JPS61228049A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition having extremely improved oil resistance, resistance to heat distortion and flame retardance, obtained by blending EVA and/or EEA with LPE, Sb2O3, a specific flame-retardant and silica or silica and one or more of ZnO, calcined fine powder wet type silica, etc. CONSTITUTION:(A) 100pts.wt. A1: ethylene-vinyl acetate copolymer having <=20wt% vinyl acetate content and 0.2-5 melt index and/or A2: ethylene-ethyl acrylate copolymer having <=20wt% ethyl acrylate content and 0.2-1 melt index is blended with (B) 5-120pts.wt. straight-chain polyethylene having preferably 0.91-0.93g/cm<3> density and 50,000-500,000 molecular weight, (C) 20-80pts. wt. bromine type and/or chlorine type flame-retardant, (D) 5-50pts.wt. Sb2O3, (E) 5-100pts.wt. E1: silica or E2: silica and one or more of ZnO, calcined fine powder silica, Al2O3, barium sulfate, etc.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a resin composition, and more specifically to an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA). At least one type of heavy Ah (hereinafter referred to as EEA) and a resin component of linear polyethylene (hereinafter referred to as LPE) contain two specific types of compounds and a specific ll#! The present invention relates to a composition comprising the following agents.

[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 crosslinking, and silane crosslinking 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, workability during insulated wire manufacturing, and flammability. , 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 (hereinafter referred to as LPE) were used in a specific amount, the oil resistance remained the same while retaining the properties of EVA and/or EEA. We found that there was further improvement.

In addition, at the stage of further research, we will develop a combination composition of at least one of EVA and EEA and LPE, especially 5b2o.
We have discovered a new fact that when compounding No. 3 and a bromine-based or (and) chlorine-based flame retardant, the flame retardance and heat deformation resistance are even more excellent.

As a result of continuing research on the above-mentioned specific compound, the present inventor found that silica, or silica and Zn were added to this specific compound composition.
O1 calcined fine powder wet silica, A j! 203, barium sulfate, surface-treated calcium carbonate and A1 (
When further blending at least one of OH)a,
It was discovered that each of the excellent properties of the above-mentioned specific compound composition, oil resistance and heat deformation resistance were further improved, and flame retardancy was also significantly improved, and this led to the completion of the present invention. . That is, the present invention includes (11) 100 parts by weight of ethylene-vinyl acetate copolymer or (and) ethylene-ethyl acrylate copolymer, 5 to 120 parts by weight of straight-line polyethylene, a brominated flame retardant or (
and) 20 to 80 parts by weight of chlorine flame retardant, S b 20a
(2) ZnO1 calcined fine powder wet silica, AN20. , barium sulfate, surface-treated calcium carbonate and Aj! The present invention relates to a resin composition according to claim 1, which contains 5 to 100 parts by weight of at least one type of (OH)3 and silica.

〔Effect of the invention〕

In the present invention, by adding Sb, O, and a brominated or (and) chlorinated flame retardant to a resin composition consisting of at least one of EVA and EEA, the resulting composition is particularly effective. By crosslinking the composition, oil resistance,
It has the effect of being extremely excellent in heat deformation resistance and flame retardancy. And without impairing each of these properties, silica or 7. n Os calcined fine powder wet silica, AJ203. Barium sulfate, surface treated carbonic acid.

The combination of lucium and at least one of A l (OH) 3 has the effect of greatly improving flame retardancy.

[Structure of the invention]

The composition of the present invention basically comprises at least 1 [100 parts by weight of EVA and EEA, and 25 to 120 parts by weight of LP, 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 E.R.
A also has an ethyl acrylate content of 20% by weight or less, M, 1
．． 0 and 2 may be used alone or in combination, and the ratio when used in combination may be appropriately selected from a wide range of EVAO to 100% by weight and EEAloo-0% by weight. Furthermore, it is preferable that the LPE has a low density, for example, a density of 0.91 to 0.93 g/cm'
Examples of preferable examples include those of a certain degree. Other preferred examples include those having about 4 to 8 carbon atoms. A fairly wide range of molecular weights can be used, usually from 50,000 to 500,000, preferably from 80,000 to 20,000.
Use something around 0,000. Furthermore, LPE itself is not limited 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.

The silica of the present invention includes dry silica and wet silica.

ZnO is produced by a French method, an American method, or a wet method, and has an average particle size of usually 1.0 μm or less.

By heat-treating the created wet silica at a high temperature, usually over 800°C, the surface silanol groups are reduced,
It is a silica that reduces moisture movement and has a thick refractive index, with a loss on ignition of 2.0% or less and a refractive index of 1.448 or more.
The average particle size is 1 to 4μ. As this silica, there is Carplex C55-7 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 camping 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.

A It 203 and A It (OH) z 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, is mixed with ZnO1 calcined fine powder wet silica, Al2O3, barium sulfate, surface-treated calcium carbonate, and A j!
(OH) Replaced with at least one type of 3, E
It is used in an amount of 10 to 100 parts by weight, preferably 20 to 50 parts by weight, per 100 parts by weight of at least one of VA and EEA. ZnO1 calcined fine powder wet silica, A 1203, barium sulfate, surface-treated calcium carbonate, and A
At least one of I (OH) 3 is 90ii of silica
It is preferably replaced by about 50 to 80% by weight.

In the present invention, any conventionally used brominated flame retardant can be effectively used, and specific examples include decabromodiphenyl oxide (e.g., Mikata Toatsu Fine Planelon DB-100). , poly(tribromo)styrene (Pyrocheck 68PB from Nissan Ferro Organic Chemical), ethylene glycol bis(pentabromophenyl) ether (Nissan Ferro Organic Chemical)
Pyrocheck 77B), bis(1,2,5,6-hexachlorodicyclopenteno)cyclooctane (Ilooker chemicals) as a chlorine-based flame retardant.
Dechlorane Plus 25 from andplastic Co.
) can be exemplified. These flame retardants are at least one of EVA and EEA100! 20~
It is used in a proportion of 80 parts by weight, preferably 30 to 50 parts by weight.

Further, in the present invention, 5b2o3 is blended in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on the amount of 10G, ii of at least one of EVA and EEA.

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 will be shown below to give a more concrete and sharp meaning to the present invention.

Examples 1 to 7 and Comparative Examples 1 to 2 Predetermined amounts of each component were mixed and sufficiently kneaded in the proportions shown in Table 1 to form compositions. A single annealed copper wire of 0.813 nφ as a conductor and a wire of 0.380 mm in thickness as an insulator were manufactured from this composition according to a conventional method, and crosslinked by irradiation with an electron beam dose of 30 Mrad. Various physical properties were measured.

The results are shown in Table 2. However, the physical properties were measured by the respective methods.

<Oil Resistance> After being immersed in A37M No. 2 oil at 100°C for 96 hours, it is left at room temperature, and it is judged as passing when the residual rate of tensile strength is 50% or more of the initial value and the residual rate of elongation is 65% or more.

<Flammability> According to UL 5ubject 758, a certain amount of flame is applied for 15 seconds from a burner at a certain inclination to a vertical electric wire, and then the flame is removed for 15 seconds, and this is repeated 5 times. The test is passed if a certain amount of electric wire does not burn out, or if ash does not fall and spread to the underlying cotton.

<Workability> When the compound is coated on a copper wire using a 3On+mφ extruder, if the extruded surface appearance is smooth, it is considered to be passed.

Heating deformability> If the deformation rate is 50% or less when a load of 250 g is applied to the wire for 30 minutes at a temperature of 150°C, it will be passed.

<Heat Aging Resistance> After aging at 136° C. for 7 days, it is passed if the tensile retention is 70% or more, the elongation retention is 65% or more, and the breakdown voltage is 50% or more.

However, the various polymers used as polymers in Table 1 are shown below.

LPE-1: Density 0.920 M, 1.1.0 carbon number 8 LPE-2: Density 0.925 M, 1.4.0 carbon number 4 EVA-1: Vinyl acetate (hereinafter referred to as EV) content 15w
t% M, 1.0.5 EVA-2: EV content 10 W t%M, 1.
1.0 EEA-1: Ethyl acrylate (referred to as EA) content
15 wt% M, 1.1.5 EEA-2: EA content 15 wt% M, 1.0.5 Irganox 1010 is a phenolic antioxidant, tetrakis-[methylene-3-(3', 5 '-di-tert-butyl-4'-hydroxyphenyl)propionate comethane.

Claims (2)

[Claims] (1) 100 parts by weight of ethylene-vinyl acetate copolymer or (and) ethylene-ethyl acrylate copolymer, 5 to 120 parts by weight of linear polyethylene, bromine type or (and)
Chlorine flame retardant 20-80 parts by weight, Sb_2O_35-5
0 parts by weight, and 5 to 100 parts by weight of silica. (2) ZnO, calcined fine powder wet silica, Al_2O_3
Barium sulfate, surface treated calcium carbonate and Al
At least one of (OH)_3 and silica in 5 to 1
00 parts by weight of the resin composition according to claim 1.