CN1875061A - Uv stabilizing additive composition - Google Patents
Uv stabilizing additive composition Download PDFInfo
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- CN1875061A CN1875061A CNA2004800326886A CN200480032688A CN1875061A CN 1875061 A CN1875061 A CN 1875061A CN A2004800326886 A CNA2004800326886 A CN A2004800326886A CN 200480032688 A CN200480032688 A CN 200480032688A CN 1875061 A CN1875061 A CN 1875061A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/13—Phenols; Phenolates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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Abstract
A composition of an UV stabilizing composition comprises an ortho-hydroxy tris-aryl-s-triazine compound; a hindered amine compound; and a hydroxybenzophenone compound. The ratio of the hindered amine compound to the triazine compound is about 3:1 to about 25:1; and the ratio of the hindered amine compound to the hydroxybenzophenone compound is about 1:1 to 25:1. The UV stabilizing composition can further comprise a material to be stabilized.
Description
Invention field
The present invention relates to a kind of improved uv stabilizing additive composition.More particularly, the present invention relates to a kind of uv stabilizing additive composition that comprises adjacent hydroxyl triaizine compounds, bulky amine compound and hydroxy benzophenone ketone compound.
Background of invention
The known daylight that is exposed to can make many kinds of materials, especially polymeric material degrades with other ultraviolets (UV) source of radiation.For example, owing to long-term exposure is faded, tarnished and/or become fragile in UV-light, this mainly is because the molecular weight of polymkeric substance reduces to cause to the polymeric material of plastics and so on through regular meeting.Therefore the material to the ultraviolet absorbers of this degraded that can suppress polymer product and stablizer and so on has had a large amount of research.
The inventor finds, adjacent hydroxyl triaizine compounds, bulky amine compound and hydroxy benzophenone ketone compound are combined, and the synergy protection of ultraviolet light can be provided material.This combination can provide better protection under the UV stabilizer add-on of routine, perhaps can much lower add-on provide common protection, thereby makes the uv stabilizing additive composition of its cost far below prior art.
The invention summary
The present invention relates to a kind of uv stabilizing additive composition that comprises adjacent hydroxyl triaizine compounds, bulky amine compound and hydroxy benzophenone ketone compound.This compositions of additives can be used to anti-ultraviolet radiation and makes material settling out.The invention still further relates to a kind of method that makes material settling out, this method makes it stable by described material is contacted with uv stabilizing additive composition.
Detailed Description Of The Invention
The present invention relates to a kind of adjacent hydroxyl triaizine compounds that comprises, the uv stabilizing additive composition of stable (HALS) compound of bulky amine light and hydroxy benzophenone ketone compound.
Preferably, adjacent hydroxyl triaryl-s-triaizine compounds has following chemical formula
A in the formula, each aromatics naturally of B and C, A, B is replaced R with at least one group among the C by hydroxyl on the ortho position of the position that links to each other with triazine ring
1To R
9Be selected from hydrogen separately, hydroxyl, alkyl, alkoxyl group, sulfo group, carboxyl, halogen, haloalkyl and amido, the alkyl in the above-mentioned group comprise about 1-24 carbon atom.
A compound that embodiment is a Formulae II of triaryl-s-triazine:
Ar in the formula
1And Ar
2Be identical or different, be substituted aryl or unsubstituting aromatic yl; R in the formula
20And R
21Be hydrogen independently of one another, C
1-C
24Alkyl, C
1-C
24Haloalkyl, C
6-C
24Aryl, C
2-C
24Alkenyl, C
1-C
24Acyl group, C
1-C
24Cycloalkyl, C
5-C
24The ring acyl group, C
7-C
24Aralkyl or C
6-C
24Aroyl replaces or unsubstituted biphenylene, replaces or unsubstituted naphthalene OR, NRR ', CONRR ', OCOR, CN, SR, SO
2R, R and R ' are hydrogen independently of one another in the formula, C
1-C
24Alkyl, C
1-C
24Haloalkyl, C
6-C
24Aryl, C
2-C
24Alkenyl, C
1-C
24Acyl group, C
1-C
24Cycloalkyl, C
5-C
24The ring acyl group, C
7-C
24Aralkyl or C
6-C
24Aroyl replaces or unsubstituted biphenylene or replacement or unsubstituted naphthalene.
Preferably, in following formula II, Ar
1Have Formulae II a:
R in the formula
22And R
23Be hydrogen independently of one another, C
1-C
24Alkyl, C
1-C
24Haloalkyl, C
6-C
24Aryl, C
2-C
24Alkenyl, C
1-C
24Acyl group, C
1-C
24Cycloalkyl, C
5-C
24The ring acyl group, C
7-C
24Aralkyl or C
6-C
24Aroyl replaces or unsubstituted biphenylene, replaces or unsubstituted naphthalene OR, NRR ', CONRR ', OCOR, CN, SR and SO
2R, wherein R and R ' are as mentioned above.
Also preferred R among the following formula II
20Be hydrogen or C
1-C
8Alkyl, R
21Be hydrogen, Ar
1And Ar
2Can be identical or different, be benzyl, methyl-benzyl or dimethyl benzyl.
The example of spendable suitable triaryl-s-triazine is 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazines; 2-(2-hydroxyl-4-n-octyloxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-(the different octyloxyphenyl of blended)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2, the 4-dihydroxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2, the 4-3,5-dimethylphenyl) of 4--1,3,5-triazines; 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (4-the aminomethyl phenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-dodecyloxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy-) phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-)-phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[4-dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-and the 2-hydroxy phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy propoxy-) phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-hexyloxy) phenyl-4,6-phenylbenzene-1,3,5-triazines; 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 and 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3,5-triazines.
Described bulky amine compound can be any suitable bulky amine compound, for example comprises 2,2,6,6-tetraalkyl piperidines (piperdine) or 2,2,6, the bulky amine of 6-tetraalkyl piperazine ketone (piperazinone) group.An embodiment of bulky amine compound comprises the group of at least one Formula Il I:
R in the formula
11Be hydrogen, O, OH, C
1-C
18Alkyl ,-CH
2CN, C
1-C
18Alkoxyl group, C
1-C
18The hydroxy alkoxy base, C
5-C
12Cycloalkyloxy, C
5-C
12The hydrogen cycloalkyloxy, C
3-C
6Alkenyl, C
1-C
18Alkynyl, C
7-C
9Phenylalkyl is not substituted on the phenyl, or by 1,2 or 3 C
1-C
4The C of alkyl or aliphatic series
1-C
8Acyl substituted; R
12Be hydrogen, C
1-C
8Alkyl or benzyl; R
13, R
14, R
15And R
16Be C independently of one another
1-C
18Alkyl, benzyl or styroyl, perhaps R randomly
13And R
14, and/or R
15And R
16The carbon that links to each other with them couples together and forms C
5-C
10Cycloalkyl.
Another embodiment of bulky amine compound is the compound of following formula I V:
R in the formula
10Be morpholino, C
1-C
8Alkylamine, two (C
1-C
8) alkylamine, pyrrolidyl, hexahydroaniline or its combination, X and X
1Can be identical or different, be hydrogen, C
1-20Alkyl, or go up the group shown in the formula III, R
11To R
16As mentioned above,
Z is the C of straight or branched
1-C
20Alkylidene group or insert aerobic, sulphur at least or-N (R
17)-the C of straight or branched
1-C
20Alkylidene chain, wherein R
17Be hydrogen, C
1-C
20Alkyl, C
5-C
10Cycloalkylidene, C
6-C
12Arylidene, C
8-C
14The group of inferior aralkyl or formula III;
N is the integer greater than 1;
Y is a halogen atom, C
1-C
8Alkylamine, two (C
1-C
8) alkylamine, pyrrolidyl, morpholino, hexahydroaniline, or
X in the formula, X
1With Z as mentioned above.
Preferably in following formula IV, Z is C
2-C
6Alkylidene group, R
10Be morpholino or hexahydroaniline, X and X
1Be the group of Formulae II I, R
11Be hydrogen or methyl, R
12Be hydrogen, R
13, R
14, R
15And R
16It is methyl.
Another embodiment of bulky amine is 2,2,6,6-tetraalkyl piperazine ketone.2,2,6, an embodiment of 6-tetraalkyl Piperazinone compounds comprises the group of at least one Formula I Va:
R in the formula
11As mentioned above.
The example of suitable bulky amine compound includes, but are not limited to: 1H-pyrroles-2, and the 5-diketone, the 1-octadecyl-, with (1-methyl ethylene) benzene and 1-(2,2,6,6-tetramethyl--4-piperidyl)-1H-pyrroles-2, the polymkeric substance of 5-diketone; Piperazine ketone, 1,1 ', 1 " [1,3,5-triazines-2,4,6-three bases three [(hexamethylene imino-)-2,1-ethane two bases]] three [3,3,5, the 5-tetramethyl--]; Piperazine ketone, 1,1 ', 1 " [1,3,5-triazines-2,4,6-three bases three [(hexamethylene imino-)-2,1-ethane two bases]] three [3,3,4,5, the 5-pentamethyl--]; 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; N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1,6-hexanediamine and 4-hexamethylene amino-2, the condenses of 6-two chloro-1,3,5-triazines; 1, the condenses of two (3-amino propyl amino) ethane of 2-; 2,4,6-three chloro-1,3,5-triazines and 4-butyl amino-2,2,6,6-tetramethyl piperidine; N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1,6-hexanediamine and 4-morpholino-2, the condenses of 6-two chloro-1,3,5-triazines; 2-chloro-4, two (4-normal-butyl amino-2,2,6,6-the tetramethyl-piperidyl)-1,3,5-triazines and 1 of 6-, the condenses of two (3-amino propyl amino) ethane of 2-; 2-chloro-4, two (4-normal-butyl amino-1,2,2,6,6-pentamethyl-the piperidyl)-1,3,5-triazines and 1 of 6-, the condenses of 2-pair-(3-amino propyl amino) ethane; The 2-[(2-hydroxyethyl) amino]-4, two [N-(1-cyclohexyloxy-2,2,6, the 6-tetramethyl piperidine-4-yl) butyl amino-1,3,5-triazines of 6-; Propanedioic acid, [(4-p-methoxy-phenyl)-methylene radical]-two-(1,2,2,6,6-pentamethyl--4-piperidyl) ester; Four (2,2,6,6-tetramethyl piperidine-4-yl)-1,2,3,4-butane tetracarboxylic acid esters; Phenylpropionic acid, 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyls of 5--, 1-[2-[3-[3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-]-the 1-oxopropoxy] ethyl]-2,2,6,6-tetramethyl--4-piperidyl ester; N-(1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl)-N '-dodecyl oxamide; Three (2,2,6,6-tetramethyl piperidine-4-yl) nitrilotriacetate; 1, the 5-dioxo spiro 5,5} undecane-3,3-dicarboxylic acid, two (1,2,2,6,6-pentamethyl--4-piperidyl); 1, the 5-dioxo spiro 5,5} undecane-3,3-dicarboxylic acid, two (2,2,6,6-tetramethyl--4-piperidyl); 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 piperidine-4-yl)-1,6-hexanediamine and uncle's 4-octyl group amino-2, the condenses of 6-two chloro-1,3,5-triazines; 1,2,3,4-BTCA, 1,2,2,6,6-pentamethyl--4-piperidyl ester in three last of the ten Heavenly stems; Four (2,2,6,6-tetramethyl piperidine-4-yl)-1,2,3,4-butane tetracarboxylic acid esters; 1,2,3,4-BTCA, 2,2,6,6-tetramethyl--4-piperidyl ester in three last of the ten Heavenly stems; Four (1,2,2,6,6-pentamethyl-piperidin-4-yl)-1,2,3,4-butane tetracarboxylic acid esters; 2,2,4,4-tetramethyl--21-oxo-7-oxa--3.20-diaza spiro (5.1.11.2)-heneicosane-20-propionic acid-dodecane ester; 2,2,4,4-tetramethyl--21-oxo-7-oxa--3.20-diaza spiro (5.1.11.2)-heneicosane-20-propionic acid-tetradecane ester; 1H, 4H, 5H, 8H-2,3a, 4a, 6,7a, 8a-hexanitrogen heterocycle pentadiene is [def] fluorenes-4 also, the 8-diketone, six hydrogen-2,6-two (2,2,6,6-tetramethyl--4-piperidyl)-; Poly-methyl [propyl group-3-oxygen base (2 ', 2 ', 6 ', 6 '-tetramethyl--4,4 '-piperidyl)] siloxanes; Poly-methyl [propyl group-3-oxygen base (1 ', 2 ', 2 ', 6 ', 6 '-pentamethyl--4,4 '-piperidyl)] siloxanes; Methyl methacrylate and ethyl propenoate and 2,2,6, the multipolymer of 6-tetramethyl piperidine-4-base acrylate; Blended C
20-C
24The multipolymer of alpha-olefin and (2,2,6,6-tetramethyl piperidine-4-yl) succinimide; 1,2,3,4-BTCA, β, β, β ', β '-tetramethyl--2,4,8,10-four oxaspiros [5.5] undecane-3,9-di-alcohol, 1,2,2,6, the polymkeric substance of 6-pentamethyl--4-piperidyl ester; 1,2,3,4-BTCA, β, β, β ', β '-tetramethyl--2,4,8,10-four oxaspiros [5.5] undecane-3, the polymkeric substance of 9-di-alcohol, 2,2,6,6-tetramethyl--4-piperidyl ester copolymer; 1, the 3-benzenedicarboxamide, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl; 1,1 '-(1,10-dioxo-1,10-decane two bases)-two (six hydrogen-2,2,4,4,6-pentamethyl-pyrimidines; Oxalamide, N-(1-ethanoyl-2,2,6,6-tetramethyl-piperidyl)-N '-dodecyl; Methane amide, N, N '-1, the two [N-(2,2,6,6-tetramethyl--4-piperidyl) of 6-hexane two bases; The D-sorbitol, 1,3:2,4-pair-O-(2,2,6,6-tetramethyl--4-piperidylidene)-; 2,2,4,4-tetramethyl--7-oxa--3,20-diaza-21-oxo-two spiral shell [5.1.11.2] heneicosane; Propionic acid amide, 2-methyl-N-(2,2,6,6-tetramethyl--4-piperidyl)-2-[(2,2,6,6-tetramethyl--4-piperidyl) amino]-; 7-oxa--3,20-diaza two spiral shells [5.1.11.2] heneicosane-20-propionic acid, 2,2,4,4-tetramethyl--21-oxo-, dodecyl ester; N-(2,2,6,6-tetramethyl piperidine-4-yl)-β-An Jibingsuan dodecyl ester; N-(2,2,6,6-tetramethyl piperidine-4-yl)-N '-oxamic hydrazide; Propionic acid amide, N-(2,2,6,6-tetramethyl--4-piperidyl)-3-[(2,2,6,6-tetramethyl--4-piperidyl) amino]-; 4-n-Hexadecane oxygen base-and the stearic oxygen base-2,2,6 of 4-, the mixture of 6-tetramethyl piperidine; 3-dodecyl-1-(1,2,2,6,6-pentamethyl-piperidin-4-yl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1-ethanoyl-2,2,6,6-pentamethyl-piperidin-4-yl) tetramethyleneimine-2, the 5-diketone; Two (2,2,6,6-tetramethyl piperidine-4-yl) succinate; Two (1,2,2,6,6-pentamethyl-piperidin-4-yl) normal-butyl 3,5-di-tert-butyl-4-hydroxyl benzyl malonic ester; Three (2,2,6,6-tetramethyl piperidine-4-yl) nitrilotriacetate; 1,1 '-(1,2-ethane two bases) two (3,3,5,5-tetramethyl-piperazine ketone); 4-benzoyl-2,2,6, the 6-tetramethyl piperidine; The stearic oxygen base-2,2,6 of 4-, the 6-tetramethyl piperidine; Two (1,2,2,6,6-pentamethyl-piperidyl)-2-normal-butyl-2-(2-hydroxyl-3,5-di-t-butyl benzyl) malonic ester; 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone; Two (1-octyloxy-2,2,6,6-tetramethyl-piperidyl) sebate; Two (1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate; 8-ethanoyl-3-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone; 3-dodecyl-1-(2,2,6,6-tetramethyl piperidine-4-yl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethyl piperidine-4-yl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1,2,2,6,6-pentamethyl-piperidin-4-yl) tetramethyleneimine-2, the 5-diketone; 4-n-Hexadecane oxygen base-and the stearic oxygen base-2,2,6 of 4-, the mixture of 6-tetramethyl piperidine; 2-undecyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane; 1, the 5-dioxo spiro 5, and 5} undecane-3, the 3-dicarboxylic acid, two (2,2,6,6-tetramethyl--4-piperidyl) and 1, the 5-dioxo spiro 5,5} undecane-3,3-dicarboxylic acid, two (1,2,2,6,6-pentamethyl--4-piperidyl).
Hydroxy benzophenone ketone compound of the present invention can be any suitable steric hindrance hydroxy-benzoic acid ester cpds, for example compound shown in the chemical formula V:
R in the formula
17, R
18And R
24Be hydrogen independently of one another, comprise the alkyl of 1-18 carbon atom, aryl, aralkyl, alkaryl, alkoxyl group, aryloxy, R
19Be hydrogen, C
1-C
24Alkyl or replacement or unsubstituted C
6-C
24Aryl.Preferably, R
17, R
18And R
24The hydrogen of respectively doing for oneself, R
19Be C
1-C
8Alkyl.
The example of suitable steric hindrance hydroxy benzophenone ketone compound comprises: 2,4 dihydroxyl benzophenone; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-oxygen in last of the ten Heavenly stems base benzophenone; 2-hydroxyl-4-dodecyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone; 2,2 ', 4,4 '-tetrahydroxybenzophenone; 2,4-dihydroxyl-4 '-tertiary butyl-benzophenone; 1, two (3-hydroxyl-4-benzoyl phenoxy group) hexanes of 6-; Methylene-bis (2-benzoyl-5-methoxyphenol).
In an embodiment of the present invention, can use uv stabilizing additive composition of the present invention that it is contacted or the physics contact with the composition chemistry that comprises polymkeric substance or other material, to stablize the material that those are degraded by uv-radiation easily.Can be polyolefine by the non-limitative example of the stable material of this method, polyester, polyethers, polyketone, polymeric amide, natural rubber and synthetic rubber, urethane, polystyrene, high-impact polystyrene, polyacrylic ester, polymethacrylate, polyacetal, polyacrylonitrile, polyhutadiene, polystyrene, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile, acrylate-styrene-acrylonitrile, cellulose acetate butyrate, cellulose polymer compound, polyimide, polyamidoimide, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyethersulfone, polyvinyl chloride, polycarbonate, polyketone, aliphatic polyketones, thermoplastic olefin, amino resin crosslinked polyacrylic ester and polyester, the polyester of multi isocyanate crosslinking and polyacrylic ester, resol, urea-formaldehyde resin and melamine/formaldehyde resin, the Synolac of dryness and non-dryness, Synolac, vibrin is used melamine resin, urea resin, isocyanic ester, isocyanuric acid ester, the acrylate resin of carbamate and cross linking of epoxy resin is derived from aliphatic series, alicyclic, the crosslinked Resins, epoxy of heterocycle family and aromatics glycidyl compound (this Resins, epoxy and acid anhydrides or amine are crosslinked), polysiloxane, the Michael addition polymer, amine is with active unsaturated compound and the end capped amine of methylene compound, the ketoimine that has active unsaturated compound and methylene compound, with the polyketone imines of unsaturated acrylic acid or the like polyacetoacetate resin combination, with the polyketone imines of unsaturated acrylic resin combination, radiation-hardenable composition, the epoxy melamine resin, organic dye, makeup, cellulose base paper preparation, photographic film paper, fiber, wax, printing ink and composition thereof.
Preferably, to stable material be thermoplastic olefin, acrylonitrile-butadiene-styrene (ABS), polyester, polyvinyl chloride, polymeric amide, urethane, or the homopolymer of following alkene and multipolymer: propylene, iso-butylene, butylene, methylpentene, hexene, heptene, octene, isoprene, divinyl, hexadiene, Dicyclopentadiene (DCPD), ethylidene cyclopentenes and norbornylene.More preferably this material is polypropylene and thermoplastic olefin.
The consumption of triaizine compounds is usually less than conventional consumption in the material of wanting stabilization that uses additive combination of the present invention.Amount in the material of wanting stabilization is a benchmark, and the lower limit of triazine is low to moderate about 10ppm, or about 20ppm, or about 50ppm, or about 75ppm, or about 100ppm, or about 200ppm.The amount of triazine does not have the upper limit, but is benchmark in the amount of the material of wanting stabilization, is about 5000ppm, or about 4000ppm, or about 3000ppm, or about 2000ppm, or about 1000ppm, or about 500ppm.
The consumption of hydroxy benzophenone ketone compound also is usually less than conventional consumption in the material of wanting stabilization that uses additive combination of the present invention.Amount in the material of wanting stabilization is a benchmark, and the lower limit of dihydroxy benaophenonel consumption can be low to moderate about 10ppm, or about 20ppm, or about 50ppm, or about 75ppm, or about 100ppm, or about 200ppm, or about 500ppm.The amount of dihydroxy benaophenonel does not have the upper limit, but is benchmark in the amount of the material of wanting stabilization, is about 5000ppm, or is about 4000ppm, or be about 3000ppm, or be about 2000ppm, or be about 1000ppm, or be about 500ppm.
In using the material of wanting stabilization of additive combination of the present invention the consumption of steric hindrance amine compound on different degree greater than its common consumption.Amount in the material of wanting stabilization is a benchmark, and the lower limit of bulky amine compound is about 250ppm, or is about 500ppm, or is about 1000ppm, or is about 2000ppm.The amount of bulky amine compound does not have the upper limit, but is benchmark in the amount of the material of wanting stabilization, is about 30000ppm, or be about 20000ppm, or be about 15000ppm, or be about 12500ppm, or be about 10000ppm, or be about 7500ppm, or be about 5000ppm.
The amount of bulky amine compound is usually greater than the amount of other uv-absorbing agents.The ratio of bulky amine compound and triazine ultraviolet absorber can be up to about 50: 1, or about 25: 1, or about 20: 1, or about 10: 1, or about 7: 1, or about 3: 1.The bulky amine compound is about 25: 1 with the ratio of dihydroxy benaophenonel uv-absorbing agent, or is about 20: 1, or is about 10: 1, or is about 7: 1, or is about 3: 1, or is about 2: 1, or is about 1.5: 1, or is about 1: 1.The hydroxy benzophenone ketone compound is about 10: 1 with the ratio of triazine ultraviolet absorber, or is about 5: 1, or is about 3: 1, or is about 2: 1, or is about 1: 1, or is about 1: 2.
The amount and the ratio that should be understood that above-mentioned additive are irrelevant mutually.
The present invention's expection can replace the dihydroxy benaophenonel uv-absorbing agent with benzotriazole UV absorbers.Also benzotriazole cpd can be added in other three kinds of additives.The ratio of benzotriazole UV absorbers can be identical with the ratio and the consumption of above-mentioned dihydroxy benaophenonel uv-absorbing agent with consumption.It below is the example of benzotriazole UV absorbers: 2-(2-hydroxy-5-methyl base phenyl)-benzotriazole; 2-(2-hydroxyl-5-tert-butyl-phenyl)-benzotriazole; 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-benzotriazole; 5-chloro-2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-benzotriazole; 5-chloro-2-(2-hydroxyl-3,5-di-t-butyl-5-aminomethyl phenyl)-benzotriazole; 2-(2-hydroxyl-uncle's 3-phenyl-5-methyl)-benzotriazole; 2-(2-hydroxyl-3,5-two tert-pentyls)-benzotriazole; 2-(2-hydroxyl-3-sec-butyl-5-tertiary butyl)-benzotriazole; 2-(2-hydroxyl-4-octyloxy)-benzotriazole; 2-(2-hydroxyl-uncle's 5-octyl group)-benzotriazole; 2-[2-hydroxyl-3,5-two (α, α-Er Jiajibianji) phenyl]-benzotriazole; 2-(2-hydroxyl-3-dodecyl-5-aminomethyl phenyl) benzotriazole; 2-[2-hydroxyl-3-(α, α '-dimethyl benzyl)-5-(1,1,3, the 3-tetramethyl butyl) phenyl] benzotriazole; 2,2 '-methylene-bis [4-(1,1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol]; 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalimido methyl)-5-aminomethyl phenyl] benzotriazole; The 2-[3-tertiary butyl-5-(2-(2-ethyl hexyl oxy carbonyl ethyl))-2-hydroxy phenyl] benzotriazole; The 2-[(3-tertiary butyl-5-(2-methoxycarbonyl ethyl)-2-hydroxy phenyl) benzotriazole and Mw are about the interesterification product mixture of 300 polyoxyethylene glycol; The 5-chloro-2-[2-hydroxyl-3-tertiary butyl-5-(2-carbonyl octyloxy) ethylphenyl] benzotriazole.
The present invention also comprises by described uv stabilizing additive composition is contacted with the material that needs stabilization and prepares above method for compositions.Preferably by in the kneader device of single screw rod or twin screw extruder, Banbury Banbury mixer or hot-rolling and so on, needing the material of stabilization it to be contacted with uv stabilizing additive composition blending or compounding.The use of processing parameter and these kneader device is that those skilled in the art are well-known.
Technician in field of plastics manufacture knows clearly that very except the material and UV stable adding machine composition of wanting stabilization, composition of the present invention can comprise conventional additives, described conventional additives includes but not limited to antioxidant, metal passivator, azanol, nitrone, lactone, co-stabilizer, nucleator, finings, neutralizing agent, metallic stearate, metal oxide, hydrotalcite, filler and toughener, softening agent, lubricant, emulsifying agent, pigment, rheologic additive, catalyzer, flow agent, white dyes, fire retardant, static inhibitor and whipping agent, and combination.
Can use uv stabilizing additive composition and want the material of stabilization to make goods, for example extruded product and moulded parts, coating is with and film.Goods can be by extruding, and sheet material is extruded, injection moulding, blowing, injection blow molding, rotational molding or rotational moulding, calendering, thermoforming, compression moulding, vacuum moulding, pressure forming, reaction injection molding(RIM) and other similar approach moulding known in the art.In addition, can be by powder coating, extrude application, electrophoretic painting, spraying, dip-coating and other similar approach coating coatings known in the art.
Embodiment
Provide following examples that the present invention is described.These embodiment are not construed as limiting scope of the present invention.Gloss retention, residual elongation and residual tensile strength in embodiment 1-4. new LDPE (film grade) (LDPE) composition
By doing the ultraviolet additive mixing of the technology of mixing with embodiment 1-4.Except these additives, also will comprise 0.04 weight % (1,3,5-three-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-and s-triazine-2,4,6 (1H, 3H, 5H) triketone), 0.08 weight % tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (Cytec Industries Inc., W.Paterson, NJ) the antioxidant mixture with 0.05 weight % Zinic stearas mixes with described ultraviolet additive.These additives with available from Equistar, Davis Standard Killion is used in the new LDPE (film grade) of Houston TX (Microthene, MI=3.6, density=0.9395 grams per milliliter) compounding, extrudes parameter with the single screw rod of routine and extrudes.After extruding, use the injection moulding of Arburg injection moulding machine to form 2 * 2.5 * 0.125 inch plate of standard.
According to ASTM-G-26, in xenon Weather tester, under the water spray test condition, (for gloss is 500 hours setting exposure time interval to adopt the exposure of quickening, for residual elongation and residual tensile strength is 2500 hours) measurement gloss retention, the standard of performance of residual elongation and residual tensile strength.Before carrying out gloss and color measuring, with deionized water wash sample and wiping.
On the Gardner instrument, according to ASTM Test Procedure D523,60 ° of measurement of angle gloss retention.
Breaking tenacity goes up at Instron Engineering Company Tensile Tester (Series IX AutomatedTest System 7.51.00) and measures, and each data point is measured 5 tensile bar.Measure the average tensile break strength of three kinds of specimen, and carry out normalization method, try to achieve breaking tenacity % with respect to the sample of uv-exposure not.The pinblock speed of tester for elongation be 1 inch (0.254 centimetre)/minute.
The results are shown in following table 1-3.
The gloss retention percentage ratio of table 1. embodiment 1-4
| Embodiment | Explanation | 3500 hours gloss retention % | 4500 hours gloss retention % |
| 1 | 0.900% UV-3346,0.045% UV-1164,0.045% UV-531 | 87 | 71 |
| 2 | 0.900% UV-3346,0.090% UV-531 | 67 | 44 |
| 3 | 0.900% UV-3346,0.090% UV-1164 | 91 | 75 |
| 4 | 1.0% UV-3346 | 67 | 52 |
Cyasorb UV 3346 is 1, the 6-hexanediamine, and N, N '-two (2,2,6,6-tetramethyl--4-piperidyl)-, morpholine-2,4, the polymkeric substance (HALS) of 6-three chloro-1,3,5-triazines,
Cyasorb UV 1164 is 2-[4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-]-5-(octyloxy) phenol (triazine ultraviolet absorber),
Cyasorb UV 531 is Octabenzone (uv-absorbing agents).
The residual tensile strength of table 2. embodiment 1-4
| Embodiment | Explanation | 2500 hours residual tensile strength % | 5000 hours residual tensile strength % |
| 1 | 0.900% UV-3346,0.045% UV-1164,0.045% UV-531 | 87％ | 84％ |
| 2 | 0.900% UV-3346,0.090% UV-531 | 90％ | 76％ |
| 3 | 0.900% UV-3346,0.090% UV-1164 | 90％ | 77％ |
| 4 | 1.0% UV-3346 | 73％ | 69％ |
The remaining Zhongchang of table 3. embodiment 1-4
| Embodiment | Explanation | 2500 hours residual elongation % | 5000 hours residual elongation % |
| 1 | 0.900% UV-3346,0.045% UV-1164,0.045% UV-531 | 71％ | 71％ |
| 2 | 0.900% UV-3346,0.090% UV-531 | 82％ | 60％ |
| 3 | 0.900% UV-3346,0.090% UV-1164 | 69％ | 64％ |
| 4 | 1.0% UV-3346 | 49％ | 45％ |
The result shows that the performance of the compositions of additives of the triazine ultraviolet absorber with benzophenone that comprises half amount is better than only containing the composition of the triazine ultraviolet absorber of double amount.
Claims (14)
1. composition, said composition comprises the UV stable composition that contains following component:
(i) adjacent hydroxyl triaryl-s-triaizine compounds;
(ii) bulky amine compound;
(iii) hydroxy benzophenone ketone compound.
2. composition, said composition comprises the UV stable composition that contains following component:
(i) adjacent hydroxyl triaryl-s-triaizine compounds;
(ii) bulky amine compound;
(iii) hydroxy benzophenone ketone compound
Wherein the bulky amine compound is about 3: 1 to 25: 1 with the ratio of triaizine compounds; The bulky amine compound is about 1: 1 to 25: 1 with the ratio of hydroxy benzophenone ketone compound.
3. composition as claimed in claim 2, said composition also comprise a kind of material of wanting stabilization.
4. composition as claimed in claim 3 is characterized in that, is benchmark in the weight of the material of wanting stabilization, and the amount of triaizine compounds is about 20-2000ppm, and the amount of dihydroxy benaophenonel is about 20-5000ppm, and the amount of bulky amine is about 250-20000ppm.
5. composition as claimed in claim 3, it is characterized in that, the described material of stabilization of wanting is selected from: polyolefine, polyester, polyethers, polyketone, polymeric amide, natural rubber and synthetic rubber, urethane, polystyrene, high-impact polystyrene, polyacrylic ester, polymethacrylate, polyacetal, polyacrylonitrile, polyhutadiene, polystyrene, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile, acrylate-styrene-acrylonitrile, cellulose acetate butyrate, cellulose polymer compound, polyimide, polyamidoimide, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyethersulfone, polyvinyl chloride, polycarbonate, polyketone, aliphatic polyketones, thermoplastic olefin, amino resin crosslinked polyacrylic ester and polyester, the polyester of multi isocyanate crosslinking and polyacrylic ester, resol, urea-formaldehyde resin and melamine/formaldehyde resin, the Synolac of dryness and non-dryness, Synolac, vibrin is used melamine resin, urea resin, isocyanic ester, isocyanuric acid ester, the acrylate resin of carbamate and cross linking of epoxy resin, be derived from aliphatic series, alicyclic, the crosslinked Resins, epoxy of heterocycle family and aromatics glycidyl compound, this used for epoxy resin acid anhydrides or amine are crosslinked, polysiloxane, Michael addition polymer, amine, with active unsaturated compound and the end capped amine of methylene compound, have the ketoimine of active unsaturated compound and methylene compound, with the polyketone imines of unsaturated acrylic acid or the like polyacetoacetate resin combination, polyketone imines with unsaturated acrylic resin combination, radiation-hardenable composition, epoxy melamine resin, organic dye, makeup, cellulose base paper preparation, photographic film paper, fiber, wax, printing ink and composition thereof.
6. composition as claimed in claim 2 is characterized in that, described triazine is selected from: 2,4, and 6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazines; 2-(2-hydroxyl-4-n-octyloxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-(the different octyloxyphenyl of blended)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2, the 4-dihydroxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2, the 4-3,5-dimethylphenyl) of 4--1,3,5-triazines; 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (4-the aminomethyl phenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-dodecyloxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy-) phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-)-phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[4-dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-and the 2-hydroxy phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy propoxy-) phenyl]-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-; 2-(2-hydroxyl-4-hexyloxy) phenyl-4,6-phenylbenzene-1,3,5-triazines; 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-1,3,5-triazines and composition thereof.
7. composition as claimed in claim 2 is characterized in that, described bulky amine compound is selected from: 1H-pyrroles-2,5-diketone, the 1-octadecyl-, with (1-methyl ethylene) benzene and 1-(2,2,6,6-tetramethyl--4-piperidyl)-1H-pyrroles-2, the polymkeric substance of 5-diketone; Piperazine ketone, 1,1 ', 1 " [1,3,5-triazines-2,4,6-three bases three [(hexamethylene imino-)-2,1-ethane two bases]] three [3,3,5, the 5-tetramethyl--]; Piperazine ketone, 1,1 ', 1 " [1,3,5-triazines-2,4,6-three bases three [(hexamethylene imino-)-2,1-ethane two bases]] three [3,3,4,5, the 5-pentamethyl--]; 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; N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1,6-hexanediamine and 4-hexamethylene amino-2, the condenses of 6-two chloro-1,3,5-triazines; 1, two (3-amino propyl amino) ethane of 2-, 2,4,6-three chloro-1,3,5-triazines and 4-butyl amino-2,2,6, the condenses of 6-tetramethyl piperidine; N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1,6-hexanediamine and 4-morpholino-2, the condenses of 6-two chloro-1,3,5-triazines; 2-chloro-4, two (4-normal-butyl amino-2,2,6,6-the tetramethyl-piperidyl)-1,3,5-triazines and 1 of 6-, the condenses of two (3-amino propyl amino) ethane of 2-; 2-chloro-4, two (4-normal-butyl amino-1,2,2,6,6-pentamethyl-the piperidyl)-1,3,5-triazines and 1 of 6-, the condenses of 2-pair-(3-amino propyl amino) ethane; The 2-[(2-hydroxyethyl) amino]-4, two [N-(1-cyclohexyloxy-2,2,6, the 6-tetramethyl piperidine-4-yl) butyl amino-1,3,5-triazines of 6-; Propanedioic acid, [(4-p-methoxy-phenyl)-methylene radical]-two-(1,2,2,6,6-pentamethyl--4-piperidyl) ester; Four (2,2,6,6-tetramethyl piperidine-4-yl)-1,2,3,4-butane tetracarboxylic acid esters; Phenylpropionic acid, 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyls of 5--, 1-[2-[3-[3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-]-the 1-oxopropoxy] ethyl]-2,2,6,6-tetramethyl--4-piperidyl ester; N-(1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl)-N '-dodecyl oxamide; Three (2,2,6,6-tetramethyl piperidine-4-yl) nitrilotriacetate; 1, the 5-dioxo spiro 5,5} undecane-3,3-dicarboxylic acid, two (1,2,2,6,6-pentamethyl--4-piperidyl); 1, the 5-dioxo spiro 5,5} undecane-3,3-dicarboxylic acid, two (2,2,6,6-tetramethyl--4-piperidyl); 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 piperidine-4-yl)-1,6-hexanediamine and uncle's 4-octyl group amino-2, the condenses of 6-two chloro-1,3,5-triazines; 1,2,3,4-BTCA, 1,2,2,6,6-pentamethyl--4-piperidyl ester in three last of the ten Heavenly stems; Four (2,2,6,6-tetramethyl piperidine-4-yl)-1,2,3,4-butane tetracarboxylic acid esters; 1,2,3,4-BTCA, 2,2,6,6-tetramethyl--4-piperidyl ester in three last of the ten Heavenly stems; Four (1,2,2,6,6-pentamethyl-piperidin-4-yl)-1,2,3,4-butane tetracarboxylic acid esters; 2,2,4,4-tetramethyl--21-oxo-7-oxa--3.20-diaza spiro (5.1.11.2)-heneicosane-20-propionic acid-dodecane ester; 2,2,4,4-tetramethyl--21-oxo-7-oxa--3.20-diaza spiro (5.1.11.2)-heneicosane-20-propionic acid-tetradecane ester; 1H, 4H, 5H, 8H-2,3a, 4a, 6,7a, 8a-hexanitrogen heterocycle pentadiene is [def] fluorenes-4 also, the 8-diketone, six hydrogen-2,6-two (2,2,6,6-tetramethyl--4-piperidyl)-; Poly-methyl [propyl group-3-oxygen base (2 ', 2 ', 6 ', 6 '-tetramethyl--4,4 '-piperidyl)] siloxanes; Poly-methyl [propyl group-3-oxygen base (1 ', 2 ', 2 ', 6 ', 6 '-pentamethyl--4,4 '-piperidyl)] siloxanes; Methyl methacrylate and ethyl propenoate and 2,2,6, the multipolymer of 6-tetramethyl piperidine-4-base acrylate; Blended C
20-C
24The multipolymer of alhpa olefin and (2,2,6,6-tetramethyl piperidine-4-yl) succinimide; 1,2,3,4-BTCA, β, β, β ', β '-tetramethyl--2,4,8,10-four oxaspiros [5.5] undecane-3,9-di-alcohol, 1,2,2,6, the polymkeric substance of 6-pentamethyl--4-piperidyl ester; 1,2,3,4-BTCA, β, β, β ', β '-tetramethyl--2,4,8,10-four oxaspiros [5.5] undecane-3, the polymkeric substance of 9-di-alcohol, 2,2,6,6-tetramethyl--4-piperidyl ester copolymer; 1, the 3-benzenedicarboxamide, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl; 1,1 '-(1,10-dioxo-1,10-decane two bases)-two (six hydrogen-2,2,4,4,6-pentamethyl-pyrimidines; Oxalamide, N-(1-ethanoyl-2,2,6,6-tetramethyl-piperidyl)-N '-dodecyl; Methane amide, N, N '-1, the two [N-(2,2,6,6-tetramethyl--4-piperidyl) of 6-hexane two bases; The D-sorbitol, 1,3:2,4-pair-O-(2,2,6,6-tetramethyl--4-piperidylidene)-; 2,2,4,4-tetramethyl--7-oxa--3,20-diaza-21-oxo-two spiral shell [5.1.11.2] heneicosane; Propionic acid amide, 2-methyl-N-(2,2,6,6-tetramethyl--4-piperidyl)-2-[(2,2,6,6-tetramethyl--4-piperidyl) amino]-; 7-oxa--3,20-diaza two spiral shells [5.1.11.2] heneicosane-20-propionic acid, 2,2,4,4-tetramethyl--21-oxo-, dodecyl ester; N-(2,2,6,6-tetramethyl piperidine-4-yl)-β-An Jibingsuan dodecyl ester; N-(2,2,6,6-tetramethyl piperidine-4-yl)-N '-oxamic hydrazide; Propionic acid amide, N-(2,2,6,6-tetramethyl--4-piperidyl)-3-[(2,2,6,6-tetramethyl--4-piperidyl) amino]-; 4-n-Hexadecane oxygen base-and the stearic oxygen base-2,2,6 of 4-, the mixture of 6-tetramethyl piperidine; 3-dodecyl-1-(1,2,2,6,6-pentamethyl-piperidin-4-yl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1-ethanoyl-2,2,6,6-pentamethyl-piperidin-4-yl) tetramethyleneimine-2, the 5-diketone; Two (2,2,6,6-tetramethyl piperidine-4-yl) succinate; Two (1,2,2,6,6-pentamethyl-piperidin-4-yl) normal-butyl 3,5-di-tert-butyl-4-hydroxyl benzyl malonic ester; Three (2,2,6,6-tetramethyl piperidine-4-yl) nitrilotriacetate; 1,1 '-(1,2-ethane two bases) two (3,3,5,5-tetramethyl-piperazine ketone); 4-benzoyl-2,2,6, the 6-tetramethyl piperidine; The stearic oxygen base-2,2,6 of 4-, the 6-tetramethyl piperidine; Two (1,2,2,6,6-pentamethyl-piperidyl)-2-normal-butyl-2-(2-hydroxyl-3,5-di-t-butyl benzyl) malonic ester; 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone; Two (1-octyloxy-2,2,6,6-tetramethyl-piperidyl) sebate; Two (1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate; 8-ethanoyl-3-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone; 3-dodecyl-1-(2,2,6,6-tetramethyl piperidine-4-yl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethyl piperidine-4-yl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1,2,2,6,6-pentamethyl-piperidin-4-yl) tetramethyleneimine-2, the 5-diketone; 4-n-Hexadecane oxygen base-and the stearic oxygen base-2,2,6 of 4-, the mixture of 6-tetramethyl piperidine; 2-undecyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane; 1, the 5-dioxo spiro 5, and 5} undecane-3, the 3-dicarboxylic acid, two (2,2,6,6-tetramethyl--4-piperidyl) and 1, the 5-dioxo spiro 5,5} undecane-3,3-dicarboxylic acid, two (1,2,2,6,6-pentamethyl--4-piperidyl) and composition thereof.
8. composition as claimed in claim 2 is characterized in that described dihydroxy benaophenonel is selected from: 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-oxygen in last of the ten Heavenly stems base benzophenone, 2-hydroxyl-4-dodecyloxy benzophenone, 2-hydroxyl-4-benzyloxy benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,4-dihydroxyl-4 '-tertiary butyl-benzophenone; 1, two (3-hydroxyl-4-benzoyl phenoxy group) hexanes of 6-; Methylene-bis (2-benzoyl-5-methoxyphenol) and composition thereof.
9. composition as claimed in claim 2, said composition also comprises benzotriazole cpd.
10. composition, said composition comprises the UV stable composition that contains following component:
(i) adjacent hydroxyl triaryl-s-triaizine compounds;
(ii) bulky amine compound;
(iii) benzotriazole cpd
Wherein the bulky amine compound is about 3: 1 to 25: 1 with the ratio of triaizine compounds; The bulky amine compound is about 2: 1 to 10: 1 with the ratio of benzotriazole cpd.
11. composition as claimed in claim 10, said composition also comprise the material of wanting stabilization.
12. composition as claimed in claim 11 is characterized in that, is benchmark in the weight of the material of wanting stabilization, the amount of triaizine compounds is about 20-2000ppm, and the amount of benzotriazole is about 20-5000ppm, and the amount of bulky amine is about 250-20000ppm.
13. composition as claimed in claim 10, it is characterized in that, described benzotriazole cpd is selected from: 2-(2-hydroxy-5-methyl base phenyl)-benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl)-benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-benzotriazole, 5-chloro-2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-benzotriazole, 5-chloro-2-(2-hydroxyl-3,5-di-t-butyl-5-aminomethyl phenyl)-benzotriazole, 2-(2-hydroxyl-uncle's 3-phenyl-5-methyl)-benzotriazole, 2-(2-hydroxyl-3,5-two tert-pentyls)-and benzotriazole, 2-(2-hydroxyl-3-sec-butyl-5-tertiary butyl)-benzotriazole, 2-(2-hydroxyl-4-octyloxy)-benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl group)-benzotriazole, 2-[2-hydroxyl-3,5-two (α, α-Er Jiajibianji) phenyl]-benzotriazole; 2-(2-hydroxyl-3-dodecyl-5-aminomethyl phenyl) benzotriazole; 2-[2-hydroxyl-3-(α, α '-dimethyl benzyl)-5-(1,1,3, the 3-tetramethyl butyl) phenyl] benzotriazole; 2,2 '-methylene-bis [4-(1,1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol]; 2, [2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalimido methyl)-5-aminomethyl phenyl] benzotriazole; The 2-[3-tertiary butyl-5-(2-(2-ethyl hexyl oxy carbonyl ethyl))-2-hydroxy phenyl] benzotriazole; The 2-[(3-tertiary butyl-5-(2-methoxycarbonyl ethyl)-2-hydroxy phenyl) benzotriazole and Mw are about the interesterification product mixture of 300 polyoxyethylene glycol; The 5-chloro-2-[2-hydroxyl-3-tertiary butyl-5-(2-carbonyl octyloxy) ethylphenyl] benzotriazole and composition thereof.
14. composition as claimed in claim 2 is characterized in that, the bulky amine compound is about 3: 1 to 25: 1 with the ratio of triaizine compounds; The bulky amine compound is about 2: 1 to 10: 1 with the ratio of hydroxy benzophenone ketone compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51730203P | 2003-11-04 | 2003-11-04 | |
| US60/517,302 | 2003-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1875061A true CN1875061A (en) | 2006-12-06 |
Family
ID=34590150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800326886A Pending CN1875061A (en) | 2003-11-04 | 2004-11-03 | Uv stabilizing additive composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1680465A1 (en) |
| JP (1) | JP2007510781A (en) |
| KR (1) | KR20060113934A (en) |
| CN (1) | CN1875061A (en) |
| WO (1) | WO2005047384A1 (en) |
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| CN103255501A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| CN105237882A (en) * | 2014-09-25 | 2016-01-13 | 黄秀茹 | Polypropylene composition |
| CN105486558A (en) * | 2015-12-24 | 2016-04-13 | 上海微谱化工技术服务有限公司 | Separation and detection methods of benzotriazole light stabilizer in polyphenyl ether engineering plastics |
| CN106661365A (en) * | 2014-06-25 | 2017-05-10 | 3M创新有限公司 | Fluoropolymer composition including at least one oligomer |
| CN109135395A (en) * | 2018-09-03 | 2019-01-04 | 烟台新秀化学科技股份有限公司 | A kind of preparation method of water dispersible light stabilizer |
| WO2019072202A1 (en) * | 2017-10-12 | 2019-04-18 | 优缔新材料科技(苏州)有限公司 | Novel triazine compound, composition thereof, and preparation method therefor |
| CN111116982A (en) * | 2014-11-20 | 2020-05-08 | 塞特工业公司 | Stabilizer composition and method for protecting organic materials from UV light and thermal degradation using the same |
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| TW200829637A (en) | 2007-01-03 | 2008-07-16 | Double Bond Chemical Ind Co Ltd | Liquid containing 2-(-hydroxyl-3-α-cumylphenyl-5-tertiery-octylphenyl) -2-hydrogen-benzotriazole |
| JP2009066241A (en) * | 2007-09-14 | 2009-04-02 | Sri Sports Ltd | Golf ball |
| DE102008001475A1 (en) | 2008-04-30 | 2009-11-05 | Evonik Degussa Gmbh | Phenolic resin-containing polymer composition |
| JP5693274B2 (en) * | 2011-02-07 | 2015-04-01 | 積水フィルム株式会社 | Agricultural film |
| EP2647664A1 (en) * | 2012-04-04 | 2013-10-09 | Cytec Technology Corp. | Method for stabilizing polyolefin films against UV degradation |
| TWI624519B (en) | 2012-12-20 | 2018-05-21 | ３Ｍ新設資產公司 | Fluoropolymer composition including an oligomer having an ultraviolet absorbing group |
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| MA57229A1 (en) * | 2020-02-10 | 2022-11-30 | Basf Se | Light stabilizer mixture |
| JPWO2022065230A1 (en) * | 2020-09-28 | 2022-03-31 | ||
| EP4373886A1 (en) * | 2021-07-17 | 2024-05-29 | Basf Se | An additive mixture for stabilization of organic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6051164A (en) * | 1998-04-30 | 2000-04-18 | Cytec Technology Corp. | Methods and compositions for protecting polymers from UV light |
| WO2003057772A2 (en) * | 2001-12-27 | 2003-07-17 | Cytec Technology Corp. | Uv stabilized thermoplastic olefins |
-
2004
- 2004-11-03 EP EP04800664A patent/EP1680465A1/en not_active Withdrawn
- 2004-11-03 CN CNA2004800326886A patent/CN1875061A/en active Pending
- 2004-11-03 JP JP2006538454A patent/JP2007510781A/en active Pending
- 2004-11-03 WO PCT/US2004/036602 patent/WO2005047384A1/en not_active Application Discontinuation
- 2004-11-03 KR KR1020067010795A patent/KR20060113934A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103255501A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| CN106661365A (en) * | 2014-06-25 | 2017-05-10 | 3M创新有限公司 | Fluoropolymer composition including at least one oligomer |
| CN106661365B (en) * | 2014-06-25 | 2019-03-01 | 3M创新有限公司 | Fluoro-containing copolymer composition comprising at least one oligomer |
| CN105237882A (en) * | 2014-09-25 | 2016-01-13 | 黄秀茹 | Polypropylene composition |
| CN111116982A (en) * | 2014-11-20 | 2020-05-08 | 塞特工业公司 | Stabilizer composition and method for protecting organic materials from UV light and thermal degradation using the same |
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| CN105486558B (en) * | 2015-12-24 | 2018-05-29 | 上海微谱化工技术服务有限公司 | The separation of benzotriazole light stabilizer and detection method in polyphenyl ether engineering plastic |
| WO2019072202A1 (en) * | 2017-10-12 | 2019-04-18 | 优缔新材料科技(苏州)有限公司 | Novel triazine compound, composition thereof, and preparation method therefor |
| CN109651275A (en) * | 2017-10-12 | 2019-04-19 | 优缔新材料科技(苏州)有限公司 | Novel compound in triazine class, its composition and preparation method thereof |
| CN109651275B (en) * | 2017-10-12 | 2022-12-06 | 江苏裕事达新材料科技有限责任公司 | Triazine compound, composition and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20060113934A (en) | 2006-11-03 |
| EP1680465A1 (en) | 2006-07-19 |
| JP2007510781A (en) | 2007-04-26 |
| WO2005047384A1 (en) | 2005-05-26 |
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