JPH0788445B2 - Polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a polyolefin resin composition.
The present invention relates to a polyolefin resin composition containing a specific antioxidant and a perchloric acid compound, which is improved in processing stability, heat resistance, gas contamination by nitrogen oxide, and the like.

[Prior art and its problems]

Polyolefins such as polyethylene and polypropylene are
It is known that it deteriorates due to the action of heat, light, oxygen, nitric oxide, etc., and is colored or its mechanical strength is lowered, making it unusable.

For the purpose of preventing such deterioration of the polyolefin, many additives have been used singly or in various combinations. Among these additives, it is known that a combination of a phenol compound and an organic phosphite compound and / or an organic sulfur compound has a relatively large effect of improving heat resistance and suppressing coloring.

However, the effect is still insufficient, and further improvement has been demanded.

[Means for solving problems]

The inventors of the present invention have conducted extensive studies in order to improve these drawbacks. As a result, tetrakis [methylene-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane and peroxidase have been added to polyolefin resins. The inventors have found that when at least one kind of chloric acid compound is blended, heat resistance and coloration-preventing property are improved to a satisfactory level, and a polyolefin resin composition having extremely excellent processability is obtained, and the present invention has been accomplished.

The polyolefin composition according to the present invention will be described in detail below.

The tetrakis [methylene-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate] methane can be used together with phosphorus-based and sulfur-based antioxidants.

Tetrakis [methylene-3- (3,5-di-tert-butyl-4]
-Hydroxyphenyl) propionate] methane is added in an amount of 0.001 to 5 relative to 100 parts by weight of the polyolefin resin.
Parts by weight, preferably 0.01 to 3 parts by weight.

Examples of phosphorus-based antioxidants include trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, triphenyl phosphite, tris (2,4
-Di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (mono / di mixed nonylphenyl) phosphite, hexa (tridecyl) -1,
1,3-Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphate, tetra (C
_12-15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, hydrogenated-4-4 '-Isopropylidene diphenol polyphosphate, bis (octylphenyl) .bis [4,4'-butylidene bis (3-methyl-6)
-Tertiary butylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidenediphenol-pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (tridecyl) Pentaerythritol diphosphite,
Bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphate, di (nonylphenyl) pentaerythritol diphosphate, bis (2,6-ditertiary butyl-4-methylphenyl) pentaerythritol diphosphate Phosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-
Examples thereof include 10-oxide, tetrakis (2,4-ditertiary butylphenyl) -4,4'-biphenylene diphosphonite and the like.

The addition amount of these phosphorus-based antioxidants is 0.001 to 5, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the polyolefin.

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl-, distearyl-, dimyristyl-, and lauryl-stearyl-, and polyvalent alkylthiopropionic acids such as butyl-, octyl-, lauryl-, and stearyl-. Alcohol (eg glycerin,
Trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) ester (for example, pentaerythritol tetralauryl thiopropionate) and the like can be mentioned.

The addition amount of these sulfur-based antioxidants is 100
The amount is 0.001-5, preferably 0.01-3 parts by weight.

Examples of the perchloric acid compound used in the present invention include perchloric acid such as Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al and NH _4.
Examples include salts, hydrotalcites, zeolites, and various inorganic acid salts treated with perchloric acid. Especially perchloric acid
Group IIa metal (Mg, Ca, Sr, Ba) salts are preferred.

The addition amount of the perchloric acid compound is the polyolefin resin 10
0.001 to 1 part by weight, preferably 0.005 to 0 part by weight
0.5 parts by weight.

The polyolefin stabilized in the present invention includes ethylene, propylene, butene, pentene, hexene, 4-methylpentene, heptene, octene and other α-olefin homopolymers or copolymers; Random, block or graft copolymers of vinyl esters such as vinyl acetate, unsaturated organic acids such as acrylic acid, maleic anhydride and methyl methacrylate (including salts, amides and amines), vinylsilane such as vinyltrimethoxysilane, etc. Or a modified product of these polymers such as chlorination, sulfonation, or oxidation.

Specifically, for example, low, medium or high density polyethylene, polypropylene, polybutene, ethylene-propylene random or block copolymer, ethylene-propylene-butene copolymer, ethylene-butene copolymer,
Examples thereof include ethylene-bilr acetate copolymer, ethylene-4-methylpentene copolymer, propylene-hexene copolymer, propylene-hexene-butene copolymer.

By adding a light stabilizer to the composition of the present invention, its light resistance can be further improved.

Examples of these light stabilizers include 2-hydroxy-4-
Hydroxybenzophenones such as methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-isooctoxybenzophenone and 2,4-dihydroxybenzophenone, 2- (2'-hydroxy-3'-second 3-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-
Benzotriazoles such as methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertiary amylphenyl) benzotriazole, phenyl salicylate, p-tertiary butylphenyl salicylate, 2,4-di Tert-Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-
Benzoates such as 4-hydroxybenzoate, 2,2 '
-Thiobis (4-tertiary octylphenol) Ni salt, [2,
Nickel compounds such as 2′-thiobis (4-tertiary octylphenolate)] butylamine Ni salt, 3,5-ditertiarybutyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt, α-cyano-β -Substituted acrylonitriles such as methyl-β- (p-methoxyphenyl) methyl acrylate, N- (2-ethylphenyl) -N '-(2-ethoxy-5-tert-butylphenyl) oxalic acid diamide, N
Oxalic acid dianilides such as-(2-ethylphenyl) -N '-(2-ethoxyphenyl) oxalic acid diamide and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2) 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, tris (2,
2,6,6-Tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl)
-Di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4 -Butane tetracarboxylate, N- (2-hydroxyethyl) -2,
2,6,6-Tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tertiary octylamino-4,6-dichloro-s-triazine / 1,6-bis (2,2,6,6- Examples thereof include piperidine compounds such as tetramethyl-4-piperidylamino) hexane condensate.

If necessary, the composition of the present invention contains fillers, pigments, foaming agents, antistatic agents, flame retardants, lubricants, processing aids, nucleating agents, peroxide cross-linking agents, metal soaps, etc. depending on the purpose. Can be included.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples.
However, the invention is not limited to these examples.

Example 1 The following composition was extruded at 230 ° C. and 25 rpm and injection-molded at 250 ° C. to prepare a sheet having a thickness of 1 mm. Using this sheet, measure the thermal stability in a gear oven at 150 ° C,
In addition, using a dyeing fastness tester in accordance with JIS LO855,
The resistance to gas pollution by nitrogen oxide gas (yellowness of the specimen after 144 hours of immersion and one week after immersion) was measured.

The obtained results are shown in Table-1.

(Compounding) parts by weight polypropylene (Profax 6501) 100 calcium stearate 0.05 tetrakis [methylene-3- (3,5-di0.13 butyl-4-hydroxyphenyl) propionate] methane perchlorate compound (Table-1) 0.05 Example 2 A sheet having a thickness of 1 mm was prepared in the same manner as in Example 1 using the following composition. Using this sheet, the same test as in Example 1 was performed.

The results are shown in Table 2.

(Compounding) parts by weight polypropylene (Profax 6501) 100 calcium stearate 0.05 tetrakis [methylene-3- (3,5-di0.13 butyl-4-hydroxyphenyl) propionate] methane barium perchlorate 0.05 phosphite compound 0.1 Example 3 The following composition was extruded at 250 ° C. and 20 rpm and injection-molded at 250 ° C. to prepare a sheet having a thickness of 1 mm. Using the obtained sheet, thermal stability was measured in a gear oven at 160 ° C.

The results are shown in Table-3.

(Compounding) parts by weight polypropylene (Profax 6501) 80 food additive talc 20 melamine 0.05 calcium stearate 0.05 distearyl thiodipropionate 0.15 barium perchlorate 0.05 phenolic antioxidant (Table-3) 0.05 Example 4 The following composition was extruded at 230 ° C. and 25 rpm and injection-molded at 250 ° C. to prepare a sheet having a thickness of 1 mm. Using this sheet, measure the thermal stability in a gear oven at 160 ° C,
In addition, using a dyeing fastness tester in accordance with JIS LO855,
Resistance to gas pollution by nitrogen oxide gas (yellowness of the sample after 144 hours) was measured. Further, the fluorescent lamp colorability (yellowness after irradiation for 48 hours and 72 hours) at 55 ° C. was measured. The obtained results are shown in Table 4.

(Compounding) Parts by weight Polypropylene (Profax 6501) 100 Calcium stearate 0.05 Tetrakis [methylene-3- (3,5-di-0.13 butyl-4-hydroxyphenyl) propionate] methane Barium perchlorate 0.05 Light stabilizer (Table- 4) 0.1 Example 5 The following composition was kneaded at 160 ° C. for 5 minutes with a mixing roll, and then pressed under the conditions of 160 ° C. and 180 kg / cm ² to prepare a sheet having a thickness of 1 mm.

Using this sheet, a thermal stability test was performed in a gear oven at 150 ° C.

The results are shown in Table-5.

(Compounding) Low-density polyethylene 100 parts by weight Phenolic antioxidant (Table 5) 0.1 Barium perchlorate 0.02

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshimitsu Numajiri 52-113 Shirahata, Urawa-shi, Saitama ADEKA ARGUS CHEMICAL CO., LTD. (72) Shunichi Iizuka 5-213 Shirahata, Urawa-shi, Saitama No. ADEKA ARGUS CHEMICAL CO., LTD. (56) Reference JP 61-34042 (JP, A) JP 59-140261 (JP, A) JP 59-30839 (JP, A) JP 58-173159 (JP, A)

Claims (1)

[Claims] 1. A stabilizer comprising a polyolefin resin and at least one compound selected from tetrakis [methylene-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane and a perchloric acid compound. Polyolefin resin composition.