Stabilized polyolefin resin composition

Information

  • Patent Grant
  • 5081170
  • Patent Number
    5,081,170
  • Date Filed
    Friday, March 22, 1991
    33 years ago
  • Date Issued
    Tuesday, January 14, 1992
    32 years ago
Abstract
The present invention provides a stabilized polyolefin resin composition having improved resistances to oxidation and to weather which is prepared by adding (a) a phenol antioxidant, (b) a sulfur antioxidant, (c) a hindered amine light stabilizer and (d) an aliphatic monocarboxylate of a metal belonging to the group Ia or IIb to a polyolefin resin containing an inorganic filler.
Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a stabilized polyolefin resin composition. More particularly, it relates to a polyolefin resin composition having improved resistances to oxidation and to weather which is prepared by adding a phenol antioxidant, a sulfur antioxidant, a hindered amine light stabilizer and an aliphatic monocarboxylate of a metal belonging to the group Ia or IIb to a polyolefin resin containing an inorganic filler.
2. Description of the Prior Art
It is known that a polyolefin resin such as polyethylene or polypropylene is deteriorated by, for example, heat, light, oxygen or nitrogen oxide and consequently becomes inavailable any more since it is colored or its mechanical strengths are lowered.
In order to prevent such deterioration of a polyolefin resin, there have been applied a number of additives either alone or as various mixtures.
Among these additives, a phenol antioxidant is widely employed as a basic stabilizer. However it can exert only a limited effect when employed alone. Thus it is combined with other additive(s) depending on the purpose of the application. For example, it is combined with a sulfur antioxidant such as a dialkyl thiodipropionate in order to achieve a high heat resistance. Further it is combined with various light stabilizers in order to achieve a high weather resistance. Furthermore it is combined with both of a sulfur antioxidant and a light stabilizer in order to achieve high resistances to heat as well as to weather.
Examples of the light stabilizer to be combined with a phenol antioxidant include benzophenone, benzotriazole and benzoate UV absorbers and hindered amine compounds. In particular, the application of hindered amine light stabilizers such as a polyalkylpiperidine has been more and more increasing since they are noncoloring, exert a high photostabilizing effect and improve the heat resistance.
However it is known that the combined use of a hindered amine light stabilizer and a sulfur antioxidant would offset the effects with each other. In this case, the weather resistance of the obtained product would be particularly lowered. Thus a composition containing a hindered amine light stabilizer is generally free from any sulfur anitoxidant.
A carboxylate of a metal belonging to the group IIa, such as calcium stearate, has been commonly used in order to neutralize a residual catalyst in a polyolefin resin or to improve the lubricity thereof, though this additive would scarcely affect the resistance to heat or to weather thereof.
An inorganic filler such as talc or calcium carbonate is added to a polyolefin resin in order to improve the stiffness, mechanical properties and dimentional accuracy thereof. A polyolefin resin containing an inorganic filler is generally used in a product which should have a high weather resistance, for example, an automotive part or an electrical appliance to be used outdoor or under a fluorescent lamp. Therefore an inorganic filler should be combined with a light stabilizer. A hindered amine light stabilizer is commonly employed therefor since it is noncoloring and can exert a high stabilizing effect.
However the effect of an antioxidant on a polyolefin resin containing an inorganic filler is significantly lower than that on a polyolefin resin free from any inorganic filler. Accordingly a two-component system comprising a phenol antioxidant and a hindered amine light stabilizer cannot give any sufficient heat resistance. Thus it is required to further add a sulfur antioxidant thereto in order to achieve a satisfactory heat resistance. As described above, however, the combined use of a hindered amine light stabilizer and a sulfur antioxidant would significantly lower the effect of the hindered amine light stabilizer in improving the weather resistance. Namely, it is impossible to satisfactorily improve both of the resistances to weather and to heat by this system.
Accordingly there has been urgently required to develop a polyolefin resin composition containing an inorganic filler wherein the combined use of a phenol antioxidant, a sulfur antioxidant and a hindered amine light stabilizer would lower none of the effects of these additives.
SUMMARY OF THE INVENTION
Under these circumstances, the present inventors have conducted extensive studies and consequently found that the decrease in the effect of a hindered amine light stabilizer can be significantly inhibited by simultaneously employing a phenol antioxidant, a sulfur antioxidant, a hindered amine light stabilizer together with an aliphatic monocarboxylate of a metal belonging to the group Ia or IIb and that not only the stability but also the thermal stability of the resulting composition are higher, in some cases, than those of a composition free from any sulfur antioxidant, thus completing the present invention.
Accordingly, the polyolefin resin composition of the present invention is prepared by adding (a) a phenol antioxidant, (b) a sulfur antioxidant, (c) a hindered amine light stabilizer and (d) an aliphatic monocarboxylate of a metal belonging to the group Ia or IIb to a polyolefin resin containing an inorganic filler.
DETAILED DESCRIPTION OF THE INVENTION
Examples of the polyolefin resin to be used in the present invention include poly-.alpha.-olefins and .alpha.-olefin copolymers such as low-density polyethylene, high-density polyethylene, straight-chain low density polyethylene[ethylene/.alpha.-olefin (C.sub.3 -C.sub.8) copolymers such as ethylene/butene-1 copolymer], polypropylene, propylene/ethylene copolymer, polybutene-1, poly-3-methylbutene, poly-4-methylpentene and ethylene/vinyl acetate copolymer.
Examples of the phenol antioxidant (a) to be used in the present invention include 2,6-di-tert-butyl-p-cresol, stearyl (3,5-dimethyl-4-hydroxybenzyl)-thioglycolate, stearyl .beta.-(4-hydroxy-3,5-di-tert-butylphenol)propionate, distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydrohybenzylthio)1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], bis[3,5-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,6-di(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol), stearyl .beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionate, triethylene glycol bis[.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate] and 3,9-bis[1,1-dimethyl-2-(.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane. Among these phenol antioxidants, esters of .beta.-(3,5-dialkyl-4-hydroxyphenyl)propionic acids and those having an isocyanuric acid ring, for example, stearyl .beta.-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris[3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, stearyl .beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol bis[.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]and 3,9-bis[1,1-dimethyl-2-(.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane are highly effective and thus particularly preferable.
The phenol antioxidant may be added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, to 100 parts by weight of the abovementioned polyolefin resin.
Examples of the sulfur antioxidant (b) to be used in the present invention include dialkyl thiodipropionates such as dilauryl, dimyristyl and distearyl thiodipropionates, esters of alkylthiopropionic acids such as butyl-, octyl-, lauryl- and stearylthiopropionic acids with polyhydric alcohols such as glycerol, trimethylolethane, trimethylolpropane, pentaerythritol and trishydroxyethyl isocyanurate, such as pentaerythritol tetrakisdodecylthiopropionate.
The sulfur antioxidant may be preferably added in an amount of 0.001 to 5 parts by weight, still preferably 0.01 to 3 parts by weight, to 100 parts by weight of the abovementioned polyolefin resin.
The hindered amine light stabilizer (c) to be used in the present invention is a compound having a group represented by the formula ##STR1##
Examples are as follows:
No. 1: 4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
No. 2: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
No. 3: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
No. 4: bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-butyl-2-(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate,
No. 5: bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
No. 6: bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate,
No. 7: tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
No. 8 tris(2,2,6,6-tetramethyl-4-piperidyl) butanetricarboxylate,
No. 9: tris(2,2,6,6-tetramethyl-4-piperidyl) trimellitate,
No. 10: tetra(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
No. 11: tris(2,2,6,6-tetramethyl-4-piperidyl) mono(isotridecyl) 1,2,3,4-butanetetracarboxylate,
No. 12: tetra(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
No. 13: tris(1,2,2,6,6-pentamethyl-4-piperidyl) mono(isotridecyl) 1,2,3,4-butanetetracarboxylate,
No. 14: bis(1,2,2,6,6-pentamethyl-4-piperidyl) di(tridecyl) 1,2,3,4-butanetetracarboxylate,
No. 15: bis(2,2,6,6-tetramethyl-4-piperidyl) di(tridecyl) 1,2,3,4-butanetetracarboxylate,
No. 16: 3,9-bis[1,1-dimethyl-2-[tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane,
No. 17: 3,9-bis[1,1-dimethyl-2-[tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane,
No. 18: N-(2,2,6,6-tetramethyl-4-piperidyl)dodecylsuccinimide,
No. 19: 2-butylamino-4,6-bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethoxy)-s-triazine,
No. 20: N,N'-bis[4,6-bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethoxy)-s-triazin-2-yl]piperidine,
No. 21: 1,5,8,12-tetrakis[4,6-bis[N-2,2,6,6-tetramethyl-4-piperidyl)butylamino]-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane,
No. 22: bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl) hydrogenated bisphenol A dicarbonate,
No. 23: bis(2,2,6,6-tetramethyl-4-piperidyl) pentaerythritol diphosphite,
No. 24: 1-(2-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol/dimethyl succinate polycondensate,
No. 25: 2-tert-octylamino-4,6-dichloro-s-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine polycondensate,
No. 26 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate,
No. 27: bis(9-aza-8,8,10,19-tetramethyl-3-hydroxymethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl) ether,
No. 28: 3-glycidyl-8-methyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
No. 29: 3-dodecyl-8-acetyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
No. 30: 3-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
No. 31: 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosan-21-one and
No. 32: 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-2,5-pyrrolidinedione.
The hindered amine light stabilizer may be preferably added in an amount of 0.001 to 5 parts by weight, still preferably 0.05 to 1 parts by weight, to 100 parts by weight of the abovementioned polyolefin resin.
Examples of the aliphatic monocarboxylate of a metal belonging to the group Ia or IIb (d) to be used in the present invention include octylates, laurates, myristates, stearates, oleates, ricinoleates and behenates of sodium, potassium, lithium, zinc and cadmium. Among these compounds, an aliphatic monocarboxylate carrying 10 to 20 carbon atoms of a metal belonging to the group Ia is particularly preferable.
The metal salt may be preferably added in an amount of 0.01 to 5 parts by weight, still preferably 0.1 to 3 parts by weight, to 100 parts by weight of the abovementioned polyolefin resin.
Examples of the inorganic filler contained in the abovementioned polyolefin resin include talc, light and heavy calcium carbonate, calcined clay, hard clay, kaolin clay, kieselguhr, acid clay, silicic anhydride, synthetic silicic acid, white carbon, asbestos, alumina, glass flake and glass fiber.
The inorganic filler may be added in an amount of 5 to 100 parts by weight, generally 10 to 50 parts by weight, to 100 parts by weight of the abovementioned polyolefin resin.
In addition, the composition of the present invention may contain a phosphorus compound such as a phosphite to thereby further improve the light and heat resistances. Examples of the phosphorus compound include tridecyl phosphite, octyl diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol disphospite, hexa(tridecyl) 1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite, tetra (mixed C.sub.12 -C.sub.15 alkyls) 4,4'-isopropylidenediphenyl diphosphite, tetra(tridecyl) 4,4'-butylidenebis(3-methyl-6-tert-butylphenyl) disphosphite, tris(3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris(mono- and di-mixed nonylphenyl) phosphite, hydrogenated 4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl) bis [4,4'-butylidenebis(3-methyl-6-tert-butylphenyl)]1,6-hexanediol diphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritol disphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol disphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol disphoshite, tris[4,4'-isopropylidenebis(2-tert-butylphenyl)]phosphite, di(nonylphenyl) pentaerythritol disphosphite, 4,4'-isopropylidenebis(2-tert-butylphenol) di(nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenathrene 10-oxide and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite. Among these compounds, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol disphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite are particularly effective and thus preferable.
The phosphorus compound may be preferably added in an amount of 0.001 to 5 parts by weight, still preferably 0.01 to 3 parts by weight, to 100 parts by weight of the abovementioned polyolefin resin.
The composition of the present invention may contain an UV absorber to thereby further improve the light resistance. Examples of the UV absorber include benzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, benzotriazoles such as 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3,40 ,5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole and 2-(2'-hydroxy-3',5'-di-t-amylphenyl)-benzotriazole, benzoates such as phenyl salicylate, p-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate, substituted acrylonitriles such as methyl .alpha.-cyano-.beta.-methyl-.beta.-(p-methoxyphenyl)acrylate and oxalic diamides such as N-2-ethylphenyl-N'-2-ethoxy-5-tert-butylphenyloxalic diamide.
The composition of the present invention may further contain various additives such as nucleating agent, organic tin compound, plasticizer, epoxy compound, pigment, foaming agent, antistatic agent, fire retardant, lubricant or processing aid, if desired.
To further illustrate the present invention, and not by way of limitation, the following Examples will be given.





Example 1
The following composition was pelletized by extrusion at 250.degree. C. Then these pellets were injection molded at 250.degree. C. into a test piece of 1 mm in thickness. The weather resistance of this piece was evaluated with a sunshine weatherometer at a black panel temperature of 83.degree. C. while the heat resistance thereof was evaluated in a geer oven at 150.degree. C. For comparison, a composition containing no talc filler was treated in the same manner.
Table 1 shows the results.
______________________________________Composition: part by weight______________________________________polypropylene (Profax 6501) 100talc 30tetrakis[methylene-.beta.-(3,5-di- 0.1t-butyl-4-hydroxyphenyl)propionate]methaneadditive (cf. Table 1) cf. Table 1______________________________________
TABLE 1______________________________________ Amount Weather Heat (part by resistance resistanceNo. Additive weight) (hr) (hr)______________________________________Comparative Example(containing no talc)1-1 none 180 5501-2 DSTDP*.sup.1 0.3 240 21801-3 HALS*.sup.2 cpd. No. 10 0.3 1500 12601-4 DSTP 0.3 780 1950 HALS*.sup.2 cpd. No. 10 0.3Comparative Example(containing talc)1-5 none -- 120 201-6 DSTDP 0.3 180 3401-7 HALS cpd. No. 10 0.3 1020 5001-8 DSTPD 0.3 660 1170 HALS cpd. No. 10 0.31-9 DSTDP 0.3 660 1080 HALS cpd. No. 10 0.3 calcium stearate 0.3Example(containing talc)1-1 DSTDP 0.3 1260 1270 HALS cpd. No. 10 0.3 sodium stearate 0.31-2 DSTDP 0.3 1280 1250 HALS cpd. No. 10 0.3 sodium laurate 0.31-3 DSTDP 0.3 1200 1220 HALS cpd. No. 10 0.3 potassium stearate 0.31-4 DSTDP 0.3 1140 1170 HALS cpd. No. 10 0.3 zinc stearate 0.3______________________________________ *.sup.1 DSTDP: distearyl thiodipropionate. *.sup.2 : a hindered amine light stabilizer.
Example 2
A test piece was prepared from the following composition in the same manner as the one described in Example 1. The weather resistance of the piece was evaluated with a sunshine weatherometer at a black panel temperature of 83.degree. C. while the heat resistance thereof was evaluated in a geer oven at 150.degree. C.
Table 2 shows the results.
______________________________________Composition: part by weight______________________________________polypropylene (Profax 6501) 100calcium stearate 0.05talc 301,3,5-tris-(3,5-di-t-butyl-4- 0.1hydroxybenzyl) isocyanurateadditive (cf. Table 2) cf. Table 2______________________________________
TABLE 2______________________________________ Amount Weather Heat (part by resistance resistanceNo. Additive weight) (hr) (hr)______________________________________Comparative Example2-1 none -- 120 202-2 DMTDP* 0.3 180 3202-3 HALS cpd. No. 2 0.5 960 4802-4 sodium stearate 0.3 120 202-5 DMTDP 0.3 620 1030 HALS cpd. No. 2 0.52-6 DMTDP 0.3 180 350 sodium stearate 0.32-7 HALS cpd. No. 2 0.5 980 500 sodium stearate 0.32-8 DMTDP 0.3 620 1010 HALS cpd. No. 2 0.5 calcium stearate 0.3Example2-1 DMTDP 0.3 1280 1160 HALS cpd. No. 2 0.5 sodium stearate 0.32-2 DMTDP 0.3 1250 1120 HALS cpd. No. 2 0.5 sodium laurate 0.3______________________________________ *DMTDP: dimyristyl thiodipropionate.
Example 3
A test piece was prepared from the following composition in the same manner as the one described in Example 1. The weather resistance of the piece was evaluated with a sunshine weatherometer at a black panel temperature of 83.degree. C.
Table 3 shows the results.
______________________________________Composition: part by weight______________________________________polypropylene (Profax 6501) 100talc 30tetrakis[methylene-.beta.-3,5-di-t- 0.3butyl-4-hydroxyphenyl)propionate]methaneHALS compound No. 10 0.3distearyl thiodipropionate (DSTDP) 0.3metal salt (cf. Table 3) cf. Table 3______________________________________
TABLE 3______________________________________ Amount Weather (part by resistance ImprovementNo. Metal salt weight) (hr) (%)______________________________________Comparative Example3-1 none (no DSTDP) -- 1020 (100)3-2 none -- 660 (0)3-3 calcium stearate 0.1 660 (0)3-4 calcium stearate 0.3 660 (0)Example3-1 sodium stearate 0.1 980 893-2 sodium stearate 0.2 1100 1223-3 sodium stearate 0.3 1260 1673-4 sodium stearate 0.5 1300 1783-5 sodium laurate 0.1 960 833-6 sodium laurate 0.2 1160 1393-7 sodium laurate 0.3 1280 1723-8 zinc stearate 0.1 920 723-9 zinc stearate 0.2 1020 100 3-10 zinc stearate 0.3 1140 133______________________________________
Example 4
A test piece was prepared from the following composition in the same manner as the one described in Example 1. The weather resistance of the piece was evaluated with a sunshine weatherometer at a black panel temperature of 83.degree. C. For comparison, a sample containing no sodium stearate (Na-St) was treated in the same manner.
Table 4 shows the results.
______________________________________Composition: part by weight______________________________________polypropylene (Profax 6501) 100calcium stearate 0.05talc 30tetrakis[methylene-.beta.-3,5-di-t- 0.1butyl-4-hydroxyphenyl)propionate]methanedistearyl thiodipropionate 0.3sodium stearate 0.3HALS compound (cf. Table 4) cf. Table 4______________________________________
TABLE 4______________________________________ Weather resistance (hr)No. HALS compound Na-St added No Na-St______________________________________4-1 No. 2 1140 6504-2 No. 12 1420 7804-3 No. 14 1200 6604-4 No. 15 1330 7204-5 No. 17 1450 8104-6 No. 18 1330 8004-7 No. 24 1040 6004-8 No. 25 1100 6404-9 No. 26 1080 600______________________________________
Tables 1 to 4 suggest the following facts.
In the case of the compositions containing no talc filler, satisfactory resistances to weather and to heat can be obtained in a two-component system comprising a phenol anitoxidant and an HALS. On the other hand, in the case of those containing a talc filler, said two-component system shows an insufficient heat resistance. A three-component system prepared by adding a sulfur antioxidant thereto shows an improved heat resistance but a significantly lowered weather resistance. The addition of commonly employed calcium stearate to the three-component system exerts no positive effect but rather lowers the heat resistance.
In contrast thereto, the composition prepared by adding a specific metal salt of the present invention to the abovementioned three-component system shows an unexpectedly improved weather resistance without showing any decrease in the heat resistance. The weather resistance of this composition is sometimes higher than that achieved by using the two-component system as described above containing no sulfur antioxidant.
Claims
  • 1. A stabilized polyolefin resin composition prepared by adding (a) a phenol anitoxidant, (b) a sulfur antioxidant, (c) a hindered amine light stabilizer and (d) an aliphatic monocarboxylate of a metal belonging to the group Ia or IIb to a polyolefin resin containing from 10 to 50 parts by weight of talc as an inorganic filler, to 100 parts by weight of said polyolefin resin.
  • 2. The polyolefin resin composition as set forth in claim 1, wherein 0.001 to 5 parts by weight of said phenol antioxidant (a) 0.001 to 5 parts by weight of said sulfur antioxidant, (b) 0.001 to 5 parts by weight of said hindered amine light stabilizer, (c) and 0.01 to 5 parts by weight of said aliphatic monocarboxylate of a metal belonging to the group Ia or IIb are added to 100 parts by weight of said polyolefin resin containing from 10 to 50 parts by weight of talc as the inorganic filler.
  • 3. The polyolefin resin composition of claim 2, wherein said polyolefin resin is selected from among poly-.alpha.-olefins and .alpha.-olefin copolymers selected from the group consisting of low-density polyethylene, high-density poly-ethylene, linear low-density polyethylenes, polypropylene, propylene/ethylene copolymer, polybutene-1, poly-3-methylbutene, poly-4-methylpentene and ethylene/vinyl acetate copolymer.
  • 4. The polyolefin resin composition of claim 3, wherein said polyolefin resin is an ethylene/.alpha.-olefin (C.sub.3 -C.sub.8) copolymer.
  • 5. The polyolefin resin composition of claim 2, wherein said polyolefin resin is an ethylene/butene-1 copolymer; polypropylene, propylene/ethylene copolymer, polybutene-1, or poly-3-methylbutene, poly-4-methylpentene and ethylene/vinyl acetate copolymer;
  • said phenol antioxidant is 2,6-di-tert-butyl-p-cresol, stearyl (3,5-dimethyl-4-hydroxybenzyl)-thioglycolate, stearyl 8-(4-hydroxy-3,5-di-tert-4-hydroxybenzylphosphonate, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydrohybenzylthio)1,3,5-triazine, distearyl(4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate, 2,4'-methylenebis(4-methyl-6-tertbutylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'--methylenebis[6-(1-methylcyclohexyl)-p-cresol], bis[3,5-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5methylbenzyl)phenyl]terephthalate,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethyl-benzene, 2,6-diphenyl-4-octadecyloxyphenol, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,]1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,2-octylthio-4,6-di(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol), stearyl .beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionate, tuethylene glycol bis [.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate] and 3,9-bis[1,1-dimethyl-2-(8-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro [5.53]-undecane.
  • said sulfur antioxidants are dilauryl, dimyristyl and distearyl thiodipropionates; esters of butyl-, octyl-, lauryl- and stearylthiopropionic acids with glycerol, trimethylolethane, trimethylol-propane, pentaerythritol and trishydroxyethyl isocyanurate;
  • said hindered amine light stabilizer is 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-butyl-2-(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl)sebacate, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tris(2,2,6,6-tetramethyl-4-piperidyl) butanetricarboxylate, tris(2,2,6,6-tetramethyl-4-piperidyl) trimellitate, tetra(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tris(2,2,6,6-tetramethyl-4-piperidyl)mono(isotridecyl) 1,2,3,4-butanetetra-carboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tris(1,2,2,6,6-pentamethyl-4-piperidyl) mono(isotridecyl) 1,2,3,4-butanetetra-carboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)di(tridecyl) 1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)di(tridecyl)1,2,3,4-butanetetracarboxylate, 3,9-bis[1,1-dimethyl-2-]tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butyl-carbonyloxy]ethyl3-2,4,8,10-tetraoxaspiro-[5.5]undecane, 3,9-bis[1,1-dimethyl-2-tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butyl-carbonyloxy[ethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane, N-(2,2,6,6-tetramethyl-4-piperidyl)dodecyl-succinimide, 2-butylamino-4,6-bis(9-aza-8,8,10,10-tetra-methyl-3-ethyl-1,5-dioxaspiro[5.5]-3 -undecylmethoxy)-s-triazine, N,N'-bis[4,6-bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethoxy)-s-triazin-2-yl]piperidine, 1,5,8,12-tetrakis[4,6-bis[N-2,2,6,6-tetramethyl-4-piperidyl)butylamino]-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane, bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl)hydrogenated bisphenol A dicarbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) pentaerythritol diphosphite, 1-(2-hydroxymethyl-2,2,6,6-tetramethyl-4-piperidinol/dimethyl succinate polycondensate, 2-tert-octylamino-4,6-dichloro-s-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate, bis(9-aza-8,8,10,19-tetramethyl-3-hydroxy-methyl-1,5-dioxaspiro[5.5]-3-undecylmethyl) ether, 3-glycidyl-8-methyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-8-acetyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5.1.11.2]heneicosan-21-one and or 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-2,5-pyrrolidinedione.
  • 6. The polyolefin composition of claim 5, wherein said aliphatic monocarboxylate of metal belonging to the group Ia or IIb is an octylate, laurate, myristate, stearate, oleate, ricinoleate and behenate of sodium, potassium, lithium, zinc and cadmium.
Priority Claims (1)
Number Date Country Kind
62-193483 Jul 1987 JPX
Parent Case Info

This application is a continuation of application Ser. No. 07/224,066, filed July 25, 1988 (abandoned).

US Referenced Citations (3)
Number Name Date Kind
4590231 Seltzer et al. May 1986
4703073 Winter et al. Oct 1987
4812500 Hayden Mar 1989
Non-Patent Literature Citations (2)
Entry
Kazumi, Kikkawa et al "Antagonism Between Hundered Amine Stabilizers and Sulfur-Containing Compounds" Polymer Degradation and Stability 18(1987) pp. 237-245.
Stephen W. Bigger et al, "The Effect of Hindered Amine Light Stabilizers on the Photooxidative Stability of High Density Polyethylene" J. Polymer Science: Part A: Polymer Chemistry, 27, 63-73 (1989).
Continuations (1)
Number Date Country
Parent 224066 Jul 1988