JP3133375B2 - Polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition, and more particularly to a talc-containing polyolefin resin containing a specific phenolic antioxidant and a specific sulfur antioxidant. The present invention relates to a stabilized polyolefin resin composition.

[0002]

2. Description of the Related Art Polyolefin resins, such as polyethylene and polypropylene, are deteriorated by the action of heat, light, oxygen or nitrogen oxides, and are colored or have reduced mechanical strength. It is known that it cannot withstand use.

For the purpose of preventing such polyolefin-based resins from deteriorating, many additives have been used alone or in various combinations.

[0004] Among these additives, phenolic antioxidants and organophosphorus antioxidants are widely used as basic stabilizers, but the effect of using them alone is relatively small. For example, in a field where high heat resistance is required, it is used in combination with a sulfur-based antioxidant represented by dialkylthiodipropionate.

On the other hand, talc, which is an inorganic filler, is added for the purpose of improving the rigidity, mechanical properties, and dimensional accuracy of the polyolefin resin, and the polyolefin resin containing talc is It is mainly used in fields such as automobile parts and home electric appliances.

However, when talc is blended with a polyolefin resin, the effect of the antioxidant is significantly reduced as compared with the case where no talc is blended. However, sufficient heat resistance cannot be obtained, and improvement of heat resistance by further using a sulfur-based antioxidant has been proposed. However, it has not been sufficient yet, and it has been strongly desired to provide heat resistance for a long time.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present inventors have found that a polyolefin resin containing talc and a specific phenol antioxidant and a specific sulfur antioxidant are used in combination. It was found that heat resistance over a long period of time can be exhibited.

The present invention has been made on the basis of the above findings. A polyolefin resin composition containing 10 to 60 parts by weight of talc based on 100 parts by weight of a polyolefin resin has the following general formula: 0.01 to 10 parts by weight of a phenolic antioxidant represented by (I) and (b) 0.01 to 10 parts by weight of a sulfur-based antioxidant represented by the following general formula (II)
An object of the present invention is to provide a polyolefin-based resin composition to which 10 parts by weight are added.

[0009]

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Hereinafter, the polyolefin resin composition of the present invention will be described in detail.

The talc compounded in the polyolefin resin of the present invention is a powder obtained by pulverizing talc, and its main component is hydrous magnesium silicate. There are various types of talc depending on the type of talc, the degree of whiteness, and the particle size of the powder. Any of the talc used in the present invention may be used.

The talc is added in an amount of 10 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the polyolefin resin.

Further, the phenolic antioxidant of component (a)
In the general formula (I) representing the agent, ₁Carbon source indicated by
Examples of the alkyl group having 1 to 4 atoms include methyl, ethyl,
Ropyl, isopropyl, butyl, sec-butyl, tert-butyl
And isobutyl, and the residue R_TwoGive 1-4
Methanol, ethanol, butyl alcohol
Tanol, octanol, 2-ethylhexanol, a
Sooctanol, decanol, dodecanol, tetrade
Such as canol, hexadecanol, octadecanol, etc.
Monohydric alcohol; ethylene glycol, propylene glycol
Coal, 1,4-butanediol, 1,6-hexanedi
All, 1,10-decanediol, diethylene glyco
, Triethylene glycol, dipropylene glycol
Thiodiethylene glycol, 3,9-bis (2-
Droxy-1,1-dimethylethyl) -2,4,8,1
0-tetraoxaspiro [5,5] undecane, 2,2
-Bis [4- (hydroxyethoxy) phenyl] propa
Dihydric alcohols such as glycerin, trimethylol
Ethane, trimethylolpropane, tris (2-hydro
Trihydric alcohols such as (xethyl) isocyanurate;
Pentaerythritol, diglycerin, ditrimethylo
And tetrahydric alcohols such as lupropane.
You.

The amount of the phenolic antioxidant added is
0.01 parts by weight based on 100 parts by weight of the polyolefin resin.
10 to 10 parts by weight, preferably 0.05 to 3 parts by weight.

In the above general formula (II) representing the sulfur-based antioxidant of the component (b), the compound represented by R has 4 carbon atoms.
Examples of the alkyl group of -20 include butyl, isobutyl, tertiary butyl, amyl, isoamyl, tertiary amyl,
Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like.

The alkyl groups having 1 to 18 carbon atoms represented by R 'and R "include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tertiary amyl, Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, decyl, isodecyl,
Undecyl, dodecyl, tetradecyl, hexadecyl,
Octadecyl and the like.

Further, 1 to 1 represented by A in the general formula (II)
Examples of the trivalent amine residue include monovalent amines such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, laurylamine, myristylamine, stearylamine, piperidine, 2-pipecoline, N-methylpiperazine, and morpholine. Residues: hydrazine, 1,4-diaminobutane, 1,6-hexanediamine, 1,11-undecanediamine, piperazine, 2-
Methylpiperazine, 2,2-dimethyl-1,3-diaminopropane, 3,9-bis (aminopropyl) -2,
Divalent amine residues such as 4,8,10-tetraoxaspiro [5,5] undecane; trivalent amine residues such as 1,6,11-triaminoundecane and 4-aminomethyl-1,8-octanediamine Amine residues.

Further, an ammonium salt of alkylthiopropionic acid can also be used as the sulfur-based antioxidant of the component (b) of the present invention.

Specific examples of the sulfur-based antioxidant include the following compounds.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The amount of the sulfur-based antioxidant to be added is 0.1 to 100 parts by weight of the polyolefin-based resin composition.
The amount is from 0.01 to 10 parts by weight, preferably from 0.05 to 3 parts by weight.

The polyolefin resin to be stabilized in the present invention includes homo- or copolymers of α-olefins such as ethylene, propylene, butene, pentene, hexene, 4-methylpentene, heptene and octene;
The majority of these α-olefins and vinyl esters such as vinyl acetate, unsaturated organic acids (including esters, salts, amides and amines) such as acrylic acid, maleic anhydride and methyl methacrylate, and vinyl trimethoxysilane Examples thereof include random, block or graft copolymers such as vinylsilane; and modified polymers such as chlorination, sulfonation, and oxidation of these polymers.

Specifically, low, medium or high density polyethylene, polypropylene, polybutene, ethylene-propylene random or block copolymer, ethylene-propylene
Examples thereof include a propylene-butene copolymer, an ethylene-butene copolymer, an ethylene-4-methylpentene copolymer, a propylene-hexene copolymer, and a propylene-hexene-butene copolymer.

Among these polymers, particularly effective ones include propylene such as polypropylene, propylene-ethylene random or block copolymer, propylene-ethylene-butene copolymer and propylene-hexene-butene copolymer. Based copolymers.

The polyolefin resin composition of the present invention has
By adding an organic phosphorus antioxidant, its heat resistance can be further improved.

Examples of the organophosphorus antioxidants include trisnonylphenyl phosphite, tris (2,4-ditertbutylphenyl) phosphite, and tris [2-tert-butyl-4- (3-tert-butyl). Tributyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite , Distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2
6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, Tetra (tridecyl) -4,4'-
n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,
1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9- Oxa-10
-Phosphaphenanthrene-10-oxide and the like.

Among the above organic phosphorus antioxidants, dialkylpentaerythritol diphosphite and diarylpentaerythritol diphosphite are particularly preferred because of their large combined effect.

The organic phosphorus antioxidant is preferably used in an amount of 0.01 to 100 parts by weight of the polyolefin resin.
To 10 parts by weight, more preferably 0.05 to 5 parts by weight.

The polyolefin resin composition of the present invention may further comprise an ultraviolet absorber or 2,2,
By adding a light stabilizer such as a hindered amine compound represented by a 6,6-tetramethylpiperidine compound, the light stability can be further improved.

As the above-mentioned ultraviolet absorber, for example,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-dicumylphenyl)
2- (2'-hydroxyphenyl) benzotriazoles such as benzotriazole and 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4- Di-tert-butylphenyl-3 ', 5'
Benzoates such as di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 ' Substituted oxanilides such as dodecyl oxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-
And cyanoacrylates such as cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

The hindered amine light stabilizers include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6
-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, tetrakis (2,2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) -1,2,2,6,6
-Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- Butyl-2- (3 ', 5'-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2
-Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate,
1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate,
1,6-bis (2,2,6,6-tetramethyl-4-
Piperidylamino) hexane / 2,4-dichloro-6
Tertiary octylamino-s-triazine polycondensate, 1,6
-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-chloro-6-morpholino-s-triazine polycondensate and the like.

If necessary, the composition of the present invention may contain metal soaps such as calcium stearate and calcium stearyl lactate, heavy metal deactivators, nucleating agents, pigments, organotin compounds, plasticizers, epoxy compounds. , Foaming agent,
Antistatic agents, flame retardants, lubricants, processing aids and the like can be included.

The composition of the present invention can be prepared by injection molding, extrusion molding,
It can be molded by a conventionally known method such as blow molding, and is not limited by the molding method or its form.

Further, the surface properties of the composition of the present invention can be improved by subjecting the composition to a well-known treatment such as a low-temperature plasma treatment after molding.

[0041]

Next, the stabilizing effect of the composition of the present invention will be specifically described by way of examples. However, the present invention is not limited by the following examples.

Example 1 Pellets were prepared by extrusion at 250 ° C. according to the following formulation. Next, a test piece having a thickness of 1 mm was prepared by injection molding at 250 ° C. Using this test piece, 150
The sample was placed in a gear oven at 24 ° C., and after 24 hours, the yellowness of the test piece was measured using a Hunter colorimeter. In addition, a heat resistance test was performed in the same oven until deterioration occurred. Table 1 shows the results.

[Combination] parts by weight Polypropylene 100 talc 30 tetrakis [methylene-β- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane 0.05 sulfur-based antioxidant (Table 1) ) 0.1

[0044]

Example 2 A test piece was prepared in the same manner as in Example 1 with the following composition.
A weather resistance test was conducted in a sunshine weather meter at 83 ° C (without rain). Further, the test piece was also tested for heat resistance in the same manner as in Example 1. Table-
It is shown in FIG.

[Combination] parts by weight ethylene-propylene block copolymer 100 talc 25 calcium stearate 0.05 phenolic antioxidant (Table 2) 0.05 bis (2,4-di-tert-butylphenyl) pentaerythritol Diphosphite 0.1 Sulfur-based antioxidant (No. 4) 0.1 Bis (2,2,6,6-tetramethyl-4-pipedyl) sebacate 0.1

[0047]

As is clear from the results of the examples, the composition according to the present invention is excellent not only in the initial coloring resistance and weather resistance of the polyolefin resin containing the filler but also in the heat resistance. It is effective.

On the other hand, those using a normal sulfur-based antioxidant or a phenolic antioxidant other than the component (a) of the present invention have an effect on a polyolefin resin containing no filler (talc). However, it is clear that the addition of a filler significantly reduces weather resistance and heat resistance, and the filler-containing polyolefin resin composition of the present invention has excellent effects.

[0050]

The polyolefin resin composition of the present invention has a long-term heat resistance despite containing talc.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08K 5:36) (58) Investigation field (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3 / 00-13/08

Claims (1)

(57) [Claims] 1. A polyolefin resin composition containing 10 to 60 parts by weight of talc based on 100 parts by weight of a polyolefin resin, wherein (a) a phenolic antioxidant represented by the following general formula (I): A polyolefin resin composition comprising 0.01 to 10 parts by weight and (b) 0.01 to 10 parts by weight of a sulfur-based antioxidant represented by the following general formula (II). Embedded image