JPS62265333A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition excellent in heat resistance, low-temperature flexibility, strength, etc. and suitable for coating wires, etc., by mixing polyethylene with a benzimidazole compound, a hindered phenol compound and a sulfur compound. CONSTITUTION:The purpose heat-resistant resin composition is obtained by mixing 100pts.wt. polyethylene with 5-20pts.wt. benzimidazole compound (e.g., 2-mercaptobenzimidazole), 2-15pts.wt. hindered phenol compound [e.g., 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzoyl) isocyanurate] and 0.5-5pts.wt. sulfur compound (e.g., dilauryl thiodipropionate) as effective components. This resin composition is suitable as a composition for coating wires of aircraft which must have particularly excellent heat resistance and low-temperature flexibility.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a heat-resistant resin composition, and more specifically, it has excellent heat resistance and low-temperature flexibility and is extremely suitable as a resin composition for aircraft electric wires. The present invention relates to a resin composition.

(Prior Art) As is well known, resin compositions are widely used in various fields.
．． One type of these is a polyolefin resin composition. This polyolefin resin composition is most commonly used due to its various excellent properties. For example, it is used as a composition for coating various electric wires and a composition for molded articles.

However, based on recent advances in technology, even more excellent properties are being required for this type of resin composition, especially polyolefin compositions. Resin compositions, especially polyolefin compositions, having low temperature flexibility have become required.

[Problem that the invention seeks to solve]

The problem to be solved by the present invention is to meet the demands of conventional resin compositions of this type. More specifically, the object is to develop a resin composition, particularly a polyolefin composition, which has extremely excellent heat resistance and low-temperature flexibility.

[Means for solving problems]

The problem with this is that the resin component made of polyethylene or ethylene-vinyl acetate copolymer (hereinafter referred to as EVA),
A resin component consisting of polyethylene and at least one of an ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) and an ethylene-methyl acrylate copolymer (hereinafter referred to as EMA), a hindered phenol compound, a sulfur compound, and a benzene compound. This is achieved by blending each imidazole compound.

That is, the present invention comprises (A) polyethylene, optionally (E) ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, and ethylene-ethyl acrylate copolymer (both of which are one type of copolymer); (B) benzimidazole-based The present invention relates to a heat-resistant resin composition containing a compound, (C) a hindered phenol compound, and (D) a sulfur compound as active ingredients.

[Function and structure of the invention]

In the composition of the present invention, a benzimidazole compound (component B), a hindered phenol compound (component C), and a sulfur compound (component D) are used in combination, and these are combined with polyethylene (component A) or In addition to this A component, E
VA%At least one of EMA and EEA (E component)
When blended into a resin component consisting of the following, the synergistic effect of these three results in a resin composition that has extremely excellent heat resistance and low-temperature flexibility. For example, it is extremely suitable as a coating resin composition for aircraft electric wires, and has the characteristics of passing a heat resistance test at 0.200°C for 7 days and a flexibility test at -65°C. It is.

The polyethylene used as component A in the present invention can be widely used from high density polyethylene to low density polyethylene. High density polyethylene has a density of 0.9
35 or higher, and low-density polyethylene refers to
Refers to those with a density of less than 0.935. Preferred polyethylenes include high-density polyethylene with a density of 0.935 or more, linear polyethylene with a density of less than 0.935, and so-called very low-density polyethylene (VeryLo
w density polyethylene),
Examples include various polyethylenes called Tafmer (manufactured by Mitsui Petrochemical Industries, Ltd.). These polyethylenes include
It includes not only ethylene homopolymer but also copolymers of ethylene and other olefins, usually α-olefins having about 4 to 16 carbon atoms, and the content of other α-olefins is usually 3 to 15% by weight. That's about it. In general, polyethylene is preferably linear, especially polyethylene with a density of 0.90 to 0.935 at 20°C, and with a melt index (hereinafter referred to as Ml) measured by ASTM D1238. 0.1-10, particularly 0.3-5 is preferred.

In addition, as extremely low density polyethylene preferably used in the present invention, rDFDA 1137 NT7'' (density: 0.906.Ml: 0.8. manufactured by Nippon Unica Co., Ltd.), rDFDA1138NTJ (density: 0.900)
．． Mll, 4. (manufactured by Nippon Unica) is 0. Examples of Tafmer include Tafmer A, which is an ethylene-butene-1 co-i1 combination, and Tafmer P, which is a propylene-ethylene copolymer (density: 0.89, Mitsui Petrochemical Co., Ltd.).

In the present invention, any EVA that has been used conventionally can be used as the EVA component (IE) if necessary, but preferably has a vinyl acetate content of 10 to 30% by weight. 0. Various types of EEA are also widely used, but those with an ethyl acrylate content of 10 to 30% by weight are preferred;
Even if it is EV161, it is about 0.2 to 5, and E
EA is 0.2-1. Preferably, it is about O.

In addition, in the present invention, all or a part of EEA is ethylene-methyl acrylate copolymer (hereinafter referred to as EMA).
It can also be used instead.

At this time, the methyl acrylate content and Ml are approximately E
This is the same as in the case of EA. These are EVA, EEA and E
MA may be used alone or in combination, and the proportions when used in combination may be appropriately selected from a wide range of EVAO to 100% by weight and EEA or EMA from 100 to 0% by weight.

As the benzimidazole compound used as component (B) in the present invention, those having at least one benzimidazole structure (2B) shown below in the molecule and having a molecular weight of 150 or more are preferably used. Ru.

Preferred specific examples include compounds represented by (ii).

More preferable specific examples include 5, such as 2-mercaptobenzimidazole (r Nocrac M8 (Irunai Shinko) MW150), 2-mercaptomethylhenzimidazole [Nocr
ac MMB J (Iriuchi Shinko) MW164) 2-
Zinc salt of mercaptobenzimidazole [rNocra
c MBZJ (Shinko Iriuchi) MW363) Zinc salt of 2-mercaptomethylbenzimidazole (rNocra
c MMBZ J (Iruuchi Shinko) MW393) can be exemplified. All of the above MW indicate molecular weight. However, as M in formula (B-11), for example, 2 such as Zn
I can give an example of a valence metal.

In addition, the high molecular weight hindered phenol compound used as component (C) in the present invention has at least one 3,5-di(-butyl-4-hydroxyphenyl structure) shown below in the molecule. ) and a molecular weight of 500 or more, preferably 600 to 1200, are preferably used.

(However, t-Bu represents a t-butyl group).

More specifically, it is as shown in the first blue below.

Table 1 Also, particularly preferred are, for example, the following.

(However, R+ to Ra represent Cn Hz*-rl, and n represents an integer of 12 or more).

In the present invention, the blending ratio of each component is as follows: (A) component to
The amount of component (B) is about 5 to 20 parts by weight, preferably about 8 to 15 ffl parts, based on the omm part.

(C) component is 2 to 15 parts by weight per 100 parts of component (A), preferably 4 to 10 parts by weight, and component (D) is the same, 0.5 parts by weight per 100 parts by weight of component (A). ~
It is 5 parts, preferably 1 to Afflfft parts.

In the present invention, at least one of EV8, EEA, and EMA can be further blended as required. The blending ratio of these is 0 parts per 10.0 parts by weight of component (A).
~50 parts by weight, preferably about 10 to 40 parts by weight.

Other conventional additives can simply be incorporated into the compositions of the invention. For example, HP machine if combustion aid, organic flame retardant, antioxidant, antioxidant aid, insulation reinforcing agent,
One or more types of polyfunctional compounds etc. as resin component (A)
The amount can be about 1 to 100 parts by weight per 100 parts by weight. As inorganic flame retardant aids, antimony compounds,
Examples include molybdenum compounds and hydrated metal oxides, with 5bzoz being preferred. Specific examples of the AT flame retardant include bromine-based or nitrogen-based flame retardants. Preferred examples of the antioxidant include phenolic or amine antioxidants, silica powder as the insulation reinforcing agent, and Zn-based compounds, preferably ZnO and titanium-based compounds, as the antioxidant aids. Examples of polyfunctional compounds include isocyanate compounds, and a preferred one is triallylisocyanurate (hereinafter referred to as TAIC).

Since the composition of the present invention consists of components (A) to (D), in other words, the resin component (A) contains (B) to (D).
By blending a specific compound, it imparts extremely excellent heat resistance, even in the case of non-crosslinking, but especially in the case of crosslinking, such as the ability to pass even under extremely harsh conditions such as 7 days at 200°C. Not only is it flexible at -65℃, it also passes the test at low temperatures! Q property is given. Moreover, it also exhibits the effect of providing excellent mechanical properties such as tensile strength and cut-through properties.

The composition of the present invention can be crosslinked by various methods such as a dry or wet crosslinking method using a chemical crosslinking agent such as an organic peroxide, an electron beam irradiation crosslinking method, or a water crosslinking method. In the case of the water-crosslinking method, water-crosslinking may be performed using a water-crosslinkable polyethylene such as a copolymer of ethylene and an unsaturated organic silane such as vinyltrimethoxysilane or a silane-modified polyethylene as the component (A). Well, again (A)
~In addition to component (D), a chemical agent for silane-modifying component (A), such as an organic peroxide and an unsaturated organic silane, is mixed together and extrusion molded to simultaneously make component (A) water-crosslinkable. It may also be degenerated into.

Note that a particularly preferred method for crosslinking the composition of the present invention is an electron beam irradiation crosslinking method.

The composition of the present invention may further include other additives normally used in the rubber and plastics industries, such as carbon blanks, higher fatty acids, waxes, pigments, process oils, lubricants, anti-aging agents, blowing agents, There is no problem in using a retarder, a vulcanization accelerator, a tackifying agent, etc. as appropriate.

Furthermore, the composition of the present invention containing the above-mentioned conventional additives can be easily produced using conventional kneading means and equipment such as a kneader, roll mill, or Banbury. In the production of the composition of the present invention, there are no restrictions on the order in which the essential and optional components are added, and may be carried out as appropriate in accordance with common technical knowledge in the art. Therefore, regardless of the order of compounding, as long as the result contains at least all the essential components of the present invention and achieves or exhibits the purpose or effect of the present invention. It belongs to the technical scope of the present invention.

The composition of the present invention can be used as described above. Crosslinkable and vulcanizable
．． Moreover, it has excellent performance, so it can be used in various applications that require flame retardancy and heat resistance, such as covering electric wires and cables,
Suitable as a constituent material for hoses, pipes, sheets, films, fibers, various profiles, etc. It is particularly suitable as an aircraft wire coating composition that requires excellent heat resistance and low-temperature flexibility.

〔Example〕

Examples are shown below. However, in the following description, parts indicate parts by weight.

Examples 1 to 8, Comparative Examples 1 to 3 Predetermined components shown in Table 3 below were mixed in a predetermined amount to prepare each composition. Using these compositions using an extruder, 19
/29TA tin-plated annealed copper wire was coated to a thickness of 0.35@cm, and then cross-linked by irradiation with 20 Mrad using an electron beam accelerator. Further, polyvinylidene fluoride resin was coated thereon to a thickness of 0.125 m and irradiated at 6 Mrad to produce the final wire.

Various physical properties of each wire were measured using the following measurement methods. The results are shown in Table 4.

However, each component used in Table 3 is as follows.

Components used> PE-1: Low density polyethylene, OF[lA 11
37NT density: 0.906. Old: 0.8 (manufactured by Nippon Unicar) PE-2: Scratched low density polyethylene, 0FDA 113
8NT density: o, 9oo, MI: 0.4 (manufactured by Nippon Unicar) PE-3: Linear polyethylene, MORETECH0
138N density: 0.920. MI:1. O (manufactured by Idemitsu Petrochemical Industries, Ltd.) EVA-1: ethylene-vinyl acetate copolymer, evatate) 11011. Vinyl acetate content: 15% by weight,
MI: 0.5 (manufactured by Sumitomo Chemical Co., Ltd.) EVA-2: Ethylene-vinyl acetate copolymer, Evaflex EV-270,
Vinyl acetate content: 28% by weight, MI: 1. O (manufactured by Mitsui Polychemical Co., Ltd.) EEA: Ethylene-ethyl acrylate copolymer, A710. Contains ethyl acrylate 1:15
Double star%, old: 0.5 (manufactured by Mitsui Polychemical Co., Ltd.) E blend: ethylene-methyl acrylate copolymer,
XG300E, methyl acrylate content: 12x4%
, MI: 0.4 (manufactured by Mitsubishi Yuka Co., Ltd.) Tsukurak MB:
Nocrac l'lB+ (manufactured by Irinai Shinkosha) Nocrac MMB: Nocrac MMB+ (manufactured by Iriuchi Shinkosha) Nocrac MBZ: Nocrac MBZ+ (
(Manufactured by Iriuchi Shinkosha) Mark ^ Q-18: Mark ^ 0-1
8. (Manufactured by Adeka Argus Chemical Co., Ltd.) ■ Constant 1 Wide Heat Resistance The center part of a 600 am wire is suspended from a 1.0 inch diameter mantle, and a load of 2 lds is applied to both ends of the wire. - After aging in the oven for 7 days, the mantle was wrapped at room temperature to determine if it would crack. Items that did not break were marked with an ○, while items that did crack were marked with an X.

Flexibility (-65℃) Wire soaked at -65℃ for 4 hours with 51d
It was determined whether or not it would break by winding it around a 1.5 inch diameter Nomandono C under a load of 0. Those that did not break were marked O, while those that did crack were marked X.

Tensile Characteristics A tube with a length of 50 meters between the gauge lines was pulled at a speed of 2001 m/akin with a tension of 0. Breaking tensile strength 1.76 kg/w” or more,
Those with an elongation of 150% or more were deemed to be acceptable and marked with an O, and those with a failure were marked with an X.

〔Effect of the invention〕

It is clear from Table 4 above that 0. The composition of the present invention has excellent heat resistance and flexibility at low temperatures, and other properties such as mechanical strength. Therefore, it can be used very effectively in various fields, and is particularly suitable for use as a wire coating composition for aircraft, and its industrial utility value is extremely high.

r ``Akihito Ne...Main ζ Book (self-motivated) August 27, 1981 411, IT Agency Director Kuro [11 Myojo Tono L ( 1, If ft display Showa fl 161 Special 81 Application No. 108800 Bow 2 , Name of the invention fiJ heat t'i !I fat composition 3, supplement i [relationship with small P1 Applicant 11 8, Higashimukojima Nishinocho, Ezaki City, Takashi Prefecture Name Representative: Mitsubishi Cable T Gyo Co., Ltd. Old Yuki Brewery 4, generation 1111 people〒', +30 1-1-25 Minamimorimachi, Kita-ku, Osaka Yachiyo Building South Building 1!+06 (314) 02a8 (8ti41) Bentoshi O [Shout Yumu]
: 5. The pair of amendments, the range of KomaaTi+^, and Specification 11: Content 1 of the one-bit amendment of the detailed explanation for the middle element, and the scope of the claims will be corrected as shown in the attached sheet.

2. End of page 10 in details fit ”Yo 1; O Takumi Ino.

3, page 12, line 5 in table 1 [5hell
Correct J to rshellJ.

4. In the 5th line from the bottom of Table 1, page 12 of the specification, "oxymethyl" is corrected to "oxyethyl."

5. Specification Yamanaka, page 13, line 5 [(however, X represents hydrogen or CnH:L+1, and n is an integer of 12 or more)" 1Uf/su1 is 0.n
is an integer greater than or equal to 1).”

6. In the fourth line from the bottom of page 19 of the specification, the text [(manufactured by Mitsui Polychemical Co., Ltd.)] is corrected to [(manufactured by Mitsui Polychemical Co., Ltd.)].

7. In the first line of page 20 in Yamanaka, the text [(manufactured by Mitsui Polychemical Co., Ltd.)] is corrected to "(Mitsui Polychemical Co., Ltd.'!l) J.

(Above) Claim +11 A heat-resistant resin composition comprising (A) polyethylene, (B) a benzimidazole compound, (C) a hindered phenol compound, and (D) a sulfur compound as active ingredients. .

(2) The ratio of the above (A), (B), (C), and (D) components is 5 parts by weight (B) to 100 parts by weight of (A), respectively.
~20 parts by weight, (C) 2 to 1 sffl parts, (D) 0.
A composition according to claim 1 in which the amount is 5 to 5 parts by weight.

(3) The composition according to claim 1 or 2, wherein the polyethylene has a density of 0.935 or more.

(4) The composition according to claim 1 VA or claim 2, wherein the polyethylene has a density of less than 0.935.

(5) the polyethylene is linear low density polyethylene;
The composition according to claim 4, which is at least one of Tafmer and low density polyethylene.

(6) The benzimidazole compound has at least one benzimidazole structure shown below in the molecule and has a molecular weight of 150 or more. (7) Hinder The dophenol compound has at least one of the following 3,5-
It has a di-t-butyl-4-hydroxyphenyl structure,
Claim 1, wherein the amount is 500 or more (provided that t-Bu represents a t-butyl group).

(8) The sulfur-based compound has at least two or more of the following structures in the molecule, and the amount thereof is 500 or more, or (wherein, X is hydrogen or Cn1I2?l 1, and n is a number greater than or equal to 1).

(9) Furthermore, as component (E), ethylene-vinyl acetate copolymer, ethylene-ethyl 7-acrylate copolymer, and ethylene-methyl acrylate copolymer (both 1
The composition according to claim 1, which contains seeds.

QQI The composition according to claim 9, wherein the component (E) is blended in an amount of 10 to 50 parts by weight per 100 parts by weight of component (A).

Claims (10)

[Claims] (1) A heat-resistant resin composition comprising (A) polyethylene, (B) a benzimidazole compound, (C) a hindered phenol compound, and (D) a sulfur compound as active ingredients. (2) The ratio of the above (A), (B), (C), and (D) components is 5 parts by weight (B) to 100 parts by weight of (A), respectively.
~20 parts by weight, (C) 2 to 15 parts by weight, (D) 0.5 to
5 parts by weight of a composition according to claim 1. (3) The composition according to claim 1 or 2, wherein the polyethylene has a density of 0.935 or more. (4) The composition according to claim 1 or 2, wherein the polyethylene has a density of less than 0.935. (5) the polyethylene is linear low density polyethylene;
The composition according to claim 4, which is at least one of Tafmer and very low density polyethylene. (6) Claim 1, wherein the benzimidazole compound has at least one benzimidazole structure shown below in its molecule, and has a molecular weight of 150 or more.
There are compositions described in Section 2 or Section 2, ▲mathematical formulas, chemical formulas, tables, etc.▼. (7) The hindered phenol compound has at least one of the following 3,5-di-t-butyl-4-hydroxyphenyl structures in its molecule, and the amount thereof is 500 or more. The composition described in Section 1 or Section 2, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, t-Bu indicates t-butyl group). (8) The composition according to claim 1 or 2, wherein the sulfur-based compound has at least two or more of the following structures in the molecule, and the amount thereof is 500 or more, ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X represents hydrogen or C_nH_2_n_+_1, and n is an integer of 12 or more). (9) Furthermore, as a component (E), at least one of an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-methyl acrylate copolymer.
The composition according to claim 1, which contains seeds. (10) Component (E) is blended in an amount of 10 to 50 parts by weight per 100 parts by weight of component (A).
The composition described in Section.