JPH0635523B2 - Modified ethylene copolymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a modified product of (A) a copolymer containing ethylene as a main component and a polar group-containing monomer (monomer), and (B)
Carbon black, inorganic material having Si-O bond, Si-
It relates to a composition comprising at least two inorganic fillers selected from the group consisting of inorganic substances having no O-bond. More specifically, (A) (1) an ethylene copolymer containing ethylene as a main component and a (meth) acrylate unit and an unsaturated carboxylic acid unit and / or its half ester unit (2) at least one double bond Modified ethylene copolymer modified with an unsaturated amine or unsaturated alcohol having (B) carbon black and (C) Si-
TECHNICAL FIELD The present invention relates to a modified ethylene copolymer composition comprising at least one inorganic filler selected from the group consisting of an inorganic substance having an O bond and an inorganic substance not having a Si—O bond (however, carbon black is not included). It is an object of the present invention to provide a rubber-like composition having not only excellent mechanical strength (for example, tensile strength) but also various physical properties such as weather resistance, abrasion resistance and heat resistance. It is a thing.

2. Description of the Related Art At present, rubber having excellent physical properties such as heat resistance and oil resistance is required in the fields of automobile parts, industrial parts, coating of electric wires, electric equipment parts and electronic equipment parts. As a rubber mainly composed of ethylene having excellent physical properties, a copolymer with an acrylic ester which is a monomer having a polar group has been industrially produced and used in various fields. And various physical properties are well known (for example, Japanese Examined Patent Publication Nos. 50-6348 and 55-5527, JP-A-58-1).
No. 11814, No. 58-196217). Since the cross-linking site of this rubber is a carboxyl group, diamine cross-linking and ionic cross-linking are possible. However, in order to exhibit the heat resistance which is a characteristic of this rubber, it is necessary to carry out crosslinking with di (poly) amine, but an uncrosslinked rubber mixture obtained by kneading this rubber with di (poly) amine is even at room temperature. Also has poor storage stability because it easily reacts. In addition, there are drawbacks such as being likely to cause scorch during the crosslinking operation.
This means that when an inorganic filler such as carbon black which is generally used in the rubber industry is blended in order to improve the tensile strength, mechanical properties such as modulus, abrasion resistance and the like of this rubber, the above-mentioned drawbacks are caused. Increase. From these, even if vulcanized using sulfur or sulfur or a sulfur donor widely used in the rubber industry, there is no such drawback as described above, and further heat resistance, oil resistance,
As a copolymer rubber containing ethylene as a main component, which has excellent physical properties such as weather resistance, and a monomer having a polar group, some of the inventors of the present invention have ethylene as a main component, a (meth) acrylate unit and an unsaturated albon. A modified ethylene copolymer rubber prepared by modifying an ethylene copolymer comprising an acid anhydride unit with an unsaturated amine or unsaturated alcohol having at least one double bond has been proposed (Japanese Patent Laid-Open No. 59-100351). However, this modified ethylene copolymer rubber has a problem (defect) that the physical properties such as tensile strength, abrasion resistance, weather resistance and modulus are not always sufficient.

Problems to be Solved by the Invention From the above, the present invention does not have these drawbacks (problems) and is not only good in heat resistance, oil resistance and weather resistance, but also in tensile strength, wear resistance, and modulus. Such as ethylene as a main component having excellent characteristics, a composition of an ethylene copolymer or a modified product of the copolymer with a monomer having a polar group, and having these characteristics, sulfur or The purpose is to obtain a composition that is vulcanizable with a sulfur donor.

Means and Action for Solving Problems According to the present invention, these problems are (A) (1) a monomer unit represented by the following formula (I), a monomer unit represented by the formula (II) and ( It comprises a monomer unit represented by the formula (III) and / or a monomer unit represented by the formula (IV), and the copolymerization ratio of the monomer unit represented by the formula (II) is 8 to 45 mol%. The copolymerization ratio of the monomer unit represented by the formula (4) and / or the monomer unit represented by the formula (IV) is 0.05 to 5.0 as the total amount thereof.
Mol% ethylene copolymer (2) 100 parts by weight of a modified ethylene copolymer modified with an unsaturated amine or unsaturated alcohol having at least one double bond, (B)
At least one inorganic selected from the group consisting of 5 to 150 parts by weight of carbon black and (C) an inorganic substance having a Si-O bond and an inorganic substance having no Si-O bond (however, carbon black is not included). The present invention will be specifically described below, which can be solved by a modified ethylene copolymer composition containing 10 to 200 parts by weight of a filler as a total amount of carbon black (B).

(A) Copolymer The copolymer used in the present invention is a monomer unit represented by the following formula (I), a monomer unit represented by the formula (II) and a monomer unit represented by the formula (III) and / or (IV ) A copolymer composed of monomer units represented by the formula.

That is, this copolymer has a monomer unit represented by the formula (I), a monomer unit represented by the formula (II) and (III)
A copolymer comprising a monomer unit represented by the formula [hereinafter referred to as "copolymer (A)"], a monomer unit represented by the formula (I), a monomer unit represented by the formula (II) and a formula (IV) A copolymer comprising a monomer unit represented by the formula [hereinafter referred to as "copolymer (B)"], a monomer unit represented by the formula (I), a monomer unit represented by the formula (II), a formula (III) It is any one of a copolymer comprising a monomer unit and a monomer unit represented by the formula (IV) [hereinafter referred to as "copolymer (C)"]. In producing the modified product of the present invention, these copolymers may be used alone or as a mixture of two or more kinds.

(1) Copolymer (A) This copolymer (A) is obtained by copolymerizing ethylene, an alkyl (meth) acrylate and maleic anhydride, and its production method is described in Japanese Patent Application No.
59-100391. The copolymerization ratio of the monomer unit represented by the formula (II) in this copolymer is 8 to 45 mol%, preferably 10 to 45 mol%,
10-40 mol% is preferred. Occupy in this copolymer (I
The copolymerization ratio of the monomer unit represented by the formula I) is 8% by weight.
When it is less than 1, the resulting modified ethylene copolymer loses rubber elasticity, and permanent elongation and compression set become large, which is not preferable. On the other hand, when it exceeds 45 mol%, the low temperature brittleness of the obtained modified ethylene copolymer becomes large, which is not desirable. Further, the copolymerization ratio of the monomer unit represented by the formula (III) is 0.05 to 5.0 mol%, preferably 0.05 to 4.0 mol%, and particularly preferably 0.1 to 4.0 mol%. When the copolymerization ratio of the monomer unit represented by the formula (III) in this copolymer is less than 0.05 mol%, the maleic anhydride group in the copolymer and the dicarboxylic acid and / or half ester group described later are all included in the copolymer. To a compound having an unsaturated group,
Even with sufficient sulfur vulcanization, a modified ethylene copolymer having desired rubber elasticity and heat resistance cannot be obtained. On the other hand, 5.0
If it exceeds mol%, not only the flexibility of the modified olefin copolymer to be obtained is impaired but also it is not preferable to obtain the desired rubber property. Therefore, the copolymerization ratio of the monomer unit represented by the formula (I) is 50 to 91.5 mol%,
89 mol% is preferable, and 60 to 88 mol% is particularly preferable.

The melt index of the copolymer (measured according to JIS K-7210 at a temperature of 190 ° C. and a load of 2.16 Kg, hereinafter referred to as “MI”) is generally 0.01 to 1000 g / 10 minutes, 0.1 ~ 500g / 10min is desirable, especially 0.1 ~ 3
00g / 10 minutes is the best. When an ethylene copolymer with an MI of less than 0.01 g / 10 minutes is used, the modified ethylene copolymer finally obtained is mixed uniformly with an inorganic filler such as carbon black and other additives. Not only is it difficult to produce, but the moldability is also poor.

(2) Copolymer (B) and copolymer (C) To produce the copolymer (B) and copolymer (C) of the present invention, the above copolymer (A) is treated with water and / or By reacting with an alcohol, hydrolysis and / or half-esterification reaction occurs to cause all or part of the monomer unit (maleic anhydride group) represented by the formula (III) of the copolymer (A) ( IV) a monomer unit represented by the formula (ie,
Modification to a dicarboxylic acid or half-esterification) gives the copolymer (B) or the copolymer (C).

(a) Hydrolysis To produce the copolymer (B) or the copolymer (C) by hydrolysis, the copolymer (A) is dissolved in an organic solvent (for example, toluene) in which the copolymer is dissolved. With water in the presence of a catalyst (eg, a tertiary amine) at a temperature of 80-100 ° C for 0.5-10 hours (preferably 2-6 hours, preferably 3-6 hours).
It can be obtained by reacting and then neutralizing with an acid.

(b) Half-esterification In order to produce the copolymer (B) or the copolymer (C) by half-esterification, the copolymer (A) can be obtained by a solution method or a kneading method described below.

The solution method is similar to the case of hydrolysis in the presence or absence of the above catalyst in an organic solvent (the reaction is slow in the absence)
The reflux temperature of the alcohol used in 2 minutes to 5 hours (desirably 2 minutes to 2 hours, preferably 15 minutes to 1)
Time) is a method of reacting.

On the other hand, the kneading method is usually based on 100 parts by weight of the copolymer (A).
0.01 to 1.0 parts by weight (preferably 0.05 to 0.5 parts by weight) of the tertiary amine and the monomer unit represented by the formula (III) in the copolymer are generally 0.1 to 3.0 times by mole (desirably, 1.0-2.0 times mole) saturated alcohol copolymer
(A) above the melting point, but below the boiling point of the alcohol used, using a kneading machine such as a Banbury mixer, kneader, extruder ordinarily used in the field of rubber and synthetic resins, a few minutes to several tens of minutes. Minutes (desirably,
This is a method of reacting while kneading.

The saturated alcohol used in the above half esterification is a linear or branched saturated alcohol having 1 to 12 carbon atoms, and examples thereof include methyl alcohol, ethyl alcohol and primary butyl alcohol.

In the case of the above hydrolysis, even in the case of the half-esterification reaction, the conversion rate to the dicarboxylic acid and the half-esterification rate are both 0.5 to 100%, preferably 1 to 100%, and 10 to 100% is It is suitable.

(B) Production of Copolymer (B) and Copolymer (C) by Copolymerization Method Also, copolymer (B) and copolymer (C) by this method
To produce a monomer unit represented by formula (I),
By copolymerizing a monomer unit represented by the formula (II), a monomer unit represented by the formula (III) and a monomer corresponding to the monomer unit represented by the formula (IV) under the polymerization conditions for producing the ethylene copolymer. Manufactured.

That is, it is obtained by copolymerizing four components of ethylene, alkyl (meth) acrylate, maleic anhydride and maleic acid ester.

Occupy in the obtained copolymer (B) and copolymer (C) (I
The copolymerization ratio of the monomer unit represented by the formula (I) is 8 to 45 mol% for the same reason as described above (the same applies to the preferred range and the preferred range), and the monomer unit represented by the formula (III) and ( For the same reason as above, the copolymerization ratio of the monomer units represented by the formula IV) is 0.05 to 0.05% as their total amount.
It is 5.0 mol%.

(C) Production of modified ethylene copolymer Any one of the above-mentioned copolymer (A), copolymer (B) and copolymer (C), or a mixture thereof may be used as an unsaturated amine or unsaturated alcohol described below. The modified ethylene copolymer of the present invention can be produced by modifying with.

(1) Unsaturated amine The unsaturated amine used has at least one double bond, and primary or secondary amines are preferably used. That is, the general formula is shown by the following formula.

In the formula, R and R ′ are hydrogen atoms or hydrocarbon groups having at least one double bond, but cannot be hydrogen atoms at the same time.

In the above general formula, those having at most 30 carbon atoms are preferable, and those having 1 to 20 carbon atoms are particularly preferable. Further, those which are liquid or solid at room temperature or the reaction temperature described later are desirable.

As typical examples of the unsaturated amine, 1-amino-9-nonadecene, 1-amino-9-octadecene, 1-amino-7-hexadecene, 1-amino-5-pentadecene,
1-amino-4-tetradecene, 1-amino-4-tridecene, 1-amino-3-dodecene, 1-amino-2-
Decene, 1-amino-2-octene and 1-amino-
2-hexene can be mentioned.

(2) Unsaturated Alcohol The unsaturated alcohol used in the present invention has at least one double bond and is preferably liquid or solid at room temperature to the reaction temperature described later. Also, it is desirable that the number of carbon atoms is at most 30,
The number of 1 to 25 is preferable. Further, an aliphatic or aromatic compound having one hydroxy group is preferable.

Typical examples of the unsaturated alcohol include 1-hydroxy-9-octadecene, 1-hydroxy-7-heptadecene, 1-hydroxy-5-tetradecene, 1-hydroxy-5-dodecene, 1-hydroxy-3-octene and They include unsaturated aliphatic alcohols such as acrylic alcohol and unsaturated aromatic alcohols (or phenols) such as para-vinylphenol, vinylhydroxybiphenyl and vinylnaphthol.

(3) Ratio of use The ratio of unsaturated amine and unsaturated alcohol to the total amount (sum) of the monomer units represented by the formula (III) and the monomer unit represented by the formula (IV) of the ethylene copolymer is the total amount. As 0.2 to 2.0 times mol, 0.2
The molar ratio is preferably 1.5 to 1.5 times, more preferably 0.2 to 1.0 times. If the total amount of the unsaturated amine and the unsaturated alcohol to the total amount (sum) of the monomer unit represented by the formula (III) and the monomer unit represented by the formula (IV) of the ethylene copolymer is less than 0.2 times mol However, it is not possible to obtain a modified ethylene copolymer having a desired modifying effect. On the other hand, if it exceeds 2.0 times by mole, unreacted unsaturated amine and modified alcohol remain in the modified ethylene copolymer, causing odor and bleeding, which is not preferable.

(4) Modification Method The modified ethylene copolymer of the present invention is produced, for example, as follows.

That is, as described above, the ethylene copolymer having a specific constitution and the unsaturated amine and / or the unsaturated alcohol are dissolved in a solvent, or without being dissolved in the solvent, a kneader such as a Banbury or a vent type uniaxial or twin screw. Obtained by kneading using an axial extruder for 3 to 20 minutes (preferably 3 to 15 minutes) at a temperature not lower than the melting point of the ethylene copolymer but not thermally decomposed (that is, 120 to 300 ° C). To be In addition, when modifying with an unsaturated alcohol, it is desirable to add a small amount of catalyst (for example, a tertiary amine).

The MI of the modified ethylene-based copolymer obtained as described above
Is usually 0.01 to 1000 g / 10 minutes, preferably 0.05 to 500 g / 10 minutes, particularly preferably 0.1 to 300 g / 10 minutes. MI of this modified ethylene copolymer is 0.01 g
When it is less than / 10 minutes, when it is blended with an inorganic filler such as carbon black described later and other additives, not only the kneading property is bad but also the moldability is not good.

(D) Carbon Black Furthermore, the carbon black used as the inorganic filler in the present invention generally has a non-surface area of ²⁰ to 1800 m ² / g and a fine pore volume measured by the low temperature nitrogen adsorption method and the BET method. 1.5-4.0cc / g measured by mercury porosimetry in the range of pore radius 30 ~ 7500Å, especially the specific surface area
Those of 600 to 1200 m ² / g are effective.

Examples of the carbon black include channel black, thermal black, acetylene black, and carbon black produced by the furnace black method. About these carbon blacks, "Carbon Black Handbook" edited by the Carbon Black Association (book publisher, published in 1972), "Handbook edited by Rubber Digest",
Its production method and physical properties are well known from "Rubber / Plastic Compounded Chemicals" (Rubber Digest, published in 1974), "Synthetic Rubber Handbook", etc. Among these carbon blacks, conductive Carbon black and acetylene black obtained by the acetylene method (generally, the specific surface area is
600 to 1200 m ² / g) is not suitable because it has high conductivity and high modulus. In addition, channel black obtained by the channel method (generally, a specific surface area of 50-12
00 m ² / g) is used for a special purpose, but it is not suitable as the carbon black used in the present invention because of its acidic pH. On the other hand, thermal method, thermal black obtained by furnace method and furnace black are reinforcing properties for chlorinated polyethylene,
Since it has flexibility, abrasion resistance, heat resistance, oil resistance and alcal resistance (as pH), it is suitable for the reason that high characteristics can be imparted with a relatively small amount of compounding.

(E) Inorganic substance having Si-O bond Further, the content of SIO _{2 in} the inorganic substance having a Si-O bond used in the present invention is usually at least 10% by weight, preferably 30% by weight or more, particularly 50% by weight or more. Weight% or more is suitable. Further, the content of H ₂ O is usually 1.0 to 20% by weight, preferably 1.0 to 15% by weight, and particularly 1.5 to 15% by weight.
Is preferred. Further, the particle size of the inorganic material is generally 10
Millimicron to 30 micron, especially 10 millimicron to 25 micron are preferred, and especially inorganic material having a particle size of 15 millimicron to 25 micron is suitable.

Typical examples of the inorganic material having a Si-O bond are wet-process white carbon, calcium silicate, colloidal silica, and synthetic silicate-based white carbon containing some oxides of calcium, aluminum, sodium, iron, etc. Ultrafine magnesium silicate, aluminum silicate (clay), talc, nepheline syenite, mica powder, silica stone powder, diatomaceous earth, silica sand and the like. Regarding these inorganic substances having Si-O bonds, their production methods are described in "Handbook Rubber / Plastic Blended Chemicals" edited by Rubber Digest Co. (Rubber Digest Co., 1974), pages 221 to 253, etc. The physical properties and trade names are well known and well known.

(F) Inorganic substance having no Si-O bond Further, the inorganic substance having no Si-O bond (not including carbon black) used in the present invention is generally a filler in the rubber industry and the synthetic resin industry, It is widely used as a reinforcing agent. Typical examples are light calcium carbonate, heavy calcium carbonate,
Examples thereof include barium sulfate, graphite, carbon fiber, aluminum hydroxide (alumina hydrate), magnesium hydroxide and alumina. Among these inorganic fillers containing no Si-O bond, the particle size of the powdery material is generally 10 microns to 7 microns, preferably 20 microns to 6 microns. The fibrous material usually has a diameter of 2 to 25 μm (preferably 2 to 15 μm) and a length of 5 μm to 10 mm (preferably 5 μm to 6 mm). These inorganic fillers are well known from "Handbook, Rubber / Plastic Blended Chemicals" and the like which will be described later.

The composition of the present invention is prepared by blending at least one inorganic filler selected from carbon black, an inorganic substance having a Si—O bond and an inorganic substance having no Si—O bond to the modified ethylene copolymer. The thing is obtained.

(G) Mixing ratio The mixing ratio (mixing ratio) of carbon black to 100 parts by weight of the modified ethylene copolymer is 5 to 150 parts by weight, preferably 10 to 150 parts by weight, and particularly preferably 10 to 120 parts by weight. is there. When the mixing ratio of carbon black is less than 5 parts by weight, the resulting composition has poor tensile strength, heat resistance and abrasion resistance. On the other hand, when it exceeds 150 parts by weight, the flexibility of the composition is not good.

Further, the blending ratio (mixing ratio) of the inorganic filler with respect to 100 parts by weight of the modified ethylene copolymer is 10 to 200 parts by weight in total with the carbon black, preferably 10 to 120 parts by weight, particularly 10 to 100 parts by weight. Parts are preferred. If the mixing ratio of the total amount is less than 10 parts by weight, the compounding effect is poor, that is, the obtained composition has insufficient tensile strength, heat resistance, wear resistance, modulus and the like.

On the other hand, if the amount exceeds 200 parts by weight, the flexibility of the composition decreases,
Moldability is not good.

(H) Mixing method, vulcanization method, molding method, etc. Although the composition (mixture) of the present invention can be obtained by uniformly blending the above substances, a filler which is generally used in the rubber industry, Sulfur, sulfur donors, vulcanization accelerators, vulcanization accelerator assistants, organic peroxides, crosslinking assistants, plasticizers, oxygen, ozone, heat and light (ultraviolet rays)
Additives such as stabilizers, lubricants and colorants may be added depending on the intended use of the composition.

In order to obtain the composition of the present invention, it is possible to apply the mixing which is commonly used in the rubber industry. In making this composition, it is important that the modified ethylene copolymer does not inherently vulcanize or crosslink. For this reason, mixing is generally carried out at room temperature to 100 ° C.

The composition thus obtained is formed into a desired shape using an extrusion molding machine, an injection molding machine, a compression molding machine, a transfer molding machine or the like which is generally used in the general rubber industry.

In the case of vulcanization or crosslinking, the vulcanization or crosslinking is usually heated to a temperature range of 100 to 200 ° C during molding, or by a steam can, an air bath or the like. The vulcanization or crosslinking time depends on the vulcanization or crosslinking temperature,
Generally, it is 0.5 to 120 minutes.

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples.

In the examples and comparative examples, a JIS hardness tester (Shore A) was used for the hardness test, JIS No. 3 dumbbells were manufactured in accordance with JIS K6301, and three dumbbells were superposed and measured. did. In addition, tensile strength (hereinafter "T
_B "and referred to) and elongation (hereinafter referred to as" E _B ") is JIS
It measured using the Shopper type tester according to K6301.
Furthermore, the heat resistance test was left at a temperature of 200 ° C for 70 hours,
The residual tensile elongation (elongation) was measured according to JIS K6301. In addition, the wear resistance test was performed using an AKRON type wear tester under the conditions of a load of 3 Kg and a rotation speed of 1000 times.
The measurement of c) was performed. The content of maleic anhydride was determined by nuclear magnetic resonance and infrared absorption spectroscopy. In addition, the reaction rate of unsaturated amine or unsaturated alcohol was calculated by extracting the modified ethylene copolymer with Soxhlet in a non-solvent and quantifying the unreacted amount in the extract by gas chromatographic analysis. Similarly, the modified ethylene-based copolymer was extracted with a non-solvent [mixture of carbon tetrachloride and methyl alcohol (volume ratio 6: 4)] using Soxhlet, and the unreacted unsaturated amine in the extract was extracted. Alternatively, the reaction rate was calculated by determining the iodine value of unsaturated alcohol.

[Hydrolysis of ethylene copolymer (1)] A terpolymer consisting of 79 mol% of ethylene, 18.5 mol% of methyl acrylate and 1.5 mol% of maleic anhydride [MI 220 g / 10 min, hereinafter "copolymer" 20g of the compound (1) "was dissolved in 200 ml of toluene. 100 in this solution
3 ml of water and 3 times mol% of triethylamine based on the maleic anhydride portion of the copolymer were added, and heating (hydrolysis) was carried out at a temperature of 80 ° C. for 5 hours while stirring. Then, hydrochloric acid was added for neutralization, and hydrochloric acid was added until it became weakly acidic, and the mixture was allowed to stand overnight. Then, hexane was added as a precipitation solvent to precipitate the polymer, and the hexane was exchanged several times to wash the polymer. Then, the polymer was vacuum dried at 40 ° C. for one day. The hydrolysis rate was calculated from the decrease in absorption due to the acid anhydride at 1760 cm ⁻¹ by infrared absorption spectrum measurement (the same applies hereinafter). The hydrolysis rate was 100%.

[Modification of unsaturated amine or unsaturated alcohol]

0.5 times mole of oleylamine was added to the dicarboxylic acid group in the hydrolyzate of the copolymer (1) obtained as described above, and the oleylamine was added at 4 ° C. at 120 ° C. with a Labo Plastomill.
The reaction was carried out while kneading for 20 minutes each under the condition of 0 revolutions / minute. The obtained reaction product [hereinafter referred to as "reaction product"
(a) ”] had 84% of the theoretical value of oleylamine reacted.

Also, instead of the oleylamine used above,
The reaction was carried out while kneading under the same conditions as the reaction product (a) except that 1.0 times mol of oleyl alcohol was used with respect to the dicarboxylic acid group in the hydrolyzate of the copolymer (1). The obtained reaction product [hereinafter referred to as "reaction product (b)"]
Had reacted 76% of theory with oleyl alcohol.

[Half-esterification of Copolymer (2)] A terpolymer consisting of 72.2 mol% ethylene, 26.8 mol% methyl acrylate and 1.0 mol% maleic anhydride [MI 9.1 g / 10 min. Polymer (2) "] was dissolved in 200 ml of toluene, 100 ml of methyl alcohol and 1 ml of triethylamine were added, and the reaction was carried out for 6 hours under the reflux condition of methyl alcohol.
Then, washing and drying were performed in the same manner as the hydrolysis of the ethylene copolymer (1). The half-esterification rate was 60% from the measurement of infrared absorption spectrum analysis as described above.
Met.

[Modification of unsaturated amine or unsaturated alcohol]

The half-esterified product of the copolymer (2) thus obtained was modified with oleylamine or oleyl alcohol in the same manner as in the case of the reaction product (a) or the reaction product (b). The reaction rates of the obtained reaction products [hereinafter referred to as "reactant (c)" and "reactant (d)" with respect to the theoretical values were 85% and 78%, respectively.

As in the case of the reaction product (a), instead of the copolymer (1) used in the above, a copolymer (MI 250 g / 10 min) consisting of 90 mol% and 10 mol% of methyl methacrylate was used. The reaction was carried out by adding oleylamine to the mixture [This copolymer does not have a maleic anhydride group and therefore does not undergo a hydrolysis reaction, and of course, does not react with oleylamine. The obtained polymer is referred to as "reaction product (e)".
]].

In place of the copolymer (2) used in the above, a copolymer (MI 9.4 g / 10 minutes) consisting of 74 mol% and 26 mol% of methyl methacrylate was used as a reactant (c). The reaction was carried out by adding oleylamine in the same manner as in the case [1] [The hydrolysis reaction is not carried out for the same reason as the above reaction product (e). Of course, it does not react with oleylamine. The obtained polymer is referred to as "reactant (f)"].

79 mol% instead of the copolymer (1) used above
Ethylene, 11 mol% methyl methacrylate and 10
Copolymer consisting of mol% maleic anhydride (MI 300
g / 10 min), hydrolysis, neutralization, washing and drying were carried out in the same manner as described above. The hydrolysis rate was 100%. Oleylamine was added to the obtained hydrolyzate under the same conditions as in the case of the reaction product (a) to carry out a reaction. As a result, 80% of theory of oleylamine was reacted [the obtained reaction product is referred to as "reactant (g)"].

Instead of the copolymer (1) used above, a copolymer consisting of 96.7 mol% ethylene, 1.0 mol% methyl methacrylate and 2.3 mol% maleic anhydride (MI
Hydrolysis, neutralization, washing and drying were carried out in the same manner as described above except that 6.7 g / 10 min) was used. Hydrolysis rate is 10
It was 0%. Oleylamine was added to the obtained hydrolyzate under the same conditions as in the case of the reaction product (a) to carry out a reaction.
As a result, 80% of theory of oleylamine was reacted [the obtained reaction product is referred to as "reactant (h)"].

Also, as carbon black, carbon black manufactured by the furnace method (manufactured by Showa Cabot Co., trade name Show Black FEF, average particle size 51 mm, specific surface area 4
1 m ² / g, FEF, hereinafter referred to as “CB-1”) and carbon black produced by the same method (Asahi Carbon Co., Ltd., trade name Asahi Thermal, average particle size 118 mm, specific surface area 19 m
² / g, SRF, hereinafter referred to as "CB-2").
Furthermore, as an inorganic substance having a Si-O bond, ultrafine magnesium silicate (density 2.75 g / cm ³ , specific surface area 20 m
² / g, particle size 0.32 to 6 microns, SiO ₂ content 62.5% by weight, NgO content 30.6% by weight, Fe ₂ O ₃ content 1.0% by weight, H ₂ O content 4.99% by weight, hereinafter referred to as “MgO · SiO ₂ ”) was used. In addition, calcium carbonate (average particle size 1.7 μm, hereinafter referred to as “CaCO ₃ ”) was used as an inorganic substance having no Si—O bond. Further, n-butyl-bis (tertiary-butylperoxy) valerate (hereinafter referred to as "V") is used as the organic peroxide, and isocyanurate (hereinafter referred to as "TAIC") is used as a crosslinking assistant. used. Further, sulfur powder (200 mesh pass, hereinafter referred to as "S") is used as a vulcanizing agent, and as a vulcanization accelerator,
Tetramethyl monosulfide (hereinafter referred to as "TS"),
Use of tetramethylthiuram disulfide (hereinafter referred to as "TT"), 2-mercaptobenzothiazole (hereinafter referred to as "M"), tetrabutylthiuram disulfide (hereinafter referred to as "TBT"), and further vulcanization acceleration Stearic acid (hereinafter referred to as "St") and zinc oxide (hereinafter referred to as "ZnO") were used as agents, and 4,4'-as the sulfur donor.
Dithiosimorpholine (hereinafter referred to as "R") and poly (2,2,4-trimethyl-1,2-dihydroquinoline) (hereinafter referred to as "224") were used as an antioxidant.

The reactants (a) to (h) (each type is first
(Shown in the table) 5.0 parts by weight Zn for every 100 parts by weight
A sheet was produced by thoroughly kneading O and 0.5 parts by weight of 224 and the respective mixed components whose respective mixing ratios are shown in Table 1 at room temperature for 20 minutes using an open roll. Each sheet formed in this way has a temperature of 160
A sheet was prepared by pressing for 30 minutes under conditions of ° C and pressure of 200 kg / cm ² (Geese pressure). T of each obtained sheet
_B (tensile strength), E _B (tensile elongation), hardness test (Shore A) and heat resistance test (elongation rate) were measured. Further, a sheet was prepared by pressing for 40 minutes under the above temperature and pressure conditions. A sample of the abrasion resistance test of each of the obtained sheets was prepared and the abrasion resistance test was performed. The results obtained are shown in Table 2.

Effect of the Invention The modified ethylene copolymer composition obtained by the present invention is also capable of being subjected to sulfur vulcanization and cross-linking with an organic peroxide, which are widely used in the general rubber industry. Also,
The vulcanized products and crosslinked products obtained also have the following effects.

(1) Good heat resistance.

(2) Excellent solvent resistance, weather resistance, UV resistance and ozone resistance.

(3) Good low temperature characteristics.

(4) It has excellent rubber-like properties (for example, tensile strength and elongation) and hardness.

(5) Good wear resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Iwashita Oita City, Oita Prefecture, Nakano 2 Showa Denko Co., Ltd. Oita Research Institute (72) Inventor Hitoshi Funada, Oita City, Oita Prefecture 2 Showa Denko Co., Ltd. Oita Research Center (56) Reference JP-A-60-15409 (JP, A) JP-A-62-121746 (JP, A) JP-A-62-124140 (JP, A) JP-A-62-124141 (JP, A) JP 62-121747 (JP, A) JP 62-121748 (JP, A) JP 58-53932 (JP, A)

Claims (1)

[Claims] (A) (1) A monomer unit represented by the following formula (I), a monomer unit represented by the formula (II) and (III)
A monomer unit represented by the formula (III) and / or a monomer unit represented by the formula (IV), wherein the copolymerization ratio of the monomer unit represented by the formula (II) is 8 to 45 mol%. The copolymerization ratio of the unit and the monomer unit represented by the formula (IV) is 0.05 to 5.
0 mol% ethylene copolymer (2) 100 parts by weight of a modified ethylene copolymer modified with an unsaturated amine or unsaturated alcohol having at least one double bond, (B) 5 to 150 parts by weight of carbon black, and (C) Si-O bond The total amount of at least one inorganic filler selected from the group consisting of an inorganic substance having a hydrogen atom and an inorganic substance having no Si—O bond (however, carbon black is not included) with carbon black (B) is 10 to A modified ethylene copolymer composition comprising 200 parts by weight.