JP2003268170A - Adherent polyethylene resin composition, its production method and extruded article obtained therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an improved adherent polyethylene resin which uses an polyethylene resin to secure excellent electrical properties, mechanical properties, and moldability of the polyethylene resin, has high adhesion, and suppresses the deterioration of adhesion with time under severe conditions, to provide its production method, an extruded article obtained therefrom, an electric wire and cable, and a submarine optical fiber cable. <P>SOLUTION: The adherent polyethylene resin composition comprises (A) the polyethylene resin, (B) an organic peroxide having a hydroperoxy group to be represented by formula (1): R<SP>1</SP>-O-O-H (wherein R<SP>1</SP>is an alkyl group or a cycloalkyl group, and these alkyl groups may be substituted with a phenyl group, an alkylphenyl group, a cycloalkyl group or an alkylcycloalkyl group, and (C) a silicone macromer. The production method, the extruded article to be produced therefrom, the electric wire and cable, and the submarine optical fiber cable are disclosed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive ethylene-based resin composition, a method for producing the same, and an extrusion-molded article obtained therefrom, and more specifically, excellent adhesiveness and little deterioration of adhesiveness with time, and processability. The present invention relates to an adhesive ethylene resin composition capable of obtaining an extruded product having good mechanical properties and the like, a method for producing the same, and an extruded product, an electric wire / cable and a submarine optical fiber cable obtained therefrom.

[0002]

2. Description of the Related Art Ethylene resins are excellent in electrical properties such as electrical insulation and high frequency properties, mechanical properties such as abrasion resistance, strength, low temperature brittleness, and processability such as extrusion moldability. Widely used as an insulating coating material for electric wires and communication cables. However, the ethylene-based resin does not have sufficient adhesiveness, that is, it has a problem that it is not sufficiently adhered to a core wire such as a metal conductor or an optical fiber, or a resin having a polar group such as polyester or polyamide.

Therefore, as described in JP-A-61-153612 and JP-A-4-13744, an ethylenic resin is used as an unsaturated carboxylic acid, an acid anhydride,
A modified ethylene resin having improved adhesion by graft modification with an epoxy compound, a hydroxy compound, an organic acid metal salt, a silane compound or the like has been developed and widely used.
However, these techniques require a step of heat treatment for graft modification, and if the temperature is not adjusted well and the temperature is too high, the organic peroxide excessively reacts,
For example, decomposition odor may be generated, or "crosslinks" may be partially generated to generate "bugs", and unevenness may be recognized on the extruded outer cover, which may affect the adhesiveness.

Therefore, Japanese Patent Application No. 20 filed by the applicant of the present application
In No. 01-234570, from the finding that the ethylene-based resin is blended with a specific organic peroxide to impart adhesiveness to the ethylene-based resin, graft modification is not required, and therefore, the decomposition odor caused by the organic peroxide is not required. We have proposed an adhesive ethylene-based resin composition that does not cause the risk of cross-linking of ethylene-based resin, but it was confirmed that the adhesiveness deteriorates with time when used under severe conditions such as the coating layer of a submarine optical fiber cable. Therefore, it is required to further improve the deterioration with time of the adhesiveness.

[0005]

SUMMARY OF THE INVENTION Therefore, in view of the problems of the prior art, an object of the present invention is to use an ethylene-based resin to secure its excellent electric characteristics, mechanical characteristics and workability, and to achieve high adhesion. PROBLEM TO BE SOLVED: To provide an adhesive ethylene-based resin composition having improved adhesiveness and little improvement in adhesiveness over time even under severe conditions, a method for producing the same, and an extrusion molded article, an electric wire / cable, and a submarine optical fiber cable obtained from the same. Especially.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors focused their attention on a silicone macromer, which was converted into an ethylene-based resin composition containing a specific organic peroxide. It has been found that by further compounding, the problem of deterioration of the adhesiveness over time under severe environmental conditions of the ethylene resin composition is greatly improved, and the present invention has been completed.

That is, according to the first aspect of the present invention,
Adhesive ethylene-based resin comprising an ethylene-based resin (A) and an organic peroxide (B) having a hydroperoxy group represented by the following formula (1) and a silicone macromer (C). A resin composition is provided. R ¹ —O—O—H (1) (In the formula, R ¹ represents an alkyl group or a cycloalkyl group, and those alkyl groups represent a phenyl group, an alkylphenyl group, a cycloalkyl group, or an alkylcycloalkyl group. Further, according to the second invention of the present invention, in the first invention, the silicone macromer (C) is a silane coupling agent (c- represented by the following formula (2). 1), an alkylalkoxysilane (c-2) represented by the formula (3), and a polycondensation polymer (c-3) represented by the formula (4), which is a partially condensed polymer. An ethylene resin composition is provided. _{^{X-Si (R 2) a}} (OR 3) b (2) ( wherein, X is an ethylenically unsaturated group, ^{R 2} is a carbon number 1
~ 3 alkyl group, R ³ represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 9 carbon atoms, a
Is 0 or 1, b is 3 or 2, and a + b = 3. _{^{) R 4 -Si (R 5)}} c (OR 6) d (3) ( wherein, ^{R 4} is an alkyl group having 4 to 10 carbon atoms, R
⁵ is an alkyl group having 1 to 3 carbon atoms, R ⁶ is 1 to 1 carbon atoms
Represents an alkyl group having 8 or an alkoxyalkyl group having 2 to 9 carbon atoms, c is 0 or 1, d is 3 or 2, and c + d = 3.
Is. ) Si _n O _n-1 (OR ⁷ ) _{2n + 2} (4) (In the formula, R ⁷ represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 9 carbon atoms, and n is 2 on average. Further, according to the third invention of the present invention, in the first or second invention, the blending amount of the organic peroxide (B) having a hydroperoxy group and the silicone macromer (C) is ,
An adhesive ethylene-based resin composition is provided, which is 0.005 to 2 parts by weight and 0.005 to 2 parts by weight, respectively, relative to 100 parts by weight of the ethylene-based resin (A).

According to a fourth aspect of the present invention, the first aspect
1 to 3, the organic peroxide (B) having a hydroperoxy group has a decomposition temperature of 170 ° C. or higher for obtaining a half-life of 1 minute. A resin composition is provided. Furthermore, according to the 5th invention of the present invention, in any one of the 1st to 4th inventions, the silicone macromer (C) is an alkylalkoxysilane () relative to 1 mole of the silane coupling agent (c-1). c-2) is 0.01 to 5 mol, and polyalkyl silicate (c-3) is 0.05 to 25 mol (calculated as silicon atom), which is a partially condensed polymer, and is an adhesive ethylene-based compound. A resin composition is provided.

On the other hand, according to the sixth aspect of the present invention, the ethylene-based resin (A), the organic peroxide having a hydroperoxy group (B) and the silicone macromer (C) are stored in a closed container at room temperature or higher. Mixing at a temperature below the melting temperature of the ethylene resin (A) to allow the organic peroxide (B) having a hydroperoxy group and the silicone macromer (C) to permeate and impregnate the ethylene resin (A). A method for producing the adhesive ethylene resin composition according to any one of the first to fifth inventions is provided. According to the seventh aspect of the present invention, the ethylene-based resin (A), the organic peroxide having a hydroperoxy group (B) and the silicone macromer (C) are added at a temperature not lower than the melting temperature of the ethylene-based resin (A). Also, the adhesion according to any one of the first to fifth inventions, characterized in that the organic peroxide (B) having a hydroperoxy group is melted and kneaded at a temperature lower than a decomposition temperature for obtaining a one-minute half-life. Provided is a method for producing a volatile ethylene resin composition.

According to an eighth aspect of the present invention, there is provided an extrusion-molded article obtained by extrusion-molding the adhesive ethylene resin composition according to any one of the first to fifth aspects. According to a ninth aspect of the present invention, there is provided an electric wire / cable having a coating layer obtained by extrusion-molding the adhesive ethylene resin composition according to any one of the first to fifth aspects. To be done. Further, according to a tenth aspect of the present invention, there is provided a submarine optical fiber cable having an insulating layer obtained by extruding the adhesive ethylene resin composition according to any one of the first to fifth aspects. To be done.

As described above, the present invention is characterized in that the ethylene resin (A) is blended with the organic peroxide (B) having a hydroperoxy group and the silicone macromer (C). The present invention relates to a polymerizable ethylene-based resin composition and the like, and preferred embodiments include the following.

(1) In the first invention, the adhesive ethylene resin composition is characterized in that the ethylene resin (A) is high-pressure low density polyethylene. (2) In the first invention, the organic peroxide (B) having a hydroperoxy group is p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide,
An adhesive ethylene-based resin composition, which is at least one selected from cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide. (3) In the second invention, the silane coupling agent (c
-1) is an adhesive ethylene resin composition characterized by being selected from vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, or γ-methacryloxypropyltriethoxysilane. object. (4) In the second invention, the alkylalkoxysilane (c-2) is n-hexyltrimethoxysilane, n-
An adhesive ethylene-based resin composition, which is an alkyltrialkoxysilane selected from hexyltriethoxysilane, n-octyltrimethoxysilane, or n-octyltriethoxysilane. (5) The adhesive ethylene resin composition according to the first invention, further comprising an acid-modified ethylene resin (D). (6) In the above (5), the compounding amount of the acid-modified ethylene-based resin (D) is 2.0 to 20 parts by weight with respect to 100 parts by weight of the ethylene-based resin (A). Ethylene resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the adhesive ethylene resin composition of the present invention, a method for producing the same, an extruded product obtained therefrom, an electric wire / cable having a coating layer obtained therefrom, and an electric wire / cable obtained from the same The submarine optical fiber cable having an insulating layer will be described in detail for each item.

1. Ethylene-based resin (A) The ethylene-based resin (A) used in the present invention is not particularly limited, and its kind, molecular weight, etc. are not limited.
As the ethylene resin (A), an ethylene homopolymer,
Examples thereof include ethylene-α-olefin (having 3 to 12 carbon atoms) copolymer, ethylene-α, β-unsaturated carboxylic acid (or ester derivative thereof) copolymer, ethylene-carboxylic acid vinyl ester copolymer and the like.

Specifically, high-pressure low-density polyethylene produced by high-pressure radical polymerization, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene Examples thereof include butyl methacrylate copolymer and ethylene-vinyl acetate copolymer. Further, the temperature is 0 to 250 ° C., the pressure is 50 MPa or more (in the case of high pressure), 10 to 50 MPa.
Ziegler catalyst, Phillips catalyst by a method such as a solution polymerization method, a suspension polymerization method, a slurry polymerization method, a gas phase polymerization method, etc. under any condition (in the case of medium pressure) or normal pressure to 10 MPa (in the case of low pressure) Ethylene-butene-1 copolymer, which is a linear low-density (or ultra-low density) ethylene-α-olefin copolymer produced by using a standard catalyst, a single-site catalyst (metallocene catalyst), or the like,
Examples thereof include ethylene-hexene-1 copolymer and ethylene-octene-1 copolymer. In addition, medium density polyethylene and high density polyethylene can also be used. Of these, high-pressure low-density polyethylene can be preferably used. Furthermore, ethylene resin (A) is
It is also possible to use one kind or a mixture of two or more kinds. The melt mass flow rate of the ethylene-based resin (A) is 0. 0 from the workability and the mechanical strength of the molded product.
05-50g / 10 minutes, preferably 0.1-10g
/ 10 minutes, more preferably 0.1 to 1 g / 10 minutes (1
(Measured at 90 ° C.), these can be preferably used.

2. Organic Peroxide Having Hydroperoxy Group (B) Hydroperoxy Group Used in the Present Invention
Also called an eroxy hydroperoxy group. The organic peroxide (B) having) is a derivative of hydrogen peroxide having a hydroperoxy group represented by the following formula (1) in its chemical structure. R ¹ —O—O—H (1) (In the formula, R ¹ is an alkyl group or a cycloalkyl group, and those alkyl groups are a phenyl group, an alkylphenyl group, a cycloalkyl group, or an alkylcycloalkyl group. It may be replaced.)

Specifically, p-menthane hydroperoxide (199.5 ° C.), diisopropylbenzene hydroperoxide (232.5 ° C.), 1,1,3,3-tetramethylbutyl hydroperoxide (246. 6 ° C),
Cumene hydroperoxide (254.0 ° C.), t-hexyl hydroperoxide (250.9 ° C.), t-butyl hydroperoxide (260.7 ° C.) and 2,5-dimethylhexane 2,5-dihydro Examples thereof include peroxide. The value in parentheses is the decomposition temperature (° C) for obtaining a half-life of 1 minute. As the organic peroxide (B) having a hydroperoxy group, one having a decomposition temperature of 170 ° C. or higher for obtaining the one-minute half-life can be preferably used. The organic peroxide (B) having a hydroperoxy group can be used alone or in combination of two or more. Furthermore, although the detailed mechanism by which the organic peroxide (B) having a hydroperoxy group imparts adhesiveness to the ethylene-based resin is not clear, it is presumed that it is due to hydrogen bonding.

In the present invention, the amount of the organic peroxide (B) having a hydroperoxy group is 0.005 to 2 parts by weight based on 100 parts by weight of the ethylene resin (A).
It is preferably 0.01 to 0.5 part by weight, more preferably 0.03 to 0.25 part by weight. This blending amount is 0.
When the amount is less than 005 parts by weight, the adhesiveness is insufficiently imparted, while when the amount is more than 2 parts by weight, the effect on the adhesiveness is saturated and the ethylene resin (A) is contacted with a large amount of organic peroxide. Then, even if the temperature is relatively lower than the decomposition temperature of the organic peroxide, a heterogeneous cross-linking reaction may occur at the contact portion, which may cause "burn" or "bucks" during molding, or It is not desirable because it may affect the mechanical properties such as flexibility of the composition.

3. Silicone Macromer (C) The silicone macromer (C) used in the present invention is a silane coupling agent (c-1), an alkylalkoxysilane (c-2), and a polyalkylsilicate (c-).
It is a partial polycondensate obtained by hydrolysis and dehydration of 3).

Examples of suitable silane coupling agents (c-1) include unsaturated silane compounds represented by the following formula (2). _{^{X-Si (R 2) a}} (OR 3) b (2) ( wherein, X is an ethylenically unsaturated group, ^{R 2} is a carbon number 1
~ 3 alkyl group, R ³ represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 9 carbon atoms, a
Is 0 or 1, b is 3 or 2, and a + b = 3. ) Specific examples of X in the above formula (2) include groups represented by the following formula (5) or formula (6). _{^{CH 2 = CR 8 (CH 2}} ) g - (5) ( wherein, ^{R 8} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, g is an integer of 0 or 1-6.)

[0021]

[Chemical 1]

(In the formula, R ⁹ is a hydrogen atom or a carbon number of 1 to
5 represents an alkyl group, and h is 0 or an integer of 1 to 6. ) Examples of preferable X include vinyl group, γ-acryloxypropyl group, γ-methacrylopropyl group and the like. R ² in the formula (2) is preferably a methyl group, and
R ³ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a methoxymethyl group, a methoxyethyl group. , Ethoxymethyl group, ethoxyethyl group and the like,
Of these, a methyl group, an ethyl group, an isopropyl group, or a propyl group is preferable, and further, a and b are preferably a = 0 and b = 3.

Specific examples of the silane coupling agent (c-1) represented by the above formula (2) include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane and vinyltris ( 2-methoxyethoxy) silane, vinyltris (n-butoxy) silane, vinyltris (n-pentoxy) silane, vinyltris (n-hexoxy) silane, vinylbis (n-butoxy) methylsilane, vinylbis (n-pentoxy) methylsilane, vinylbis (n)
-Hexoxy) methylsilane, γ-acryloxypropylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ -Methacryloxypropyldimethoxysilane or γ-methacryloxypropyltris (2-methoxyethoxy) silane. Among these, vinyltrimethoxysilane, vinyltriethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, or γ-
Methacryloxypropyltriethoxysilane can be preferably used. In addition, a silane coupling agent (c
-1) may be partially hydrolyzed in advance, dehydrated, and partially polycondensed to have an average of about 2 to 10 monomers, and then the silicone macromer (C) may be prepared.

Suitable examples of the alkylalkoxysilane (c-2) used in the present invention include compounds represented by the following formula (3). _{^{R 4 -Si (R 5) c}} (OR 6) d (3) ( wherein, ^{R 4} is an alkyl group having 4 to 10 carbon atoms, R
⁵ is an alkyl group having 1 to 3 carbon atoms, R ⁶ is 1 to 1 carbon atoms
Represents an alkyl group having 8 or an alkoxyalkyl group having 2 to 9 carbon atoms, c is 0 or 1, d is 3 or 2, and c + d = 3.
Is. )

R ⁴ in the formula (3) is butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Or, a decyl group can be mentioned, one having 5 to 8 carbon atoms is preferable, and an n-hexyl group or an n-octyl group is particularly preferable. Further, R ⁵ is preferably a methyl group, and R ⁶ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group. , Octyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group,
Examples include ethoxyethyl group, methyl group, ethyl group,
An isopropyl group or a propyl group is preferable, and further c
As for d and d, it is preferable that c is 0 and d is 3.

Specific examples of the alkylalkoxysilane (c-2) represented by the above formula (3) include n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane and n-octyl. Triethoxysilane etc. can be mentioned.

The amount of the alkylalkoxysilane (c-2) used in the silicone macromer (C) is 0.0 based on 1 mol of the silane coupling agent (c-1).
It is desirable that the amount is 1 to 5 mol, preferably 0.1 to 2 mol, and particularly preferably 0.2 to 1 mol. The amount of the alkylalkoxysilane (c-2) used is lower than the lower limit (0.
If it is less than 01 mol), the affinity with the ethylene-based resin (A) becomes insufficient, and the effect of improving the deterioration of adhesiveness with time deteriorates. On the other hand, when the amount is more than the upper limit (5 mol), the compounding amount of the silane coupling agent (c-1) which relatively imparts the affinity with the metal becomes small, and the effect of improving the deterioration with time of the adhesiveness is also obtained. become worse. The alkylalkoxysilane (c-2) may be partially hydrolyzed in advance, dehydrated, and partially polycondensed to have an average of about 2 to 10 mer, and then the silicone macromer (C) may be prepared.

A suitable polyalkyl silicate (c-3) used in the present invention is a partial condensation polymer obtained by dehydrating a partial hydrolyzate of tetraalkoxysilane, and is represented by the following formula (4). The compounds represented may be mentioned. Si _n O _n-1 (OR ⁷ ) _{2n + 2} (4) (In the formula, R ⁷ represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 9 carbon atoms, and n is 2 to an average value. Note that R ⁷ in the formula (4) is specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, Hexyl group, heptyl group, octyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like, methyl group,
Ethyl group, isopropyl group or propyl group is preferable,
The average value n is preferably 4 to 6. As the compound corresponding to the compound represented by the above formula (4), those commercially available from Colcoat Co., Ltd. as silicate 40 (trade name) and the like can be preferably used.

The amount of the polyalkyl silicate (c-3) to be used in the silicone macromer (C) is 0.05 to 25 mol, preferably silicon atom conversion, based on 1 mol of the silane coupling agent (c-1). Is 0.5-10
It is desirable that the amount is 1 mol, particularly preferably 1 to 5 mol. Here, the number of moles in terms of silicon atom is a value obtained by multiplying the actual number of moles by the value of n in the above formula (4).
If the amount of the polyalkyl silicate (c-3) used is less than the lower limit value (0.05 mol), the molecular weight of the obtained silicone macromer (C) does not increase and its volatility increases, so that an accurate blending is possible. In addition to the difficulty, the effect of improving the adhesiveness over time deteriorates. On the other hand, if the amount is more than the upper limit (25 mol), gel or "bugs" may occur, which is not desirable.

The above silane coupling agent (c-1),
The silicone macromer (C), which is a partial polycondensate obtained by hydrolyzing an alkylalkoxysilane (c-2) and a polyalkylsilicate (c-3), and dehydrating it,
Gel permeation chromatography (hereinafter GP
Also called C. The polystyrene-equivalent number average molecular weight (Mn) is from 300 to 10,000, preferably from 500 to
It is desirable that it is in the range of 5,000, more preferably 600 to 2,000. If the number average molecular weight (Mn) is less than the above lower limit (300), the volatility becomes high, making it difficult to accurately blend the ethylene resin (A), and the adhesive property with the passage of time. It is not desirable because the improvement effect on deterioration deteriorates. On the other hand, this is the upper limit (1
Above 10,000), gels and “bugs” may be formed in the composition, which is not desirable.

The method for producing the silicone macromer (C) may be any known hydrolysis reaction or dehydration polycondensation reaction and is not particularly limited. For example, the above-mentioned predetermined amount of the silane coupling agent (c-1), Alkylalkoxysilane (c-2) and polyalkyl silicate (c-3) are mixed, and a hydrolysis reaction and a condensation reaction are carried out by mixing them with water using an alkali catalyst. It can be prepared by removing the alcohol and filtering. Examples of the alkali catalyst at this time include sodium hydroxide, potassium hydroxide, and an aqueous ammonia solution,
Sodium hydroxide and potassium hydroxide are preferred. Also,
Examples of the acid used for neutralization include acetic acid, hydrochloric acid and sulfuric acid. The water and the generated alcohol can be removed by distillation under reduced pressure and heating. The filtration can be performed using a filter aid such as diatomaceous earth or activated carbon, or using various filters. It should be noted that the order of removing water and the generated alcohol and the steps of filtration may be performed first. The degree of polymerization of the silicone macromer (C) can be controlled by increasing the blending amount of water, and can be controlled by checking the progress of the reaction by GPC and terminating the reaction at an appropriate level. it can. The silicone macromer (C) is a polymer precursor having a net-like or branched structure, and in the present invention, a liquid at room temperature can be preferably used.

In the adhesive ethylene resin composition of the present invention, the blending amount of the silicone macromer (C) is 0.005-2 based on 100 parts by weight of the ethylene resin (A).
Parts by weight, preferably 0.01 to 0.5 parts by weight, more preferably 0.03 to 0.25 parts by weight. If the amount is less than 0.005 parts by weight, the improvement of the adhesive property with time is insufficient, whereas if it exceeds 2 parts by weight, the effect of the adhesive property with time is saturated and the ethylene resin The excellent workability and mechanical properties originally possessed by (A) may be affected, which is not desirable.

4. Other Compounds (D) The adhesive ethylene resin composition of the present invention may contain various additives and auxiliary materials depending on the purpose of use. These various additives and auxiliary materials include stabilizers, compatibilizers, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, nucleating agents, lubricants, processability improvers, fillers, dispersants, copper. Harm prevention agent, neutralizing agent, foaming agent, anti-foaming agent, coloring agent, carbon black, wax, bactericide, fungicide,
Examples thereof include acid-modified olefin resin.

It is preferable to add an antioxidant to the adhesive ethylene resin composition of the present invention. Examples of the antioxidant include phenol-based, phosphorus-based, amine-based, and sulfur-based antioxidants, which may be used alone or as a mixture of two or more thereof, and the blending amount thereof is the ethylene-based resin (A). 1
It is about 0.001 to 5 parts by weight with respect to 00 parts by weight.

In addition to the ethylene-based resin (A), other olefin-based resins may be added to the adhesive ethylene-based resin composition of the present invention depending on the purpose of use, as long as the characteristics of the present invention are not impaired. A small amount can be added. For example, the adhesive ethylene resin composition of the present invention can be blended with an acid-modified olefin resin, preferably an acid-modified ethylene resin. The functional group-containing compound for producing the acid-modified ethylene-based resin, fumaric acid, acrylic acid, itaconic acid, methacrylic acid, sorbic acid, unsaturated carboxylic acid such as crotonic acid or citraconic acid, and maleic anhydride, Itaconic anhydride, citraconic anhydride, 5
-Norbornene-2,3-dicarboxylic anhydride or 4
Examples thereof include acid anhydrides such as -methylcyclohexene-1,2-dicarboxylic acid anhydride. Particularly preferable acid-modified ethylene-based resin is maleic anhydride-modified ethylene-based resin.

The ethylene resin to be modified is not particularly limited, and any of the ethylene resins listed in the section of the above-mentioned ethylene resin (A) can be used. Further, the amount of the functional group-containing compound used in the modification treatment is usually about 0.
001 to 5% by weight. The modification treatment may be any known method, and a solution method, a suspension method, a melting method or the like is preferably used.

In the adhesive ethylene resin composition of the present invention,
As the acid-modified ethylene resin (D) of the acid-modified olefin resin that can be used as the other compound (D), the melt mass flow rate is 0.05 to 50 g / 10.
Those having a minute and a density of 0.86 to 0.95 g / cm ³ are preferable. In the present invention, the acid-modified ethylene resin (D)
Gives adhesiveness, but by using together with the organic peroxide (B) having a hydroperoxy group, the initial adhesiveness can be further increased. The acid-modified ethylene-based resin (D) may be used alone or in combination of two or more, and the compounding amount thereof is 0 to 20 parts by weight, preferably 2 to 100 parts by weight of the ethylene-based resin (A). ˜15 parts by weight, more preferably 4 to 12 parts by weight. In the adhesive ethylene-based resin composition of the present invention, the lower limit of the compounding amount of the acid-modified ethylene-based resin (D) is 0 parts by weight, because it is not necessary to impart adhesiveness with the acid-modified ethylene-based resin (D). On the other hand, when a synergistic effect is required for the adhesiveness with the organic peroxide (B) having a hydroperoxy group, the acid-modified ethylene resin (D) is It is preferable to add more than one part by weight. If the blending amount exceeds 20 parts by weight, mechanical properties such as flexibility of the resulting adhesive ethylene-based resin composition and electrical properties such as core wire corrosion deteriorate,
Furthermore, the adhesiveness itself may be reduced, which is not desirable.

5. Preparation of Adhesive Ethylene-Based Resin Composition The adhesive ethylene-based resin composition of the present invention may be prepared by various known preparation methods and is not particularly limited, but typical preparation methods are shown below.

5.1 Preparation Method (1) -Permeation / Impregnation Method As a preferred embodiment of the permeation / impregnation method, a predetermined amount of the ethylene resin (A) and the other compound (D) are respectively added in the first step. Using a general method such as a kneader, a Banbury mixer, a continuous mixer or a single-screw or twin-screw extruder, melting and kneading at a temperature not lower than the melting temperature of the resin component, for example, 110 to 170 ° C. Granulate. Then, in a second step, the granulated product is placed in a closed container together with a predetermined amount of an organic peroxide (B) having a hydroperoxy group and a silicone macromer (C), and after sealing, at room temperature or higher. And not more than the melting temperature of the ethylene resin (A), for example, 15 to 90
° C, preferably 25-80 ° C, more preferably 50-
An example is a method in which the resin is mixed at 70 ° C., the organic peroxide (B) having a hydroperoxy group and the silicone macromer (C) are uniformly permeated and impregnated in the resin, and then the resin is taken out and prepared. in this way. There is an advantage that there is substantially no loss due to the decomposition of the organic peroxide (B) having a hydroperoxy group, and the addition amount thereof can be accurately controlled.

5.2 Preparation Method (2) -Melting / Kneading Method As a preferable embodiment of the melting / kneading method, a predetermined amount of the ethylene resin (A) and an organic peroxide having a hydroperoxy group are respectively used as the first step. The compound (B), the silicone macromer (C), and the other compound (D) are mixed with a resin component by a general method, for example, a kneader, a Banbury mixer, a continuous mixer or a single-screw or twin-screw extruder. Above the melting temperature and lower than the decomposition temperature (° C.) for obtaining the 1 minute half-life of the organic peroxide (B) having a hydroperoxy group, preferably 1 minute as a temperature at which substantially no decomposition occurs. A temperature lower than the decomposition temperature (° C) for obtaining the half-life by 50 ° C or more, specifically 110
A method of preparing by melting and kneading at about 170 ° C. can be mentioned. In this preparation method, the organic peroxide (B) having a hydroperoxy group, the silicone macromer (C) and the other compound (D) are contained in a high concentration by using the ethylene resin (A) in advance. Of course, a so-called masterbatch may be prepared and blended.

In the present invention, the organic peroxide (B) having a hydroperoxy group is not blended in order to generate radicals by this and to modify the ethylene resin (grafting reaction or crosslinking reaction). However, since it is added for imparting adhesiveness, it can be melted and kneaded at a temperature sufficiently lower than the above decomposition temperature, so that a homogeneous and high-quality adhesive ethylene resin composition can be prepared.
The prepared adhesive ethylene resin composition can be granulated into pellets having a particle size of about 2 to 7 mm, and preferably processed by extrusion molding or the like.

6. Uses of the Adhesive Ethylene-Based Resin Composition of the Present Invention The adhesive ethylene-based resin composition of the present invention can be molded into various extruded products for use. The extrusion-molded article according to the present invention comprises the adhesive ethylene-based resin composition of the present invention,
It can be produced by melt extrusion using an extruder. Examples of the extruded product include an electric wire / cable coating layer having an adhesive property, an insulating protective cover, a pipe, a resin-coated metal pipe, a film, a sheet, and the like. The adhesive ethylene-based resin composition of the present invention has excellent adhesiveness to core wires (copper wires, aluminum wires, etc.) of electric wires / cables, metallic outer tubular conductors, etc. ) Has excellent mechanical properties against changes in the surrounding environment, damage due to twisting, etc., does not require processing at high temperatures, and adheres even under severe conditions. It is a high-quality product with significantly improved deterioration of sex. In addition, examples of applications of electric wires / cables include distribution lines and communication lines.

Furthermore, the adhesive ethylene resin composition of the present invention also has excellent performance as a coating layer constituting an insulating layer of a submarine optical fiber cable used under particularly severe conditions. Generally, a submarine optical fiber cable is made of silica glass, is essentially fragile and easily broken, and its transmission characteristics change due to the action of external pressure such as lateral pressure. Therefore, its structure is disclosed in JP-A-54-130038.
As described in JP-A-58-48003, basically, from the core to the outside, (1) optical fiber unit, (2) inner tubular conductor, (3) steel wire, (4).
It is composed of an outer tubular conductor, (5) an insulating layer and (6) an outer skin. The (5) insulating layer is mainly made of high-pressure low-density polyethylene, and the (6) outer skin for protection is
High density polyethylene is used. (4) In order to insulate the outer tubular conductor from seawater, the submarine optical fiber cable (4) is particularly required to have adhesiveness and adhesion with the insulating layer. If this performance is insufficient, when submarine optical fiber cable is laid, etc. When tension and bending force are added with,
The (4) outer tubular conductor and (5) the insulating layer separate and move separately, causing the insulating layer to break in the middle of the cable or at the end of the cable, which in turn leads to damage to the cable itself. The adhesive ethylene-based resin composition of the present invention has sufficiently satisfactory adhesiveness / adhesiveness as an insulating layer of this submarine optical fiber cable, and further has excellent mechanical properties,
It has uniform extrusion processability, and its adhesive property is significantly improved over time, so that it can withstand long-term use.

[0044]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. The physical properties and evaluations used in this specification are based on the following methods.

[Physical Properties and Evaluation] 1. Melt mass flow rate Measured at a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210.

2. Adhesiveness evaluation test Using an adhesive ethylene-based resin composition, the diameter of the core wire 2.
A coated cable having an outer diameter of 7 mm was prepared by extrusion molding on a 4 mm copper conductor wire. This coated cable was cut into a length of 15 cm, and the core wire was exposed while leaving a coating layer having a length of 5 cm on one side. The core wire was gripped and fixed with a tool, and the coating layer portion was pulled out at a pulling speed of 100 mm / min using a tensile tester (AG5-5KNG manufactured by Shimadzu Corporation). At that time, the strength (Newton: N) required for pulling out was measured and used as an adhesiveness evaluation test. When the adhesive strength was too strong and core wire breakage was observed, it was specified and the strength at breakage was measured.

3. Adhesive deterioration evaluation test To determine the optimum evaluation conditions for the adhesive deterioration evaluation test,
First, the coated electric wire obtained in Comparative Example 1 shown below was
Each sample was exposed and stored under 5 conditions of 3 ° C., 50% relative humidity, 60 ° C., outdoors, 60 ° C. purified water, and 4 ° C. purified water for 4 weeks, and used as a sample for an adhesion deterioration evaluation test. Part 5
About 15 cm of the end portion of the covered electric wire under the conditions was discarded, and the adhesiveness evaluation test described in 2 above was performed using the central portion of 15 cm. The results are shown in Table 1 below.

[0048]

[Table 1]

As is clear from Table 1, the sample of Comparative Example 1 had a good initial adhesiveness, and the adhesiveness was not significantly deteriorated under the normal use conditions, but the submarine optical fiber cable etc. Considering the application, we selected the exposure and storage conditions in 60 ° C water, which had the greatest deterioration over time. Therefore, in the adhesion deterioration evaluation test, 4
Adhesion after storage for a week of 200 N or more was regarded as acceptable.

4. Preparation of Silicone Macromer (C) [Silicone Macromer 1] In a four-necked flask equipped with a thermometer, mechanical stirrer, condenser and nitrogen gas inlet tube,
1 mol of vinyltrimethoxysilane (c-1), 1 mol of n-hexyltriethoxysilane (c-2), polyethylsilicate (c in which R ⁷ in the formula (4) is an ethyl group and n is 5; -3) 1 mol (5 in terms of silicon atom)
Mol) and 2 mol of water in which potassium hydroxide was dissolved so that the total amount was 400 ppm (weight unit) in advance, and the mixture was stirred at 25 ° C. for 24 hours. Then, the mixture was neutralized with acetic acid, water and alcohol were removed under heating and reduced pressure, and then filtered to prepare Silicone Macromer 1. About the obtained silicone macromer 1, GPC measurement system TRI ROTER-V (manufactured by JASCO), column Sho
dex-805L (manufactured by Showa Denko) and refractive index (RI) detector RL540R (manufactured by GL Science) at 40 ° C.
Chloroform was flowed at a flow rate of 1.0 ml / min to measure the average molecular weight. At that time, standard polystyrene (manufactured by Showa Denko) was used as a standard sample. The obtained Silicone Macromer 1 has a number average molecular weight (Mn) of 657, a weight average molecular weight (Mw) of 1485, and a weight average molecular weight (Mw).
And the number average molecular weight (Mn) ratio (Mw / Mn) is 2.2.
It was 6.

[Silicone macromer 2] The vinyltrimethoxysilane (c-1) was mixed in an amount of 3 mol, and 4 mol of water in which potassium hydroxide was dissolved so that the total amount was 400 ppm (weight unit) was added. Silicone Macromer 2 was prepared in the same manner as Silicone Macromer 1 except that the above was performed. The obtained Silicone Macromer 2 has a number average molecular weight (Mn) of 761 and a weight average molecular weight (Mw).
Was 1604 and the ratio (Mw / Mn) was 2.11.

[Comparative Example 1 and Examples 1-5] As Comparative Example 1 and Examples 1-5, first, high-pressure process low-density polyethylene (melt mass flow rate 0.2 g / 10 min, density 0.919 g / cm ³ ) 100 parts by weight of tetrakis [methylene-3- (3 ', 5'-
Di-t-butyl-4'-hydroxyphenyl) propionate] 0.1 part by weight was charged into a Banbury mixer,
The mixture was melted and kneaded at 145 ° C. for 5 minutes and granulated to a particle size of about 4 mm. Then, Comparative Example 1 and Example 1 shown in Table 2 below.
Diisopropylbenzene hydroperoxide as an organic peroxide and Silicone Macromer 1 as a silicone macromer were placed in a closed container at a blending ratio of 5 to 5 and, after closed, the mixture was stirred at 60 ° C. for 15 minutes to be granulated. An organic peroxide and a silicone macromer were uniformly permeated and impregnated into the ethylene resin composition. The resulting adhesive ethylene-based resin composition was used with a screw diameter of 50 mm and the ratio of the screw length (L) to the screw diameter (D) (L /
D) has a diameter of 2.4 using a single screw extruder with L / D = 24.
On a copper core wire of mm, extrusion temperature 210 ° C, take-up speed 15m
/ Min, and a covered electric wire having an outer diameter of 7 mm was produced. Any of the covered electric wires could be produced appropriately. When the adhesive properties of the coated electric wires using the adhesive ethylene resin compositions of Comparative Example 1 and Examples 1 to 5 were evaluated, all had a good initial adhesive force of 1000 N or more.

The coated electric wire thus obtained was exposed and stored in water at 60 ° C. and taken out every week for up to 4 weeks, and the deterioration property of adhesiveness was evaluated. The evaluation results are shown in Table 2. The sample of Comparative Example 1 containing no silicone macromer had an adhesive force of 200 N after 1 week, and the adhesive force thereafter gradually decreased, but after 4 weeks. At 90 N, the deterioration of the adhesiveness with time was remarkably observed. On the other hand, the coated electric wires obtained from Examples 1 to 5 had the same decrease in the adhesive force in the first week as in Comparative Example 1, although the decrease in the adhesive force was larger than the subsequent decrease. Example 1 containing 1 part
In Example 5, the adhesive strength after 4 weeks was 230 N, and the silicone macromer 1 was blended in an amount of 0.2 parts by weight.
Then, the adhesive strength in the first week dropped to 640N, but
After that, it was confirmed that the degree of deterioration of the adhesive strength with time was significantly reduced, and that good adhesiveness was maintained even after 4 weeks.

[0054]

[Table 2]

[Examples 6 and 7] The same proportions as in Examples 3 and 4, except that the silicone macromer 1 was replaced by the silicone macromer 2 to produce an adhesive ethylene resin composition and a coated electric wire in the same manner, evaluated. Any of the coated electric wires could be produced appropriately. The evaluation results are shown in Table 3, and these adhesive ethylene resin compositions of the present invention have less adhesive deterioration over time than in Examples 1 to 5 and have excellent adhesiveness. It was

[0056]

[Table 3]

[0057]

As described in detail above, the adhesive ethylene-based resin composition of the present invention contains the ethylene-based resin (A).
Is a composition in which a specific amount of an organic peroxide having a hydroperoxy group (B) and a specific amount of a silicone macromer (C) are blended. With this structure, excellent initial adhesiveness and harsh conditions are provided. Even when exposed to, the deterioration of the adhesiveness with time is remarkably improved. At the same time, it is not necessary to treat the ethylene-based resin at a temperature higher than the decomposition temperature of the organic peroxide. Therefore, there is virtually no concern about the decomposition odor due to organic peroxides and the risk of crosslinking of ethylene-based resin, and the homogeneity and high quality of the ethylene-based resin are maintained while maintaining the excellent electrical properties, mechanical properties, and processability. An adhesive ethylene resin composition having improved deterioration over time is provided. In addition, the extruded product obtained from this is a covering layer for electric wires and cables that require adhesiveness, an insulating protective cover, a pipe, a film,
It can be suitably used for sheets and the like. Furthermore, the adhesive ethylene-based resin composition of the present invention has the processability, adhesiveness, and mechanical properties required for the coating layer of electric wires and cables, particularly the insulating layer of submarine optical fiber cables under severe processing and use conditions. It is possible to provide a coating layer with high quality that is filled and homogeneous, and an electric wire / cable and a submarine optical fiber cable having the coating layer formed of the coating layer have excellent performance such that the adhesive property is not deteriorated with time and the life is long.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/541 C08K 5/541 5G309 C08L 83/07 C08L 83/07 5G311 C09J 123/04 C09J 123/04 183 / 02 183/02 183/04 183/04 183/07 183/07 H01B 7/02 H01B 7/02 Z 7/14 7/14 11/00 11/00 L (72) Inventor Akinori Hayashi Yokohama City, Kanagawa Prefecture 1-17-2-102 Saito, Konan-ku (72) Inventor Yumi Oki 1-10-5-601 F-term, Kyomachi, Kawasaki-ku, Kanagawa Prefecture (reference) 4F070 AA13 AA59 AC52 AC56 FA03 FC05 GA01 GB07 GB09 GC05 4F071 AA15 AA81 AA88 AC08A AC16 AE02 AE02A AE22A AF58 AH12 AH19 BA01 BB06 BC01 4J002 BB021 BB051 BB061 BB071 BB081 BB212 CP033 CP123 EK016 EX017 EX037 FD070 FD200 GQ00 GQ01 404020503 03J0427 EK022 EK082 HB41 HD30 KA16 KA38 LA06 LA08 NA19 5G309 LA12 RA04 RA07 RA12 5G311 FA03

Claims (10)

[Claims] 1. An ethylene-based resin (A) comprising an organic peroxide (B) having a hydroperoxy group represented by the following formula (1) and a silicone macromer (C). Adhesive ethylene resin composition. R ¹ —O—O—H (1) (In the formula, R ¹ represents an alkyl group or a cycloalkyl group, and those alkyl groups represent a phenyl group, an alkylphenyl group, a cycloalkyl group, or an alkylcycloalkyl group. May be replaced with.) 2. The silicone macromer (C) is a silane coupling agent (c-1) represented by the following formula (2):
Alkylalkoxysilane (c-
2. The adhesive ethylene-based resin composition according to claim 1, which is a partially polycondensation product composed of 2) and a polyalkyl silicate (c-3) represented by the formula (4). _{^{X-Si (R 2) a}} (OR 3) b (2) ( wherein, X is an ethylenically unsaturated group, ^{R 2} is a carbon number 1
~ 3 alkyl group, R ³ represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 9 carbon atoms, a
Is 0 or 1, b is 3 or 2, and a + b = 3. _{^{) R 4 -Si (R 5)}} c (OR 6) d (3) ( wherein, ^{R 4} is an alkyl group having 4 to 10 carbon atoms, R
⁵ is an alkyl group having 1 to 3 carbon atoms, R ⁶ is 1 to 1 carbon atoms
Represents an alkyl group having 8 or an alkoxyalkyl group having 2 to 9 carbon atoms, c is 0 or 1, d is 3 or 2, and c + d = 3.
Is. ) Si _n O _n-1 (OR ⁷ ) _{2n + 2} (4) (In the formula, R ⁷ represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 9 carbon atoms, and n is 2 on average. It is ~ 10.) 3. The blending amount of the organic peroxide (B) having a hydroperoxy group and the silicone macromer (C) is
It is 0.005-2 weight part and 0.005-2 weight part, respectively with respect to 100 weight part of ethylene resin (A), The adhesive ethylene resin of Claim 1 or 2 characterized by the above-mentioned. Composition. 4. An organic peroxide (B) having a hydroperoxy group has a decomposition temperature of 170 to obtain a half-life of 1 minute.
The adhesive ethylene resin composition according to any one of claims 1 to 3, which has a temperature of not less than ° C. 5. The silicone macromer (C) comprises 0.01 to 5 moles of alkylalkoxysilane (c-2) per mole of silane coupling agent (c-1).
And polyalkyl silicate (c-3) 0.05-2
The adhesive ethylene-based resin composition according to any one of claims 1 to 4, which is a partial polycondensation product with 5 mol (calculated as silicon atom). 6. The ethylene-based resin (A), the organic peroxide (B) having a hydroperoxy group, and the silicone macromer (C) in a closed container at room temperature or above and below the melting temperature of the ethylene-based resin (A). 6. The organic peroxide (B) having a hydroperoxy group and the silicone macromer (C) are permeated and impregnated into the ethylene-based resin (A) by mixing at the temperature of 1. A method for producing an adhesive ethylene-based resin composition as described in 1. 7. An ethylene-based resin (A), an organic peroxide (B) having a hydroperoxy group, and a silicone macromer (C) having a hydroperoxy group at a melting temperature of the ethylene-based resin (A) or more. The adhesive ethylene-based resin composition according to any one of claims 1 to 5, which is melted and kneaded at a temperature lower than the decomposition temperature for obtaining the one-minute half-life of the organic peroxide (B). Manufacturing method. 8. An extrusion-molded article obtained by extrusion-molding the adhesive ethylene resin composition according to any one of claims 1 to 5. 9. An electric wire / cable having a coating layer obtained by extrusion-molding the adhesive ethylene resin composition according to any one of claims 1 to 5. 10. A submarine optical fiber cable having an insulating layer obtained by extrusion-molding the adhesive ethylene resin composition according to any one of claims 1 to 5.