JPH03207733A - Polyolefin resin composition containing carbon black - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat-stability and useful for automobile parts, electrical parts, etc., by compounding a polyolefin resin containing carbon black with a phenolic compound, a metal- inactivation agent and a sulfur compound. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a polyolefin resin containing 0.05-5wt.% (preferably 0.1-1wt.%) of carbon black having an average particle diameter of preferably <=20mu and 0-60wt.% of other inorganic filler such as various metal oxides with (B) 0.01-1.0 pt.wt. of a phenolic compound of formula I, (C) 0.01-10 pts.wt. of a metal- inactivation agent of formula II, (D) 0.01-1.0 pt.wt. of a sulfur compound of formula III (R1 is 4-20C alkyl or formula IV (R2 is 4-20C alkyl) and, as necessary, (E) a light stabilizer, an antioxidant, etc., and kneading the obtained mixture with a roll, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a stabilizing composition for a polyolefin resin containing carbon black. More specifically, the present invention relates to a carbon black-containing polyolefin resin composition that has improved stability against deterioration due to contact with heavy metals.

<Prior art> Synthetic resins such as polyethylene, polypropylene, and polybutene have excellent mechanical properties, so! Although it is extremely useful as a material for polyolefin fibers, molded products, films, etc., inorganic fillers are rarely added to improve the rigidity, heat distortion temperature, or dimensional stability of polyolefin molded products. do not have.

Synthetic resins containing inorganic fillers are often used in automobile parts, electrical product parts, etc., but in such cases, contact with heavy metals such as copper, iron, and nickel is unavoidable.
The thermal stability of molded products is much lower than that of molded products that do not come into contact with heavy metals, which is a major problem.

In order to solve these problems, it is well known that various phenol-based, phosphorus-based, sulfur-based, and other antioxidants are added and used during the production and processing steps of synthetic resins. For example, 2.6-di-t-butyl-4-methylphenol, 2.2-methylenebis(4-methyl-
6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), n-octadecyl 8-(3,5-di-t-butyl-4-hydroxyphenyl)propione), 1,1. a-Tris(2-methyl-4-hydroxy-5-butylphenyl)butane, pentaerythritol tetrakis[-(
Phenolic antioxidants such as 8,5-di-t-butyl-4-hydroxyphenyl)propionate may be used alone, or these phenolic antioxidants may be combined with tris(nonylphenyl)phosphite or distearyl. A combination of phosphorus-based antioxidants such as pentaerythritol diphosphite, or sulfur-based antioxidants such as dilauryl thiodipropionate, simiristyl thiodipropionate, and distearyl thiodipropionate can be used in combination with the above phenolic antioxidants. Methods of using drugs in combination are known. However, these antioxidants have little effect on deterioration due to contact with heavy metals.

Therefore, for the purpose of providing stability to polyolefins against deterioration caused by heavy metals, h,N-dibenzoylhydrazine, hebenzoyl-N-salicyloylhydrazine, N,N-dibutyrylhydrazine, N,N
-distearoylhydrazine, N,N'-bis[8
-(3,5-di-t-butyl-4-hydroxyphenyl)propionylhydrazine, N,N-bissalicyloylhydrazine, oxalobis(benzylidenehydrazide), N-salicylidene-N-salicyloylhydrazine, 8 Metal deactivators such as -(N-salicyloyl)amino-1,2,4-triazole have been used.

Further, JP-A-47-89141 discloses that thermal stability can be improved by adding a metal deactivator to filler-containing polypropylene.

<Problems to be Solved by the Invention> However, even if the above-mentioned antioxidants and metal deactivators are added to polyolefin resins containing fillers,
The effect of preventing deterioration due to contact with heavy metals is insufficient and is still far from satisfactory.

The present inventors previously discovered that a combination of a phenolic compound with a specific structure, a metal deactivator, and a sulfur compound is effective in solving the above problems, and published JP-A-62-1
This was proposed in Publication No. 12642. Subsequently, as a result of further intensive research, a stabilizer formulation that is more effective in preventing the deterioration of polyolefin resins containing carbon black as a filler due to contact with heavy metals was discovered, leading to the present invention.

Means for Solving the Problems> That is, the present invention provides a polyolefin tree BI110 containing 0.05 to 5% by weight of carbon black and 0 to 60% by weight of an inorganic filler other than carbon black as an optional component.
0! Based on the amount of parts, quaternary formula (I) part (g) metal deactivator represented by the following formula (7) o, oi to 10 parts by weight, 0 the following general formula (l[-1) or (I -2-1 (R1-0-C-CH2CH2+-5 (IN-1) (In the formula, R1 represents an alkyl group having 4 to 20 carbon atoms) (Rz-5-CHzCHz-C-0-CH2+-5 (IN-1) (1-
2) Provides a carbon black-containing polyolefin resin composition containing 0.01 to 1.0 parts by weight of a sulfur-based compound represented by the formula (wherein Rz represents an alkyl group having 4 to 20 carbon atoms) It is.

The polyolefin used in the present invention is a homopolymer of α-olefin such as ethylene, propylene, butene-1, hexene-1,4-methylpentene-1, or
Random or block copolymers obtained from more than one α-olefin, including polyethylene, polypropylene, polybutene-1, polyisobutyne, poly-3-methylbutene-1, poly-4-methylpentene-1, and ethylene/propylene copolymer. Copolymer, ethylene/butene-1 copolymer, ethylene/4-methylpentene-1 copolymer, propylene/butene-1 copolymer, propylene/4-methylpentene-1 copolymer, decene-1/4- Examples include methylpentene-1 copolymer and ethylene/propylene/butene-1 copolymer. In addition to α-olefins, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes,
It also includes those containing other unsaturated compounds such as acrylic acid, methacrylic acid, and vinyl acetate as a copolymer component. These polymers may be acid-modified, for example, polymers graft-modified with α, β-unplated fatty acids, alicyclic carboxylic acids, or conductors thereof, and may have a rubbery or resinous shape. , containing a waxy polymer. Moreover, these polyolefins may be a blended product.

In the present invention, carbon black is essential as an inorganic filler, and its average particle diameter is preferably 20 μm or less, more preferably 0.05 to 5 μm.

Other inorganic fillers can also be used if necessary. For example, the average particle diameter is 20μ or less, preferably 0.05
~5μ various metal oxides, hydroxides, carbonates, sulfates,
Examples include silicates, silicate minerals, carbides, and seratyx. Specific examples include titanium oxide, zinc oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, calcium silicate,
Folded magnesium, talc, micas, celite, kaolin, zeolite, silica, asbestos, glass fiber,
Examples include carbon fiber, barium titanate, lead titanate, etc.

The blending ratio of the inorganic filler to the polyolefin resin is 0.05 to 6
It is used in an amount of % by weight, preferably 0.1-1% by weight. Inorganic fillers other than carbon black can be used from O to 60M depending on the purpose! If the amount exceeds 60% by weight, problems such as moldability will occur. When using an inorganic filler other than carbon black, the preferred blending amount is 1 to 50% by weight. In the following description, when expressing the blending ratio of each component, the term "inorganic filler" includes both carbon black and other fillers, unless otherwise specified.

In the present invention, the phenolic compound of the formula (υ) is
0.01 to 1.0 parts by weight, preferably 0.0 parts by weight, based on 100 parts by weight of the total amount of polyolefin resin and inorganic filler.
5 to 0.51 parts by weight are used. Even if it is added in an amount exceeding 1.0 parts by weight, it is difficult to obtain an effect commensurate with the amount added, and it is also economically disadvantageous.

In addition, the metal deactivator of the formula (formula) above is 0.01 parts by weight per 100 parts by weight of the total amount of the polyolefin resin and inorganic filler.
~10 parts by weight, preferably 0.05-1. Parts of OI are used. Even if more than 10 parts by weight is added, it is difficult to obtain an effect commensurate with the amount added, and it is also economically disadvantageous.

The sulfur-based compound used in the present invention has the general formula (ffi
-1) or (1-2). In the compound E represented by the general formula (N-1), the substituent R1
is preferably an alkyl group having 12 to 18 carbon atoms, and for example, distearyl thiodipropionate, similystyl thiodipropionate, dilauryl thiodipropionate, etc. are preferably used. Also, the general formula (
In the compound represented by 11-2), it is preferable that the substituent Rz is an alkyl group having 6 to 18 carbon atoms, such as pentaerythritol tetrakis (β-hexylthiopropionate), pentaerythritol tetrakis (β- laurylthiopropionate), pentaerythritol tetrakis (β-stearylthiopropionate), and the like are preferably used.

This sulfur-based compound exhibits its effect by blending 0.01 to 1.0 parts by weight, preferably 0.05 to 0.5 parts by weight, to 1001 L parts of the total amount of polyolefin and inorganic filler. be done.

Depending on the purpose, the composition of the present invention may contain other additives, such as ultraviolet absorbers, light stabilizers, antioxidants, metal soaps, nucleating agents, lubricants, and antistatic agents, as long as they do not impair its properties. ,
Flame retardants, pigments, plasticizers, etc. may be added.

Among the antioxidants, phosphorus compounds are preferred. Stability is further improved by adding phosphorous compounds. Preferred phosphorus compounds include distearin pentaerythritol diphosphite, tris(2゜4-di-t-butylphenyl)phosphite, tetrakis[2,4-di-t-butylphenyl]4,4'-biphenylene diphosphite, bis (
2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and the like. When using a phosphorus compound, it is preferably blended in about 2.0 parts by weight, more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of the total amount of polyolefin and inorganic filler. be done.

In addition, in the present invention, propylene/ethylene rubber, styrene/butadiene rubber, maleic anhydride-modified polyolefin, silane compound-modified polyolefin, etc. can also be blended.

The method of blending polyolefins with carbon dioxide, phenolic compounds, metal deactivators, and sulfur compounds, or other inorganic fillers and other additives used as necessary, is to form a homogeneous composition. You can use any suitable method to obtain something. That is, these raw materials may be blended simultaneously or individually in multiple steps 8, or some or all of these raw materials may be mixed as a masterbatch. These raw materials can be mixed in a conventional manner, for example, using a roll, a Banbury mixer-screw extruder, a twin-screw extruder, or the like.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Using a propylene-ethylene block copolymer (ethylene content: 7.3% by weight), pellets shown in Table 11 were molded using a 6.6-ounce injection molding machine to create a sheet with a thickness of 1 inch. . This sheet is made from a smaller copper plate 2.
Place it between the sheets and put it in a gear oven at 160℃.
Its thermal stability was evaluated. Thermal stability was evaluated by observing the boundary between the copper plate and the copolymer sheet with the inner eye and measuring the time until embrittlement was observed on the surface of the copolymer sheet. The results are shown in Table-1.

In Table 1, the weight percent of carbon black and glass fiber is the ratio to the total amount of the above copolymer carbon black and glass, 5111m, and the other components are the total amount of 100 parts by weight of the above copolymer carbon black and glass #i11Im. It is expressed as a weight percentage.

In addition, among the symbols of the test compounds in Table 1, I and I are those represented by the above-mentioned formulas, and the others represent the following compounds.

A-1: Pentaerythritol Tetrakis [8-(8
,5-di-t-butyl-4-hydroxyphenyl]propionate] A-2: n-octadecyl 8-(815-di-t-butyl-4-hydroxyphenyl)propionate B-1: N,N-bis( 8-(8,5-di-monobutyl-4-hydroxyphenyl)propionyl]hydrazine B-2: 8-(he-saliteroyl]amino-1°2.4
-) Riazole C-1 = Similystyl thiodipropionate C-2:
Pentaerythritol Tetrakis (β-lauryl thioprobionate) (Hereinafter referred to as the margin) <Effects of the Invention> According to the present invention, carbon black and other inorganic fillers are blended into polyolefin as necessary, and a specific phenol compound, The incorporation of a metal deactivator and a sulfur-based compound provides a composition that is extremely stable against contact with heavy metals. This composition has improved thermal stability, especially when it comes into contact with heavy metals at high temperatures, and therefore can be effectively used for automotive parts and electrical parts that often come into contact with heavy metals.

(Margin below)

Claims (1)

[Claims] For 100 parts by weight of a polyolefin resin containing 0.05 to 5% by weight of carbon black and 0 to 60% by weight of an inorganic filler other than carbon black as an optional component, (A) the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) 0.01 to 1.0 parts by weight of the phenolic compound represented by (B) The following formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) 0.01 to 10 parts by weight of a metal deactivator represented by (C)
The following general formula (III-1) or (III-2) ▲ Numerical formula, chemical formula, table, etc. ▼ (III-1) (In the formula, R_1 represents an alkyl group having 4 to 20 carbon atoms) ▲ Numerical formula, There are chemical formulas, tables, etc. ▼ (III-2) (In the formula, R_2 represents an alkyl group having 4 to 20 carbon atoms) 0.01 to 1.0 parts by weight of a sulfur-based compound is blended. A carbon black-containing polyolefin resin composition characterized by: