CN100482726C - Highly compatible and non-migratory polymeric uv-absorber - Google Patents
Highly compatible and non-migratory polymeric uv-absorber Download PDFInfo
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- CN100482726C CN100482726C CNB2004800143550A CN200480014355A CN100482726C CN 100482726 C CN100482726 C CN 100482726C CN B2004800143550 A CNB2004800143550 A CN B2004800143550A CN 200480014355 A CN200480014355 A CN 200480014355A CN 100482726 C CN100482726 C CN 100482726C
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Abstract
The present invention relates to highly compatible hydroxyphenyltriazine UV-absorbers and to their use in organic polymers, especially for protecting the contents of transparent plastic packages such as pharmaceuticals, cosmetics, personal care products, shampoos and the like, and especially foodstuffs such as beverages, fresh vegetables or meat, from the deleterious effects of ultraviolet radiation. Especially advantageous is the combined use of a UV absorber and an oxygen scavenger. It has been found that certain highly compatible tris-aryl-s-triazines are especially effective towards this end when incorporated in the containers or films in which such materials are stored.
Description
Technical field
The present invention relates to the hydroxyphenyl-triazine UV light absorber of highly compatible, and relate to the organic polymer material that contains this UV light absorber, especially thermoplastic polymer film.The polymer materials that obtains like this can be used as packaging film, avoids the harmful effect of uv-radiation with the food, beverage, medicine, makeup, personal care product, shampoo etc. of protection packaging.It can be further used for protecting the plant in the greenhouse. the invention further relates to the method that prevents the photoxidation of packaging food by being used in combination of UV light absorber and oxygen scavenqer. have been found that to be used for storage be effective especially like this in some container of material or the film time to some triaryl-s-triazine when mixing. and compound of the present invention is more effective being used for the cosmetic formulations that human (or animal) skin of protection avoids the uv-radiation injury.
Background technology
In addition, a lot of wrapped products are some fruit juice, soft drink, beer, grape wine, foodstuff products, milk series products, makeup, shampoo, VITAMIN and medicine for example, when using the packaged with plastic container that allows ultraviolet (uv) transmission, can be subjected to harmful effect because of the influence of such light and promptly degrade.
It is well-known that UV light absorber is used to protect the purposes of bottle and film content.Yet, the tendency of using transparent or light container is arranged now.The aesthetic container that makes us pleasing more can be from also allowing the people see that the transparent plastics of content forms. unfortunately, transparent and light container and film allow the interior light transmission of the promptly about 280～about 400nm scope of UV-light of signal portion. and then, favor the more more tendency of thin-walled pressure vessel of lightweight thereby have at present.Thin-walled pressure vessel is because light path is shorter thereby will allow more UV-light to pass through. because these tendencies of packing aspect, thereby more high efficiency UV light absorber need be used in this field.
Now, a lot of cooking oil and salad oil provide with clear PET [(ethylene glycol terephthalate)] packing. in fact all vegetables oil or kind subsystem oil for example soybean oil, sweet oil, Thistle oil, Oleum Gossypii semen and Semen Maydis oil all contain the unsaturated olefin(e) acid or the ester (for example linoleate) of different levels, photo-induced degraded easily takes place in these.Most of departments of botany oils also contains natural chlorophyll or other pigment photosensitizers.Pascall etc., J.Food Sci.,
60(5), 1116 (1995) use is disclosed
326 to mix the co-extrusion multi-layer polypropylene be soybean oil ultraviolet protection in the container.
The 326th, a kind of benzotriazole UV absorbers, i.e. 5-chloro-2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-2H-benzotriazole can be available from Ciba SpecialtyChemicals Corp.
WO 03/004557 has described among the good hydroxyphenyl-triazine UV light absorber .WO 01/57124 of some persistence in polyolefin film and has also mentioned plastic containers or the film that contains durable UV absorbers.
This hydroxyphenyl-triazine UV light absorber demonstrates excellent compatibility and persistence in various plastic materials; and protect these materials not to be subjected to ultraviolet harmful effect. simultaneously, these UV light absorber provide high-level efficiency and the selectivity ultraviolet ray barrier in greenhouse film, window sheet material and the wrapping material.Because extremely long alkyl segment, thereby they are highly compatibles with a lot of polymkeric substance, thus allow to mix comparatively high amts UVA. they be heat-staple, and can from polymkeric substance, not ooze out, this point is important when contacting with Foods or drinks.
Summary of the invention
The present invention relates to the oligomer ester or the polyester of formula (I)
-[A-O-D-O]
x- (1)
In the formula
X is 1～50 number
A is the group of formula (II)
One of or the implication that provides for T;
D is C
4-C
12Alkylidene group perhaps has the OH replacement or has O insertion or existing OH to replace the described alkylidene group that also has O to insert;
L is C
1-C
18Alkylidene group; C
5-C
12Cycloalkylidene; C
3-C
18Alkylene group; Phenyl, C are perhaps arranged
7-C
11Alkyl phenyl, C
5-C
12Cycloalkyl; OH, halogen, C
1-C
18Alkoxyl group, C
5-C
12Cycloalkyloxy, C
3-C
18One of described residue that alkenyloxy, COOH replace;
Each R
1Be H, OR independently of one another
7Or OH, prerequisite is R
1Or R
13In at least one is OH;
Each R
7Be H, C independently of one another
1-C
12Alkyl or formula-L-CO-O-R
9Group;
R
9Be H, C
1-C
18Alkyl, C
2-C
12Hydroxyalkyl;
R
10Be H, C
1-C
4Alkyl, Cl, phenyl or group-OR
7
R
11Be H or methyl;
R
13Be H, methyl, OH or OR
7With
T is the aliphatics of 13～60 carbon atoms or cycloaliphatic dicarboxylic acid's divalence acyl group;
With contain at least one formula (II) segment and at least one T segment person.
In a kind of compound preferably, L is C
1-C
4Alkylidene group, C especially
2-C
4Inclined to one side alkylidene group or methylene radical.
D is C advantageously
4-C
12Alkylidene group or the C that has O to insert
4-C
10Alkylidene group.
T as the aliphatics of 13～60 carbon atoms or cycloaliphatic dicarboxylic acid's divalence acyl group comprises, for example, the aliphatics diacyl, wherein 2 carbonyls are by C
11-C
58Alkylidene group or alkenylene, the alkylidene group that perhaps has cycloalkylidene or inferior cycloalkenyl group to insert, wherein each all is that nothing replaces or has alkyl to replace, and contain 11～58 carbon atoms, better 20～50 carbon atoms altogether. alkylidene group or alkenylene can be branching or do not have branching, or better do not adjoin alkene double bond, aerobic inserts. in compound preferably, T is-CO-T '-CO-that T ' is C in the formula
20-C
50Alkylidene group or the C that has one or more Sauerstoffatoms to insert
20-C
50Alkylidene group; That especially good is the C of no branching
20-C
50Alkylidene group.Further preferably in the compound, T is-CO-T '-CO-that T ' has C in the formula
5-C
12Cycloalkylidene or C
5-C
12Inferior cycloalkenyl group or described cycloalkylidene that alkyl replaces is arranged or inferior cycloalkenyl group inserts and contains altogether 11～58 carbon atoms, the alkylidene group of 20～50 carbon atoms especially; Good especially cycloalkylidene is a cyclohexylidene; Good especially inferior cycloalkenyl group is a phenylidene. valuable spacer groups T ' is all groups suc as formula IX.
R in the formula
20Be-(C
bH
2b)-, R
21Be-(C
cH
2c)-, and R
22, R
23And R
24Be respectively-(C
dH
2d)-H ,-(C
eH
2e)-H and-(C
fH
2f)-H, the scope of a is 0～7 in the formula, and the scope of each all is 0～20 among index b～f, its condition is that the scope of a+b+c+d+e+f sum is 15～45.
Or the group of formula X
R in the formula
25And R
26Each all is C
1-C
18Alkylidene group, R
27, R
28, R
29And R
30In each all is H or C independently
1-C
18Alkyl, and R
29And R
30Lumping together also can be a chemical bond, and its condition is that the total number of carbon atoms scope is 20～50. among the formula X
That special technical significance is arranged is the spacer groups T ' of formula X, R in the formula
25And R
26Be the alkylidene group of 4～12 carbon atoms independently, R
27And R
28In each all is C independently
4-C
12Alkyl, and R
29And R
30Be hydrogen.
The diacid that is suitable for can, for example, the dimerization by a kind of monounsaturated fatty acids and a kind of two unsaturated fatty acidss obtains; The product that contains the cycloalkenyl group structure can be used as it is or better carried out hydrogenation before being used for this compound; Under latter event, the diacid of hydrogenation is open chain (" alkylidene group ") type compound and the mixture that has inserted the compound of cycloalkylidene often.The example for preparing diacid from lipid acid A and B provides following scheme:
In the compound of formula I of the present invention, best is
R
1Be OH;
R
7Be hydrogen or methyl;
R
10Be hydrogen, methyl or group-OR
7
R
11Be hydrogen;
R
13Be hydrogen, OH or methyl.
The oligopolymer of formula (I) or the end group of polymkeric substance normally-O-D-OR
12, or (formula I left side) is-OR when with the A bonding
12, or-A-OR
12For example-T '-COOR
12Or-[formula II]-OR
12, or (formula I right side) is-R when with the O bonding
12, R wherein
12Be H or C
1-C
8Alkyl.
For example, the ester of formula (I) can meet formula (III).
X is 1～20 number in the formula;
Y be at least 1 and scope for (x+z-1)～(x+z+1);
Z is 1～20 number; And
R
8Be hydrogen, C
1～C
12Alkyl; C
5～C
12Cycloalkyl; C
2～C
12Alkenyl; Phenyl; C
7～C
11Alkyl phenyl; The C that has phenyl, OH, halogen to replace
1～C
12Alkyl; C
1～C
18Alkoxyl group, C
5～C
12Cycloalkyloxy, C
3～C
18Alkenyloxy or COOH; Especially hydrogen or C
1～C
4Alkyl;
R
12Be hydrogen or C
1～C
8Alkyl;
R
18Be hydrogen or C
1～C
4Alkyl;
D is C
4～C
8Alkylidene group or the C that has O to insert
4～C
10Alkylidene group; And T ' is C
20～C
50Alkylidene group or the C that has one or more Sauerstoffatom to insert
20～C
50Alkylidene group;
And all other symbols are all with the definition with following formula I.
T ' has C
5～C
12Cycloalkylidene or have described cycloalkylidene that alkyl replaces especially cyclohexylidene insert and contain the alkylidene group of 20～50 carbon atoms altogether.
In the oligomer ester or polyester of formula (III), by each all is bonded to last and/or be bonded to end group R by the structural unit-O-D-of index y sign in the divalence structural unit of index x and z sign
12Or OR
12On.
In the compound of formula (I), x better is 2～50 scope, be more preferably 2～20 scope, especially 4～12; The triazine segment number of formula II better is about 1: 3～about 10: 1, better about 1: 1～about 5: 1 with the scope of the ratio of diacid residues T.In the compound of formula (III), the scope of each is preferably 1～16 among x and the z; Better, the scope of x be 1～10 and the scope of z be 2～12.
Oligomer ester of the present invention or poly-vinegar, for example those of formula I or III have the molecular weight (with the number-average molecular weight Mn of gel permeation chromatography GPC mensuration) in 1000～50000g/mol, better 1500～20000g/mol, the best 2000～10000g/mol scope usually.
Alkyl phenyl is the phenyl that has alkyl to replace; C
7-C
14Alkyl phenyl is contained following example: aminomethyl phenyl (tolyl), and 3,5-dimethylphenyl (xylyl), trimethylphenyl (
Base), ethylphenyl, propyl group phenyl, butyl phenyl, dibutyl phenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl and octyl phenyl.
Phenylalkyl is the alkyl that has phenyl to replace; C
7-C
11Phenylalkyl is contained following example: benzyl, α-Jia Jibianji, α-Ethylbenzyl, α, α-Er Jiajibianji, styroyl, hydrocinnamyl, benzene butyl and benzene amyl group.
The alkyl that has O to insert generally can comprise one or more non-Sauerstoffatoms that adjoin. and better, alkylidene chain is a carbon atom and no more than 1 the heteroatoms bonding of D or T ' for example.
In the scope of described definition, this alkyl is alkyl branching or that do not have branching, methyl for example, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, the 2-ethyl-butyl, n-pentyl, isopentyl, the 1-methyl amyl, 1, the 3-dimethylbutyl, n-hexyl, 1-methyl hexyl, n-heptyl, different heptyl, 1,1,3, the 3-tetramethyl butyl, the 1-methylheptyl, the 3-methylheptyl, n-octyl, the 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 and octadecyl.
The alkylidene group of L or D etc. is by capturing a hydrogen atom deutero-from such alkyl.
In the scope of described definition, this alkenyl comprises allyl group, pseudoallyl, crotyl, 3-butenyl, isobutenyl, positive penta-2,4-dialkylene, 3-methyl but-2-ene base, positive oct-2-ene base, positive 12 carbon-2-thiazolinyl, different dodecenyl succinic, positive 18 carbon-2-thiazolinyl and positive moroctic acid-thiazolinyl.
The heavy chain of T, for example the alkylidene group of T ' has certain molecular distribution around its principal constituent.Scope can be, for example 22-26,28-32 or 34-38C atom.Yet, also possiblely be, use wideer scope, for example 20-40,30-50 or 30-40C atom, each all is the total number of carbon atoms of T '.
Since formula (I) or (III) the compound educt be commerical prod, thereby they can change in some specification. specifically, when T is C
20-C
60During alkylidene group (this alkylidene group can have insertion as the above), the situation of the high molecular diacid of this T group that is used for deriving comes to this.
Commercial diacid that gets or two acid esters also can contain a small amount of C
20Following chain.Therefore, the mixture of compound, wherein T can reach two following acyl chains of 10% 20C atom and 90～100% 20～60 carbon atom, the mixture of two acyl chains of 20～40 carbon atoms especially a kind of containing, and also is problem of the present invention. and percentage is to be the weight percent of benchmark with the total mixture.
Formula (I) and compound (III) or its precursor can be similar to WO 03/004557 or the publication wherein mentioned (for example, EP-A-434,608, H.Brunelti and C.E.L ü thi, Helv.Chim.Acta55,1566 (1972), US-3118887, EP-A-165608) method described in prepares like that.
The preparation of formula (I) or (gathering) ester (III) is advantageously from containing 2 carboxylic acid groups or its suitable derivative for example acid chloride group, anhydride group or the triaryl piperazine of ester group especially.Such educt or its homologue see for details, among others, US-4826 978, US-5736597 (seeing for example the 11st～13 hurdle), US-5686233, US-5959008 (seeing that for example the 30th hurdle the 35th row is until the 31st hurdle the 11st row), and the further educt of same type for example aliphatics, cyclic aliphatic or aromatic dicarboxylic acid or its contain the derivative of group T.For esterification, the dicarboxylic acid educt is better according to the glycol HO-D-OH reaction of known method and an amount of for example 0.9～1.1mol/mol dicarboxyl or equimolar amount in the industry; Glycol comprises ethylene glycol, glycerine, various polyoxyethylene glycol preferably, or the α of various different chain length, the alpha, omega-dihydroxy alkane, for example butyleneglycol, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, undecane glycol, dodecanediol, tridecane glycol, pentadecane glycol, octadecandiol, eicosane glycol, and composition thereof.For example solvent (for example aliphatics alcohols, ethers of further composition can be added or do not added to the carrying out of reaction, aromatic hydrocarbon based or halogenated hydrocarbon such as chlorobenzene, or solvent mixture) or catalyzer such as transesterification catalyst such as inorganic or organic (Louis's type or Bronsted type) acid or alkali.Under the situation of not using added solvent, the educts such as suitable esters of glycol or dicarboxylic acid can excessively use, and serve as solvent simultaneously.Temperature and pressure is very unimportant usually, and therefore, reaction is usually-5 ℃～200 ℃, the temperature in 10～170 ℃ of scopes and approach 1 normal atmosphere, for example 10 for example
4～about 10
6The pressure of Pa, have or the existence of anaerobic under, for example under nitrogen or argon gas, carry out.
The present invention also relates to triaryl triazine and formula R by making formula V
12-O-T-O-R
12Compound and glycol HO-D-OH the reaction oligomer ester or the polyester that obtain.
Y is CO in the formula, and all other symbols are with above definition.
The present invention also relates to a kind of composition that protects the uv-radiation infiltration, comprise
(a) a kind of organic polymer material, for example the synthesising thermoplastic copolymer and
(b) at least a formula (I) compound or its mixture.
A further problem of the present invention is a kind of transparent plastic container or film that can protect the harmful effect of uv-radiation, and the latter comprises
(a) a kind of transparent for example limpid or light plastics and
(b) at least a formula (I) compound or its mixture.
The definition of formula (I) compound and preference are as above given.
The example of container is bottle, box, bubble or cup, and these can be with thick-wall materials or for example use diaphragm seal. this container can be a transparent or partially transparent fully; Under these circumstances, formula I compound of the present invention is present in this transparent part usually at least, for example the film envelope of the colored cup of pigment.Commercial examples with such container package comprises food and drink, makeup, medicine and pharmaceutical preparation etc.
Especially under the situation of greenhouse film, the present composition can further contain for example composition (b) of disclosed composition among the EP-A-1413599 of growth stimulant, can adopt formula I compound of the present invention as the UVA in these systems (the composition C1 of EP-A-1413599) simultaneously.
These compounds can be used for can be used to making the plastic material of the many types of container, sheet material, film and woven fabric or supatex fabric. and example is listed below.
1. the polymkeric substance of monoolefine and diolefine, polypropylene for example, polyisobutene, poly-but-1-ene, poly--4-methylpent-1-alkene, polyvinyl eyclohexane, polyisoprene or polyhutadiene, and the cycloolefin polymkeric substance of cyclopentenes or norbornylene for example, polyethylene (randomly can be crosslinked), for example high density polyethylene(HDPE) (HDPE), high-density and High molecular weight polyethylene (HDPE-HMW), high-density and ultrahigh molecular weight polyethylene(UHMWPE) (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), LLDPE (LLDPE), very new LDPE (film grade) (VLDPE) and ultra-low density polyethylene (ULDPE).
Polyolefine, i.e. the monoolefine polymer enumerated of the preceding paragraph, better polyethylene and polypropylene, can use different methods, especially prepare in order to the below method:
A) radical polymerization (under high pressure, high temperature, carrying out usually).
B) catalyzed polymerization of use catalyzer, this catalyzer contains a kind of or more than a kind of metal of periodic table of chemical element IVb family, Vb family, VIb family or VIII family usually.These metals have one or a more than part usually, oxide compound, halogenide, alcoholate, ester, ether, amine, alkyl, alkenyl and/or aryl typically, and these can be π coordination or σ coordinate.These metal complexs can be free form or be fixed on the base material, typically are fixed on active magnesium chloride, titanium chloride (III), aluminum oxide or the silicon oxide. and these catalyzer can dissolve in or be insoluble in the polymerisation medium.These catalyzer can self be used for polymerization, also can further use activator, metal alkyl, metal hydride, metal alkyl halides, metal alkyl oxide compound or metal alkyl oxygen alkane typically, described metal is the element of periodic table of chemical element Ia family, IIa family and/or IIIa family.These activators can be easily with further ester group, ether, amido or the modification of silicomethane ether.These catalyst systems are commonly referred to Phillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), metallocenes or single site catalysts (SSC).
2. the 1st mixture of polymers of mentioning, for example, the mixture of polypropylene and polyisobutene, polypropylene and poly mixture (for example PP/HDPE, PP/LDPE) and dissimilar poly mixture (for example LDPE/HDPE).
Monoolefine and diolefine each other multipolymer or with the multipolymer of other vinyl monomer, for example ethylene/propene copolymer, LLDPE (LLDPE) and with the mixture of new LDPE (film grade) (LDPE), propylene/but-1-ene multipolymer, propylene/isobutylene copolymers, ethene/but-1-ene multipolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, ethylene/vinyl basic ring hexane multipolymer, ethene/cyclic olefine copolymer (for example ethene/norbornylene such as COC), ethene/1-olefin copolymer (wherein 1-alkene is that original position takes place), propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/vinyl basic ring hexene copolymer, the ethylene/acrylic acid alkyl ester copolymer, the ethylene/methacrylic acid alkyl ester copolymer, ethylene, or ethylene/acrylic acid copolymer and salt (ionomer) thereof and ethene and propylene and a kind of diene hexadiene for example, the terpolymer of dicyclopentadiene or inclined to one side ethylidene norbornene; Such multipolymer each other mixture and with above the 1st mixture of polymers of mentioning, for example polypropylene/ethylene-propylene copolymer, LDPE/ vinyl-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and alternately or random polyalkylene/carbon monoxide multipolymer and with other polymkeric substance mixture of polymeric amide for example.
4. hydrocarbon resin (C for example
5-C
9), comprise the mixture of its hydrogenation modification thing (for example tackifier) and polyolefine and starch.
The 1st～the 4th homopolymer and multipolymer can have any three-dimensional arrangement, comprise syndiotaxy, isotaxy, half isotaxy or atactic; Wherein, nonstereospecific polymer is preferably.Also comprise the stereoblock multipolymer.
5. polystyrene gathers (p-methylstyrene), poly-(alpha-methyl styrene).
6. aromatic series homopolymer and multipolymer, derived from ethylene base aromatic monomer, all isomer that comprise vinylbenzene, alpha-methyl styrene, Vinyl toluene are especially to Vinyl toluene, all isomer of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene and vinyl anthracene, and composition thereof.Homopolymer and multipolymer can have any three-dimensional arrangement, comprise syndiotaxy, isotaxy, half isotaxy or atactic; Wherein, nonstereospecific polymer is preferably.Also comprise stereoblock polymer.
6a. multipolymer, comprise above-mentioned vinyl aromatic monomers and be selected from following comonomer: ethene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl-acetic ester and vinylchlorid or acrylic acid derivative and composition thereof, for example phenylethylene/butadiene, styrene/acrylonitrile, styrene/ethylene (multiple copolymer), styrene/methacrylic acid alkane ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; High impact strength of styrene multipolymer and another kind of polymkeric substance be the mixture of polyacrylic ester, diene polymer or ethylene/propene/diene terpolymer for example; With styrene block copolymer for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
6b hydrogenation aromatic polymer, the hydrogenation derived from the 6th polymkeric substance of mentioning especially comprises the random isotactic polystyrene hydrogenation preparing, the be commonly referred to polyvinyl eyclohexane poly-cyclohexyl ethene (PCHE) of (PVCH).
6c. the hydrogenation aromatic polymer, the hydrogenation of polymer of mentioning derived from the 6a item.
Homopolymer and multipolymer can have any three-dimensional arrangement, comprise syndiotaxy, isotaxy, half isotaxy or atactic; Wherein nonstereospecific polymer is preferably.Also comprise stereoblock polymer.
7. for example graft copolymer of vinylbenzene or alpha-methyl styrene, for example vinylbenzene/polyhutadiene, vinylbenzene/Polybutadiene-styrene or polybutadiene-acrylonitrile copolymer of vinyl aromatic monomers; Vinylbenzene and vinyl cyanide (or methacrylonitrile)/polyhutadiene; Vinylbenzene, vinyl cyanide and methyl methacrylate/polyhutadiene; Vinylbenzene and maleic anhydride/polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide/polyhutadiene; Vinylbenzene and maleimide/polyhutadiene; Vinylbenzene and alkyl acrylate or alkyl methacrylate/polyhutadiene; Vinylbenzene and vinyl cyanide/ethylene-propylene-diene terpolymer; Vinylbenzene and vinyl cyanide/polyacrylic acid alkane ester or polymethyl acrylic acid alkane ester, vinylbenzene and vinyl cyanide/acrylate-butadienecopolymer, with and with the mixture of the 6th multipolymer of enumerating, for example, be known as the copolymer mixture of ABS, MBS, ASA or AES polymkeric substance.
8. polymer containing halogen, for example multipolymer, Epicholorohydrin homopolymer and the multipolymer of the isobutylene-isoprene copolymer of sovprene, chlorinated rubber, chlorination and bromination (halobutyl rubber), chlorating or sulphur chlorating polyethylene, ethene and ethylene chloride, the polymkeric substance of especially halogen-containing vinyl compound, for example polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride), with and multipolymer, for example vinylchlorid/vinylidene chloride, vinylchlorid/vinyl-acetic ester or vinylidene chloride/vinyl acetate copolymer.
9. from α, beta-unsaturated acid and derivative derived polymers thereof, for example polyacrylic ester and polymethacrylate; Polymethylmethacrylate (PMMA), polyacrylamide and polyacrylonitrile, it uses the impact modified person of butyl acrylate.
The 9th monomer of mentioning, each other or with the multipolymer of other unsaturated monomer, for example acrylonitrile/butadiene multipolymer, vinyl cyanide/alkyl acrylate ester copolymer, vinyl cyanide/alkyl acrylate oxyalkyl ester or vinyl cyanide/halogen ethylene copolymer or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.
11. how unsaturated alkohol and amine or acyl derivative or its acetal derived polymers, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, polyvinyl butyral acetal, poly-O-phthalic allyl propionate or polyene propyl group melamine; Ethylene-vinyl alcohol copolymer (EVOH); With and with the multipolymer of above the 1st alkene of mentioning.
12. the homopolymer of cyclic ether and multipolymer, for example multipolymer of polyalkylene glycol, polyethylene oxide, poly(propylene oxide) or itself and two (epoxypropyl) ether.
13. polyacetal for example polyoxymethylene contains the polyoxymethylene of oxyethane as comonomer with those; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.
14. the mixture of polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide.
15. from the one hand for have polyethers, polyester or the polyhutadiene of C-terminal and on the other hand for aliphatics or aromatic polyisocyanate with and precursor-derived urethane.
16. from diamines and dicarboxylic acid and/or from the polymeric amide and the copolyamide of aminocarboxylic acid or corresponding lactam derivative, 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, from the aromatic polyamide of m-xylene diamine and hexanodioic acid; From hexamethylene-diamine and m-phthalic acid and/or terephthalic acid and have or nonelastic body as the polymeric amide of properties-correcting agent preparation, for example poly-paraphenylene terephthalamide-2,4,4-trimethylhexamethylenediamine or poly; Also have, above-mentioned polymeric amide and polyolefine, olefin copolymer, ionomer, chemical bonding the grafted elastomerics or with polyethers for example with the segmented copolymer of polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; And with the polymeric amide or the copolyamide of EPDM or ABS modification; Polymeric amide (RIM polymeric amide system) with condensation during the processing.
17. polyureas, polyimide, polyamide-imide, polyetherimide, polyester-imide, poly-beta-lactam and polybenzimidazole.
18. from dicarboxylic acid and glycol and/or from hydroxycarboxylic acid or corresponding lactone deutero-polyester, for example polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid-1,4-two (methylol) hexanaphthene ester, poly-naphthalic acid alkane diol ester (PAN), biodegradable poly-propyl ester and poly-hydroxybenzoate, and from the polyethers deutero-block copolyether ester of C-terminal is arranged; Also have, with the polyester of polycarbonate or MBS modification.
19. polycarbonate and polyestercarbonate.
20. polyketone.
21. polysulfones, polyethersulfone and polyetherketone.
22. the blend composition of above-mentioned polymkeric substance (alloyed polymer), for example PP/EPDM, 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/ABS or PBT/PET/PC.
The compounds of this invention can be used for plastic material many types, that can be used for making container, sheet material, film and woven fabric or supatex fabric.The better polymer materials that can be used for such as film or plastic containers is polyolefine, polyester, polyvinyl alcohol, poly-ethyl acetate or polycarbonate; Especially for food product packing film or container, best is polyethylene terephthalate (PET) and polyolefine, especially polyethylene (PE), polypropylene (PP), new LDPE (film grade) (LDPE), LLDPE (LLDPE), (VLDPE) and (ULDPE).For sheet material, better material is polycarbonate, polymeric amide, polyacrylate(s) or transparent ABS, polycarbonate especially.
Best is that composition of the present invention is a kind of plastic containers or film that is used as food or medical packaging material; Better, the thickness of this film is 10 μ m～200 μ m, better 20 μ m～80 μ m, and the thickness of plastic containers is that 200 μ m～1000 μ m. are better, is benchmark with the weight of plastic material, and formula (I) compound is to exist with 0.005%～10% quantity.
Better, this organic polymer material is a kind of plastic containers, film or sheet material, and wherein, this plastic material is transparent, and is for example limpid or light color.
Especially under the situation of polyester, this organic polymer material advantageously can contain a kind of additive that is used to reduce acetaldehyde (to be seen, for example, WO 01/02489, WO 01/23475, WO 02/53643, EP-A-1239006, WO 03/16401) and/or optical brightener (white dyes; Be similar to known system, see for example US-5985389, US-6166852).The optical brightener that is suitable among others, comprises for the known Stilbene class of this purposes, coumarins and two benzoxazole compounds, and among others can be in trade(brand)name
Under available from some manufacturerss; Compounds suitable for use is, for example, CAS NO.91-44-1 (4-methyl-7-diethylin tonka bean camphor), 53850-91-2 (3-phenyl-7-(4-methyl-6-butoxy benzo oxazole) tonka bean camphor), 5089-22-5,5242-49-9,3333-62-8,40470-68-6, especially 7128-64-5 (2,5-two (5-tertiary butyl benzo oxazole-2-yl) thiophene) and/or the compound of 1533-45-5 (4,4 '-two (benzoxazole-2-yl) Stilbene).
UV light absorber of the present invention also can be mixed optical lens or glasses for example in esters of acrylic acid glasses or the coating on it.For example sun glasses uses is polypropylene ester class or polycarbonate than good material for optical lens or glasses, especially polymethylmethacrylate (PMMA).
A kind of further important use be sun power control film or building glass (see, US-6166852 for example, US-6191199).
Better, the thickness of this sheet material can not wait at about 0.5～8mm (for example being used for real chip material)～about 3～100mm (for example being used for double-walled or multi-wall sheet).
Except that stablizer of the present invention, plastic material of the present invention also can comprise other stablizer or other additive, for example phenol antioxidant, bulky amine and/or phosphorous acid ester or phosphinate. below provide the example of further stablizer and additive.
1. antioxidant
1.1. alkylation monophenolFor example, 2, the 6-di-tert-butyl-4-methy phenol, the 2-tertiary butyl-4, the 6-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4, the 6-xylenol, 2,6-two (octadecyl)-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxyl methyl phenol, the nonylphenol of line style or branching on the side chain, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(phenol of 1 '-methyl undecane-1 '-yl), 2,4-dimethyl-6-(phenol of 1 '-methyl heptadecane-1 '-yl), 2,4-dimethyl-6-(phenol and composition thereof of 1 '-methyl tridecane-1 '-yl).
1.2. alkane thiomethyl phenol, for example, 2,4-two hot thiomethyl-6-tert.-butyl phenols, 2,4-two hot thiomethyl-6-ethylphenols, 2,6-two (dodecane thiomethyl)-4-nonylphenol.
1.3. quinhydrones and alkylation quinhydronesFor example, 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-two amyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-BHA, 3,5-di-t-butyl-4-BHA, stearic acid 3,5-di-t-butyl-4-hydroxylphenyl ester, hexanodioic acid two (3,5-di-t-butyl-4-hydroxylphenyl ester).
1.4. tocopherol, for example, alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and composition thereof (vitamin-E).
1.5. hydroxylation diphenyl sulfideFor example, 2,2 '-sulphur two (the 6-tertiary butyl-4-methylphenol), 2,2 '-sulphur two (4-octyl phenol), 4,4 '-sulphur two (6-tertiary butyl-3-methylphenol, 4,4 '-sulphur two (the 6-tertiary butyl-2-methylphenol), 4,4 '-sulphur two (3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulphide.
1.6. inclined to one side alkylidene group biphenolFor example, 2,2 '-methylene radical two (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene radical two (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene radical two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol], 2,2 '-methylene radical two (4-methyl-6-cyclohexylphenol), 2,2 '-methylene radical two (6-nonyl-4-methylphenol), 2,2 '-methylene radical two (4, the 6-DI-tert-butylphenol compounds), 2,2 '-partially ethylene (4, the 6-DI-tert-butylphenol compounds), 2,2 '-partially ethylene (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene radical two [6-(α-Jia Jibianji)-4-nonylphenol], 2,2 '-methylene radical two [6-(α, α-Er Jiajibianji)-the 4-nonylphenol], 4,4 '-methylene radical two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical two (the 6-tertiary butyl-2-methylphenol), 1,1 '-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 2,6-two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1,1-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-3-n-dodecane sulfenyl butane, two [3,3-two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric acid] glycol ester, two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) dicyclopentadiene, terephthalic acid two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the methyl-benzyl)-6-tertiary butyl-4-methyl phenyl ester], 1,1-two (3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propane, 2,2-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-n-dodecane sulfenyl butane, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.
1.7.0-, N-and S-benzyl compounds, for example, 3,5,3 ', 5 '-tetra-tert-4,4 '-dihydroxyl dibenzyl ether, 4-hydroxyl-3,5-dimethylbenzyl ethyl thioglycollic acid octadecane ester, 4-hydroxyl-3,5-di-t-butyl benzylthio-acetate tridecane ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, dithio terephthalic acid two (the 4-tertiary butyl-3-hydroxyl-2,6-dimethylbenzyl ester), sulfuration two (3, the 5-di-tert-butyl-4-hydroxyl benzyl), 3,5-di-t-butyl-4-hydroxyl benzylthio-2-ethyl hexyl ethanoate.
1.8. acrinyl malonic esterFor example, 2,2-two (3,5-di-t-butyl-2-hydroxybenzyl) propanedioic acid two (octadecane ester), 2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) propanedioic acid two (octadecane ester), 2,2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) propanedioic acid two (dodecane sulfenyl ethyl ester), 2,2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) [4-(1 for propanedioic acid two, 1,3, the 3-tetramethyl butyl) phenyl ester].
1.9. aromatic series acrinyl compound, for example, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, 1,4-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5,6-tetramethyl-benzene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol.
1.10. triaizine compounds, for example, 2,4-two (hot sulfenyl)-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1,3,5-triazines, the hot sulfenyl-4 of 2-, 6-two (3,5-di-t-butyl-4-hydroxybenzene amido)-1,3,5-triazines, the hot sulfenyl-4 of 2-, 6-two (3,5-di-t-butyl-4-hydroxyphenoxy)-1,3,5-triazines, 2,4,6-three (3,5-di-t-butyl-4-hydroxyphenoxy)-1,2, the 3-triazine, isocyanuric acid-1,3,5-three (3,5-di-t-butyl-4-hydroxyl benzyl ester), isocyanuric acid-1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethylbenzyl ester), 2,4,6-three (3,5-di-t-butyl-4-leptodactyline)-1,3, the 5-triazine, 1,3,5-three (3,5-di-t-butyl-4-hydroxybenzene propionyl) six hydrogen-1,3,5-triazines, isocyanuric acid-1,3,5-three (3,5-dicyclohexyl-4-hydroxyl benzyl ester).
1.11. benzylphosphonic acid esterFor example, 2,5-di-tert-butyl-4-hydroxyl benzyl dimethyl phosphonate, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids two (octadecane ester), 5-tertiary butyl-4-hydroxy-3-methyl-benzyl phosphonic acids two (octadecane ester), 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester calcium salt.
1.12. amide group phenol, for example, 4-hydroxy-n-lauroyl aniline, 4-hydroxy-n-stearanilide, N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
1.13. β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcoholEster, the example of alcohol comprises methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.14. β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcohol Ester,The example of alcohol comprises methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyl ethyl ester), N, N '
-Two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.15. β-(3,5-dicyclohexyl-4-hydroxy phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcohol Ester,The example of alcohol comprises methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.16.3, the ester of 5-di-tert-butyl-hydroxy phenyl acetate and monohydroxy-alcohol or polyvalent alcohol,The example of alcohol comprises methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.17. the acid amides of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid,For example, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hexamethylene-diamine, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) trimethylene diamines, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, N, N '-two [2-(3-[3,5-di-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxamide (
XL-1, Uniroya1 company).
1.18. xitix(vitamins C)
1.19. amine antioxidantsFor example, N, N '-di-isopropyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-two (1,4-dimethyl amyl group) Ursol D, N, N '-two (1-ethyl-3-methyl amyl) Ursol D, N, N '-two (1-methylheptyl) Ursol D, N, N '-dicyclohexyl Ursol D, N, N '-diphenyl-para-phenylene diamine, N, N '-two (2-naphthyl) Ursol D, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, N-(1-methylheptyl)-N '-diphenyl-para-phenylene diamine, N-cyclohexyl-N '-diphenyl-para-phenylene diamine, 4-(to the toluino sulphonyl) pentanoic, N, N '-dimethyl-N, N '-di-sec-butyl-p-phenyl enediamine, pentanoic, N-allyl group pentanoic, 4-isopropoxy pentanoic, the N-phenyl-1-naphthylamine, N-(uncle's 4-octyl phenyl)-naphthalidine, N-phenyl-2-naphthylamines, octylated diphenylamine, p for example, p '-two uncle octyl diphenylamine, 4-n-butylamine-based phenol, 4-amide-based small phenol, 4-nonanoyl aminocarbonyl phenyl, 4-dodecanoyl amino-phenol, 4-stearyl amido phenol, two (4-p-methoxy-phenyl) amine, 2,6-di-t-butyl-4-dimethylamino methyl phenol, 2,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, N, N, N ', N '-tetramethyl--4,4 '-diaminodiphenylmethane, 1,2-two [(2-aminomethyl phenyl) amino] ethane, 1,2-two (anilino) propane, (o-tolyl) biguanides, two [4-(1 ', 3 '-dimethylbutyl) phenyl] amine, uncle's octyl group N-phenyl-1-naphthylamine, the mixture of one alkylation and the dialkyl group tertiary butyl/uncle's octyl diphenylamine, the mixture of one alkylation and dialkyl group nonyl diphenylamine, the mixture of one alkylation and dialkyl group dodecyl diphenylamine, the mixture of one alkylation and dialkyl group sec.-propyl/isohexyl pentanoic, the mixture of one alkylation and dialkyl group tertiary butyl pentanoic, 2,3-dihydro-3,3-dimethyl-4H-1, the 4-benzothiazine, thiodiphenylamine, the mixture of one alkylation and the dialkyl group tertiary butyl/uncle's octyl group thiodiphenylamine, the mixture of one alkylation and dialkyl group uncle octyl group thiodiphenylamine, N-allyl group thiodiphenylamine, N, N, N ', N '-tetraphenyl-1,4-diamino but-2-ene, N, N-two (2,2,6,6-tetramethyl piperidine-4-yl) hexamethylene-diamine, sebacic acid two (2,2,6,6-tetramethyl piperidine-4-ester), 2,2,6,6-tetramethyl piperidine-4-ketone, 2,2,6,6-tetramethyl piperidine-4-alcohol.
2. UV light absorber and photostabilizer
(2.12-2 '-hydroxy phenyl) benzotriazole categoryFor example, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole phenyl), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two (α, α-Er Jiajibianji)-2 '-and hydroxy phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different hot oxygen carbonyl ethyl of 2-) phenyl) benzotriazole, 2, [4-(1 for 2 '-methylene radical two, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol]; The 2-[3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl]-ester exchange offspring of 2H-benzotriazole and Liquid Macrogol; [R-CH
2CH
2-COO-CH
2CH
2]
2, R=3 ' in the formula-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base phenyl, 2-[2 '-hydroxyl-3 '-(α, α-Er Jiajibianji)-5 '-(1,1,3, the 3-tetramethyl butyl) phenyl] and benzotriazole; 2-[2 '-hydroxyl-3 '-(1,1,3, the 3-tetramethyl butyl)-5 '-(α, α-Er Jiajibianji) phenyl] benzotriazole.
2.2.2-hydroxy benzophenone ketone, for example, 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-dimethoxy derivative.
2.3. replacement and benzoic ester that do not have to replace are arrangedFor example, Whitfield's ointment 4-tertiary butyl phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinol, two (4-tert.-butylbenzene formyl) Resorcinol, benzoyl Resorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-t-butyl phenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid n-Hexadecane ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecane ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-t-butyl phenyl ester.
2.4. esters of acrylic acidFor example, alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl p-methoxycinnamic acid methyl esters, alpha-cyano-Beta-methyl p-methoxycinnamic acid butyl ester, α-methoxycarbonyl p-methoxycinnamic acid methyl esters and N-(beta-carbomethoxy-3-beta-cyano vinyl)-2 methyl indole.
2.5. nickel compound classFor example, 2, [4-(1 for 2 '-sulphur two, 1,3, the 3-tetramethyl butyl) phenol] nickel complex, for example 1: 1 or 1: 2 complex compound, and have or do not have other part such as n-Butyl Amine 99, trolamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamate, 4-hydroxyl-3, single alkane ester of 5-di-t-butyl benzylphosphonic acid be the nickel salt of methyl esters or ethyl ester for example, the nickel complex of ketoxime, as the nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketoxime, the nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazoles and have or do not have other part.
2.6. steric hindrance amine, for example, sebacic acid two (2,2,6,6-tetramethyl--4-piperidines ester), succsinic acid two (2,2,6,6-tetramethyl--4-piperidines ester), sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidines ester), sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidines ester), normal-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidines 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 4-tert-Octylamine base-2,6-two chloro-1,3, the line style of 5-triazine or ring-shaped condensate, nitrilotriacetic acid(NTA) three (2,2,6,6-tetramethyl--4-piperidines ester), 1,2,3,4-BTCA four (2,2,6,6-tetramethyl--4-piperidines ester), 1,1 '-(1,2-second two bases) two (3,3,5,5-tetramethyl-piperazine ketone), 4-benzoyl-2,2,6, the 6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine, 2-normal-butyl-2-(2-hydroxyl-3,5-di-t-butyl benzyl) propanedioic acid two (1,2,2,6,6-pentamethyl-piperidines ester), 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2, the 4-diketone, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl piperidine ester), succsinic acid two (1-octyloxy-2,2,6,6-tetramethyl piperidine ester), N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2,6-two chloro-1,3, the line style of 5-triazine or ring-shaped condensate, 2-chloro-4,6-two (4-n-butylamine-based-2,2,6, the 6-tetramethyl-piperidyl)-1,3,5-triazines and 1, the condenses of 2-two (the amino Propylamino of 3-) ethane, 2-chloro-4,6-two (4-n-butylamine-based-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazines and 1, the condenses of 2-two (the amino Propylamino of 3-) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2, the 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, the stearic oxygen base-2 of 4-n-Hexadecane oxygen base and 4-, 2,6, the mixture of 6-tetramethyl piperidine, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-cyclohexylamino-2,6-two chloro-1,3, the condensation product of 5-triazine, 1,2-two (the amino Propylamino of 3-) ethane and 2,4,6-three chloro-1,3,5-triazine and 4-butylamine base-2,2,6, the condensation product of 6-tetramethyl piperidine (CAS accession number [136504-96-6]); N-(2,2,6,6-tetramethyl--4-piperidyl)-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-oxo spiral shell [4.5] decane, 7,7,9,9-tetramethyl--2-encircles undecyl-1-oxa--3, the reaction product of 8-diaza-4-oxo spiral shell [4.5] decane and Epicholorohydrin, 1,1-two (1,2,2,6,6-pentamethyl--4-piperidines oxygen carbonyl)-2-(4-p-methoxy-phenyl) ethene, N, N '-two formyls-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-4-(2,2,6,6-tetramethyl--4-piperidyl)] siloxanes, maleic anhydride/alpha-olefin copolymer and 2,2,6,6-tetramethyl--4-amino piperidine or 1,2,2,6, the reaction product of 6-pentamethyl--4-amino piperidine, 5-(2-ethyl hexanoyl) oxygen methyl-3,3,5-trimethylammonium-2-morpholone mai; Especially for the purposes in films such as greenhouse film, sebacic acid two (2,2,6,6-tetramethyl--4-piperidines ester) particularly importantly; Sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidines ester); 1-(2-hydroxyethyl)-2,2,6, the condenses of 6-tetramethyl--4-hydroxy piperidine and succsinic acid (CAS 65447-77-0); N, N ', N ", N " and '-four (4,6-two (butyl-(N-methyl-2,2,6,6-tetramethyl piperidine-4-yl) amino) triazine-2-yl)-4,7-diaza decane-1,10-diamines (CAS 106990-43-6);
N or n ' are mainly from 3～5 these scopes in the formula; Or the mixture of these compounds.
2.7. OxamidesFor example, 4,4 '-two octyloxies-N, N '-oxalyl pentanoic, 2,2 '-diethoxy-N, N '-oxalyl pentanoic, 2,2 '-two octyloxies-5,5 '-di-t-butyl-N, N '-oxalyl pentanoic, 2,2 '-two (dodecyloxy)-5,5 '-di-t-butyl-N, N '-oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl-N, N '-oxalyl pentanoic, N, N '-two (3-dimethylamino-propyl) oxamide, 2-oxyethyl group-5-the tertiary butyl-2 '-ethyl-N, N '-oxalyl pentanoic and with 2-oxyethyl group-2 '-ethyl-5,4 '-di-t-butyl-N, the mixture of N '-oxalyl pentanoic, O-methoxy is arranged and to the dibasic N of methoxyl group, the mixture of N '-oxalyl pentanoic, with adjacent oxyethyl group is arranged and to the dibasic N of oxyethyl group, the mixture of N '-oxalyl pentanoic.
2.8. further 2-(2-hydroxy phenyl)-1,3,5-triazinesFor example, 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2, the 4-dihydroxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2,4-two (2-hydroxyl-4-propoxy-phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (4-aminomethyl phenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-[2-ethylhexyl] the oxygen phenyl)-4,6-two (4-phenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-[2-carbonyl in heptan oxygen base oxethyl] phenyl)-4,6-phenylbenzene-1,3, the 5-triazine, 2-[4-(dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-(2-ethylhexyl) oxygen) phenyl-4,6-two (4-phenyl)-1,3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl 3-dodecyloxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-hexyloxy phenyl)-4,6-phenylbenzene-1,3, the 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3,5-triazines, 2,4,6-three [2-hydroxyl-4-(3-butoxy-2-hydroxyl propoxy-) phenyl]-1,3,5-triazines, 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3, the 5-triazine, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen)-2-hydroxyl propoxy-] phenyl }-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine.
3. metal deactivators, for example, N, N '-phenylbenzene oxamide, N-salicylic aldehyde-N '-salicylyl hydrazine, N, N '-two (salicylyl) hydrazine, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, 3-salicylamide base-1,2,4-triazole, two (benzylidene partially) oxalyl two hydrazines, N, N '-oxalyl pentanoic, m-p-hthaloyl dihydrazide, sebacoyl biphenyl hydrazine, N, N '-diacetyl adipyl dihydrazide, N, N '-two (salicylyl) oxalyl two hydrazines, N, N '-two (salicylyl) sulfo-propionyl two hydrazines.
4. phosphorous acid ester and phosphiinic acid esterFor example, triphenyl phosphite, phosphorous acid diphenyl ester alkane ester, the phenyl-phosphite dialkyl, tricresyl phosphite (nonyl phenyl ester), trilauryl phosphite, tricresyl phosphite (octadecane ester), diphosphorous acid distearyl ester pentaerythritol ester, tricresyl phosphite (2,4-di-t-butyl phenyl ester), diphosphorous acid two isodecyl ester pentaerythritol esters, diphosphorous acid two (2,4-di-t-butyl phenyl ester) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-methyl phenyl ester) pentaerythritol ester, diphosphorous acid two isodecyl oxygen base pentaerythritol esters, diphosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) pentaerythritol ester, diphosphorous acid two (2,4,6-tri-tert phenyl ester) pentaerythritol ester, three tricresyl phosphite stearyl ester sorbitol esters, 4,4 '-biphenyl, two phosphonous acid four (2,4-di-t-butyl phenyl ester), 6-iso-octyl-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-two oxa-phosphocin, phosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) methyl esters, phosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) ethyl ester, 6-fluoro-2,4,8,10-tetra-tert-12-methyldiphenyl is [d, g]-1 also, 3,2-two oxa-phosphocin, 2,2, ' 2 "-nitrilo three [the phosphorous acid ethyl ester (3; 3 '; 5,5 '-tetra-tert-1,1 '-biphenyl-2; 2 '-diester]; and phosphorous acid 2-ethylhexyl (3; 3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-diester), 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-two oxa-phosphirane.
Good especially is following phosphorous acid ester:
Tricresyl phosphite (2,4-di-t-butyl phenyl ester (
168, Ciba-Geigy), tricresyl phosphite (nonyl phenyl ester),
5. azanol classFor example, N, N-dibenzyl hydroxylamine, N, N-diethyl hydroxylamine, N, N-dioctyl azanol, N, N-dilauryl azanol, N, N-two (tetradecyl) azanol, N, N-two (hexadecyl) azanol, N, N-two (octadecyl) azanol, N-hexadecyl-N-octadecyl azanol, N-heptadecyl-N-octadecyl azanol, from hydrogenation tallow amine deutero-N, N-dialkyl group azanol.
6. nitrone classFor example, N-benzyl-alpha-phenyl nitrone, N-ethyl-Alpha-Methyl nitrone, N-octyl group-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, from N derived from the hydrogenation tallow amine, N-dialkyl group azanol deutero-nitrone.
7. sulphur synergist, for example, thiodipropionic acid two lauryls or thiodipropionic acid distearyl ester.
8. peroxide scavenger classFor example, the ester of β-thiodipropionic acid such as lauryl, stearyl ester, myristin or tridecane ester, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, curing two (octadecyl), four (β-dodecane thiohydracrylic acid) pentaerythritol ester.
9. polymeric amide stablizer, for example, with iodide and/or the mantoquita of phosphorus compound combination and the salt of bivalent manganese.
10. alkaline auxiliary stablizerFor example, for example calcium stearate, Zinic stearas, docosoic magnesium, Magnesium Stearate, natrium ricinoleicum and potassium palmitate, pyrocatechol antimony or pyrocatechol zinc of an alkali metal salt of melamine, Polyvinylpyrolidone (PVP), Dyhard RU 100, triallyl cyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, higher fatty acid and alkaline earth salt.
11. nucleating agent, for example, phosphoric acid salt, carbonate or the vitriol of inorganic substance such as talcum, metal oxides such as titanium dioxide or magnesium oxide, better alkaline-earth metal; Organic compound is monocarboxylic acid or poly carboxylic acid and salt thereof for example, 4-p t butylbenzoic acid, hexanodioic acid, diphenyl acetic acid, sodium succinate or Sodium Benzoate; Polymer compound is ionic multipolymer (ionomer) for example. and good especially is 1,3: 2,4-two (3 ', the inclined to one side benzylidene of 4 '-dimethyl) Sorbitol Powder, 1,3: 2,4-two (to methyl two inclined to one side benzylidenes) Sorbitol Powder and 1,3: 2,4-two (benzylidene partially) Sorbitol Powder.
12. filler and toughener, for example, the powder of lime carbonate, silicate, glass fibre, glass sphere, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, wood powder, other natural product or fiber, synthon.
13. other additive, for example, oxygen absorbent, acetaldehyde scavenger, softening agent, processing aid, lubricant, emulsifying agent, finings, pigment, rheological additives, catalyzer, flow control agent, optical brightener, fire retardant, static inhibitor and whipping agent.
14. benzofuranone and dihydroindole ketone, for example, U.S.4,325,863; U.S.4,338,244; U.S.5,175,312; U.S.5,216,052; U.S.5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; Those disclosed among EP-A-0589839 or the EP-A-0591102, or 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-t-butyl benzo furans-2-ketone, 5,7-di-t-butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl] benzofuran-2-ones, 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones], 5,7-di-t-butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones, 3-(4-acetoxy-3, the 5-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone, 3-(3,5-dimethyl-4-new pentane acyloxy phenyl)-5,7-di-t-butyl benzo furans-2-ketone, 3-(3, the 4-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone, 3-(2, the 3-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone.
The kind of the further stablizer that is added and quantity are decided by the kind and the purpose purposes thereof of base material that will be stable; To want stable polymer is benchmark, uses 0.01～5wt% under many circumstances.
What certain technical significance was arranged is to add for example fluoroelastomer of a kind of processing aid, this can prevent during the cast-film extrusion or sedimental afterwards formation. for the weight of base polymer (for example polyethylene), and the addition of these processing aids often 0.1～2%, typically 0.2～1%.Therefore, the typical LLDPE according to the present invention's preparation except that formula I compound, also contains the 500ppm fluoroelastomer of having an appointment, for example
FX9614 (can available from 3M company).
These plastic containers or film also can contain a kind of oxygen absorbent extraly, especially a kind of iron is that additive is as oxygen absorbent (oxygen scavenqer).
Have been found that the freshness that is sealed in the food in the transparent food packing of using oxygen absorbent can unexpectedly be improved when this transparent packaging material contains UV light absorber.In normal atmosphere or (use for example nitrogen of vacuum or rare gas element; carbonic acid gas; argon gas) reduces after the following packing of modified atmospheres and airtight sealing of oxygen partial pressure; this scavenging agent works; make the oxygen partial pressure of this moment be reduced to harmless level. because of the oxygen absorbent type that is adopted; temperature; parameters such as packing measurement and different; typically continue some hrs this inductive phase to some days; oxidising process during this period; especially fast photooxidation reaction may continue to change the character of food. by the major part with the blocking-up of the UV light absorber in transparent vessel wall UV-light, the protection gap during just can preventing photoxidation and making this inductive phase up.Fruits and vegetables, especially fresh provisions for example meat, fish, the milk product etc. of high protein and/or lipid content just can keep the longer time and keep better quality and outward appearance on shelf.
Therefore, a further theme of the present invention is a kind of sealing food packing or container, comprises a kind of transparent, especially limpid or light sheet material or film of making from plastic material, it is characterized in that
A) this plastic material contain UV light absorber and
B) this packing further comprises oxygen scavenqer.
UV light absorber in this plastic material is selected from hydroxyphenyl-S-triazines class, 2-(2 '-hydroxy phenyl) benzotriazole category, 2-hydroxy benzophenone ketone and composition thereof, for example above 2.1 joints, 2.2 joints and cited compound and the formula of the present invention (I) of 2.8 joints; Good especially is for example above-described formula of hydroxyphenyl-S-triazines class (I) compound, and following compounds
2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole,
2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorobenzotriazole,
2-(2-hydroxy-5-methyl base phenyl) benzotriazole,
2-(2-hydroxyl-3,5-di-tert-butyl-phenyl) benzotriazole,
2-hydroxyl-4-octyloxy benzophenone,
2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines,
2-[4-(dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines,
2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (4-phenyl)-1,3,5-triazines.
Advantageously, the type of UV light absorber (a) and quantity be enough in the inductive phase of oxygen scavenqer (b), especially by make via light intensity this transparent polymer material transmission, in 280～380nm scope be reduced to 10% or following, especially be reduced to 5% or followingly make the daylight uv-radiation in this packing be reduced to the level that does not cause photoxidation in fact.
Different because of the definite type and the desirable barrier effect of employed UV light absorber, the UV light absorber of mixing in this transparent film or the wall of container advantageously causes every m
2Film or wall of container 0.01～10g, for example about 0.05～about 5g, 0.1～1g UV light absorber especially.
Packaging film of the present invention or sheet material often contain more than one deck, and wherein one deck contains the UV light absorber (multilayer material is seen following) of formula I at least.
This polymer materials is suitable for containing formula (I) compound compositions as the above, for example, being selected from polyester, polyolefine or vinyl-vinyl acetate copolymer. this polymer materials can comprise one or more and plant further additive, for example is selected from for example stearate of finings, phenol antioxidant, phosphorous acid ester and phosphinate, metal oxide and hydrotalcite, white dyes, softening agent, carboxylate salt.
Packaging film or ultraviolet screener film that a kind of often 10～200 μ m of transparent polymer materials are thick, or a kind of plastic container wall. oxygen scavenqer (b) can mix in this transparent polymer material maybe in another part of this packing or be stored in separately in this packing.
Therefore, the invention further relates to a kind of method that prevents the wrap food photoxidation, it is characterized in that this food is sealed in a kind of packing, this packing comprises a kind of transparent, especially limpid or light container or film of making from plastic material, wherein this plastic material contains a kind of UV light absorber, and this packing further contains a kind of oxygen scavenqer, also relates to oxygen scavenqer and contains the transparent plastic container of UV light absorber or the purposes that the film conduct prevents the packaging material for food of wrap food generation photoxidation.
The oxygen absorbent that will use according to the present invention can be known composition, comprises compound described in following patent or the patent gazette or system: United States Patent(USP) Nos. 5 ＇ 364 ＇ 555; 4 ＇, 536 ＇ 409; 4 ＇, 702 ＇ 966; 5 ＇, 605 ＇ 996; 5 ＇, 866 ＇ 649; 5 ＇, 096 ＇ 724; 5 ＇, 202 ＇ 052; 94/09,084; 6 ＇, 162 ＇ 806; 6 ＇, 083 ＇ 585; 6 ＇, 346 ＇ 308; 6 ＇, 406 ＇ 766; 6 ＇, 506 ＇ 463; 6 ＇, 509 ＇ 436; 5 ＇, 955 ＇ 527; 5 ＇, 639 ＇ 815; 5 ＇, 627 ＇ 239; 5 ＇, 641 ＇ 825; 5 ＇, 660 ＇ 761; 5 ＇, 736 ＇ 616; 5 ＇, 744 ＇ 246; 5 ＇, 776 ＇ 361; 5 ＇, 859 ＇ 145; 6 ＇, 139 ＇ 770; 6 ＇, 323 ＇ 288; 6 ＇, 333 ＇ 087; 5 ＇, 744 ＇ 056; 6 ＇, 369 ＇ 148; 5 ＇, 021 ＇ 515; 5 ＇, 049 ＇ 624; 5 ＇, 239 ＇ 016; 5 ＇, 952 ＇ 066; 5 ＇, 759 ＇ 653; 6 ＇, 210 ＇ 601; 6 ＇, 290 ＇ 871; 5 ＇, 981 ＇ 676; 6 ＇, 133 ＇ 352; 6 ＇, 143 ＇ 197; 6 ＇, 214 ＇ 254; 6 ＇, 254 ＇ 802; 6 ＇, 387 ＇ 461; 6 ＇, 139 ＇ 770; 5 ＇, 958 ＇ 254; 6 ＇, 346 ＇ 200; 6 ＇, 517 ＇ 728; 6 ＇, 410 ＇ 156; 6 ＇, 423 ＇ 776; 6 ＇, 479 ＇ 160; 5 ＇, 176 ＇ 849; 5 ＇, 211 ＇ 875; 5 ＇, 310 ＇ 497; 5 ＇, 346 ＇ 644; 5 ＇, 350 ＇ 622; 5 ＇, 425 ＇ 896; 5 ＇, 492 ＇ 742; 5 ＇, 529 ＇ 833; 5 ＇, 648 ＇ 020; 5 ＇, 798 ＇ 055; 5 ＇, 811 ＇ 027; 6 ＇, 284 ＇ 153; 6 ＇, 391 ＇ 406; 6 ＇, 465 ＇ 065; 5 ＇ 744'056; 5'885'481; 6 ＇, 369 ＇ 148; WO 98/04,558; WO 01/29,116; WO 01/88,023; WO 00/37,321; WO 98/12,127; WO 99/15,432; WO 99/15,433; US-A-2001-0023025; WO 95/02,616; WO 95/04,776; WO96/08,371; WO 96/40,799; WO 99/48,963; WO 00/011,972; WO 01/90,202; WO01/90,238; WO 02/28,944; WO 02/33,024; WO 02/36,670; WO 02/57,328; US-A-2002-0037377; US-A-2002-0022144; WO 96/18,685; WO 96/18,686; US-A-2002-0063238; WO00/64,775; WO 01/34,479; WO 01/03,521; WO 99/10,251; WO 02/051,825; WO02/076,916; WO 01/89,830; US-A-2002-0099125; US-A-2003-0036605; WO 97/32,925; WO 98/12,250; WO 98/53,026; WO 91/17,044, comprises pure organic system (being basic person with Whitfield's ointment, lactic acid, amine etc. for example); Or based on oxidizable metal composition (for example metal Fe, Zn, Co, Al, Mg, Cu, Sn or its oxidable alloy, salt, complex compound or organometallics) and the optional auxiliary system of ionogen, phosphoric acid salt, binding agent, souring agent for example.The using and mix of oxygen scavenqer can be respectively abideed by the above method of document.
Better, this oxygen scavenqer is a kind of additive based on oxidable iron or iron cpd, and US-5 for example is disclosed in 744,056, US-5,885,481, US-6,369,148.
Additive of the present invention and optional further composition can be individually or are added in this polymer materials with being mixed with each other. when wishing, each composition can be in mixing this polymkeric substance before such as mix by doing, compacting or fusion be mixed with each other.
Additive of the present invention and optional further composition mixing in this polymkeric substance are for example to do with powder type with currently known methods to mix or to carry out such as the solution in inert solvent, water or the oil, dispersion liquid or form of suspension wet mixing. mixing of additive of the present invention and optional further additive can be such as carrying out before or after being shaped, also can be by being administered to dissolved or dispersive additive or additive agent mixture on this polymer materials and having or the evaporation subsequently of solvent-free or suspension/dispersion agent is carried out.They can be such as directly adding in this processing unit (plant) (for example extruding machine, Banbury mixer etc.) as dry mixture or powder or as solution or dispersion liquid or suspension or melt.
This mixes can be in the heatable container of any outfit agitator, for example a kind of closed unit for example kneader, mixing roll or have in the stirred vessel carry out.This mixes better and carries out in an extruding machine or in a kneader.No matter process in inert atmosphere or in the presence of oxygen, carry out unimportant, as long as this oxygen scavenqer does not lose activity when existing.
This additive or the interpolation of additive adulterant in this polymkeric substance can be carried out in all usual mixing machines, wherein, make this polymer melt and mix with this additive.The machine that is suitable for is that those skilled in the art are known.They mainly are mixing machine, kneader and extruding machine.
This process is better undertaken by importing this additive during processing in an extruding machine.
Good especially processing machine is single multiple screw extruder, reverse rotation and co-rotating twin screw extruding machine, sun and planet gear extruding machine, ring-like extruding machine or common kneader. also can use the processing machine that is equipped with at least one degas chamber that can vacuumize.
The extruding machine and the kneader that are suitable for see the Kunststoffex-trusion such as Handbuch der for details, Vol.1 Grundlagen, Editors F.Hensen, W.Knappe, H.Potente, 1989, pp.3-7, / SBN:3-446-14339-4 (Vol.2 Extrusionsanlagen 1986 ,/SBN 3-446-14329-7).
For example, spiro rod length is 1～60 times of screw diameter, better 35～48 times of screw diameters.The rotating speed of screw rod better is 10～600 rev/mins (rpm), especially very good 25～300rpm.
Maximum extrusion capacity depends on screw diameter, rotating speed and power.Method of the present invention also can be carried the weighing machine of each dose quantity and carries out in the level that is lower than maximum extrusion capacity by changing the parameter mentioned or adopting.
When adding multiple composition, these compositions can also can individually add by premix.Also can be to this polymer materials with additive of the present invention and optional further additive spray.They can dilute other additive (for example above-indicated usual additive) or its solution, thereby they also can be sprayed on this material with these additives. and by the interpolation of spraying during this polymerizing catalyst inactivation is particularly advantageous; In this case, the water vapor that is discharged can be used for the inactivation of this catalyzer.Under the polyolefinic situation of spherical polymerization, for example, it may be favourable by spraying additive of the present invention randomly being used with other additive.
Additive of the present invention and optional further additive also can add in this polymkeric substance with masterbatch (" master batch ") form, this masterbatch with such as mix the about 1wt%～about 40wt% in a kind of polymkeric substance, the concentration of better 2～about 20wt% contains each composition.This polymkeric substance not necessarily must have and final polymer phase structure together of adding this additive.In such operation, this polymkeric substance can use with the form of powder, particle, solution, suspension or with the form of latex.
Mix can before the forming operation or during carry out, also can by with dissolved or dispersive compound administration to this polymkeric substance and have or the evaporation subsequently of not having this solvent is carried out.Under elastomeric situation, also can make these stable and become latex.With additive of the present invention mix a kind of further possibility in the polymkeric substance be before the corresponding monomer polymerization, during or finish after add them immediately or before crosslinked.In this category, additive of the present invention can former state add, and also can add with encapsulated form (for example using wax, oil or polymkeric substance encapsulate).
In a kind of particular, these plastic containers or film or sheet material are a kind of multi-ply constructions that contains 2～7 polymer layers of UV light absorber of the present invention in one deck at least.In this case, polymer composition of the present invention can contain a large amount of relatively can compatible hydroxyphenyl-triazine stablizer, 1～15wt% for example, and use or mix a kind of from containing seldom or do not have formed article that the polymkeric substance of stablizer of the present invention makes for example the film with skim (for example 5～100 μ m).This use can such as by co-extrusion with this basis shaping goods in carry out.Substituting, using can be after this basis shaping goods, such as by a kind of film of lamination or be coated with a kind of solution and come it is carried out.One or more skins of this finished product have the ultraviolet filter function that can protect this article inside and/or internal layer not influenced by ultraviolet ray.
Another further problem of the present invention is the purposes of formula (I) or compound (III) or its mixture, is about to it and mixes the content protection that is used for wrap food, beverage, medicine, makeup or personal care product in plastic containers or film or the sheet material.
Embodiment
Following examples explanation the present invention.In an embodiment, in this specification sheets rest part that coexists with the same in claims, all shares or percentage all by weight, except as otherwise noted.Room temperature is represented the temperature in 20～30 ℃ of scopes, except as otherwise noted. the data that ultimate analysis provides are Elements C, H and N to be calculated the wt% of (cal) or measuring (exp).In an embodiment, use following shortenings:
%w/w weight percent (wt%);
1 liter;
M.p. fusing point or scope;
The PP polypropylene;
The LDPE new LDPE (film grade);
The DSC dsc;
The NMR nucleus magnetic resonance (is not pointed out in addition if having, then is
1The nucleus magnetic resonance of H);
ε at λ
MaxAt the peaked molar extinction coefficient (1mol of long wavelength ultraviolet line absorption
-1
cm
-1)；
Several mean values of the molecular mass (g/mol) that Mn measures with GPC;
The GPC gel permeation chromatography;
PDI polymolecularity (the matter average of molecular weight and the ratio of number average value).
In following examples, molecular weight parameter (Mn, Mw, PDI) is to measure with GPC (gel permeation chromatography).It is to carry out with a Perkin Elmer LC50 liquid chromatograph that is equipped with refractive index Perkin ElmerLC30 that GPC measures, and data are calculated with Perkin Elmer software (Turbo SEC).All GPC measure all to use with the 0.02M diethanolamine solution of chromatographic grade tetrahydrofuran (THF) (THF) as solvent and carry out at 45 ℃.Employed post is PLGEL (Polymer Laboratories) 300mm * 7.5mm, and stationary phase 3mm Mixed E is supplied by Polymer Laboratories.Working curve uses polystyrene standards.Visual fusing point and fusion range are with a Gallenkamp measuring apparatus.Optical extinction coefficient is to calculate by the UV spectrum of this product in record methylene dichloride or the toluene solution on a Perkin Elmer Lambda 2S spectrophotometer.
A. preparation example
Embodiment A 1
n：m：z＝0.6：1：0.4
In a reaction flask, in 210ml dimethylbenzene, add 103.59g (0.18mol) monomer (A), 35.4g (0.3mol) 1,6-hexylene glycol, 68.4g (0.12mol) hydrogenation dimer acids and 2g tosic acid. this mixture refluxed 9 hours, steam dimethylbenzene, water and methyl alcohol. reaction mass is cooled to 120 ℃, add 750ml dimethylbenzene. solution is cooled to 80 ℃, wash with water 4 times. then, organic layer vacuum-drying produces a kind of melting range and is 80～92 ℃ product.
Embodiment A 2
In a reaction flask, in 210ml dimethylbenzene, add 103.59g (0.18mol) monomer (A), 35.4g (0.3mol) 1,6-hexylene glycol, above-mentioned cycloalkanes diacid (the CAS 68783-41-5 of 68.4g (0.12mol); Isomer mixture; Can be available from Cognis company or Sigma company) and the 2g tosic acid.This mixture refluxed 9 hours, and dimethylbenzene, water and methyl alcohol are steamed. and reaction mass is cooled to 120 ℃, adds 750ml dimethylbenzene.This solution is cooled to 80 ℃, washes with water 4 times.Then, with organic layer vacuum-drying, obtain the product of 80～92 ℃ of melting ranges.
The educt of CAS No.68783-41-5 is a kind of compound; Outside the main educt that shows in the last scheme, it contains open chain and/or unsaturated composition usually, and molecular weight ranges is about 562～about 566g/mol.
Embodiment A 3
In a reaction flask, in 100ml dimethylbenzene, add 57.50g (0.10mol) monomer (A), 17.70g (0.15mol) 1,6-hexylene glycol, above-mentioned cycloalkanes diacid (the CAS No.68783-41-5 of 28.50g (0.05mol); Isomer mixture; Can be available from Cognis company or Sigma company) and the 1.2g tosic acid. this mixture refluxed 10 hours, and dimethylbenzene, water and methyl alcohol are steamed. and reaction mass is cooled to 120 ℃, adds 500ml dimethylbenzene.Solution is cooled to 80 ℃, washes with water 4 times.With organic layer vacuum-drying, obtain the product of 90～99 ℃ of melting ranges then.
B: application examples
Embodiment B 1
With the product of 17g embodiment A 2 and 983g pulverize LLDPE (
NG 5056E, the supply of Dow Chemical company is characterized in that density is 0.919g/cm
3, melt flow index (190 ℃/2.16kg) be 1.1) mixes.This mixture is with an OMC
Bitruder is at 230 ℃ of extrusion moldings. and resulting granules is at 230 ℃ of inflation (Formac
Laboratory scale blown extrusion machine) becomes a kind of about 50 μ m thick film.
Record is via uv-vis spectras film, in 200～800 mu m ranges (Perkin-ElmerLambda 20 spectrophotometers are equipped with RSA-PE-20 Labsphere integrating sphere), and being presented at about 336nm has wide absorption maximum value; During transmissivity and integration transmisivity data are listed in the table below.
Wavelength (nm) 315 365 280-370 280-390 400-700
Transmissivity (%) 2.0 5.2 3.2 8.1 92
Correspondingly prepare a kind of film sample that does not have UV light absorber and be used for comparison purpose (blank film), the transmissivity that demonstrates in 400～700nm scope is 93%.
Film of the present invention shows following further performance:
With the yellowness index of blank film poor (ASTN E 313-96): 1.5
Optical haze value (ASTM D 1003-61): 8.6%
Polymer composition of the present invention shows good ultraviolet radiation absorption, excellent visible light transmissivity and low yellow and optical haze.
Embodiment B 2
The product of processing 20g embodiment A 3 provides the thick LLDPE film of a kind of about 50 μ m under the condition identical with Embodiment B 1.
Record is via uv-vis spectra this film, in 200～800nm scope, and being presented at about 337nm has wide absorption maximum value. during transmissivity of measuring in Embodiment B 1 and integration transmisivity data are listed in the table below.
Wavelength (nm) 315 365 280-370 280-390 400-700
Transmissivity (%) 1.0 2.2 1.5 5.1 91
Film of the present invention shows following further performance:
With the yellowness index of blank film poor (ASTM E 313-96): 1.8
Optical haze value (ASTM D 1003-61): 14.3%
Polymer composition of the present invention demonstrates excellent ultraviolet radiation absorption, good transmission of visible light and low yellow degree and optical haze.
Embodiment B 3
The product of 13g embodiment A 2 mixes with 6g micron zinc oxide or 2g micron oxide/titanium dioxide respectively, pulverizes LLDPE with 981g or 985g respectively again and mixes, and processes under the condition identical with the embodiment of front then, provides the thick film of about 50 μ m.
During integration transmisivity data of measuring in embodiment in front and optical haze value are listed in the table below:
Polymer composition of the present invention demonstrates good ultraviolet radiation absorption, good transmission of visible light and low optical haze.
Embodiment B 4
Utilize the product of embodiment A 2 to prepare a kind of industrial multi layer extrusion cast film.A kind of like this film constitutes (approximate thickness of each layer be reported in bracket) by 5 by the layer that descends array structure and form from a surface to another surface:
-LLDPE (
NG 5056E, Dow Chemical company), contain 1.7wt% embodiment A 2 products (20 μ m)
-binder layer (
NF 518E, Mitsui Chemicals company, 3 μ m)
-EVOH (F171B type, Eval Europe company) barrier layer (10 μ m)
-binder layer (
NF 518E, Mitsui Chemicals company, 3 μ m)
-LLDPE (
NG 5056E, Dow Chemical company), contain 1.7wt% embodiment A 2 products (20 μ m)
Correspondingly the film sample of the another kind of no UV light absorber of preparation is used for comparison purpose (blank film).
During the integration transmisivity data of measuring in former embodiment is listed in the table below:
Wavelength (nm) 280-370 280-390 400-700
Transmissivity (%) 8.8 14.6 92
Film of the present invention demonstrates following further performance:
With the yellowness index of blank film poor (ASTM E 313-96): 0.5
Optical haze value (ASTM D 1003-61): 3.6%
Polymer composition of the present invention demonstrates good ultraviolet radiation absorption, excellent visible light transmissivity, low-down yellow and inappreciable optical haze.
Embodiment B 5
For the uv-radiation of estimating polymer composition of the present invention shields the favourable influence that edible item is stored, the polymer composition of Embodiment B 1 is used for following experiment, wherein, a slice cooked ham is placed in the packing that constitutes as follows: this packing has gas purging to constitute with the Glass Containers of inlet valve and outlet valve and quartz cover that can airtight sealing by one.A kind of atmosphere that contains 2% oxygen is fed in this container, and will place by the film that the polymkeric substance of Embodiment B 1 is formed on this quartz caping.This container places under 4 " cold white " type luminescent lamps at 5 ℃.After 4 days, measure the colour index a of this ham with a colorimeter
*(ASTM E 313-96), with the film of packing under the same conditions and storing but do not have a ultraviolet screener relatively.The result is reported in the following table:
Keep the red color tone of meat with the ham of film packaging of the present invention, significantly be better than the ham of packing with usual film (blank film).
Embodiment B 6
In following experiment, use Embodiment B 4 gas barriers 5 layer films as food product packing film. open-top and be equipped with gas purging with the Glass Containers of inlet valve and outlet valve (diameter is called A, B and C as 105mm, height 60mm) in some cooked hams of storage.
Container A covers with the gas barrier film described in the Embodiment B 4 (film of the present invention that contains the UVA of embodiment A 2).This film places this container top and carries out the silicon envelope. a kind of atmosphere that contains 5% oxygen fed in this packing. and about 200cm
2Inner side-wall is coated with the thick extrusion molding curtain coating of 125 μ m ldpe film (6401, Dow Chemicals company), and the latter is contained 50% oxygen scavenqer
O
2, in the hope of further reducing the oxygen level in this packing.
Container B (comparative sample) has with the film same structure of container A and composition but does not wherein have the blank gas barrier diaphragm seal of UVA product with a kind of. the identical film of film that the inner side-wall coating and the container A of container B used.The atmosphere of this package interior is identical with the atmosphere of container A.
The blank diaphragm seal that container C (comparative sample) is used with container B, but cover the black cardboard of a slice on this film again, make light can not enter this packing. the identical film of film that the inner side-wall coating and the container A of container C used. the atmosphere of this package interior is identical with the atmosphere of container A.
These containers are stored under 4 " cold white type " luminescent lamps at 5 ℃; Outward appearance according to vision proterties and change in color assessment packaging ham.
Keep the red color tone of meat according to the ham of the present invention packing, significantly be better than the ham of usual film (B, blank film) packing.
Claims (18)
1. the oligomer ester or the polyester of formula (I)
-[A-O-D-O]
x- (I)
In the formula
X is 1～50 number
A is the group of formula (II)
One of or the implication that provides for T;
D is C
4-C
12Alkylidene group perhaps has the OH replacement or has O insertion or existing OH to replace the described alkylidene group that also has O to insert;
L is C
1-C
18Alkylidene group; C
5-C
12Cycloalkylidene; C
3-C
18Alkylene group; Phenyl, C are perhaps arranged
7-C
11Alkyl phenyl, C
5-C
12Cycloalkyl, OH, halogen, C
1-C
18Alkoxyl group, C
5-C
12Cycloalkyloxy, C
3-C
18One of described residue that alkenyloxy, COOH replace;
Each R
1Be H, OR independently of one another
7Or OH, prerequisite is R
1Or R
13In at least one is OH;
Each R
7Be H, C independently of one another
1-C
12Alkyl or formula-L-CO-O-R
9Group;
R
9Be H, C
1-C
18Alkyl, C
2-C
12Hydroxyalkyl;
R
10Be H, C
1-C
4Alkyl, Cl, phenyl or group-OR
7
R
11Be H or methyl;
R
13Be H, methyl, OH or OR
7With
T is the aliphatics of 13～60 carbon atoms or cycloaliphatic dicarboxylic acid's divalence acyl group;
With contain at least one formula (II) segment and at least one T segment person.
2. the oligomer ester of claim 1 or polyester, wherein
D is C
4-C
12Alkylidene group or the C that has O to insert
4-C
10Alkylidene group;
L is C
1-C
4Alkylidene group;
T is divalence acyl group CO-T '-CO, and T ' is C in the formula
20-C
50Alkylidene group or the C that has one or more Sauerstoffatoms to insert
20-C
50Alkylidene group; C is perhaps arranged
5-C
12Cycloalkylidene or C is arranged
5-C
12The alkylidene group that inferior cycloalkenyl group inserts, wherein each all is not have replacement or have alkyl to replace, and T ' contains 20～50 carbon atoms altogether;
R
7Be hydrogen or methyl;
R
10Be hydrogen, methyl or group-OR
7
R
11Be hydrogen;
R
13Be hydrogen, OH or methyl.
3. the oligomer ester of claim 1 or polyester, it meets formula (III)
X is 1～20 number in the formula;
Y be at least 1 and scope for (x+z-1)～(x+z+1);
Z is 1～20 number; And
R
8Be hydrogen, C
1～C
12Alkyl; C
5～C
12Cycloalkyl; C
2～C
12Alkenyl; Phenyl; C
7～C
11Alkyl phenyl; The C that has phenyl, OH, halogen to replace
1～C
12Alkyl; C
1～C
18Alkoxyl group, C
5～C
12Cycloalkyloxy, C
3～C
18Alkenyloxy or COOH;
R
12Be hydrogen or C
1～C
8Alkyl;
R
18Be hydrogen or C
1～C
4Alkyl;
D is C
4～C
8Alkylidene group or the C that has O to insert
4～C
10Alkylidene group; And
T ' is C
20～C
50Alkylidene group or the C that has one or more Sauerstoffatom to insert
20～C
50Alkylidene group; C is perhaps arranged
5-C
12Cycloalkylidene or C is arranged
5-C
12The alkylidene group that inferior cycloalkenyl group inserts, wherein each all is not have replacement or have alkyl to replace, and T ' contains 20～50 carbon atoms altogether;
And all other symbols all with in the claim 1 to the definition of formula I.
4. the oligomer ester of claim 3 or polyester, wherein R
8Be hydrogen or C
1～C
4Alkyl.
5. the oligomer ester of claim 1 or polyester, wherein X is in 2～50 scopes, and the ratio of the triazine segment number of formula II and dihydric acid residue T is 1:3～10:1.
6. oligomer ester or polyester, it is by triaryl triazine that makes formula V and formula R
12-O-OC-T '-CO-O-R
12Compound and the glycol of formula HO-D-OH reaction obtain,
Y is CO in the formula, and all other symbols all with in the claim 2 to the definition of formula (III).
7. prevent the composition of uv-radiation infiltration, comprise
(a) a kind of organic polymer material and
(b) at least a oligomer ester of claim 1 Chinese style (I) or polyester or its mixture.
8. the composition of claim 7, it is a kind of transparent plastic containers or film or multilayer film.
9. the composition of claim 7, wherein this organic polymer material is a kind of thermoplastic polymer.
10. the composition of claim 9, wherein this thermoplastic polymer is polyolefine, polyester, polyvinyl alcohol, polyvinyl acetate, polylactone or polycarbonate.
11. the composition of claim 7, wherein this organic polymer material is the plastic containers of the thick film of a kind of 10 μ m～200 μ m or a kind of 200 μ m～1000 μ m wall thickness, and the weight with this organic polymer material is benchmark, contains quantity and be 0.005%～10% formula (I) compound.
12. the composition of claim 7 contains a kind of following further composition that is selected from: phenol antioxidant, bulky amine, further UV light absorber, phosphorous acid ester and phosphinate, an alkali metal salt and calcium stearate, Zinic stearas, docosoic magnesium, Magnesium Stearate, natrium ricinoleicum and potassium palmitate, filler, oxygen scavenqer, acetaldehyde scavenger, softening agent, finings, emulsifying agent, pigment, catalyzer, processing aid, optical brightener, fire retardant, static inhibitor and whipping agent.
13. the composition of claim 7 contains a kind of following further composition that is selected from: metal oxide, hydrotalcite, lubricant, and flow control agent.
14. the composition of claim 7 contains a kind of following further composition that is selected from: rheological additives.
15. protection transparent plastic container or film and content thereof are not subjected to the method for uv-radiation harmful effect, this method comprises the oligomer ester or polyester the mixing in described plastic containers or film of claim 1.
16. the oligomer ester of claim 1 or polyester are used to protect transparent plastic container or film and content thereof not to be subjected to the purposes of the harmful effect of uv-radiation.
17. prevent the method for wrap food photoxidation, it is characterized in that this food is sealed in the transparent plastic container or film or multilayer film of claim 8.
18. prevent the method for wrap food photoxidation, it is characterized in that this food is sealed in the packing or container that comprise transparent film of claim 8, and this packing further contain oxygen scavenqer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03405374.4 | 2003-05-26 | ||
| EP03405374 | 2003-05-26 | ||
| EP03103976.1 | 2003-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1795232A CN1795232A (en) | 2006-06-28 |
| CN100482726C true CN100482726C (en) | 2009-04-29 |
Family
ID=34924340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800143550A Expired - Fee Related CN100482726C (en) | 2003-05-26 | 2004-05-14 | Highly compatible and non-migratory polymeric uv-absorber |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100482726C (en) |
| ZA (1) | ZA200508713B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604184A (en) * | 2012-02-22 | 2012-07-25 | 江南大学 | Light-blocking PE (polyethylene) film for food packaging |
| CN112805844A (en) * | 2018-10-05 | 2021-05-14 | 三星显示有限公司 | Display device and light absorbent included in the same |
| EP3898233B1 (en) * | 2018-12-17 | 2024-04-10 | PolyCine GmbH | Flexible multilayer film with uv-vis barrier layer for medical packaging |
-
2004
- 2004-05-14 CN CNB2004800143550A patent/CN100482726C/en not_active Expired - Fee Related
-
2005
- 2005-10-27 ZA ZA200508713A patent/ZA200508713B/en unknown
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|---|---|
| CN1795232A (en) | 2006-06-28 |
| ZA200508713B (en) | 2006-07-26 |
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