JPS62112642A - Polyolefin composition containing filler - Google Patents

Abstract

PURPOSE:To contemplate an improvement in stability against deterioration caused by contact with heavy metals, by blending a resin compsn. consisting of a polyolefin and an inorg. filler with a specified phenol compd., a metal inactivating agent and a sulfur compd. CONSTITUTION:100pts.wt. resin compsn. consisting of 98-35wt% polyolefin and 2-65wt% inorg. filler is blended with 0.01-1.0pt.wt. phenol compd. (A) of formula I (wherein R1 is a 1-3C alkyl group), 0.01-10pts.wt. metal inactivating agent (B) having at least one group of formula II on its side chain and 0.01-1.0pt.wt. sulfur compd. (C) of formula III (wherein R2 is a 4-20C alkyl group), formula IV (wherein R3 is a 4-20C alkyl group), formula V (wherein R4 is a 3-18C alkyl group; R5, R6 are independently H, a 1-6C alkyl group) or formula VI (wherein R7 is a 3-18C alkyl group).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to stabilized compositions of polyolefins containing fillers. More specifically, it relates to a filler-containing polyolefin composition that is particularly stable against deterioration due to contact with heavy metals and has improved colorability.0 <Prior Art> Synthesis of polyethylene, polypropylene, polybutene, etc. Resins have excellent mechanical properties and are extremely useful as materials for fibers, molded products, films, etc.
Furthermore, in order to improve the rigidity, heat distortion temperature, or dimensional stability of polyolefin molded products, inorganic fillers, especially talc, calcium carbonate, etc., are often added.◎Synthetic resins containing such inorganic fillers is often used for automobile parts, electrical product parts, etc., but contact with heavy metals such as copper, iron, and nickel is unavoidable, and the thermal stability of molded products is lower than that of cases where there is no contact with heavy metals. It is very poor and has become a big problem.

In order to solve these problems, it is well known that various phenol-based, phosphorus-based, and sulfur-based antioxidants are added and used during the production and processing of synthetic resins. For example, 2.6-di-t-buty/L/-4
-Methylphenol, 2,2'-methylenebis(4-methyl-6-t-butylpheno-/L/), 4,4'-butylidenebis(3-methy/l/-6-t-butylpheno-/I/) , n-octadeci! -8-(8,5-di-
t-Butyne l/-4-hydroxyphenylene/I/)propionate, 1,1.8-)linu(2-methyl-4-hydroxy-5-2-butylphenyl)butane, pentaerythritol tetrakis[8-(8 , 5-di-t-butyl-4-hydroxyphenylv)propionate] alone, and these pheno-lV acid antioxidants tri-7 (nonylphenylphenylv) propionate 2 l/) Honupite, distearyl ρ bentaerynritol diphosphite, and other phosphorus-based antioxidants, or the above-mentioned phenolV-based acid antioxidants cyfuryl thiodipropionate, dimyristyl thiodiglo Methods of using sulfur-based antioxidants such as pionate and distearylthiodipropionate in combination are known. However, the above-mentioned antioxidants have little effect on deterioration due to contact with heavy metals. .

Therefore, for the purpose of imparting stability to polyolefins against deterioration due to heavy metals, N,N'-dibenzoylhydrazine, N-pencil μ-N-cytyloylhydrofuzine, and N are generally used.

N-dibutyrylhydrazine, N,N'-distearoylhydrazine, N,i-bisCB-(8°5-!/-
t-Butyl-4-hydroxylpheny/V)propionyl]hydrazine, N,N'-bissalycyloylhydrazine, oxalobis(benzylidenehydrazide), N-
Salicylidene-N-salicyloylhydrazine, 8-(N
Metal deactivators such as -Sarichiroi/I/)-amino-1,2,4 triazole have been used.

Furthermore, JP-A-47-89141 discloses that adding a metal deactivator to filler-containing polypropylene improves thermal stability.<Problems to be Solved by the Invention> However, when a polyolefin composition obtained by blending the above-mentioned antioxidant and metal deactivator with a filler-containing polyolefin is used as a molded product in applications that come into contact with heavy metals, improvements in deterioration prevention are observed. The effect is insufficient and cannot be called satisfactory. Furthermore, when a metal deactivator is blended, there is a problem that the polyolefin becomes colored and noisy during molding, processing, or use of the polyolefin.

The present invention aims to improve the above-mentioned problems of filler-containing polyolefins used in applications that come into contact with heavy metals. 98 to 85f (general formula fI) (wherein, R1 represents an alkyl group having 1 to 3 carbon atoms). 0.01 to 1.0 parts by weight/l of a phenolic compound represented by 0.01 to 1.0 parts by weight/l or a metal deactivator that is a phenolic compound.
01 to 10 parts by weight (C) General formula (II-1>, (II-2),
(II-8> or (II-4) (Rt-0-8-CH
t CHt+T-8(ll-1) (In the formula, R1 represents an alkyl group having 4 to 20 carbon atoms.) (Rs-8-CHtCHt-C-OCHt-C(II
-2) (In the formula, R8 represents an alkyl group having 4 to 20 carbon atoms) (0) (In the formula, R4 represents an alkyl group having 3 to 18 carbon atoms, R6
and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) (n-4) (In the formula, R represents an alkyl jv group having 3 to 18 carbon atoms.

) is a filler-containing polyolefin composition characterized by blending 0.01 to 10 parts by weight of a sulfur compound represented by - A homopolymer of α-olefin such as methyl-pentene-1, or a random or block copolymer consisting of two or more molecules,
Polyethylene, polypropylene, polybutene-1, polyisobutyne, poly-8-methyl-butene-1, poly-
4-methyl-pentene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-
Methyl-pentene-1 copolymer, propylene-butene-
Examples thereof include propylene-4-methyl-pentene-1 copolymer, decene-1-4-methylpentene-1 copolymer, and ethylene-propylene-propylene-1 copolymer. In the case of copolymerization, copolymerization includes polyunsaturated compounds such as conjugated dienes and non-conjugated dienes, or acrylic acid, methacrylic acid, vinyl acetate/l', etc. as copolymerization components together with α-olefin. These polymers may be acid-modified, for example, polymers graft-modified with α, β-unsaturated fatty acids, alicyclic carboxylic acids, or derivatives thereof, and may be rubbery, resinous, or waxy. It contains a polymer of In addition, these polyolefins may be blended products. The inorganic filler used in the present invention has an average particle diameter of 2.
Examples include various metal oxides, hydroxides, carbonates, sulfates, silicates, silicate minerals, carbides, and ceramics having a particle size of 0 μ or less, preferably 0.05 to 5 μ or less. Specific examples include titanium oxide, zinc oxide, aluminum hydroxide,
Calcium carbonate, magnesium carbonate, calcium sulfate,
Barium sulfate, calcium silicate, magnesium silicate, talc, clouds, cephite, kaolin, zeophyte,
Examples include silica, anupest, gaffus ln pheasant, carbon fiber, carpump hook, barium titanate, lead titanate, etc., and these may be blended into the polyolefin alone or as a mixture thereof.

The blending ratio of polyolefin and inorganic filler is 98 to 85% by weight of polyolefin, preferably 95 to 60'M
k:%, non-pregnant filler is 2-65% by weight, preferably 5-40% by weight. If the blending ratio of the inorganic filler is less than 2% by weight, the effect of the inorganic filler will not be exhibited easily;
If it exceeds 65N'Jkg6, problems will arise in moldability, etc.

The phenolic compound (3) represented by the general formula (11) used in the present invention is 3,9-bis(2-hydroxy-1,1-dimethylethyl A/)-2゜4.8.10-tetofuoxa Spiro(5,5)undecane and 8-(3-Aμ/L/-5-t-buty-1v-4-hydroxyphenylene/I/)propionic acid, or its acid halide, acid anhydride, or its lower It can be produced by conventional transesterification reactions with alkyl esters.

In the phenolic compound represented by the general formula fI), %R1 is a methyl group, an ethyl group, or a propylene group.

Although it represents a y group, a methyl group is preferred from the viewpoint of deterioration prevention effect.

The phenol/l/based compound is added in an amount of 0.01 to 1 part by weight of a resin composition consisting of a polyolefin and an inorganic filler.
The effect is exhibited by combining 1.0 parts by weight, and preferably 0.05 to 0.6 parts by weight. It is not preferable to add more than 1.0 parts by weight of the metal deactivator (B) used in the present invention because the effect commensurate with the amount added will not be obtained and it will be economically disadvantageous. Craftsmanship on the chain? :
/V or a phenolic compound. Specific examples include Hato 1 and Hato 4, but compounds of Taki 1 and Kai 8 are particularly preferably used.

The metal deactivator is synthesized by combining 0.01 to 10 parts by weight, preferably 0.05 to 1.0 parts by weight, with respect to 100 parts by weight of a modified resin consisting of a polyolefin and an inorganic filler. Even if the amount of sulfur-based compounds (Q exceeds 010 parts), which is effective, is added, it is difficult to obtain an effect commensurate with the added amount, and it is economically disadvantageous.
Examples include compounds represented by II-1'), (II-2), (If-8), or (II-4).

〇(R,-0-C-CH,CH,i S (If
-1) (in the formula, R≦ represents an alkyl group having 4 to 20 carbon atoms) (R, -5-an, ca, -e-o-cH, soup C
(II-2) (In the formula, R1 represents an alkyl group having 4 to 20 carbon atoms ◇) (In the formula, R4 represents an alkyl group having 8 to 18 carbon atoms, R
, and R6 are each independently a hydrogen atom or a carbon number of 1 to 6
In the compound represented by the general formula (II-1), Distearyl thiodipropionate, similystyl thiodipropionate, cyfuryl thiodipropionate, etc., in which the substituent R2 is a furkyl group with #l prime number of 12 to 18, are preferably used.

Moreover, in the compound represented by general formula (II-2),
Substituent R3 is preferably an alkyl group having 6 to 18 carbon atoms.

Representative examples of such compounds are shown in Table-1.

Table 1 (n, -5-CH, CH, C-0-CH, -5C゛Also, in the compound represented by the general formula (II-8), the substituent R4 is a l/ group is also R
1 and R6 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Representative examples of such compounds are shown in Table 2.
2 Regarding the compound represented by general formula (II-4),
Substituent R7 is preferably an alkyl group having 12 to 18 carbon atoms, and representative examples of such compounds are shown in Table 8.

Table 8 The sulfur compound was added in an amount of 0.01 parts per 100 ffiffi parts of a resin composition consisting of a polyolefin and an inorganic filler.
The composition of the present invention exhibits its effect by adding ~1.0 parts by weight, preferably 0.06 to 0.5 parts by weight.Other additives, such as Ultraviolet absorbers, light stabilizers, antioxidants, metal soaps, nucleating agents, lubricants, antistatic agents, S refueling agents, pigments, plasticizers, etc. may be self-mounting 0 Preferred among antioxidants Examples of compounds include phosphorus compounds. By adding O-phosphorus compounds,
Stability and colorability are improved.

Preferred phosphorus compounds include distearyl μbentaerynritol diphosphite, tris(2,4-di-t-butylpheny/I/)phosphite, and tetrakis(
2,4-di-t-butylphenyl/I/)4. Ibiphenylene diphosphite, bis(2,4-di-t-butylphenyl)bentaerythritol diphosphite, and the like can be mentioned.

The phosphorus compound is blended in an amount of 0.1 to 1.0 parts by weight, preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of a resin composition comprising a polyolefin and an inorganic filler.

In addition, propylene-ethylene rubber, nutylene-butadiene rubber, maleic anhydride-modified polyolefin, silane compound-modified polyolefin, etc. can also be blended. Alternatively, as a method for blending other additives, any method suitable for obtaining a homogeneous composition can be used. That is, these raw materials may be blended simultaneously or individually, or some or all of these raw materials may be mixed as a masterbatch.

These raw materials may be kneaded using a conventional mixing method, such as a P-ru, a Banbury mixer, a twin-screw extruder, or the like.

<Examples> The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 5 Brobylene-ethylene block copolymer (limiting viscosity:
[Leopard = 2.45, Ethylene Lightning Lua, 3% by weight] powder and Merck (Miku Pn Why) 000 as an inorganic filler.
0.05 parts of calcium nateate, pheno-/I/based compounds, metal deactivators, sulfur-based compounds, and bis(2,4 parts) per 100 parts of a resin composition consisting of 0.05 i part of -y-t-butylphenyl/l/) pentaerythritome μ diphosphite) was blended, mixed in a Henschel mixer, kneaded and pelletized using a 65 φ extruder. The resulting pellet was heated to 280°C.
A press sheet having a thickness of 1 inch was prepared by preheating for 10 minutes. The resulting sheet was placed in a gear oven at 150° C. in contact with a copper plate to measure thermal stability.

In addition, the melt index (MI) of the beret is
Measured according to SK7210. Y@ on press sheet
Lowness Ind@x (Yl) ASTM D
Measured according to 1925. The above results are shown in Table 4 together with the raw material composition. /I/) Gropionate] (Irgnox 1
010) was carried out in the same manner as in Example 1 except for using A-8: Pentaerythritol Tetofukis 1”8-(8
, 5-di-t-butyl-4-hydroxyphenylene/L/)propionate] Metal deactivator B-2: OH Sulfur thread compound C-1 = Similis tL-μ thiodipropionate Examples 6-8 Shown .

Comparative Example 8 Irtcanox 10 as a pheno-/'v-based compound
◇The results are also shown in Table 4〇〇<Effects of the Invention> According to the present invention, the specific phenol compound of the present invention was added to the inorganic filler-containing polypropylene. A heavy metal stabilizing composition containing a metal deactivator, a sulfur thread compound, and a sulfur thread compound is provided. This composition has greatly improved thermal stability compared to conventional compositions, especially when brought into contact with a copper plate at high temperatures, and also has improved colorability.

Procedural amendment (voluntary) September 30, 1986

Claims (1)

[Claims] 98 to 35% by weight of polyolefin and 2 to 65% by weight of inorganic filler
(A) General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 represents an alkyl group having 1 to 3 carbon atoms) ) 0.01 to 1.0 parts by weight of a phenolic compound shown in Parts by weight, (C) General formula (II-1), (II-2), (II-3) or (II-4) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II-1
) (In the formula, R_2 represents an alkyl group having 4 to 20 carbon atoms.) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II-2) (In the formula, R_3 represents an alkyl group having 4 to 20 carbon atoms. ) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II-3) (In the formula, R_4 is an alkyl group having 3 to 18 carbon atoms, and R_
5 and R_6 are each independently a hydrogen atom or a carbon number of 1 to
6 shows the alkyl group. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II-4) (In the formula, R_7 represents an alkyl group having 8 to 18 carbon atoms.) 0.01 to 1.0 parts by weight of a sulfur-based compound represented by A filler-containing polyolefin composition characterized in that it is blended with a filler-containing polyolefin composition.