JPS62112643A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To contemplate an improvement in stability against deterioration caused by contact with heavy metals, by blending a polyolefin with a specified phenol compd., a metal inactivating agent and a sulfur compd. CONSTITUTION:100pts.wt. polyolefin 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 2-13C alkyl group; R5, R6 are independently H or a 1-6C alkyl group) or formula VI (wherein R7 is a 3-13C alkyl group).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application> The present invention relates to stabilizing compositions for polyolefins. More specifically, the present invention relates to a preolefin composition that is particularly stable against deterioration due to contact with heavy metals and has improved colorability.

<Prior Art> Conventionally, polyolefins such as polyethylene, polypropylene, and polybutene have been used in many fields due to their excellent mechanical and chemical properties. However, as is well known, polyolefins deteriorate due to the effects of heat, light, and oxygen during processing or use, resulting in phenomena such as softening, embrittlement, surface cracks, and discoloration, resulting in a significant deterioration of their mechanical properties. There were stability issues.

In order to solve this problem, it is well known that various phenol-based, phosphorus-based, sulfur-based, and other antioxidants have been added and used during the production and processing of synthetic sea bile. , 2゜6-di-t-butyl-4-methylphenol, 2.2'-methylenebis(4-methyl-6-butylphenol), 4.4'-butylidenebis(3
-methyl-6-t-butylphenol), n-octadecyl 8-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,1.8-tris(2-
Methyl-4-hydroxy-5-t-butylphenyl)phthane, pentaerythritol tetrakis (:3-(
8゜5-di-t-butyl-4-hydroxyphenyl) propionate] may be used alone, or these phenolic oxidation Fj inhibitors may be combined with tris(nonylphenyl)phosphite or distearylpenta A combination of phosphorus-based antioxidants such as erythritol diphosphite, or combination of the above phenolic antioxidants with sulfur-based antioxidants such as dilaurylthiodipropionate, simiristylthiodipropionate, and distearylthiodipropionate Methods have been used in which antioxidants are used in combination.

However, if contact between polyolefin and heavy metals such as copper, iron, or nickel cannot be avoided, for example, coating polyolefin on copper wire, plating polyolefin with heavy metals, coloring polyolefin with pigments containing heavy metals,
In the case of polyolefin molded products that are used in applications that come into contact with heavy metals, such as vehicles and electrical products, it is difficult to prevent deterioration due to contact between polyolefin and heavy metals by simply using the above-mentioned ordinary antioxidants. Shows little thermal stability.

As a method to solve such problems,
Publication No. 5826 shows that thermal stability is improved by adding an ester compound having a group shown in the molecule and dilaurylthiodipropionate to polypropylene, and also that polyethylene: / l': Although it has been disclosed that the addition of an ester compound and distearyl thiodipropionate improves the thermal stability when in contact with aluminum foil, this is still unsatisfactory from a practical level.

On the other hand, for the purpose of imparting stability to polyolefins against deterioration due to heavy metals, N,N.-dibenzoylhydrazine, N-benzoyl-N'-cytyloylhydrazine, N.

NI-dibutyrylhydrazine, N,N'-distearoylhydrazine, N,N'-bis(t3-(8゜5-di-
t-butyl-4-hydroxyphenyl)propionyl]
hydrazine, N, NI-bissalycyloylhydrazine,
Oxalobis (benzylidene hydrazide), N-salicylidene-N'-salicyloylhydrazine, 8-(N-
Metal deactivators such as salicyloyl)-amino-1,2,4 triazole have been used.

<Problems to be solved by the invention> However, even when the above-mentioned antioxidants and metal deactivators are blended into polyolefin and used in applications that come into contact with heavy metals, the improvement effect in preventing deterioration is insufficient. and
I can't say I'm satisfied with it yet. Furthermore, when a metal deactivator is blended, there is a problem that the polyolefin is likely to be colored during molding, processing, or use.

The present invention aims to improve the above-mentioned problems of polyolefins used in applications that come into contact with heavy metals.

<Means for Solving the Problems> The present invention provides polyolefin 100i [in parts] represented by (A) general formula (I) (wherein R2 represents an alkyl group having 1 to 3 carbon atoms). (A) Fe+1 containing one or more -C-N- groups in the side chain;
1 H Metal deactivator which is a nyl or phenolic compound 0.0
1 to 10 parts, (q General formula (I-1), (II-2), (I-3) or (R2-0-C-CH2CH2 monomer (I-1>
(In the formula, R2 represents an alkyl group having 4 to 20 carbon atoms.) (R3-sc-C-0-CH2-C(If
-2) (In the formula, R3 represents an alkyl group having 4 to 20 carbon atoms.) (In the formula, 1 represents an alkyl group having 3 to 18 carbon atoms, and bird and bird each independently represent a hydrogen atom or a carbon number (In the formula, R7 represents an alkyl group having 3 to 6 carbon atoms.) (In the formula, R7 represents an alkyl group having 3 to 18 carbon atoms.) This is a polyolefin composition.

The polyolefin used in the present invention is a homopolymer of α-olefin such as ethylene, propylene, butene-1, hexene-1,4-methyl-pentene-1, or
Random and block copolymers consisting of polyethylene, polypropylene, polybutene-11 polyisobutyne, poly-8-methyl-butene-1, poly-
4-methyl-pentene-11 ethylene-propylene copolymer, ethylene-butene-1 copolymer! Coalescence, ethylene-4-
Methyl-pentene-1 copolymer, propylene-butene-
1 copolymer, propylene-4-methyl-pentene-1 copolymer, decene-1-4-methylpentene-1 copolymer, and ethylene-propylene-butene-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, 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

Moreover, these polyolefins may be a blended product.

The phenolic compound (2) represented by the general formula (I) used in the present invention is 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2゜4,8.10-tetraoxane. Produced by a conventional transesterification reaction between spiro(5,5)undecane and 3-(]-]alkyl-5-t-butyl-4-hydroxyphenylpropionic acid, or its acid halide, acid anhydride, or lower alkyl ester thereof. can do.

In the phenolic compound represented by the general formula (I), R1 represents a methyl group, an ethyl group, or a propyl group, and a methyl group is preferable from the viewpoint of deterioration prevention effect.

The phenolic compound is used in an amount of 0.00 parts by weight per 100 parts by weight of the polyolefin. The effect is exhibited by adding 2.0 parts by weight of O2N, preferably 0.05 to 0.5 parts by weight. Adding more than 1.0 parts by weight is not preferred because it is difficult to obtain an effect commensurate with the amount added and is economically disadvantageous.

The metal deactivator ◎ used in the present invention is a phenyl or phenol compound in the side chain. A specific example is Lung 1 to 2 u3, but a compound of Nul and NcL3 is particularly preferably used. The metal deactivator is polyolefin 100
0.01 to 10 parts by weight, preferably 0
．． The effect is exhibited by blending 05 to 1.0 parts by weight. Even if it is added in an amount exceeding 10 parts by weight, it is difficult to obtain an effect commensurate with the amount added, which is also economically disadvantageous.

On the other hand, the sulfur-based compound (q is represented by the following general formula (I1
-1), (I1-2), (na) or c (II-4)
).

(R20CCH2CH2+rS (I1) (wherein, R2 represents an alkyl group having 4 to 20 carbon atoms) (R3
-8-CH2CH2-C-0-CH2-jT-C(It
-2) (In the formula, R3 represents an alkyl having 4 to 20 carbon atoms.) (In the formula, a bird represents an alkyl having 3 to 18 carbon atoms, and a circle and a bird each independently represent a hydrogen atom. Masuko represents an alkyl having a carbon number of 1 -6 alkyl group.) (In the formula, R7 represents an alkyl group having 3 to 18 carbon atoms.) In the compound (lt) represented by the general formula (lt-1), 1i
, alkyldistearyl thiodipropionate, simi-nostyl thiodipropionate, dilauryl thiodipropionate, etc. in which the substituent R2 has 12 to 18 carbon atoms are preferably used.

Further, in the compound represented by the general formula (I-2), the 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 (R3-8-CH, CH, C-0-C-h-C also,
In the compound represented by general formula (I-8), the substituent is preferably an alkyl group having 12 to 18 carbon atoms, and the substituents are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Representative examples of such compounds are shown in Table-2.

Table 2 In addition, for the compound represented by the general formula (...-4), the substituent R7 is preferably an alkyl group having 12 to 18 carbon atoms,
Representative examples of such compounds are shown in Table-8.

Table 8 The sulfur compound is 0.0% per 100 parts by weight of polyolefin. 2.0 parts by weight of O2N, preferably 0.05-0
．． The effect is exhibited by blending 5 parts by weight.

The composition of the invention may contain other additives, such as ultraviolet absorbers, light stabilizers, antioxidants, metallic soaps, nucleating agents, lubricants, antistatic agents, flame retardants, as long as they do not impair its properties. Pigments, plasticizers, etc. may also be blended.

Among the antioxidants, preferable compounds include phosphorus compounds. By adding phosphorus compounds,
Stability and colorability are improved.

Preferred phosphorus-based compounds include distearylpentaerythritol-diphosphite, [-lis(2,4-di-t-butylphenyl)phosphite, and tetrakis(2
, 4-di-t-butylphenyl) 4.4'biphenylene diphosphonite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, and the like.

The phosphorus compound is 0.0% based on 100 parts by weight of the polyolefin. 2.0 parts by weight of O2N, preferably 0.05-0.5
Parts by weight are added. In addition, propylene-ethylene rubber, styrene-butadiene rubber, maleic anhydride-modified polyolefin, silane compound-modified polyolefin, etc. can also be blended.

The phenolic compound, metal deactivator, sulfur compound, or other additives may be added to the polyolefin by any method suitable for obtaining a homogeneous composition. 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, ie, a roll, a Banbury mixer, a single-screw extruder, a twin-screw extruder, or the like.

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

Examples 1 to 6 Polypropylene (homopolymer) powder (intrinsic viscosity:
η) = 2.20) 0.05 parts by weight of calcium stearate, a phenolic compound, a metal deactivator, and a sulfur-based compound were added to 100 parts by weight, mixed with a hexyl mixer, and then mixed using a 65 mm diameter extruder. It was pelletized by extrusion at 230°C under nitrogen atmosphere. The melt index (MI) of the pellets obtained in this way is determined by JIS K
Measured according to 7210.

Also, these pellets were preheated at 230 °C for 10 minutes to a thickness of l! A press sheet for IN was created. The obtained press sheet was brought into contact with a copper plate and placed in a gear oven at 150°C to measure thermal stability.

Also, press sheet Yellowness Index
(YI) was measured according to ASTM D1925.

The above results are shown in Table 4.

Comparative Examples 1 to 3 Conventional pentaerythritol tetrakis (8-(8,5-di-t-butyl-4-hydroxyphenyl)propionate) (lrganox) as a phenolic compound
The same procedure as in Example 1 was carried out except that 1010) was used. The results are also shown in Table 4.

Examples 7 to 10 Propylene-ethylene block copolymer ([η)=2.45. Ethylene content 7.8w
In addition to 0.05 parts by weight of calcium stearate, a phenol compound, a metal deactivator, and a sulfur compound, a phosphorus compound bis(2゜4-c t-butylphenyl) is added to 100 parts by weight of the powder. ) showed Pentaeris.

To the front, 1z bamboo? Near 3 + a)'; (-heart/wave piece/tophenol compound A-f3 pentaerythritol tetrakis C3-(
8,5-di-t-butyl-4-hydroxyphenyl)propionate] Metal deactivator-20H ゝN' Sulfur-based compound C-1 Simyristylthiodipropionate C2 (H25
CI2 S-CH2CH2C-0-CH2") 7C phosphorus compound D-1 Contains bis(2,4-di-t-butylphenyl)pentaerythritol-diphosphite enol compound, metal deactivator and sulfur compound Provided is a heavy metal stabilizing composition which has greatly improved thermal stability compared to conventional compositions, particularly when brought into contact with copper plates at high temperatures, and also has improved coloring properties. It has been improved.

Procedures (Amendment voluntarily) September 30, 1985 Patent Application No. 251725 of 1985 2 Name of the invention Polyolefin composition 3 Relationship with the person making the amendment Case Patent applicant 5 Kitahama, Kanohigashi-ku, Osaka 15-15 (209) Sumitomo Chemical Co., Ltd. Representative Hideo Mori 4, Agent 5-15 Kitahama, Higashi-ku, Osaka Contact information Ta, (06) 220-34046 Contents of amendment (I) Page 6 of the specification In line 10, "N'-Salicyloyl-□" is corrected to rN=-Salicyloyl.

(2) On page 19, line 13 of the same document, the phrase "-ru compound metal" is amended to read "-ru compound, metal."

(3) r on page 20, lines 11-12 (Irganox
1010) Done. -] Using r(A-3), a test was conducted in the same manner as in Example 1 under the conditions shown in Table 4. ” he corrected.

that's all

Claims (1)

[Claims] Based on 100 parts by weight of polyolefin, (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 represented by (B) The side chain has a ▲ mathematical formula, chemical formula, table, etc.
(C) General formula (II-1), (II-2), (II-3) or (II-4) ▲Mathematical formula, chemical formula, table etc.▼(II-1) (In the formula, R_2 represents an alkyl group having 4 to 20 carbon atoms.) ▲There are numerical formulas, chemical formulas, tables, etc.▼(II-2) (In the formula, R_3 represents the number of carbon atoms. ) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II-3) (In the formula, R_4 represents an alkyl group having 3 to 18 carbon atoms, 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 3 to 18 carbon atoms.) 0.01 to 1.0 weight of a sulfur-based compound is blended. A polyolefin composition characterized by: