    2001-07-26|Application filed by 시바 스폐셜티 케미칼스 홀딩 인코포레이티드
    2002-02-04|Publication of KR20020010530A
    2007-11-27|Application granted
    2007-11-27|Publication of KR100778769B1
    2011-04-29|First worldwide family litigation filed
    优先权:
    申请号 | 申请日 | 专利标题
    EP00810666.8|2000-07-26|
    EP00810666|2000-07-26|
    [返回顶部]