JPS6279246A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition having improved physical properties, obtained by blending ethylene-vinyl acetate copolymer and/or ethylene ethyl acrylate copolymer with a straight-chain polyethylene, Sb2O3, a bromine and/or chlorine flame-retardant, etc. CONSTITUTION:(A) 100pts.wt. ethylene-vinyl acetate copolymer and/or ethylene- ethyl acrylate copolymer is blended with (B) 5-120pts.wt. low-density straight- chain polyethylene, (C) 20-80pts.wt. bromine and/or chlorine flame-retardant, (D) 5-50pts.wt. Sb2O3 and (E) 5-100pts.wt. fine ZnO particles having <=0.3mu average particle diameter and >=10m<2>/g specific surface area by BET method. The composition is further blended with 5-100pts.wt. silica or mixture obtained by replacing partially silica (preferably 50-80wt%) with one or more of calcined fine powder wet silica, Al2O3, barium sulfate, calcium carbonate subjected to surface treatment and Al(OH)3, to extremely enhance flame retardance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition, and more specifically to an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) and an ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA). at least one of the following, and linear polyethylene (hereinafter referred to as LPE)
).

[Prior art]

Ethylene polymers or ethylene-ethyl acrylate copolymers (EEA) have excellent electrical insulation properties, and various crosslinking methods such as radiation crosslinking, organic peroxide structures, and silane structures using silane compounds can be appropriately employed. Because they have the advantage of being able to crosslink and improve various physical properties, they have been used in a wide variety of fields, including electrical insulating materials. However, recently the technological level in various fields has improved,
In various fields such as electrical equipment, vehicles, and automobiles, insulated wires, especially electronic wires, are required to have more advanced characteristics, such as oil resistance, processability during insulated wire manufacturing, and flame retardancy. , high temperature dielectric strength (Cut through)
h property) etc. have become more highly required.

[Object of the invention and its outline]

The present inventor has been conducting research on EVA or EEA compositions for a long time, and has particularly continued research to develop EVA or EEA compositions with particularly excellent various physical properties in accordance with the recent improvement in the level of technology. Ta.

In this research, when at least one of EVA and EEA and linear polyethylene (LPE) were used in a specific amount, oil resistance was further improved while retaining the properties of EVA and (or) EEA. We found that the EV could be further improved.
In particular, when 5b203 and a brominated or (and) chlorinated flame retardant are combined in a combined composition of at least one of A and EEA and LPE, flame retardance and heat deformation resistance are further improved. I also found out the facts.

As a result of continuing the above research, the present inventor found that when a specific compound is further added to the above composition, the initial electrical properties such as breakdown voltage and dielectric loss tangent as well as after immersion in water are excellent, and the present invention is hereby made. This led to the completion of the project. That is, the present invention provides: (a) 100 parts by weight of at least one of ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer; (b) linear polyethylene 5 to 120ii [1; (c)
20 to 80 parts by weight of at least one of brominated and chlorinated flame retardants, (d) Sb201+5 to 50 parts by weight, and (e) fine Zn.
This relates to a resin composition containing 1 part of O particles from 5 to 1003if, and further contains Al2O3, A1 (
'OH) 3, barium sulfate, surface-treated calcium carbonate, and at least one of silica, particularly preferably calcined fine powder wet silica.

〔Effect of the invention〕

In the present invention, by incorporating 5b203 and a brominated or (and) chlorinated flame retardant into a resin composition consisting of at least one of EVA and EEA, the resulting composition, in particular, this composition. By crosslinking, oil resistance,
It has the effect of being extremely excellent in heat deformation resistance and flame retardancy. Further, by adding fine l[tl Z n 0 grains to this, there is an effect that electrical properties such as breakdown voltage and dielectric loss tangent at the initial stage or after being immersed in water are greatly improved.

Additionally, silica, particularly preferably calcined finely powdered wet silica, Am! By blending with at least one of No. 203, barium sulfate, surface-treated calcium carbonate, and Af(○H)3, there is an effect that the N flammability is extremely improved.

[Structure of the invention]

The composition of the present invention basically contains 100 parts by weight of at least one of EVA and EEA, and 5 to 120 parts by weight of LPE, preferably 20 to 80 parts by weight.

The EVA used in the present invention has a vinyl acetate content of 20% by weight or less, preferably 15% by weight or less, and its melt index (hereinafter referred to as M, 1.) is 0.2 to 5. It is preferable that the degree of EE
A also has an ethyl acrylate content of 20% by weight or less, M, 1
．． is preferably 0.2 to 1.0. These are EVA and EE
A may be used alone or in combination,
The proportions when used together are EVAO ~ 100% by weight and E
EAI may be appropriately selected from a wide range of 00 to 0% by weight. Further, LPE having a low density is preferable, and for example, one having a density of about 0.91 to 0.93 g/cn+3 can be exemplified as a preferable LPE. Other preferred examples include those having about 4 to 8 carbon atoms. A fairly wide range of molecular weights can be used, and it is usually from 50,000 to 500,000, preferably from 80,000 to 200,000. Furthermore, the LPE itself is not limited in any way to its manufacturing method, and any LPE manufactured by various manufacturing methods can be used as long as LPE that meets the purpose of the present invention can be obtained.

In the present invention, any conventionally used brominated flame retardant can be effectively used, and specific examples include decabromodifenyl oxide (for example, plastic plastic manufactured by Mitsui Toatsu Fine Co., Ltd.). Ron DB-100>, poly(tribromo)styrene (Pyrocheck 68PB manufactured by Ferro Organic Chemical Co., Ltd.), ethylene glycol bis(
Pentabromophenyl) ether (Nissan Ferro 18
Pyrocheck 77B manufactured by Hooker Chemical Co., Ltd.), and bis(1,2,5,6-hexachlorodicyclopenteno)cyclooctane (Hooker Chemical Co., Ltd.) as a chlorine-based flame retardant.
An example is Dechlorane Plus 25) from Isand Plastic Co. These flame retardants are used in an amount of 20 to 80 parts by weight, preferably 30 to 50 parts by weight, per 100 parts by weight of at least one of EVA and EEA.

In the present invention, 5b203 is blended in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of at least one of EVA and EEA.

The fine ZnO particles used in the present invention have an average particle diameter of 0.3 μ or less by the air permeation method and a specific surface area of 10 m2/g or more by the BET method. It has a small average particle size and a large specific surface area of 10 m2/g or more. For example, normal ZnO
The average particle size is about 0.5 μ and the specific surface area is 4 to 5 m2/g.
These two points make it possible to clearly distinguish the fine ZnO grains of the present invention from ordinary ZnO. The amount of the fine ZnO particles is about 5 to 100 parts by weight, preferably about 30 to 80 parts by weight, per 100 parts by weight of at least one of EVA and ERA. In particular, it is preferable to blend these fine ZnO grains in a larger amount than normal Zn○, and the above effects are more prominently exhibited by blending in a larger amount.

In the present invention, silica, or silica and All
, 203, barium sulfate, surface-treated calcium carbonate, and at least one of A1 (OH)3, the flame retardance is further improved. The silica used in this case includes dry silica and wet silica, and calcined fine powder wet silica is particularly preferred. In this case, the calcined fine powder silica is produced by heat-treating wet silica produced by a conventional method at a high temperature, usually 800°C or higher, to reduce surface silanol groups, reduce water movement, and increase the refractive index. It is a silica with a loss on ignition of 2.0 or less,
It has a refractive index of 1.448 or more and an average particle size of 1 to 4 μm. As this sled force, there is Carplex C85-7 manufactured by Shionogi & Co., Ltd.

Barium sulfate preferably has a sedimentary plate-like or columnar particle shape, has high purity, and has an average particle size of several microns or less.

Surface-treated calcium carbonate refers to calcium carbonate that has been surface-treated with a coupling agent such as silane or titanium to improve extrusion processability and dispersibility. It is desirable that the purity is high and the average particle size is several microns or less.

A6203 and All(OH)3 also have high purity, and the particle size is preferably several microns or less.

In the present invention, silica (at least one of dry silica and wet silica), or a part of this silica,
Calcined fine powder wet silica, /M! 203, barium sulfate,
EVA and EE were replaced with surface-treated calcium carbonate and at least one of Al2(OH)3.
10 to 100 parts by weight of at least one of A
Parts by weight, preferably 20 to 50 parts by weight, are used. In addition, at least one of calcined finely powdered wet silica, Al2O3, barium sulfate, surface-treated calcium carbonate, and All (OH)3, which is used to replace a part of the silica if necessary, is preferably 90% by weight or less of the silica. is substituted by about 50 to 80% by weight. In addition, in the present invention, ordinary Zn
It does not prevent the addition of O.

The composition of the present invention may further contain various other conventional additives, if necessary. Other additives in this case include, for example, other flame retardants, various anti-aging agents, inorganic fillers, etc., and crosslinking agents, crosslinking aids, etc. can also be used.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

However, in the following examples, "parts" means parts by weight.

Examples 1 to 3 and Comparative Examples Predetermined amounts of each component were blended in the proportions shown in Table 1 and thoroughly kneaded to form a composition. Using this composition, a sheet with a thickness of 1 m+s was prepared. This sheet was irradiated and cross-linked with an electron dose of 30 Mrad, and various electrical properties were determined according to JIS C300.
5. The results are also listed in Table 1.

In addition, each component used in Table 1 is after the respective method.

EVA: Vinyl acetate content 15wt% M,! , 0.5 EEA: Ethyl acrylate (referred to as EA) content 15
wt% M, 1. 1.5 LLDPE: Density 0.925 M, 1.4.0 Carbon number 4 Halogen-based flame retardant: Decabromodiphenyl oxide Antioxidant: Irganox 1010 Fine ZnO particles 2 Carplex C5-5 However, Irganox 101O is phenol It is a tetrakis-[methylene-3-(3') antioxidant.

5'-di-tert-butyl-4'-hydroxyphenyl)
It is comethane propionate.

Table 1

Claims (6)

[Claims] (1) (a) At least one of ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer10
0 parts by weight, (b) 5-120 parts by weight of linear polyethylene, (c) 20-120 parts by weight of at least one of brominated and chlorinated flame retardants.
80 parts by weight, (d) 5 to 50 parts by weight of Sb_2O_3, and (e) 5 to 100 parts by weight of fine ZnO particles. (2) The resin composition according to claim 1, further comprising 5 to 100 parts by weight of silica. (3) Calcined fine powder wet silica, Al_2O_3, barium sulfate, surface-treated calcium carbonate and Al(OH
)_3 The resin composition according to claim 1, containing 5 to 100 parts by weight of at least one of the following. (4) Calcined fine powder wet silica, Al_2O_3, barium sulfate, surface-treated calcium carbonate and Al(OH
)_3 and silica in an amount of 5 to 100 parts by weight. (5) Fine ZnO has an average particle size of 0.
3μ or less and a specific surface area of 10m by BET method
^2/g or more, the resin composition according to any one of claims 1 to 4. (6) The resin composition according to any one of claims 1 to 5, wherein the silica is fired fine powder wet silica.