Polymeric composition

A polymeric composition in which (D) a phenol antioxidant having a specific skeleton 5-t-butyl-3-methyl-4-hydroxyphenyl, (C) a hindered amine photostabilizer having a molecular weight of not less than 400, and (D) a specific phosphorus compound dihydrooxaphosphaphenanthrene are included in (A) a polymeric compound. This polymeric composition is excellent in thermal oxidation degradation resistance and discoloration of coloring resistance in contacting with a combustion gas or the like.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a polymeric composition, more particularly 
a polymeric composition which comprises a specific phenol antioxidant, a 
specific light stabilizer and a specific phosphorus compound in a 
polymeric compound. 
2. Description of the Prior Art 
Polymeric compound such as polyethylene and polypropylene are known to 
contain a phenol antioxidant, phosphorus compound, light stabilizer and 
the like to improve thermal oxidation degradation and photodegradation. 
For example, it is known that 
tetrakismethylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate!methane 
having a 2,6-di-t-butylphenol skeleton, a hindered amine light stabilizer 
and a phosphorus compound are added to a polymeric compound (for example, 
Japanese Patent Kokai Publication 351669/1992). 
However, this composition does not necessarily withstand thermal oxidation 
degradation, therefore improvement in oxidation degradation resistance is 
desirable. 
In consideration of such circumstances, the present inventors have 
developed a polymeric compound with greatly improved thermal oxidation 
degradation resistance. As the result, the present inventors have found 
that, when a phenol antioxidant having a specific skeleton, 
o-t-butyl-o'-methyl-phenolic group, a hindered amine light stabilizer 
having a molecular weight of not less than 400 and a specific phosphorus 
compound, dihydrooxaphosphaphenanthrene are added, thermal oxidation 
degradation resistance is remarkably improved and also discoloration or 
coloring in contacting with a combustion gas and the like is prevented, 
and have accomplished the present invention. 
SUMMARY OF THE INVENTION 
The present invention provides a polymeric composition having excellent 
thermal oxidation degradation resistance and discoloration or coloring 
resistance, which comprises 
(A) a polymeric compound; 
(B) a phenol antioxidant represented by the general formula (I): 
##STR1## 
wherein R.sup.1 is a hydrogen atom or lower alkyl group; n is 2 or 3; 
R.sup.2 is a divalent alcohol residue when n is 2, and is a isocyanuric 
acid residue when n is 3; X is a lower alkylenecarbonyloxy group when n is 
2, and is a lower alkylene group when n is 3); 
(C) a hindered amine photostabilizer having a molecular weight of not less 
than 400; and 
(D) a dihydrooxaphosphaphenanthrene compound represented by the general 
formula (II) 
##STR2## 
wherein R.sup.3 and R.sup.4, which are same or different, are a hydrogen 
atom, halogen atom or lower alkyl group. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The phenol antioxidant (B) represented by the above-described general 
formula (I) of the present invention has a specific skeleton, 
o-t-butyl-o'-methyl-phenolic group, and the substituent R.sup.1 is a lower 
alkyl group such as a hydrogen atom, methyl, ethyl, propyl, i-isopropyl, 
butyl, i-butyl, sec-butyl, t-butyl and pentyl. R.sup.1 is preferably a 
hydrogen atom or methyl group. 
Further, n is 2 or 3, R.sup.2 is a divalent alcohol residue which may 
include an oxygen atom in the residue when n is 2 and is an isocyanuric 
acid residue when n is 3. 
Here, example of the divalent alcohol residue includes a diol residue 
having approximately 4 to 15 carbon atoms such as diethylene glycol, 
triethylene glycol, tetraethylene glycol, pentaethylene glycol, 
hexaethylene glycol, 
3,9-bis(1,1-dimethyl-2-dihydroxyethyl)-2,4,8,10-tetraoxaspiro5.5!undecane 
, 2-(1,1-dimethyl-2-hydroxyethyl)-5-ethyl-1,3-dioxane-5-yl!methane and 
neopentyl glycol hydroxypivalate; and an alkylene diol residue having 
approximately 2 to 16 carbon atoms such as ethylene glycol, 1,3-propane 
diol, 1,4-butane diol, 1,2-pentane diol, 1,5-pentane diol, 2,4-pentane 
diol, neopentyl glycol, hexane diol, octane diol, decane diol and 
hexadecane diol. 
The divalent alcohol residue is preferably a diol residue, more preferably 
a triethylene glycol residue or 
3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro5.5!undecane 
residue. 
X is a lower alkylenecarbonyloxy group when n is 2 and is a lower alkylene 
group when n is 3, and example of the lower alkylenecarbonyloxy group 
includes methylenecarbonyloxy, dimethylenecarbonyloxy, 
trimethylenecarbonyloxy, tetramethylenecarbonyloxy and 
pentamethylenecarbonyloxy. Among them, dimethylenecarbonyloxy is 
preferable. 
Example of the lower alkylene group includes methylene, dimethylene, 
trimethylene, tetramethylene and pentamethylene, and, among them, 
methylene is preferable. 
Representative example of the phenol antioxidant (B) represented by the 
above-described general formula (I) includes 
3,9-bis2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethy 
lethyl!-2,4,8,10-tetraoxaspiro5.5!undecane, triethylene glycol 
bis3-(5-t-butyl-3-methyl-4-hydroxyphenyl)propionate!, 
tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate and the mixture 
thereof. 
The phenol antioxidant (B) is includes in an amount from 0.01 to 5 parts by 
weight, preferably from 0.02 to 0.8 parts by weight based on 100 parts by 
weight of the polymeric compound (A). 
When the content of the phenol antioxidant (B) is less than 0.01 parts by 
weight, sufficient thermal oxidation degradation resistance is not 
obtained, and when the antioxidant content is more than 5.0 parts by 
weight, high thermal oxidation degradation resistance that corresponds to 
the amount of antioxidant present is not achieved, which is neither 
economical nor protective of the physical properties of the polymeric 
compound. 
The hindered amine photostabilizer ;(C) in the present invention, is a 
compound having a molecular weight of not less than 400 which has a 
2,2,6,6-tetramethylpiperidine skeleton in its molecule. It is preferable 
that two or more of 2,2,6,6-tetramethylpiperidine skeleton exist in the 
molecule. 
Representative examples of such a hindered amine photostabilizer (C) 
include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (molecular weight; 
480), bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (molecular weight; 
508), bis(1,2,2,6,6-pentamethyl-4-piperidyl) 
2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate (molecular weight; 
685), poly6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl!(2 
,2,6,6-tetramethyl-4-piperidinyl)imino!-1,6-hexamethylene(2,2,6,6-tetramet 
hyl-4-piperidinyl)imino!! (molecular weight; not less than 2500), 
poly(6-morpholino-1,3,5-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperid 
yl)imino!hexamethylene(2,2,6,6-tetramethyl-4-piperidyl)imino!! (molecular 
weight; not less than 1000), a polycondensate (molecular weight; not less 
than 3000) of dimethyl succinate and 
1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and a 
condensate (molecular weight; not less than 2000) of 
N,N'-bis(3-aminopropyl)ethylenediamine and 
2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-6-chloro-1,3,5 
-triazine. These may be used in combination. 
Among them, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 
poly6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl!(2,2,6,6 
-tetramethyl-4-piperidinyl)imino!-1,6-hexamethylene(2,2,6,6-tetramethyl-4- 
piperidinyl)imino!!, a polycondensate of dimethyl succinate and 
1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and the like 
are preferably used. 
The hindered amine photostabilizer (C) is usually present in an amount from 
0.01 to 5 parts by weight, preferably from 0.02 to 0.8 parts by weight 
based on 100 parts by weight of the polymeric compound (A). 
When the contact of the hindered amine photostabilizer (C) is less than 
0.01 parts by weight, sufficient photodegradation resistance ability is 
not obtained, and when it is more than 5 weight, high photodegradation 
resistance ability correspond to the amount is not obtained, i.e. giving 
uneconomical results and deterioration of the physical properties of the 
polymeric compound is tend to be generated. 
As the substituents R.sup.2, R.sup.4 in the dihydrooxaphosphaphenanthrene 
compound (D), for example, a hydrogen atom, a halogen atom such as 
chlorine, bromine and the like, a lower alkyl group such as methyl, ethyl, 
n-propyl, i-propyl, n-butyl, 1-butyl, sec-butyl, t-butyl, n-pentyl, 
i-pentyl, t-pentyl and the like, are listed. 
Representative example of the dihydrooxaphosphaphenanthrene compound (D) 
include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 
8-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-butyl-9 
and 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Among them, 
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferably used. 
This phosphorus compound (D) is usually present in an amount from 0.1 to 2 
parts by weight based on 1 part by weight of the phenol antioxidant (B) 
and from 0.01 to 1 part by weight based on 1 part by weight of the 
hindered amine photostabilizer (C). It is preferably comprised in an 
amount from 0.5 to 1 part by weight based on the phenol antioxidant (B) 
and from 0.2 to 0.5 parts by weight based on the hindered amine 
photostabilizer (C). 
When the content of the phosphorus compound (D) is less than 0.01 parts by 
weight based on the phenol antioxidant (B), sufficient discoloration 
resistance is not obtained, and when it is more than 2 parts by weight, a 
correspondingly high level of discoloration resistance is not achieved, 
and the polymeric compound tends to degrade. When, the content of the 
phosphorus compound (D) is more than 1 part by weight based on the 
hindered amine photostablizer (C), deterioration of the photo resistance 
of the composition occurs. 
The polymeric composition of the present invention may further include 
other various additives such as a processing stabilizer, antioxidant, 
light stabilizer, metal deactivator, metallic soap, nucleating agent, 
antistatic agent, lubricant, fire retardant, releasing agent, 
mildewproofing agent and filler. Specific examples of these various 
additives are listed below. 
As a processing stabilizer, for example, 
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 
2-1-2-hydroxy-3,5-di-t-pentylphenyl)ethyl!-4,6-di-t-pentylphenyl acrylate 
and the like are listed. 
As a phosphorus antioxidant or sulfur antioxidant, for example, 
tris(nonylphenyl)phosphite, tris(2,4-dibutylphenyl)phosphite, 
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl 
pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl) 
4,4'-biphenylenediphosphite, 
2,2'-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite, 
2,2'-methylidenebis(4,6-di-t-butylphenyl)octylphosphite, dilauryl 
3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 
3,3'-thiodipropionate, tetrakis(3-laurylthiopropionyloxymethyl)methane and 
the like are listed. 
As a light stabilizer, for example, a ultraviolet absorber such as; a 
benzotriazole compound such as 
2-(3-t-butyl-2-hydroxy-5-methyphenyl)-5-chlorobenzotriazole, 
2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 
2-(2-hydroxy-5-methylphenyl)benzotriazole, 
2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 
2-(3,5-di-t-pentyl-2-hydroxyphenyl)benzotriazole, 
2-2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl!benzot 
riazole, 
2-2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl!benzotriazole 
or the like; a hydroxybenzophenone compound such as 2,4-di-t-butylphenyl 
3,5-di-t-butyl-4-hydroxybenzoate or the like; and cyanoacrylate compound 
such as ethyl 2-cyano-3,3-diphenyl acrylate or the like; a nickel quencher 
such as nickel dibutyldithiocarbamate, 
2,2'-thiobis(4-t-octylphenolate)!-2-ethylhexylamine nickel or the like, 
and the like are listed. 
As a metal deactivator, for example, 
N,N'-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl!hydrazine and the like 
are listed, and as a metallic soap, for example, calcium stearate, zinc 
stearate, nickel stearate and the like are listed. 
Nucleating agents may be, for example, sorbitol compounds and phosphate 
compounds such as sodium di(4-t-butylphenyl)phosphonate, dibenzylidene 
sorbitol, sodium methylenebis(2,4-di-t-butylphenol)phosphate or the like. 
Antistatic agents may be, for example, quaternary ammonium salt and 
alkylphosphate compound such as (.beta.-lauramidepropyl)trimethylammonium 
methylsulfate and the like. 
As a lubricant, for example, erucic acid amide, stearic acid amide, stearic 
acid monoglyceride and the like are suitable, and as the fire retardant, 
for example, halogen containing phosphates such sa 
tris(2-chloroethyl)phosphate and the like, halogen compounds such as 
hexabromocyclododecane, decabromodiphenyloxide and the like, metal 
containing inorganic compounds such as antimony trioxide, antimony 
pentaoxide, aluminium hydroxide and the like, the mixture thereof, and the 
like are suitable. 
The polymeric compound (A) may be, for example, the following compounds: 
(1) polyethylene, for example, low density polyethylene(LD-PE), high 
density polyethylene(HD-PE), linear-low density polyethylene(LD-PE), 
(2) polypropylene, 
(3) .alpha.-olefin polymer, for example, 1-butene polymer, 1-hexene 
polymer, methyl butene polymer, methyl pentene polymer, 
(4) EEA (ethylene/ethyl acrylate copolymer)resin 
(5) EVA (ethylene/vinyl acetate copolymer)resin 
(6) polystyrenes, for example, polystyrene, poly(p-methylstyrene), 
poly(.alpha.-methylstyrene), 
(7) AS (acrylonitrile/styrene copolymer)resin 
(8) ABS (acrylonitrile)butadiene/styrene copolymer)resin 
(9) AAS (special acryl rubber/acrylonitrile/styrene copolymer), 
(10) ACS (acrylonitrile/chlorinated polyethylene/styrene copolymer)resin, 
(11) chlorinated ethylene, polychloroprene, chlorinated rubber, 
(12) poly vinyl chloride, poly vinylidene chloride, 
(13) methacrylic resin, 
(14) ethylene/vinyl alcohol copolymerized resin, 
(15) fluororesin, 
(16) polyacetal, 
(17) graft polyphenylene ether resin and polyphenylene sulfide resin, 
(18) polyurethane, 
(19) polyamide, 
(20) polyethylene terephthalate, polybutylene terephthalate, 
(21) polycarbonate, 
(22) polyacrylate, 
(23) polysulfone, polyether ether ketone, polyether sulfone, 
(24) aromatic polyester resin, 
(25) epoxy resin, 
(26) diallyl phthalate prepolymer, 
(27) silicone resin, 
(28) unsaturated polyester resin 
(29) acrylic modified benzoquanamine resin, 
(30) benzoquanamine/melamine resin, 
(31) urea resin, 
(32) polybutadiene, 
(33)1,2-polybutadiene, 
(34) polyisoprene, 
(35) styrene/butadiene copolymer, 
(36) butadiene/acrylonitrile copolymer, 
(37) ethylene/propylene copolymer, 
(38) silicone rubber, 
(39) epichlorohydrin rubber, 
(40) acrylic rubber, 
(41) natural rubber, 
(42) chlorinated rubber paint, 
(43) polyester resin paint, 
(44) urethane resin paint, 
(45) epoxy resin paint, 
(46) acrylic resin paint, 
(47) vinyl resin paint, 
(48) aminoalkyl resin paint, 
(49) alkyd resin paint, 
(50) nitrocellulose resin paint, 
(51) oil paint, 
(52) wax, 
(53) lubricant oil. 
They may be used alone or in combination. The polymeric compound (A) is not 
limited to the aforementioned. 
Among the, olefin polymers such as polyethylene, polypropylene and 
.alpha.-olefin polymer, are preferable. 
For inclusion of the phenol antioxidant (B), the hindered amine 
photostabilizer (C) and the phosphorus compound (D) and the other 
additives optionally used, in the polymeric compound (A), there are 
adopted various blending methods suitable for obtaining a homogeneous 
mixture, for example, methods in which an extruder, banbury mixer, kneader 
and the like can be used. 
These additives may be added simultaneously with the polymeric compound 
(A), or may be added separately. It is preferable to blend the master 
batch or a mixture of these additives obtained by homogeneous mixing of 
these additives.

EXAMPLE 
The present invention will be further explained in detail in the following 
nonlimiting examples. 
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formulation! 
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unstablized polyproplene 
100 parts by weight 
calcium stearate 0.1 
tris(2,4-di-t-butylphenyl)phosphite 
0.05 
tested compounds listed in Table 
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A0-1: 
tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate!methane 
B-1: 
3,9-bis2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethy 
lethyl!-2,4,8,10-tetraoxaspiro5.5!undecane 
B-2: triethylene glycol 
bis3-(5-t-butyl-3-methyl-4-hydroxyphenyl)propionate! 
B-3: tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate 
C-1: bis (2,2,6,6-tetramethyl-4-piperidyl)sebacate 
C-2: 
poly6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl!(2,2,6,6 
-tetramethyl-4-piperidinyl)imino!-1,6-hexamethylene(2,2,6,6-tetramethyl-4- 
piperidinyl)imino!! 
C-3: polycondensate of dimethyl succinate and 
1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine 
D-1: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 
Processing! 
The above-described components were compounded and pelletized at 
240.degree. C. using a 40 mm .phi. single-screw extruder. The resulted 
pellet was spun using a spinning machine, stretched at 135.degree. C. to 
obtain a 20 denier polypropylene fiber. 
Examples 1 to 3, Comparative Example 1 
Thermal oxidation degradation resistance was evaluated by keeping the 
temperature of the polypropylene fiber at 150.degree. C. and measuring the 
number of day before break of the fiber due to embrittlement, and the 
results are shown in Table 1. In Table 1, amounts are weight basis. 
TABLE 1 
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Thermal 
oxidation 
degradation 
No. Tested compound (content) 
resistance 
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Example 1 
B-1 (0.1) C-2 (0.1) D-1 (0.02) 
5 days 
Example 2 
B-1 (0.1) C-2 (0.1) D-1 (0.05) 
5 days 
Example 3 
B-1 (0.1) C-2 (0.1) D-1 (0.1) 
5 days 
Comparative 
AO-1 (0.1) 
C-2 (0.1) D-1 (0.1) 
3 days 
Example 1 
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Examples 4 to 16, Comparative Example 2 
The polypropylene fiber was exposed to a combustion gas at 130.degree. C. 
for 5 minutes, hue after exposure was visually evaluated by naked eyes, 
and the results are shown in Table 2. In Table 2, amounts are weight 
basis. 
TABLE 2 
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No. Tested compound (content) 
Hue 
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Example 4 
B-1 (0.1) C-2 (0.1) D-1 (0.02) 
Pale pink 
Example 5 
B-1 (0.1) C-2 (0.1) D-1 (0.05) 
white 
Example 6 
B-1 (0.1) C-2 (0.1) D-1 (0.1) 
white 
Example 7 
B-1 (0.1) C-1 (0.1) D-1 (0.1) 
White 
Example 8 
B-1 (0.1) C-3 (0.1) D-1 (0.1) 
White 
Example 9 
B-1 (0.1) C-1 (0.05) 
D-1 (0.1) 
White 
C-3 (0.05) 
Example 10 
B-1 (0.1) C-2 (0.2) D-1 (0.1) 
White 
Example 11 
B-1 (0.03) 
C-2 (0.06) 
D-1 (0.03) 
white 
Example 12 
B-1 (0.6) C-2 (0.6) D-1 (0.3) 
Pale pink 
Example 13 
B-1 (0.1) C-2 (0.3) D-1 (0.1) 
white 
Example 14 
B-1 (0.1) C-2 (0.3) D-1 (0.2) 
white 
Example 15 
B-2 (0.1) C-2 (0.1) D-1 (0.1) 
white 
Example 16 
B-3 (0.1) C-2 (0.1) D-1 (0.1) 
white 
Comparative 
B-1 (0.1) C-2 (0.1) Pale pink 
example 2 
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Example 17, Comparative Example 3 
Photo resistance test was conducted by irradiating the polypropylene fiber 
with xenon light. The irradiation energy amount until the tensile strength 
at break reduced to half of the initial value T(1/2)! was shown in Table 
3. In Table 3, amounts are weight basis. 
TABLE 3 
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No. Tested compound (content) 
T (1/2)! 
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Example 16 
.sup. B-1 (0.1) 
C-3 (0.1) 
D-1 (0.02) 
580 KJ 
Comparative 
AO-1 (0.1) C-2 (0.1) 
D-1 (0.05) 
530 
example 3 
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Effect of the Invention 
The composition can realize the prevention of discoloration or coloring in 
contacting with a combustion gas and the like and the remarkable 
improvement of thermal oxidation degradation resistance at the same time, 
by containing the phenol antioxidant having a specific skeleton 
o-t-butyl-o'-methyl-phenylic group, the hindered amine photostablizer 
having a molecular weight of not less than 400 and the specific phosphorus 
compound dihydrooxaphosphaphenanthrene.