JPS584208A - Fluorine-containing elastomer coating wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorine-containing elastomer-coated electric wire, and more particularly to a fluorine-containing elastomer-coated electric wire having a specific structure and useful as a heat-resistant flexible electric wire.

Fluorine-containing elastomers have been used in a variety of applications such as gaskets, packings, diaphragms, and hoses due to their excellent heat resistance, oil resistance, and chemical resistance, and due to these properties, they are also highly expected to be used as electrical wire coating powder. However, fluorine-containing elastomer-coated wires have not yet been put into practical use.

One of the reasons for this is that it has a structure similar to that of ordinary rubber insulated wires, with a paper separator interposed between the insulator and conductor to prevent the insulator from being inserted between the strands of the conductor. In a fluorine-containing elastomer-covered electric wire, the wire is wound around its own diameter at room temperature and heated to a temperature of 120°C or higher.The present inventors solved the above problem and developed a fluorine-containing elastomer-coated electric wire useful as a heat-resistant flexible electric wire. Elastomer coated wire tW
As a result of intensive research to provide the above crack,
Wrapping occurs when a strain that exceeds the elongation at break at high temperatures is locally concentrated on the insulator in contact with the break point that sometimes occurs in the paper separator. Fi is not often found in common insulating materials such as ethylene propylene rubber and cross-linked polyethylene, and although it is expected to be used at high temperatures from the viewpoint of heat aging resistance, the elongation at break at high temperatures decreases. It was discovered that this problem is unique to large fluorine-containing elastomers. Furthermore, by interposing an intermediate layer between the insulator and the conductor, in place of the conventional paper separator, at least the surface part that contacts the insulator is easily disintegrated, the problem of cracking can be smoothly solved. At the same time, we have found that it is possible to prevent the insulator from penetrating between the wires.

Thus, the present proposal was completed based on the above-mentioned new knowledge, and it is provided that an intermediate layer is interposed between the rubber insulating electric body having the rubber coating layer, and at least the surface of the intermediate layer that contacts the rubber coating layer. The present invention provides a fluorine-containing didistomer insulated wire characterized in that a portion thereof is easily disintegrated.

In the present invention, the fluorine-containing elastomer may be exemplified by a wide variety of conventionally known or well-known ones without being particularly limited. For example, TE, dorafluoroethylene-propylene copolymer, vinylidene fluoride-hexafluoropropene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-pentafluoropropene copolymer ,
Polyfluoroalkyl group-containing acrylate elastomer, polyfluoroalkyl group-containing polysiloxane elastomer, tetrafluoroethylene-vinylidene fluoride-propylene copolymer, tetrafluoroethylene-ethylene-inethylene copolymer, ethylene-hexafluoro Propene copolymer, tetrafluoroethylene-proden-1 co-ffi polymer, tetrafluoroethyl vinyl ether copolymer, fluorine phosphonitrile elastomer, tetrafluoroethylene
Examples include fluorovinyl ether copolymers.

Such fluorine-containing elastomers are those that can be peroxide vulcanized with less residual ionic impurities after crosslinking, for example, those containing unsaturated bonds, -0F2X or \CFX in the molecule, from the viewpoint of electrical insulation properties of the crosslinked product. (However, X
It is preferable to use a curing site having a hardening site such as a (Br) unit or -OH8 unit, and a tetrafluoroethylene-propylene copolymer is preferable if dielectric properties are also taken into consideration.

The tetrafluoroethylene-propylene copolymer suitable as a fluorine-containing distomer includes, in addition to the main components tetrafluoroethylene and propylene, components copolymerizable with these, such as ethylene, isobutylene, acrylic acid, and alkyl esters thereof. , methacrylic acid and its alkyl esters, vinyl fluoride, vinylidene fluoride, hexafluoropropene, chloroethyl vinyl ether, chlorotrifluoroethylene, -(-fluoroalkyl vinyl ether, etc.). In the copolymer, the molar ratio of tetrafluoroethylene/propylene is 9515 to
It is preferable to select from the range of 30/70, especially 90/10 to 4515v) from the viewpoint of heat resistance, moldability, etc., and the content of components other than the main component that may be added as appropriate is usually 5.
It is preferable to select from a range of 0 mol% or less, particularly 30 mol% or less.

In the present invention, the rubber coating layer is formed from a crosslinked product of a composition mainly composed of the above-mentioned fluorine-containing elastane, and the composition includes a crosslinking agent, a crosslinking accelerator, a reinforcing agent, a filler,
Various additives such as pigments, lubricants, antioxidants, and stabilizers can be added.

Such a composition has a Mooney viscosity of MLl+4
(100°C) is preferably about 20 to 150, particularly about 30 to 90, from the viewpoint of moldability during coating and surface condition of the product. It is desirable to adjust the composition etc.

In the present invention, the crosslinked product can be formed by the action of a chemical crosslinking agent or ionizing radiation, but from the viewpoint of preventing ionic impurities from remaining after crosslinking and simplifying the operation, peroxide vulcanization can be used. The method is preferably employable. In this case, specific examples of bridging include diacyl peroxide such as dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxy acetate, t-butyl peroxyimprobyl carbonate, Monoperoxy compounds such as t-butylperoxybenzoate, t-butylperoxybenzoate, and 2,5-dimethyl-2,5-di(t-
butylperoxy)-hexane-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,
4-bis-(1-butylperoxy-isopropyl)benzene, 1,3-bis-(1-butylperoxy-4-propyl)benzene, 2,5-dimethyl-2,5-di(benzoylperoxy) Examples include ciba-oxy compounds such as hexane.

These may be used alone or in combination of two or more. The amount of such a crosslinking agent used is usually about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the fluorine-containing elastomer.

When forming the above-mentioned crosslinked product, crosslinking aids can be used in combination, such as allyl compounds, sulfur, organic amines,
Crosslinking aids such as maleimides, methacrylates, divinyl compounds, etc. may be employed.

Polyallylic compounds such as triaryl, triallyl cyanurate, isocyanuric acid, cyanuric acid, and cyanuryl melamine, and oxime compounds such as para-benzoquinone dioxime and p,p'-dibenzoquinone dioxime are used, and polyallylic compounds are particularly preferred. The amount of the crosslinking aid added may be about 0.1 to 20 parts by weight, preferably about 0.2 to 10 parts by weight, based on 100 parts by weight of the fluorine-containing elastomer.

In the present invention, it is important to interpose an intermediate layer between the rubber coating layer and the conductor, the surface of which is in contact with the rubber coating layer is easily disintegrated.

Due to the presence of such an intermediate layer, the problem of cracks occurring during winding of the covered wire can be smoothly solved, and it is also possible to prevent the insulator from sinking into the spaces between the wires.

In the present invention, the term "easily collapsible" refers to the property that it collapses easily when bending stress is applied, and that the collapse is minute over the entire area where the stress is applied, and that no large local cracks remain. be. A method for making at least the surface part of the intermediate layer have such characteristics is as follows: 1. Wrap a material that easily becomes brittle when heated, such as paper, around a conductor, and then apply a composition mainly composed of a fluorine-containing elastomer on top of it. After coating, heat treatment is performed under conditions where the wire becomes brittle but deterioration of the rubber insulating layer is not noticeable, so that the material itself disintegrates easily. ■ Heat resistance such as heat-resistant resin film. A method in which a laminate having a surface layer of a thermally embrittleable material as described above on a base material is used as an intermediate layer material and the surface layer is made to disintegrate easily in the same manner as described above. After forming a coating layer of an inorganic material such as powder, granules, or hollow particles containing a substance that easily volatilizes, decomposes, or becomes brittle as a binder, the binder is removed by heating or the like. A method of making the coating layer more easily disintegrated by causing embrittlement; For example, a method for disintegration can be used, and method (2) can be preferably adopted from the viewpoint of operability.

In addition, in the case of the method (1) or (2) above, the coating with the fluorine-containing elastomer composition can be carried out not only before, but also at the same time or after the removal or embrittlement of the binder. Examples of binders include water; organic solvents such as alcohols, ketones, chlorinated hydrocarbons, and fluorinated chlorinated hydrocarbons; glucose! Sugars such as sugar starches; water-soluble salts such as sodium carpoxycellulose, gum arabic, metal soaps or aqueous solutions thereof; and inorganic materials such as talc, sericite, diasolani, boron nitride, alumina. , titanium oxide, silica, calcium silicate, carbon black, graphail, glass, zinc sulfide, molybdenum disulfide, magnesium oxide, magnesium hydroxide, calcium carbonate, silicoite, kaolin, bentonite, and the like.

Next, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention is not to be construed as being limited by such explanations.

Examples 1 to 6 and Comparative Examples 1 to 3 Tetrafluoro, ethylene with a number average molecular weight of 50,000 and a molar ratio of tetrafluoroethylene/propylene = 55/45
1,3-bis-
(t-Butylperoxy-isopropyl)benzene (crosslinking agent) 1 part by weight, triallylisocyanurate (crosslinking aid) 5 parts by weight, thermal carbon (filler) 40 parts by weight, stearic acid) IJium (lubricant) ) 1 part by weight was added and kneaded for 15 minutes with a 150+ m diameter rubber roll set at a temperature of 50 to 60°C to obtain a Mooney viscosity of ML1+4 (1
00°C) was obtained. Next, this head = 80℃, cylinder 80℃, cylinder 2 = 60℃
Using a 40X extruder (L/D=22) set to 6′□
m+)L, steam at 13 atm was applied for 3 minutes to cause crosslinking.

The coated wire thus obtained was heat-treated under various conditions shown in Table 1, and then wound around the true diameter of the wire at room temperature for 15 minutes.
The insulator was exposed to a temperature atmosphere of 0°C and 250°C for 3 hours, and the occurrence of cracks in the insulator was examined. The results are shown in Table 1.

Table 1 ○No cracks
0) Vinylidene fluoride-hexafluoropropene copolymer (DAIEL G301 manufactured by Daikin Industries, Ltd.) 100 parts by weight Thermal carbon 20 〃2.
A covered wire was prepared in the same manner as above except that 5-dimethyl-2,5-di(t-butylperoxy)hexane 1.51 triallylisocyanurate 4# was used, and it was heated under the same conditions as in Example 1. After the heat treatment, it was subjected to a similar heating winding test (Example 4).

In this case as well, no cracking was observed not only at 150°C but also at 250°C.

On the other hand, if no heat treatment was performed after coating (
In Comparative Example 4), cracking was already observed at 150°C.

Examples 5 and 6 The paper coating layer on the conductor was replaced with a coating layer mainly composed of α-alumina (
Covered wires were prepared in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3, except that the dry film length was 40 μm), and subjected to the same heating winding test 2 (Example 5). In this case as well, no cracking was observed not only at 150°C but also at 250°C.

The coating layer mainly composed of α-alumina was formed by the following method. A viscous dispersion was prepared by kneading and heating 100 parts by weight of α-aluminum's (White Morundumna 3000 manufactured by Fujimi Abrasives Industry Co., Ltd., average particle size 5 μm) with 100 parts by weight of water and 4 parts by weight of commercially available wheat flour. After immersing the conductor in this liquid, the amount of adhesion was made uniform with a brush, and then heated and dried with an infrared lamp.

Similar results were obtained when talc (LMR manufactured by Ueya Kaolin Kogyo) was used in place of α-alumina (Example 6).

Display of the case 1982 Patent Application No. 101955 Name of the invention Person who amends fluorine-containing elastomer coated electric wire Relationship to the case Patent applicant address Tokyo Prefecture, Rakusho δA-chome 1-2 Name (512
) hi1 Co., Ltd. Representative 1 Student ri Yw Address 2-1-2 Marunouchi, Chiyoda-ku, Tokyo Name (
004) 71 Kataku Co., Ltd. - Representative “V'h Kani Aburoyo Rihito 〒100 Column of inventor and patent applicant of application subject to amendment.

Detailed description of the invention in the specification.

Contents of correction (1) Correct the application as shown in the attached sheet.

(Correction: ■ Inventor's name, r
Corrected as 'WM'rJ, ■Applicant's name representative class
Area V. ) (2) Insert "ga" between "...use" and "expectation..." on page 3, line 8 of the specification.

(6) "Insulation" in the first line of page 1 of the specification is corrected to "coating."

(4) "Butene" in the second line of Part 4 of the Letter of Detail is corrected to "Butene."

(5) Between ".../70" and "especially..." on page 6, line 5 of the specification, and between "lower" and "especially..." on line 9 of the same specification.
Insert "," between each.

(6) "...2,5-di" on page 7, line 15 of the specification
and r(t-...), at the end of the 16th line, between "...kisi)" and "heki..." in the 17th line,
Insert "-" between "...xy)" and "hexane" in the first line of page 8.

(7) "Line" on page 9, line 15 of the specification is corrected to "material."

(8) Delete "wo" on page 9, line 18 of the specification.

(9) Delete “Solvent; Glucose is sugar” on page 10, line 17 of the specification, and replace it with “Solvent; Glucose is sugar.”
Insert.

tJω Correct "Yu" in line 18 of page 10 of the specification to "tsu".

αη The word ``technique'' in the first line of page 11 of the specification is corrected to ``earth''.

(2) "U" in the third line of page 11 of the specification is corrected to "t".

"Comparative Examples 1 to 6" on page 11, line 10 of f151 specification
is corrected to "Comparative Example 1.2".

a4 Page 13 of the specification is corrected as shown in the attached sheet.

(2) "4" on page 14, line 8 of the specification is corrected to "3".

αG "Comparative Examples 1 to 3" on page 14, line 13 of the specification is corrected to "Comparative Example 1.2."

List of attached documents (1) Correction application form (1 original and 1 copy each) (2)
One or more documents stating page 13 of the revised specification fML, medium.

(100℃)=803 Vinylidene fluoride-hexafluoropropene system
-Copolymer Daikin Industries Co., Ltd. Daiel () 801)
100 parts by weight

Claims (3)

[Claims] (1) In a rubber insulated wire having a rubber coating layer,
The rubber coating layer is not a crosslinked composition mainly composed of a fluorine-containing elastomer, and an intermediate layer is interposed between the coating layer and the conductor, and at least the surface of the intermediate layer is in contact with the rubber coating layer. A fluorine-containing elastomer-coated electric wire characterized in that a portion thereof is easily disintegrated. (2) The covered electric wire according to claim 1, wherein the crosslinked body is formed by vulcanization. (3) Claim 1 in which the fluorine-containing elastomer is a tetrafluoroethylene-propylene copolymer.
Covered wire as described in section. (4) The covered electric wire according to claim 1, wherein the intermediate layer is made of paper that has been made brittle by heat treatment.