JPH10279769A - Readily peelable semiconducting resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition readily peelable and excellent in mechanical strength, semiconducting properties and extrusion processability. SOLUTION: This composition comprises (A) 5-100 pts.wt. of a modified ethylene based copolymer obtained by graft polymerization of a vinyl monomer (a2), (B) 0.5-15 pts.wt. of an unsaturated silane compound, (D) 0.5-15 pts.wt. of carbon black and (E) 0-95 pts.wt. of an ethylene based copolymer (the total of the components A and E is 100 pts.wt.). The component B is added to the composition by the melt graft reaction of the component A and/or the component E in the presence of (C) 0.01-2 pts.wt. of a radical generating agent, the amount of the component (a2) is 5-35 wt.% based on the total of the components A and E and the cross-linking degree of the composition is 30-90 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an easily peelable semiconductive resin composition and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, there is a type of power cable in which a semiconductive layer is provided on the inner and outer layers of an insulating layer for the purpose of relaxing an electric field, and the semiconductive layer is formed on the insulating layer in order to prevent corona discharge. On the other hand, it is necessary that they adhere or adhere without any gap. However, if the outer semiconductive layer and the insulating layer adhere excessively, it becomes extremely difficult to peel the outer semiconductive layer from the insulating layer, for example, when connecting cables, and as a result, it takes a long time to peel off. In addition, the insulating layer is easily damaged, and a large amount of time and labor is required for terminal treatment, or skill is required.

A semiconductive layer based on an ethylene-vinyl ester copolymer, which has been conventionally regarded as the best semiconductive layer of this type, has a property of extremely strongly adhering to an olefin polymer constituting an insulating layer. As a result, the releasability from the insulating layer is almost equal, and thus the cable terminal treatment work is extremely difficult.

According to the present invention, the insulating layer and the outer semiconductive layer are adhered to each other with an appropriate strength, and when necessary, the outer semiconductive layer can be peeled off very easily. It is an object of the present invention to provide a semiconductive resin composition having good mechanical strength without being cut into pieces.

[0005] The semiconductive layer material is described in more detail in relation to the prior art. (1) Examples of the semiconductive layer material include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate copolymer having a high content of vinyl acetate. Ethylene-vinyl ester copolymer or ethylene-acrylate copolymer blended with carbon black, (2) chlorinated polyethylene, chlorosulfonated polyethylene, E
A halogen-containing resin such as a VA-vinyl chloride graft copolymer alone or by blending an olefin polymer with the halogen-containing resin, and carbon black added thereto;
(3) polystyrene, styrene copolymer, butadiene
An acrylonitrile copolymer, polyester, or the like is blended with an olefin polymer, to which carbon black is added, and the like.

[0006] However, these conventional semiconductive resins have the following problems. (1) is as described above.
The peelability from the insulating layer is poor, and the object of the present invention cannot be satisfied. (2) is proposed for the purpose of improving the releasability from the insulating layer, and although its effect is recognized, the halogen-containing resin generates corrosive gas by thermal decomposition at a high temperature, which causes corrosion of the device. There is a problem in that it causes the copper cable tape to corrode and corrode the cable shielding copper tape to deteriorate the cable performance. (3) is intended to improve the releasability from the insulating layer, as in (2), but all have poor compatibility with the olefin polymer, and it is necessary to increase the blend amount to improve the releasability. As a result, the external semiconductive layer becomes considerably weak as a result, and there is a problem that the peeling layer is cut during the peeling process.

Further, when practically used as a covering material for an electric power cable, an organic peroxide is added to each of the materials (1), (2) and (3) in order to impart heat resistance to these materials. Thus, the production is carried out in a two-stage process of molding at a low temperature and crosslinking this with a special crosslinking device. On the other hand, a silane crosslinking method has been proposed as a method for significantly improving the productivity of a crosslinking method using an organic peroxide (hereinafter referred to as a peroxide crosslinking method). The silane crosslinking method is disclosed in
No. 8-1711, Japanese Patent Publication No. 62-23777, etc., after molding, silane-containing polyolefin is crosslinked in a moisture atmosphere in the presence of a silanol condensation catalyst, compared to a conventional peroxide crosslinking method. There is an advantage that the equipment for crosslinking is simple and the productivity is remarkably high. For this reason, silane-crosslinked polyethylene has been widely used as an insulating layer of a low-voltage cable, and more recently, Japanese Patent Publication No. 7-31947 and Japanese Patent Laid-Open No. 4-293.
As seen in Japanese Patent No. 945, application to a high-voltage cable is being studied. However, from the viewpoint of appropriate releasability from the insulating layer, no satisfactory technique has been proposed for this silane crosslinking method.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an easily peelable semiconductive resin composition which solves the above-mentioned disadvantages of the prior art and satisfies the following items. The purpose is to obtain. 1. Close contact with the insulating layer with appropriate strength. 2. It can be easily separated from the insulating layer when necessary. 3. It has excellent mechanical strength and must not be cut during peeling. 4. Good dispersibility of carbon black. 5. Have excellent extrudability. 6. Excellent thermal stability and no generation of corrosive decomposition gas. 7. Easy cross-linking process and high productivity.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to find that the above object can be achieved by using a resin obtained by subjecting a specific modified ethylene copolymer to a silane graft reaction. It is a thing.

That is, a first gist of the present invention is a composition comprising the following components (A), (B), (D) and (E), wherein the component (B) is a radical generator (C)
It is contained in the composition by being subjected to a melt grafting reaction with the component (A) and / or the component (E) in the presence of 0.01 to 2 parts by weight, and contains the following vinyl monomer (a
2) Units are contained in the composition in an amount of 5 to 35% by weight based on the total amount of the components (A) and (E), and the degree of crosslinking of the composition is 30 to 90% by weight. The semi-conductive resin composition is easily peelable. (A) Modified ethylene copolymer obtained by subjecting ethylene copolymer (a1) and vinyl monomer (a2) to graft polymerization conditions ... 5 to 100 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene copolymer: 0 to 95 parts by weight (where each component is The compounding amount of component (A) and component (E)
Are expressed as 100 parts by weight. )

The second aspect of the present invention comprises kneading the following components (A), (B), (D) and (E), wherein component (B) is a radical generator ( C)
A method for producing an easily peelable semiconductive resin composition comprising a step of subjecting a component (A) and / or a component (E) to a melt grafting reaction in the presence of 0.01 to 2 parts by weight. ,
Exists. (A) Modified ethylene copolymer obtained by subjecting ethylene copolymer (a1) and vinyl monomer (a2) to graft polymerization conditions ... 5 to 100 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene copolymer: 0 to 95 parts by weight (where each component is The compounding amount of component (A) and component (E)
Are expressed as 100 parts by weight. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

[Component (A): Modified ethylene copolymer] The modified ethylene copolymer (A) used in the present invention is obtained by graft-polymerizing an ethylene copolymer (a1) and a vinyl monomer (a2). It is a modified ethylene copolymer obtained under the conditions.

[Ethylene-based copolymer (a1)] Here, the ethylene-based copolymer (a1) is composed of ethylene as a main component and other α-olefins such as propylene, butene and octene;
Or a copolymer with a vinyl ester represented by vinyl acetate, acrylic acid, methacrylic acid, an acrylic ester, a methacrylic ester, or a derivative thereof such as an unsaturated carboxylic acid or an ester thereof. You can also. These include those polymerized with a single-site catalyst. Among them, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer and the like are preferable.

The content of the copolymerizable monomer other than ethylene in the ethylene-based copolymer (a1), such as α-olefin, vinyl ester, unsaturated carboxylic acid or an ester derivative thereof, is generally 15 to 15%. 50% by weight, preferably 20-45% by weight, particularly preferably 25% by weight
４０40% by weight. If the content is too low, the releasability tends to be insufficient, while if it is too high, the heat resistance tends to decrease.

The ethylene copolymer (a1) is:
Melt flow rate (MFR: 190 ° C., from the viewpoint of graft reaction suitability, kneadability with carbon black, moldability, etc.)
2.16 kg load) is 0.1 to 300 g / 10 min, especially 0.5 to 200 g / 10 min, especially 1 to 100 g / 10 min.
Minutes are preferred.

[Vinyl monomer (a2)] The vinyl monomer (a2) to be subjected to the graft polymerization conditions with the ethylene copolymer (a1) is, specifically, styrene, 2-
Unsaturated aromatic monomers such as methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene and chlorostyrene; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, isopropyl acrylate, n -Butyl acrylate, s-butyl acrylate, dodecyl acrylate,
2-ethylhexyl acrylate, hexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, s-
Esters of acrylic acid or methacrylic acid such as butyl methacrylate, decyl methacrylate, 2-ethylhexyl methacrylate, and glycidyl methacrylate; unsaturated such as acrylic acid, methacrylic acid, maleic anhydride, dimethyl maleate, and bis (2-ethylhexyl) maleate; Carboxylic acids or derivatives thereof; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride,
Unsaturated mono- or dihalides such as vinylidene chloride can be mentioned. Among them, styrene, ethyl acrylate or methyl methacrylate is preferable, and particularly preferable is that the property of the modified ethylene copolymer (A) from which styrene can be obtained is good and that the modification is easy.

The amount of the vinyl monomer (a2) used is such that the content in the resulting modified ethylene copolymer (A) is such that the amount of the vinyl monomer graft-bonded to the ethylene copolymer (a1) is high. The total amount of the monomer (a2) and the homopolymer of the vinyl monomer (a2) is usually set to be 10 to 60% by weight, preferably 20 to 50% by weight. Indicates that the amount used and the content substantially match. If the content is too low, the effect of improving the compatibility is small, while if it is too high, the phase transition occurs, and the effect of improving the compatibility also tends to be small.

[Production of Modified Ethylene Copolymer (A)] The above ethylene copolymer (a1) and vinyl monomer (a)
As the radical generator used in producing the modified ethylene copolymer (A) by subjecting 2) to the graft polymerization conditions, a general-purpose radical generator can be used, but a preferable graft generator described later is used. From the viewpoint of the reaction method, those having a decomposition temperature of 50 ° C. or higher and being oil-soluble are preferred.

If a material having a low decomposition temperature is used, the polymerization of the vinyl monomer (a2) may proceed abnormally, and a homogeneous modified ethylene copolymer (A) cannot be obtained. There is. However, conversely, those having a high decomposition temperature and those having a low decomposition temperature can be appropriately combined to perform the decomposition stepwise or continuously, and the graft reaction can be carried out efficiently.

Examples of such radical generators include 2,4-dichlorobenzoyl peroxide, t-butylperoxypivalate, and o-methylbenzoylperoxide.
Oxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, cyclohexanone peroxide, 2,5-dimethyl-oxide 2,5-dibenzoylperoxyhexane, t-butylperoxybenzoate, di-
t-butyl-diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, di-t
Organic peroxides such as -butyl peroxide; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile).

The amount of the radical generator used is within the range of 0.01 to 10% by weight based on the amount of the vinyl monomer (a2) used, and is appropriately adjusted depending on the type of the radical generator and the reaction conditions. If the amount is too small, the reaction does not tend to proceed smoothly, while if the amount is too large, a gel tends to be easily formed in the modified ethylene copolymer (A).

In order to obtain a modified ethylene copolymer (A) by subjecting each of these raw material components to a graft polymerization reaction, an aqueous suspension grafting method as disclosed in JP-B-63-20266 is used. Is a particularly preferred method because it is easy to control the gel content.

That is, 100 parts by weight of an ethylene copolymer (a1) particle (having a diameter of generally 1 to 7 mm, preferably 2 to 5 mm) and a vinyl monomer (a2) of 25 to 200 parts
Decomposition temperature of 5 parts by weight and half-life of 10 hours
A radical generator having a temperature of 0 to 130 ° C is converted to a vinyl monomer (a
2) 0.01 to 5 parts by weight based on 100 parts by weight of a suspending agent used for aqueous suspension polymerization, for example, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose or the like or a poorly soluble inorganic substance such as calcium phosphate, magnesium oxide or the like. At an arbitrary concentration at which the system is easily stirred in an aqueous medium (generally, ethylene copolymer (a1) particles and vinyl monomer (a2) 5 to 100 parts by weight with respect to 100 parts by weight of water) Add, stir and disperse. Then, prior to the polymerization treatment, this aqueous suspension is heated within a range where decomposition of the radical generator used does not substantially occur to convert the vinyl monomer (a2) into the ethylene copolymer (a1). Impregnated into particles.

In the impregnation treatment, the heating temperature is preferably higher in view of promoting the impregnation. However, since the vinyl monomer (a2) before impregnation is polymerized singly due to premature decomposition of the radical generator, this is prevented. The lower the heating temperature, the better
Preferably it is from room temperature to 50 ° C. Under such temperature conditions, 80% by weight or more, preferably 90% by weight or more of the vinyl monomer (a2) is impregnated or adhered to the ethylene-based copolymer (a1) particles, Monomer droplets usually less than 20% by weight, preferably 10% by weight
The aqueous suspension is left to a volume of less than 1 to 5 hours, preferably under stirring. Unimpregnated vinyl monomer (a
If the content of 2) is too large, polymer particles of the independent vinyl monomer (a2) may precipitate, and the polymer of the vinyl monomer (a2) in the ethylene copolymer (a1) particles may be precipitated. Tend to be non-uniform. Since the free vinyl monomer (a2) is impregnated in the particles of the ethylene copolymer (a1) in the next polymerization step or adheres to the surface of the particles and polymerizes, the vinyl monomer is contained in the product. It is practically not recognized that the polymer particles of the body (a2) exist independently of the particles of the ethylene-based copolymer (a1).

The aqueous suspension thus prepared is further heated to a high temperature to complete the polymerization of the vinyl monomer (a2), whereby a modified ethylene copolymer (A) is obtained. At this time, the heating temperature should be a temperature at which sufficient decomposition of the radical generator used occurs. However, it is preferred not to exceed 130 ° C. If it exceeds 130 ° C., a gel-like substance tends to be formed in the modified ethylene copolymer (A), and a temperature of 50 to 130 ° C. is generally suitable.

The modified ethylene-based copolymer (A) thus obtained is composed of an ethylene-based copolymer (a1) and a vinyl monomer (a2), a grafted ethylene-based copolymer and a vinyl monomer (a). The three components of the polymer a2) are mixed, and the compatibility of the polymer of the ethylene-based copolymer (a1) and the polymer of the vinyl monomer (a2) is improved by the presence of the graft component. The polymer of a2) is an ethylene copolymer (a1)
It is homogeneously and finely dispersed in the matrix. Therefore, even if the vinyl monomer (a2) unit is increased, its homogeneity is not impaired, and the appearance and physical properties of the molded product are excellent. In a simple blend system of an ethylene copolymer (a1) and a polymer of a vinyl monomer (a2), the compatibility is poor due to poor compatibility between the two, and the appearance is degraded due to the occurrence of delamination during the molding process. And, due to the remarkable decrease in material properties, it is not practical.

The amount of the modified ethylene copolymer (A) is generally 5 to 100 parts by weight based on 100 parts by weight of the total of the component (A) and the component (E) which will be described later. , Preferably 5 to 95 parts by weight, particularly preferably 20 parts by weight.
８０80 parts by weight. If the amount is too small, the releasability and mechanical strength become insufficient. The amount of the vinyl monomer (a2) unit in the resin composition of the present invention is 5 to 35% by weight based on the total amount of the component (A) and the component (E) described below.

[Component (B): unsaturated silane compound] The unsaturated silane compound (B) used in the present invention is preferably a compound represented by the general formula R
One represented by SiR ′ _n Y _3-n can be shown. Here, R is an ethylenically unsaturated hydrocarbon group or a hydrocarbon oxy group, and has radical reactivity. Examples of such groups include vinyl, allyl, butenyl, cyclohexenyl, cyclopentadiel, and γ- (meth) acryloxypropyl. R 'is an aliphatic saturated hydrocarbon group, such as methyl, ethyl, propyl, decyl, and phenyl. Y represents a hydrolyzable organic group, and n is an integer of 0 to 2. Examples of Y include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, alkyl and arylamino. Particularly preferred is the general formula

[0029]

Embedded image

(Wherein, R ¹ is H or CH ₃ , R ² is a linear or branched alkyl group having 4 or less carbon atoms, and R ³ is a linear or branched alkyl group having the same as R ² or 4 or less carbon atoms) Or a phenyl group), specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriacetoxysilane, vinylmethyldiethoxysilane, vinylethyldimethoxysilane, etc. Is mentioned. Further, as another preferred unsaturated silane compound (B), a compound represented by the general formula:

Embedded image

Wherein R ⁴ is H or CH ₃ , R ⁵ is a straight-chain alkyl group having 4 or less carbon atoms, R ⁶ is a straight-chain alkyl group having the same as R ⁵ or not more than 4 carbon atoms or phenyl. And n
Is an integer of 1 to 6. ), And specific examples thereof include γ-methacryloxypropylmethoxysilane. The amount of the unsaturated silane compound (B) is determined according to the desired degree of crosslinking, reaction conditions, and the like, but is generally a polymer component in terms of economy, handling before the reaction, handling during the reaction, and the like. The amount is 0.5 to 15 parts by weight, preferably 0.7 to 13 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight in total of the above component (A) and the following component (E). If the amount is too small, the graft ratio is low and a sufficient degree of crosslinking cannot be obtained. On the other hand, if the amount is too large, the effect on crosslinking is small, and conversely, the appearance may be poor due to the volatilization of the unreacted unsaturated silane compound (B), which is not preferable.

[Component (C): Radical generator] The radical generator (C) used in the present invention is capable of generating free radicals under the reaction conditions and has a half-life of less than 6 minutes at the reaction temperature. Any compound having the formula: can be used. Preferably, any compound having a half-life shorter than 1 minute is used.
All compounds described in JP-A No. 1 and the like apply. Examples of radical generators often used in the present invention are benzoyl peroxide, dicumyl peroxide,
Organic peroxides such as di-t-butyl peroxide and t-butyl peroxy-2-ethylhexanoate; and azo compounds such as azobisisobutyronitrile and methylazobisisobutyrate.

The amount of the radical generator (C) to be added is generally 0.01 to 2 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the total of the above-mentioned component (A) and the component (E). It is in the range of 0.05 to 1.5 parts by weight. If the amount is too small, the amount of grafting of the unsaturated silane compound (B) is small, while if it is too large, undesired crosslinking by the radical generator (C) often proceeds, resulting in poor flow characteristics. In some cases, the appearance of the molded product may be deteriorated.

[Component (D): Carbon Black] As the carbon black used in the present invention, any carbon black can be used as long as the resin composition of the present invention satisfies the desired semiconductivity. Therefore, even for carbon black having low conductivity, the desired semiconductivity can be satisfied by increasing the blending amount relatively.

Examples of such carbon black include commercially available furnace black, acetylene black, Ketjen black, channel black, and thermal black. The compounding amount is generally 10 to 110 parts by weight, preferably 20 to 90 parts by weight, particularly preferably 40 to 80 parts by weight based on 100 parts by weight of the total of the components (A) and (E) which are polymer components. Parts by weight. If the amount is too small, good semiconductivity cannot be obtained, while if it is too large, extrudability and mechanical properties are impaired, which is not preferable.

[Component (E): Ethylene-based copolymer] As the ethylene-based copolymer (E) used in the present invention, an ethylene-based copolymer (a1) which is a component of the above-mentioned component (A) is used. Can be appropriately selected and used.
At this time, it is possible to select a different type of ethylene copolymer (E) from the ethylene copolymer (a1), but it is preferable to select the same type from the viewpoint of compatibility of both components. . Further, it is preferable that the content of the comonomer other than ethylene is in the above-mentioned range, but it is preferable that the copolymers in the copolymers of the ethylene copolymer (E) and the ethylene copolymer (a1) be used. There is no problem even if different monomers are used.

The amount of the ethylene copolymer (E) to be blended is generally 0 to 95 parts by weight, preferably 100 parts by weight of the total of the component (A) and the component (E) which are polymer components. Is 5 to 95 parts by weight, particularly preferably 20 to 95 parts by weight.
80 parts by weight. If this amount is too large, the releasability will be insufficient.

[Other optional components] In the present invention, if necessary, other components such as additives such as antioxidants, weathering agents, ultraviolet absorbers, corrosion inhibitors, and the like, as long as the effects of the present invention are not significantly impaired, Lubricants, adhesives, dispersants and the like may be added as optional components.

[Semiconductive resin composition and method for producing the same]
The semiconductive resin composition of the present invention is a composition comprising the above-mentioned components, that is, a composition comprising the following components (A), (B), (D) and (E), The component (B) is contained in the composition by being subjected to a melt grafting reaction with the component (A) and / or the component (E) in the presence of 0.01 to 2 parts by weight of the radical generator (C). And the following vinyl monomer (a2) unit is contained in the composition in an amount of 5 to 35% by weight based on the total amount of the components (A) and (E).
The composition has a degree of crosslinking of 30 to 90% by weight.
Which is an easily peelable semiconductive resin composition. (A) Modified ethylene copolymer obtained by subjecting ethylene copolymer (a1) and vinyl monomer (a2) to graft polymerization conditions ... 5 to 100 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene copolymer: 0 to 95 parts by weight (where each component is The compounding amount of component (A) and component (E)
Are expressed as 100 parts by weight. )

In the semiconductive resin composition, the component (B) is contained by being subjected to a melt grafting reaction with the component (A) and / or the component (E). Component (D) may be present during the graft reaction. Specifically, the following four methods are mainly mentioned as a method for producing the semiconductive resin composition of the present invention.

[Production Method 1] 100 parts by weight of a resin composed of 5 to 100 parts by weight of the modified ethylene copolymer (A) and 0 to 95 parts by weight of the ethylene copolymer (E) and carbon black (D) After melt-kneading 10 to 110 parts by weight, 0.5 to 15 parts by weight of the unsaturated silane compound (B) and 0.01 to 2 parts by weight of the radical generator (C) are added, and the mixture is further melt-kneaded to obtain a silane graft. A method of obtaining a semiconductive resin composition by reacting.

[Production Method 2] 100 parts by weight of a resin composed of 5 to 100 parts by weight of the modified ethylene copolymer (A) and 0 to 95 parts by weight of the ethylene copolymer (E), an unsaturated silane compound ( B) 0.5 to 15 parts by weight of a radical generator (C) and 0.01 to 2 parts by weight of a radical generator (C) are melt-kneaded and subjected to a silane graft reaction to obtain an unsaturated silane compound-grafted ethylene-based copolymer. Black (D) 1
0 to 110 parts by weight, and further melt-kneading to obtain a semiconductive resin composition.

[Production method 3] 100 parts by weight of a resin comprising 5 to 100 parts by weight of the modified ethylene copolymer (A) and 0 to 95 parts by weight of the ethylene copolymer (E), an unsaturated silane compound ( B) 0.5 to 15 parts by weight, 0.01 to 2 parts by weight of a radical generator (C) and 10 to 110 parts by weight of carbon black (D) are melt-kneaded and subjected to a silane graft reaction to obtain a semiconductive resin. A method of obtaining the composition. [Production Method 4] The modified ethylene-based copolymer (A) 20
To 80 parts by weight, unsaturated silane compound (B) 0.5 to 15
Parts by weight and 0.01 to 2 parts by weight of a radical generator (C) are melt-kneaded and subjected to a silane graft reaction to obtain an unsaturated silane compound graft-modified ethylene copolymer and an ethylene copolymer (E A) a method of obtaining a semiconductive resin composition by adding 10 to 110 parts by weight of carbon black (D) to a resin of 20 to 80 parts by weight and further melt-kneading the resin; [Production Method 5] 20 to 80 parts by weight of ethylene copolymer (E), 0.5 to 15 parts by weight of unsaturated silane compound (B) and 0.01 to 2 parts by weight of radical generator (C) are melt-kneaded. To a resin comprising an unsaturated silane compound-grafted ethylene copolymer obtained by subjecting to a silane grafting reaction and the modified ethylene copolymer (A) in an amount of 20 to 80 parts by weight; A method of adding a part by weight and further melt-kneading to obtain a semiconductive resin composition.

Here, the melt-kneading is generally carried out with a usual kneader such as a single-screw kneader, a twin-screw kneader, a Banbury mixer, a roll, etc., but a twin-screw kneader or a Banbury mixer is preferred in terms of efficiency. Further, in these production methods, a silanol condensation catalyst can be added as needed at the latter stage or the last kneading, and furthermore, molding can be performed at once.

The silanol condensation catalyst referred to herein includes:
Metal carboxylates such as tin, zinc, iron, lead and cobalt; organometallic compounds such as titanates and chelates;
Organic bases, inorganic acids, and organic acids. For example, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, stannous acetate, stannous caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, tetrabutyl titanate, tetranonyl titanate, Inorganic acids such as ethylamine, dibutylamine, hexylamine, pyridine, sulfuric acid, and hydrochloric acid; and organic acids such as toluenesulfonic acid, acetic acid, stearic acid, and maleic acid.

The amount of the silanol condensation catalyst to be added is usually 0.04 parts by weight based on 100 parts by weight of the copolymer (resin) component.
The amount is from 0.01 to 10 parts by weight, preferably from 0.01 to 5 parts by weight, particularly preferably from 0.01 to 1 part by weight.

As an addition method, it is added before molding or
Alternatively, it is used by applying or impregnating a molded article as a solution or dispersion. When used as a laminate with a polyolefin-based resin, it may be added to either or both layers of the semiconductive resin composition or the polyolefin-based resin of the present invention. The molded article in which the silanol condensation catalyst is present can be cross-linked by exposing it to water for the purpose of imparting heat resistance and the like.

[0048] Exposure to water can be carried out by subjecting the molded body to room temperature to 200
The temperature may be about 10 ° C., usually about room temperature to about 100 ° C. (liquid or vapor) water, for about 10 seconds to about 1 week, usually about 1 minute to about 1 day. It can also be brought into contact with water under pressure. The water may contain a wetting agent or a surfactant, a water-soluble organic solvent or the like to improve the wetting of the molded body. The water can be in the form of heated water vapor or moisture in the air, in addition to normal water. Also,
Exposure to water during the preparation and molding of the composition of the present invention allows the preparation and molding of the composition and the crosslinking reaction to be carried out simultaneously. The crosslinking degree of the resin composition of the present invention is 30.
~ 90% by weight. If the degree of cross-linking is too low, the heat resistance of the resulting molded article is not sufficient, while if it is too high, the elongation of the molded article is significantly impaired, and the material tends to be brittle.

[Molding and the like] The semiconductive resin composition of the present invention can be formed into a desired shape by a usual forming method, for example, film forming, coextrusion forming, calendering and the like. The semiconductive resin composition of the present invention can make good use of the characteristic of easy peeling by being laminated with another base material to form a laminate. As a mating base material constituting the laminate, a polyolefin-based resin is preferable.

[0050]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. The method of the evaluation test in Examples and Comparative Examples is as follows.

[Peeling Test] A typical example of a test actually performed is specifically described below. The semiconductive resin composition is placed in an extruder having an L / D of 26 and a diameter of 20 mm.
mm-type extruder was charged with an ethylene-unsaturated silane compound copolymer shown in Reference Example 1 or an unsaturated silane compound grafted polyethylene shown in Reference Example 2 (both are hereinafter collectively referred to as silane-modified polyethylene). A two-layer co-extruded sheet was formed at a die setting temperature of 190 ° C. using a two-layer molding machine to obtain a sample. Note that the silane-modified polyethylene was dry-blended at a predetermined concentration in advance with the condensation catalyst master batch shown in Reference Example 3 (described later) and then charged. The configuration of the sheet was 1 mm for the semiconductive resin composition layer and 2 mm for the silane-modified polyethylene layer. The obtained two-layer sheet was immersed in hot water at 85 ° C. for 12 hours to perform a cross-linking treatment. Then, a sample having a resin flow direction of 20 cm × 0.5 inch width was cut out, and a peel angle of 180 ° in a 23 ° C.-50% atmosphere. ,
The peel strength was determined by peeling at a peel speed of 200 mm / min. In the peeling test, the presence or absence of the residue (carbon residue) of the semiconductive resin composition adhering to the silane-modified polyethylene layer was visually observed.

[Degree of Crosslinking] Using xylene as a solvent, a sample was extracted at a boiling point temperature for about 12 hours by a Soxhlet extractor, and the weight of the extraction residue was expressed in percentage according to the following formula. Degree of cross-linking (%) = [weight remaining after extraction (g) / weight of sample before extraction (g)] × 100

[Tensile strength] Measured according to JIS K-7113.

[Styrene content in resin composition] Measured using an infrared spectrophotometer. From the infrared spectrum of the resin composition, quantitative analysis was performed using a peak at 1935 cm ^-1 derived from an aromatic ring. The calibration curve shows that the ethylene-vinyl acetate copolymer and polystyrene have styrene contents of 0, 10, 20, and
Mixtures of 30, 40 and 50% by weight were uniformly melt-kneaded with a Brabender, and press sheets each having a thickness of 1 mm were prepared as standard samples and prepared by regression calculation. [Heating and pressing deformation rate] 30 x 20 mm from the semiconductive resin layer
The test piece was cut out, set between pressure plates, and under a 120 ° C. atmosphere, a predetermined amount (1 kg) of load was applied to the test piece for 1 hour, and the change in test piece thickness was measured with a dial gauge. The heating and pressing deformation rate was calculated by the following equation. Heat-press deformation ratio (%) = [sample thickness change (mm) / sample thickness (mm)] × 100 Further, with respect to each material used in Examples and Comparative Examples, production examples thereof are shown below.

Reference Example 1 Ethylene-Unsaturated Silane Compound Copolymer
A mixture of vinyltrimethoxysilane and propylene as a molecular weight regulator and a radical generator t-butylperoxyisobutyrate were continuously reacted while being supplied under the following conditions. Supply amount Ethylene 43 kg / h Vinyl trimethoxysilane 0.20 kg / h Propylene 0.45 kg / h t-butyl peroxyisobutyrate 2.3 g / h Supply monomer temperature 65 ° C Polymerization pressure 2400 kg / cm ² Maximum reaction temperature 225 C. Production amount 5.5 kg / h The obtained ethylene-unsaturated silane compound copolymer has a density of 0.923 g / cm ³ , an MFR of 0.9 g / 10 min, a vinyltrimethoxysilane content of 1.2% by weight, and after crosslinking treatment. Was 78% by weight.

REFERENCE EXAMPLE 2 Unsaturated Silane Compound Grafted Polyethylene Unsaturated silane compound grafted polyethylene has a density of 0.
With respect to 100 parts by weight of low-density polyethylene of 919 g / cm ³ and MFR of 2.0 g / 10 min, 2 parts by weight of vinyltrimethoxysilane and 0.08 part by weight of dicumyl peroxide are L / D28 and a single screw extruder having a diameter of 40 mm. At a temperature of 190 ° C. for a residence time of 1.7 minutes. The obtained unsaturated silane compound-grafted polyethylene had a density of 0.920 g / cm ³ and an MFR of 0.8 g / 1.
0 minutes, the content of vinyltrimethoxysilane was 1.2% by weight, and the degree of crosslinking after the crosslinking treatment was 75% by weight.

Reference Example 3 Silanol Condensation Catalyst Master Batch-1 100 parts by weight of polyethylene having a density of 0.919 g / cm ³ and MFR of 2.0 g / 10 minutes, 1 part by weight of dibutyltin dilaurate, 4,4′-thio -Bis (2-t-butyl-m-cresol) 1 part by weight, 2,2′-oxamide-bis [ethyl-3- (3,5-di-t-butyl-4-)
Hydroxyphenyl) propionate], 1 part by weight of zinc stearate at 180 ° C., residence time 0.7
The mixture was uniformly dispersed using a twin-screw kneader under the same conditions as described above to obtain a master batch of a silanol condensation catalyst having a density of 0.925 g / cm ³ , a MFR of 3.0 g / 10 min, and a catalyst concentration of 1% by weight.

(Reference Example 4) Modified ethylene copolymer-1 20 kg of pure water was placed in an autoclave having a content of 50 liters.
An aqueous medium was prepared by adding 600 g of tribasic calcium phosphate and 0.6 g of sodium dodecylbenzenesulfonate as a suspending agent, and an ethylene-vinyl acetate copolymer (EVA; vinyl acetate content 33% by weight, MFR 30 g /
10 minutes) and 6 kg of 3 mm diameter particles were suspended by stirring. Separately, 8 g of benzoyl peroxide and t
4 g of butyl peroxybenzoate to 6 kg of styrene
(100 parts by weight based on 100 parts by weight of EVA), and the solution was added to the suspension system, the temperature in the autoclave was raised to 50 ° C., and the temperature was maintained for 3 hours to contain a polymerization initiator. Styrene was impregnated into the ethylene-vinyl acetate copolymer particles. The aqueous suspension was kept at 60 ° C. for 7 hours and at 85 ° C. for 5 hours to complete the polymerization. It was confirmed that in the obtained modified polymer particles, the styrene polymer was present in substantially the same amount as the quantitatively used styrene, that is, about 100 parts by weight.

Reference Example 5 Modified Ethylene Copolymer-2 Instead of the ethylene-vinyl acetate copolymer used in Reference Example 4, a vinyl acetate content of 28% by weight and an MFR of 15 g were used.
A modified ethylene-vinyl acetate copolymer was obtained in the same manner as in Reference Example 4, except that an ethylene / 10-minute copolymer was used.

Reference Example 6 Modified Ethylene-Based Copolymer-3 A modified ethylene-vinyl acetate copolymer was prepared in the same manner as in Reference Example 5 except that the amount of styrene was changed to 25 parts by weight. A coalescence was obtained.

Reference Example 7 Modified Ethylene Copolymer-4 Instead of the ethylene-vinyl acetate copolymer used in Reference Example 4, an ethyl acrylate content of 25% by weight and MFR
A modified ethylene-ethyl acrylate copolymer was obtained in the same manner as in Reference Example 4 except that an ethylene-ethyl acrylate copolymer of 5 g / 10 minutes was used.

Example 1 A semiconductive resin composition was produced according to the above-mentioned [Production method 1]. That is, 60 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and 40 parts of the modified ethylene copolymer-1 of Reference Example 4 were used.
100 parts by weight of a copolymer (resin) component consisting of parts by weight, and furnace black ("Vulcan" manufactured by Cabot Corporation)
XC72 ": DBP (dibutyl phthalate) oil absorption 1
78 cc / 100 g) 40 parts by weight were melt-kneaded using a twin-screw kneader, and 3 parts by weight of vinyltrimethoxysilane and 0.4 part by weight of t-butylperoxy-2-ethylhexanoate were added. Was added and melt-kneaded with a single screw extruder under the conditions of a temperature of 190 ° C. and a residence time of 1.5 minutes, and a silane graft reaction was carried out to obtain a semiconductive resin composition. Here, 60 parts by weight of the ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and 40 parts by weight of the modified ethylene-based copolymer-1 of Reference Example 4 were melt-kneaded with a Brabender and heated at 160 ° C. To form a sheet having a thickness of 1 mm. When the styrene content of this sheet was measured, it was 20% by weight. Next, L / D26, diameter 20m
m, and 100 parts by weight of the ethylene-unsaturated silane compound copolymer of Reference Example 1 and Reference Example 3 in an extruder having an L / D of 28 and a diameter of 30 mm. Silanol condensation catalyst masterbatch-1-5
Parts by weight were dry-blended and charged, and a two-layer coextruded sheet was formed at a die setting temperature of 190 ° C. by a T-type two-layer molding machine to obtain a sample. Further, the obtained sheet was immersed and crosslinked in hot water at a temperature of 85 ° C. for 12 hours, dried, and then evaluated as shown in Table 1. There was no carbon residue, and a good result of 2 kg / 0.5 inch or less, which was targeted as an appropriate peel strength, was obtained.

(Example 2) Instead of the furnace black used in Example 1, acetylene black ("Denka Black" manufactured by Denki Kagaku Kogyo Co., Ltd .: DBP oil absorption 125
A sample was prepared in the same manner as in Example 1 except that 55 parts by weight of cc / 100 g) and 0.25 parts by weight of t-butylperoxy-2-ethylhexanoate were used. Was done.

Example 3 The copolymer components used in Example 1 were composed of 80 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight and the modified ethylene copolymer of Reference Example 5 A sample was prepared and evaluated in the same manner as in Example 1 except that the weight of Sample No. 2 was changed to 20 parts by weight.

Example 4 The copolymer components used in Example 1 were replaced by 5 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight and the modified ethylene copolymer of Reference Example 6 Example 1 except that 95 parts by weight of No. 3 was used.
A sample was prepared in the same manner as described above, and the same evaluation was performed.

(Example 5) The copolymer component used in Example 1 was prepared by mixing 60 parts by weight of an ethylene-ethyl acrylate copolymer having an ethyl acrylate content of 25% by weight and Reference Example 7
Example 2 was changed to 40 parts by weight of the modified ethylene copolymer-4, and 0.07 parts by weight of dicumyl peroxide was used in place of t-butylperoxy-2-ethylhexanoate. A sample was prepared in the same manner as in Example 1, and the same evaluation was performed.

Comparative Example 1 The procedure of Example 1 was repeated except that the copolymer component used in Example 1 was 100 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight. A sample was prepared and the same evaluation was performed.

Comparative Example 2 The copolymer component used in Example 1 was replaced with 80 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and a modified ethylene copolymer-1. A sample was prepared in the same manner as in Example 1 except that the polystyrene was 20 parts by weight, and the same evaluation was performed.

Example 6 Example 1 was repeated except that the unsaturated silane compound grafted polyethylene of Reference Example 2 was used instead of the ethylene-unsaturated silane compound copolymer of Reference Example 1 used in Example 1. A sample was prepared in the same manner as described above, and the same evaluation was performed.

Example 7 A semiconductive resin composition was produced according to the above-mentioned [Production method 2]. That is, 60 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and 40 parts of the modified ethylene copolymer-1 of Reference Example 4 were used.
2 parts by weight of vinyltrimethoxysilane and 0.3 part by weight of t-butylperoxy-2-ethylhexanoate were added to 100 parts by weight of a copolymer (resin) component consisting of parts by weight, and the temperature was 190 ° C. Melt-kneaded with a single screw extruder having an L / D of 28 and a diameter of 40 mm under the conditions of a residence time of 1.7 minutes and subjected to a silane graft reaction, 100 parts by weight, and the same furnace black as used in Example 1 Forty parts by weight, using a coaxial twin-screw extruder with a screw diameter of 45 mm, at a temperature of 180 ° C., a rotation speed of 250 rpm, and a discharge amount of 20 k
The mixture was melt-kneaded under the conditions of g / hour to obtain a semiconductive resin composition. Next, a sample was prepared in the same manner as in Example 1 except that this semiconductive resin composition was used instead of the semiconductive resin composition used in Example 1, and the same evaluation was performed. .

Example 8 A semiconductive resin composition was produced according to the above-mentioned [Production method 3]. That is, 60 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and 40 parts of the modified ethylene copolymer-1 of Reference Example 4 were used.
100 parts by weight of a copolymer (resin) component, 2 parts by weight of vinyltrimethoxysilane, 0.3 part by weight of t-butylperoxy-2-ethylhexanoate and the same as those used in Example 1. 40 parts by weight of furnace black were blended and melt-kneaded in a coaxial twin-screw extruder with a screw diameter of 30 mm connected to a two-layer molding machine under the conditions of a temperature of 190 ° C. and a residence time of 0.9 minutes, followed by a silane graft reaction. While L / D2 also connected to a two-layer molding machine
8. 100 parts by weight of the ethylene-unsaturated silane compound copolymer of Reference Example 1 and 5 parts by weight of the silanol condensation catalyst masterbatch-1 of Reference Example 3 were dry-blended and fed into an extruder having a diameter of 30 mm. In the same manner as in Example 1, a two-layer co-extrusion sheet was formed to prepare a sample, and the same evaluation was performed.

Example 9 A semiconductive resin composition was produced according to the above-mentioned [Production Method 1]. That is, 40 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and 60 parts of the modified ethylene copolymer-1 of Reference Example 4 were used.
100 parts by weight of a copolymer (resin) component consisting of parts by weight, and the same furnace black 40 as used in Example 1.
3 parts by weight of vinyltrimethoxysilane and 0.4 part by weight of t-butylperoxy-2-ethylhexanoate were added to a mixture obtained by melting and kneading parts by weight using a biaxial kneader, and The mixture was melt-kneaded with a single screw extruder under the conditions of 190 ° C. and a residence time of 1.5 minutes, and a silane graft reaction was performed to obtain a semiconductive resin composition (A). Next, the semiconductive resin composition (A) was placed in an extruder having an L / D of 26 and a diameter of 20 mm.
And an ethylene / unsaturated silane compound copolymer 10 of Reference Example 1 in an extruder having an L / D of 28 and a diameter of 30 mm.
0 parts by weight and 5 parts by weight of the master batch-1 of the silanol condensation catalyst of Reference Example 3 were dry-blended and charged, and a two-layer coextruded sheet was formed at a die setting temperature of 190 ° C. by a T-type two-layer molding machine. To obtain a sample. Further, the obtained sheet was immersed and crosslinked in hot water at a temperature of 85 ° C. for 12 hours, dried, and then evaluated as shown in Table-2.

Example 10 Vinyl acetate content: 33% by weight
2 parts by weight of vinyltrimethoxysilane and 0.35 parts by weight of t-butylperoxyoctate were added to 100 parts by weight of an ethylene-vinyl acetate copolymer of the formula (1), and at a temperature of 190 ° C. and a residence time of 1.7 minutes, The mixture was melted and kneaded with a single screw press having an L / D of 28 and a diameter of 40 mm, and a silane graft reaction was performed to obtain an unsaturated silane compound-grafted ethylene-vinyl acetate copolymer. To 100 parts by weight of a copolymer (resin) component obtained by dry blending 40 parts by weight of the unsaturated silane compound-grafted ethylene-vinyl acetate copolymer and 60 parts by weight of the modified ethylene copolymer-1 of Reference Example 4, Using the same direction twin screw extruder with a screw diameter of 45 mm, 40 parts by weight of the same furnace black as used in Example 1 at a temperature of 180
The mixture was melt-kneaded at a temperature of 250 ° C., a rotation speed of 250 rpm, and a discharge rate of 20 kg / hour to obtain a semiconductive resin composition (a). Next, this semiconductive resin composition (a) is charged into an extruder having an L / D of 26 and a diameter of 20 mm.
Into a 0 mm extruder, 100 parts by weight of the ethylene-unsaturated silane compound copolymer of Reference Example 1 and 5 parts by weight of the silanol condensation catalyst master batch-1 of Reference Example 3 were dry-blended and charged to form a T-type two-layered mold. Die set temperature 19
A sample was obtained by forming a two-layer coextruded sheet at 0 ° C.
Further, the obtained sheet was immersed and crosslinked in hot water at a temperature of 85 ° C. for 12 hours, dried, and then evaluated as shown in Table-2.

Comparative Example 3 A semiconductive resin composition was produced according to the above-mentioned [Production method 1]. That is, 40 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33% by weight and 60 parts of the modified ethylene copolymer-1 of Reference Example 4 were used.
100 parts by weight of a copolymer (resin) component consisting of parts by weight, and the same furnace black 40 as used in Example 1.
3 parts by weight of vinyltrimethoxysilane were added to the mixture obtained by melt-kneading parts by weight using a twin-screw kneader (no radical generator was added), and the temperature was 190 ° C. and the residence time was 1.5.
The mixture was melt-kneaded with a single-screw extruder under the conditions of a minute to obtain a semiconductive resin composition (C). Next, L / D26, diameter 20mm
This semiconductive resin composition (c) is put into an extruder of
On the other hand, 100 parts by weight of the ethylene-unsaturated silane compound copolymer of Reference Example 1 and 5 parts by weight of the master batch-1 of silanol condensation catalyst of Reference Example 3 were dry-blended and fed into an extruder having an L / D of 28 and a diameter of 30 mm. Then, a two-layer co-extrusion sheet was formed at a die set temperature of 190 ° C. using a T-type two-layer forming machine to obtain a sample. Further, the obtained sheet was immersed and crosslinked in hot water at a temperature of 85 ° C. for 12 hours, and dried,
The evaluation shown in Table 2 was performed.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

The easily peelable semiconductive resin composition of the present invention can be suitably used as a material for a semiconductive layer having good mechanical strength, heat resistance, and appropriate peel strength.

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Exit Jijio 1 Tohocho, Yokkaichi-shi, Mie Mitsubishi Yokkaichi Office

Claims (17)

[Claims] 1. A composition comprising the following components (A), (B), (D) and (E), wherein component (B) is a radical generator (C) 0.01 to 2 It is contained in the composition by being subjected to a melt grafting reaction with the component (A) and / or the component (E) in the presence of parts by weight, and the following vinyl monomer (a2) unit is contained in the composition. 5 to 35% by weight based on the total amount of component (A) and component (E)
The composition has a degree of crosslinking of 30 to 90% by weight.
An easily peelable semiconductive resin composition, characterized in that: (A) Modified ethylene copolymer obtained by subjecting ethylene copolymer (a1) and vinyl monomer (a2) to graft polymerization conditions ... 5 to 100 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene copolymer: 0 to 95 parts by weight (where each component is The compounding amount of component (A) and component (E)
Are expressed as 100 parts by weight. ) 2. Component (A), component (B), component (D) and component (E) have the following composition, and component (B) is a radical generator (C) in an amount of 0.01 to 2 parts by weight. 2. The composition of claim 1, wherein the composition is subjected to a melt grafting reaction with the component (A) and the component (E) in the presence thereof.
3. An easily peelable semiconductive resin composition according to item 1. (A) Modified ethylene copolymer obtained by subjecting ethylene copolymer (a1) and vinyl monomer (a2) to graft polymerization conditions ... 5 to 100 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene copolymer: 0 to 95 parts by weight (where each component is The compounding amount of component (A) and component (E)
Are expressed as 100 parts by weight. ) 3. Component (A), component (B), component (D) and component (E) have the following composition, and component (B) contains 0.01 to 2 parts by weight of radical generator (C). The easily peelable semiconductive resin composition according to claim 1, wherein the composition is contained in the composition by being subjected to a melt graft reaction with the component (A) in the presence. (A) A modified ethylene copolymer obtained by subjecting an ethylene copolymer (a1) and a vinyl monomer (a2) to graft polymerization conditions ... 20 to 80 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene-based copolymer: 20 to 80 parts by weight The compounding amount is the component (A) and the component (E)
Are expressed as 100 parts by weight. ) 4. Component (A), component (B), component (D) and component (E) have the following composition, and component (B) is a radical generator (C) in an amount of 0.01 to 2 parts by weight. The easily peelable semiconductive resin composition according to claim 1, which is contained in the composition by being subjected to a melt graft reaction with the component (E) in the presence. (A) A modified ethylene copolymer obtained by subjecting an ethylene copolymer (a1) and a vinyl monomer (a2) to graft polymerization conditions ... 20 to 80 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene-based copolymer: 20 to 80 parts by weight The compounding amount is the component (A) and the component (E)
Are expressed as 100 parts by weight. ) 5. The composition according to claim 1, wherein component (B) is subjected to a melt grafting reaction with component (A) and / or component (E) in the presence of radical generator (C) and component (D). The easily peelable semiconductive resin composition according to claim 1, which is contained therein. 6. The easily peelable semiconductive material according to claim 1, wherein the ethylene copolymer (a1) contains 15 to 50% by weight of a copolymer monomer other than ethylene. Resin composition. 7. The ethylene copolymer (a1) has a melt flow rate of 0.1 to 300 g / 10 minutes.
7. The easily peelable semiconductive resin composition according to any one of items 6 to 6. 8. The composition according to claim 1, wherein the component (A) contains 10 to 60% by weight of a vinyl monomer (a2) unit.
The easily peelable semiconductive resin composition according to any one of the above. 9. A method comprising kneading the following components (A), (B), (D) and (E), wherein component (B) is 0.01 to 2% by weight of a radical generator (C). A method for producing an easily peelable semiconductive resin composition, comprising a step of subjecting a component (A) and / or a component (E) to a melt grafting reaction in the presence of a part. (A) Modified ethylene copolymer obtained by subjecting ethylene copolymer (a1) and vinyl monomer (a2) to graft polymerization conditions ... 5 to 100 parts by weight (B) Saturated silane compound: 0.5 to 15 parts by weight (D) Carbon black: 10 to 110 parts by weight (E) Ethylene copolymer: 0 to 95 parts by weight (where each component is The compounding amount of component (A) and component (E)
Are expressed as 100 parts by weight. ) 10. Modified ethylene copolymer (A) 5-1
100 parts by weight of a resin comprising 00 parts by weight and 0 to 95 parts by weight of an ethylene copolymer (E) and carbon black (D)
After melt-kneading 10 to 110 parts by weight, 0.5 to 15 parts by weight of the unsaturated silane compound (B) and 0.01 to 2 parts by weight of the radical generator (C) are added, and the mixture is further melt-kneaded to obtain a silane graft. The method for producing an easily peelable semiconductive resin composition according to claim 9, which is subjected to a reaction. 11. A modified ethylene copolymer (A) 5-1
100 parts by weight of a resin consisting of 00 parts by weight and 0 to 95 parts by weight of an ethylene copolymer (E), 0.5 to 15 parts by weight of an unsaturated silane compound (B) and a radical generator (C)
0.01 to 2 parts by weight are melt-kneaded and 10 to 110 parts by weight of carbon black (D) are added to an unsaturated silane compound-grafted ethylene copolymer obtained by subjecting to a silane graft reaction, and further melt-kneaded. A method for producing the easily peelable semiconductive resin composition according to claim 9. 12. The modified ethylene copolymer (A) 5-1
100 parts by weight of a resin consisting of 00 parts by weight and 0 to 95 parts by weight of an ethylene copolymer (E), 0.5 to 15 parts by weight of an unsaturated silane compound (B), and 0.1 to 0.1 parts by weight of a radical generator (C).
01 to 2 parts by weight and carbon black (D) 10 to 11
The method for producing a semi-conductive resin composition according to claim 9, wherein 0 parts by weight are melt-kneaded and subjected to a silane graft reaction. 13. A modified ethylene copolymer (A) 20 to
80 parts by weight, 0.5 to 15 parts by weight of an unsaturated silane compound (B) and 0.01 to 2 parts by weight of a radical generator (C) are melt-kneaded to obtain an unsaturated silane compound obtained by a silane graft reaction. The easy-to-use composition according to claim 9, wherein 10 to 110 parts by weight of carbon black (D) is added to a resin composed of 20 to 80 parts by weight of the graft-modified ethylene-based copolymer and ethylene-based copolymer (E), and the mixture is further melt-kneaded. A method for producing a peelable semiconductive resin composition. 14. An ethylene copolymer (E) 20 to 80.
Parts by weight, an unsaturated silane compound (B) 0.5 to 15 parts by weight, and a radical generator (C) 0.01 to 2 parts by weight are melt-kneaded and subjected to a silane graft reaction to obtain an unsaturated silane compound graft. The easy peeling according to claim 9, wherein 10 to 110 parts by weight of carbon black (D) is added to a resin consisting of 20 to 80 parts by weight of the ethylene-based copolymer and the modified ethylene-based copolymer (A), and the mixture is further melt-kneaded. Method for producing conductive semiconductive resin composition. 15. The easily peelable semiconductive material according to claim 9, wherein the ethylene-based copolymer (a1) contains 15 to 50% by weight of a copolymer monomer other than ethylene. A method for producing a conductive resin composition. 16. The production of the easily peelable semiconductive resin composition according to claim 9, wherein the ethylene copolymer (a1) has a melt flow rate of 0.1 to 300 g / 10 minutes. Method. 17. Component (A) is a vinyl monomer (a2)
10. The composition according to claim 9, which contains 10 to 60% by weight of a unit.
16. The method for producing an easily peelable semiconductive resin composition according to any one of items 16.