JPH06103827A - Chlorinated polyethylene sheathed cable - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a novel chlorinated polyethylene sheathed cable capable of improving the tensile properties of a coating layer. [Structure] According to the present invention, a resin component having a content of chlorinated polyethylene and a vinyl chloride-vinyl acetate-vinyl alcohol copolymer in a weight ratio range of 95/5 to 20/80 is used.
A composition in which 1 to 50 parts by weight of an epoxy-based stabilizer and 10 to 100 parts by weight of an inorganic filler are added to parts by weight of an organosilane compound is grafted to form an insulator, and the insulator is formed on a conductor. And is exposed to water in the presence of a silanol condensation catalyst to crosslink and form.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorinated polyethylene sheathed cable having a chlorinated polyethylene composition capable of crosslinking at low temperature and atmospheric pressure as a coating layer.

[0002]

2. Description of the Related Art Cables and electric wires are produced by providing a coating layer as a sheath on a conductor or a conductor shielding layer, and crosslinking the coating layer. Chlorinated polyethylene is used as the sheath material.

This chlorinated polyethylene is reacted with an organic silane compound in the presence of peroxide and exposed to water in the presence of a silanol condensation catalyst to give
By silane-crosslinking the chlorinated polyethylene in this way, there is an advantage that a special device such as a high-sound or high-pressure vulcanizing device is not required, and a cable or the like can be produced only by a general extruder.

[0004]

However, when a composition obtained by grafting an organic silane compound on chlorinated polyethylene and crosslinking the same in the presence of a catalyst and water is applied to a sheath such as a cable, the tensile strength which is important for the cable is increased. May be inferior.

Therefore, the present invention was devised in order to effectively solve the above-mentioned problems, and an object thereof is to provide a novel chlorinated polyethylene sheath cable capable of improving the tensile properties of the coating layer. It is provided.

[0006]

In order to achieve the above object, the first invention is that the content of chlorinated polyethylene and vinyl chloride-vinyl acetate-vinyl alcohol copolymer is 95/5 to 20 / by weight. An organic silane compound is grafted to a composition obtained by adding 1 to 50 parts by weight of an epoxy stabilizer and 10 to 100 parts by weight of an inorganic filler to 100 parts by weight of a resin component in the range of 80 to form an insulator. The conductor is coated with the insulating material, exposed to water in the presence of a silanol condensation catalyst, and crosslinked to form the second invention. The second invention is the vinyl chloride-vinyl acetate-vinyl alcohol copolymerization. A vinyl chloride-vinyl acetate-maleic anhydride copolymer was used in place of the combination.

The present inventors have conducted various research and development to obtain a coating layer having excellent tensile properties, based on the knowledge that a chlorinated polyethylene composition is coated as a sheath of a cable. Vinyl chloride-vinyl acetate-vinyl alcohol copolymer or a mixture of vinyl chloride-vinyl acetate-maleic anhydride copolymer to improve the tensile properties of the coating layer, these compounds The amount of mixture was specified.

Examples of the epoxy stabilizer include bisphenol A diglycidyl ether, glycidyl vinyl ether, and epoxidized soybean oil. The amount of the epoxy stabilizer added is 1 to 100 parts by weight of the resin content.
50 parts by weight is preferable, and in this range, there is a remarkable effect in preventing the cross-linking reaction between chlorinated polyethylenes that occur during the silane graft reaction. Also, the epoxy stabilizer is
When used in combination with a lead-based stabilizer such as tribasic lead sulfate,
A greater stabilizing effect is obtained.

As the inorganic filler, any of white fillers such as talc, clay and calcium carbonate, and carbon black can be adopted. However, carbon black, particularly fine thermal furnace black (FT carbon) has good rubber elasticity. It imparts toughness and is most preferable. The addition amount of the inorganic filler is 10 to 10 with respect to 100 parts by weight of the resin content.
It is necessary to add 0 parts by weight, and if the addition amount is less than 10 parts by weight, the toughness such as abrasion resistance is inferior, and if it exceeds 100 parts by weight, the viscosity of the compound becomes too high and extrusion processing becomes difficult. It is preferably in the range of 30 to 60 parts by weight.

The organic silane compound has the general formula RR ₁
Examples thereof include silane represented by SiY. In the general formula of this silane, R represents a monovalent olefinically unsaturated hydrocarbon group or hadrocarbonoxy group, and represents a monovalent olefinically unsaturated radical composed of carbon and hydrogen and optionally oxygen. Examples of such radicals are:
Vinyl, allyl, budenyl, cyclohexenyl, cyclopentadienyl, diclohexadienyl and the like,
Vinyl radicals are preferred.

Formula CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ —, Formula CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ O (C
H ₂ ) ₃ −, And vinyl radicals are preferred.

Y represents a hydrolyzable organic group, and an alkoxy or alkoxy radical having a radical of 6 or less carbon atoms (for example, methoxy, ethoxy or butoxy), an acyloxy radical having a radical of 6 or less (for example, methoxy, ethoxy or butoxy). formyloxy, acetoxy or propionohydrazide alkoxy radicals), oxime radicals having 14 or fewer carbon atoms (e.g., formula -ON = C (CH ₃₎ -, the formula -ON
= CCH ₂ C ₂ H ₅ ).

R ₁ represents a monovalent hydrocarbon group having no aliphatic unsaturation, and includes, for example, methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl or tolyl, and R or Y ₂ It can also be shown.

The organosilane compound preferably has the formula RSiy ₃ and contains _three hydrolyzable organic groups, the most preferred silanes being vinyltriethoxysilane and vinyl. It is trimethoxysilane. It should be noted that silanes having only two hydrolyzable groups, such as vinylmethyldiethoxysilane and vinylphenyldimethoxysilane, are also effective.

The proportion of organosilane compound depends in part on the reaction conditions and in part on the degree of modification desired in the chlorinated polyethylene. The actual ratio is 0.1 to 20% by weight with respect to the weight of chlorinated polyethylene, but generally 1 to 8% by weight is preferable.

As a compound which generates a free radical when the organosilane compound is grafted onto the chlorinated polyethylene, a free radical site can be generated in the chlorinated polyethylene and the reaction temperature is 6 minutes or less, preferably 1 or less. A compound having a half-life of minutes or less is preferable. The best known and preferred radical generating compounds for use in this invention include organic peroxides and peresters [eg benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5- Diethyl-2,5-di (peroquinbenzoate) hexyne-3,1.3-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate,
2,5-Dimethyl 2.5-di (t-butylperoxy)
Hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexyne and tert-butylperbenzoate], azo compounds (e.g. azobis-isoptyronitrile and dimethylazodiisobutyrate),
The amount is 0.2-based on the weight of chlorinated polyethylene.
It is preferably 1% by weight.

For the grafting reaction of the organic silane compound, any of kneader, Banbury, and extruder can be adopted.

The content ratio of chlorinated polyethylene / vinyl chloride-vinyl acetate-vinyl alcohol copolymer or vinyl chloride-vinyl acetate-maleic anhydride copolymer is selected from the range of 95/5 to 20/80 by weight. Is preferred. If the amount of vinyl chloride-vinyl acetate-vinyl alcohol or vinyl chloride-vinyl acetate-maleic anhydride copolymer is less than 5 parts by weight, the tensile strength will not be improved, and if it is more than 80 parts by weight, the elongation and compression set will be poor.

As the silanol condensation catalyst, for example, dibutyltin dilaurate, stannous acetate, stannous octoate, lead naphthate, zinc octate, iron-2-
Metal carboxylates such as ethylhexoate and cobalt naphthenate, titanium esters and chelates such as organometallic compounds such as tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) di-isopropyl titanate, ethylamine, hexyl. Mention may be made of amines, organic bases such as dibutylamine and viveridine, acids such as mineral acids and fatty acids, preferably organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin dioctate.

The silanol condensation catalyst is usually prepared by adding 0.2 to 1 part by weight of chlorinated polyethylene into pellets of a catalyst masterbatch, which is used in the final cable extrusion to a compound grafted with an organosilane compound in an amount of 2 to 10% by weight. Added by mixing.

In the present invention, in addition to the above-mentioned components, a plasticizer such as paraffin chloride or dioctyl phthalate, and an antioxidant or the like may be appropriately added to increase thermal stability.

[0022]

As described above, according to the present invention, since the tensile properties of the coating layer coated on the conductor can be improved, it is possible to manufacture a chlorinated polyethylene sheath cable having excellent tensile properties.

[0023]

EXAMPLE An example of the present invention will be described in detail below.

First, Examples 1 to 4 and Comparative Examples 1 to 1 in Table 1
Vinyl chloride-vinyl acetate-vinyl alcohol copolymer or vinyl chloride-vinyl acetate-maleic anhydride copolymer, dicumyl peroxide, vinyltrimethoxysilane shown in Table 1 according to the formulation shown in each column of 3. The compounding ingredients other than the above were kneaded with a rubber roll having a diameter of 150 mm set to a temperature of 120 to 130 ° C for 15 minutes to form a sheet.

Next, this sheet was crushed by a crusher at room temperature, and dicumyl peroxide was added in a closed system at a temperature of 60.degree.
After impregnation with vinyltrimethoxysilane, head: 180
℃, cylinder 1: 180 ℃, cylinder 2: 130 ℃
40 for each temperature and screw rotation speed of 10 rpm
The graft reaction was carried out using an m / m extruder (L / D = 22).

Then, the above-mentioned silane-grafted compound was kneaded with a vinyl chloride-vinyl acetate-vinyl alcohol copolymer or a vinyl chloride-vinyl acetate-maleic anhydride copolymer at 180 ° C. with a roll and pelletized. Turned into

Next, 10 wt% of the pellets of the catalyst masterbatch having the composition shown in Table 2 was added to the above silane grout compound pellets, and the pellets were added using a 90 mm extruder (L / D = 22). As shown in FIG. 1, the cable conductor 1 was coated with the cross-linked polyethylene layer 2 around the four core wires with the conductive layer 3 interposed therebetween to form a sheath layer (coating layer) 4 to fabricate a cable. The extrusion conditions are as follows: cylinder 1: cylinder 2: 120 ° C., cylinder 3: cylinder 4: neck: head: die: 180 ° C., and the screw rotation speed is 20 rpm.

Next, the produced cable was exposed to saturated steam at a temperature of 80 ° C. for one day and cross-linked to obtain each sample. These samples (cables) were examined for tensile properties and compression set, and the results are shown in Tables 1 and 2.

[0029]

[Table 1]

Tensile properties are Japanese Industrial Standard JIS-K-63
According to No. 01, a sample punched out with dumbbell No. 3 was subjected to a tensile test of 500 mm / min using a Shopper type tensile tester, and the tensile strength and the elongation were examined.

For compression set, kneading the silane-grafted compound pellets and the catalyst masterbatch,
A cylinder having a thickness of 12.7 mm and a diameter of 29.0 mm was prepared, exposed to saturated steam at a temperature of 80 ° C. for one day, and cross-linked to prepare a sample.
According to IS-K-6301, compress the sample by 25% to 70
After holding at 22 ° C. for 22 hours, the compression was released, and the measurement was performed after 30 minutes. The calculation method is as follows.

Compression set (%) = [(original thickness of test piece (mm) -thickness after 30 minutes of taking out test piece from compression device (mm)) / thickness of compressed portion (mm) ] X 100

[0033]

[Table 2]

In Comparative Examples 2 and 3 in which the mixing amount of the vinyl chloride-vinyl acetate-vinyl alcohol copolymer or the vinyl chloride-vinyl acetate-maleic anhydride copolymer exceeds the specified value, the elongation and compression set are both Turns out to be inferior.

Therefore, a composition prepared by adding an epoxy stabilizer and an inorganic filler to chlorinated polyethylene is grafted with an organic silane compound, and a vinyl chloride-vinyl acetate-vinyl alcohol copolymer or vinyl chloride-vinyl acetate is grafted onto the composition. A coating layer having good tensile properties and compressive strain by mixing a specified amount of a maleic anhydride copolymer, coating the mixture on a conductor, and exposing the mixture to moisture to crosslink in the presence of a silanol composite catalyst. 4 can be coated on the conductor 1, and a chlorinated polyethylene sheath cable having excellent tensile properties can be manufactured.

[0036]

As described above in detail, according to the present invention, there is an excellent effect that a chlorinated polyethylene sheath cable having a coating layer with excellent tensile properties can be produced.

[Brief description of drawings]

FIG. 1 is an enlarged sectional view showing an embodiment of the present invention.

[Explanation of symbols]

 1 conductor 2 insulator 3 conductive layer 4 coating layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 29/04 LGP 6904-4J LGT 6904-4J 83/10 LRR 8319-4J H01B 13/22 Z 7244 -5G

Claims (2)

[Claims] 1. An epoxy-based stabilizer against 100 parts by weight of a resin component having a content ratio of chlorinated polyethylene and a vinyl chloride-vinyl acetate-vinyl alcohol copolymer in a weight ratio of 95/5 to 20/80. 1 to 50 parts by weight of an agent and 10 to 100 parts by weight of an inorganic filler are added to a composition to graft an organic silane compound to form an insulating material, and the insulating material is coated on a conductor, and a silanol condensation catalyst is also used. A chlorinated polyethylene sheath cable, which is formed by being exposed to moisture in the presence of, and cross-linked. 2. The content of chlorinated polyethylene and vinyl chloride-vinyl acetate-maleic anhydride copolymer is 9 by weight.
An organosilane compound is grafted to a composition obtained by adding 1 to 50 parts by weight of an epoxy stabilizer and 10 to 100 parts by weight of an inorganic filler to 100 parts by weight of a resin content in the range of 5/5 to 20/80. A chlorinated polyethylene sheath cable is formed by forming an insulating material, coating the insulating material on a conductor, exposing the insulating material to moisture in the presence of a silanol condensation catalyst, and cross-linking.