KR0155084B1 - RUBBER COMPOSITION CONTAINING Ñß-OLEFIN COPOLYMER - Google Patents

Abstract

According to the present invention, it is composed of a monomer unit derived from a higher α-olefin having 6 to 20 carbon atoms, an aromatic ring-containing vinyl monomer represented by the following formula [I], and a nonconjugated diene represented by the following formula [II],

(i) the molar ratio between the higher α-olefins and the aromatic ring-containing vinyl monomer is 95/5 to 30/70,

(ii) [A] higher α-olefin copolymers and [B] higher α-olefin copolymers characterized by an intrinsic viscosity [η] of 0.1 to 10 dl / g, measured in decalin at 135 ° C. Provided is a rubber composition comprising a.

Wherein n is an integer of 0 to 5, R ¹ , R ² , R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

Wherein n is an integer of 1 to 5, R ⁴ is an alkyl group of 1 to 4 carbon atoms, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group of 1 to 8 carbon atoms.

Provided that both R ⁵ and R ⁶ are not hydrogen atoms.

Description

Rubber composition containing higher α-olefin copolymer

1 is a flowchart showing the processes of the method for producing the olefin polymerization catalyst used in the preparation of the higher α-olefin copolymer of the rubber composition of the present invention.

The present invention relates to a rubber composition comprising the novel higher α-olefin copolymer. In particular, the present invention is excellent in compatibility with the aromatic ring-containing polymers such as styrene / butadiene rubber (SBR) as well as processability, covalent vulcanization ability as well as dynamic fatigue resistance (flexible fatigue resistance), weather resistance, ozone resistance, heat aging resistance and low temperature characteristics The present invention relates to a rubber composition containing a higher α-olefin copolymer which can be used in various rubber products, resin modified products, and the like.

Diene rubbers such as natural rubber, isoprene rubber, SBR and BR are widely used in tires, automobile parts, and industrial parts. This is because the workability and the strength are excellent. In addition, natural rubber has excellent dynamic fatigue resistance.

However, diene rubber has a short lifespan because of low weatherability and ozone resistance, and in particular, natural rubber has low heat resistance and ozone resistance.

As a rubber material for automobile tire floors, diene rubber, such as a mixture of styrene / butadiene copolymer rubber, has generally been used. However, tire floors made of styrene / butadiene copolymer rubber have relatively good braking performance on wet road surfaces (wet skids) but have low resilience at 50-70 ° C., resulting in high rotational resistance and low wear resistance. To cope with this problem, a mixture obtained by mixing 100 parts by weight of styrene / butadiene copolymer rubber with 10 to 50 parts by weight of polybutadiene rubber has been used.

In recent years, with the demand for energy saving, a significant reduction in fuel cost and high abrasion resistance has been required, and in addition, in view of damping performance or safety on wet road surfaces. However, conventional styrene / butadiene copolymer rubber and polybutadiene rubber mixtures have insufficient braking performance.

In order to improve this, a mixture of butyl halide rubber and polybutadiene rubber has been proposed, but braking performance, abrasion resistance and rotation resistance are still insufficient.

Therefore, there is also a desire for the appearance of rubber compositions for tire floors which are particularly excellent in braking performance and abrasion resistance on wet road surfaces, and in which rotation resistance can be greatly reduced.

In contrast to the diene rubber, ethylene / propylene / diene (EPDM) copolymers are used in rubber products, rubber fabrics and polypropylene for automotive industry parts, industrial rubber products, electrical insulation materials, civil engineering and building materials due to their high heat resistance and ozone resistance. It is widely used for plastic mixture materials for polystyrene and polystyrene.

However, EPDM copolymers have low dynamic fatigue resistance and are therefore not used for any special application, for example, rubber dustproof materials, rubber rolls, belts, tires, vibration coatings.

Regarding copolymers of higher α-olefins with non-conjugated dienes, US Pat. Nos. 3,933,769, 4,064,335 and 4,340,705 disclose copolymers of higher α-olefins, methyl-1,4-hexadiene and α, ω-dienes. Is disclosed.

Methyl-1,4-hexadiene is a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and these monomers have different reaction rates. Therefore, when performing the continuous polymerization, it is difficult to recover the monomers for reuse. In addition, 4-methyl-1,4-hexadiene has a problem of low monomer conversion and poor polymerization efficiency because copolymerization reactivity with higher α-olefin is different from 5-methyl-1,4-hexadiene. In addition, the use of α, ω-diene sometimes results in gel formation in the final copolymer, which adversely affects the physical properties of the final product. The process for preparing the higher α-olefin copolymers disclosed in the specifications introduced above uses a titanium trichloride catalyst or a catalyst made from titanium tetrachloride and organoaluminum. Therefore, there is a disadvantage in that the production cost is high because the catalytic activity is not high enough.

Therefore, it can be purchased at low cost and is excellent in dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, and low temperature characteristics, as well as processability, compatibility with aromatic ring-containing polymers such as SBR, and co-vulcanization ability. The emergence of copolymers is strongly desired.

U. S. Patent No. 4,645, 793 discloses a mixture of diene rubber and ethylene / a-olefin copolymer with improved weatherability and ozone resistance. Although this mixture has improved weatherability and ozone resistance, it tends to reduce dynamic fatigue resistance (flexural fatigue resistance) or lower adhesion to fibers.

Therefore, there is a need for a vulcanizable rubber composition that is excellent in workability, strength, weather resistance, ozone resistance and dynamic fatigue resistance as well as adhesion to fibers.

Accordingly, it is compatible with aromatic ring-containing polymers such as SBR, abrasion resistance, braking performance on wet road surface, workability, SBR, heat aging resistance, weather resistance, ozone resistance, covalent vulcanization ability, and adhesion to fiber. There is a need for the emergence of long-life rubber molded articles having excellent dynamic fatigue properties.

The inventors have steadily studied the copolymers, vulcanizable rubber compositions, in particular, tire floor rubber compositions and molded articles as described above. As a result, the following things were revealed to complete the present invention.

(1) Copolymerization of certain higher α-olefins, specific non-conjugated dienes, and specific aromatic ring-containing vinyl monomers in the presence of a specific catalyst for olefin polymerization results in dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, And higher α-olefin copolymers having excellent low temperature properties, processability, compatibility with aromatic ring-containing polymers such as SBR, and covalent vulcanization ability.

(2) When a copolymer obtained by copolymerizing a specific higher α-olefin, a specific non-conjugated diene and a specific aromatic ring-containing vinyl monomer in the presence of a specific catalyst for olefin polymerization is mixed with diene rubber, processability, strength, weather resistance, ozone resistance and It is possible to obtain a high α-olefin copolymer rubber composition having excellent adhesion to fibers as well as dynamic fatigue resistance.

(3) When the higher α-olefin copolymer obtained by copolymerizing a specific higher α-olefin, a specific non-conjugated diene, and a specific aromatic ring-containing vinyl monomer in the presence of a specific catalyst for olefin polymerization is mixed with diene rubber, It is possible to obtain a rubber composition for a tire floor, in which all of braking performance is excellent and rotational resistance can be greatly reduced.

(4) When vulcanizing the higher α-olefin copolymer obtained by copolymerizing a specific higher α-olefin, a specific non-conjugated diene and a characteristic aromatic ring-containing vinyl monomer in the presence of a specific catalyst for olefin polymerization, it has a long life and environmental resistance. In addition, a high quality α-olefin copolymer rubber molded article having excellent dynamic fatigue resistance (refractive fatigue resistance) can be obtained.

The present invention is to solve the problems related to the prior art as described above, the object of the present invention is to contain a high-quality α-olefin copolymer having excellent adhesion to fibers as well as processability, strength, weather resistance, ozone resistance and dynamic fatigue resistance To provide a rubber composition.

Another object of the present invention is to provide a tire floor rubber composition having excellent strength, wear resistance and braking performance (wet skid) in wet drawings, and having low rotational resistance.

The higher α-olefin copolymer-containing rubber composition according to the present invention

[A] a higher α-olefin copolymer having 6 to 20 carbon atoms, an aromatic ring-containing vinyl monomer represented by the following formula [I], and a non-conjugated diene represented by the following formula [II],

N is an integer of 0-5, R <^1> , R <^2> , R <^3> is a C1-C8 alkyl group or a hydrogen atom, respectively.

Wherein n is an integer of 1 to 5, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ and R ⁶ are each an alkyl group having 1 to 8 carbon atoms or a hydrogen atom. Provided that both R ⁵ and R ⁶ are not hydrogen atoms.

[B] diene rubber:

The weight ratio ([A] / [B]) of the higher α-olefin copolymer [A] and the diene rubber [B] is 1/99 to 90/10.

Tire floor rubber composition according to the present invention

[A] a higher α-olefin copolymer having 6 to 20 carbon atoms, an aromatic ring-containing vinyl monomer represented by the formula [I], and a non-conjugated diene represented by the formula [II],

[B] diene rubber:

The weight ratio ([A] / [B]) of the higher α-olefin copolymer [A] and the diene rubber [B] is 1/99 to 50/50.

The higher α-olefin copolymer-containing rubber composition of the present invention will be described in detail below.

The higher α-olefin copolymer-containing rubber composition of the present invention is composed of higher α-olefin copolymer [A] and diene rubber [B].

[[A] higher α-olefin copolymer]

The higher α-olefin copolymer is a specific copolymer comprising specific linear higher α-olefins, specific aromatic ring-containing vinyl monomers, and specific nonconjugated dienes in specific proportions.

[Advanced α-olefin]

The higher α-olefins used in the copolymer are higher α-olefins having 6 to 20 carbon atoms. For example, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-eicosene, 9 -Methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-decadecene.

In the copolymer, the higher α-olefins exemplified above may be used alone or in combination of two or more thereof. Among them, 1-hexene, 1-octene and 1-decene are particularly preferable.

[Aromatic Ring-containing Vinyl Monomer]

The aromatic ring-containing vinyl monomer used in the copolymer is represented by the following formula [I].

In said Formula [I], n is an integer of 0-5, R <^1> , R <^2> and R <^3> are a hydrogen atom or an alkyl group of 1-8 carbon atoms, respectively.

Examples of the aromatic ring-containing vinyl monomers include styrene, allylbenzene, 4-phenyl-1-butene, 3-phenyl-1-butene, 4- (4-methylphenyl) -1-butene, and 4- (3-methylphenyl)- 1-butene, 4- (2-methylphenyl) -1-butene, 4- (4-ethylphenyl) -1butene, 4- (4-butylphenyl) -1-butene, 5-phenyl-1-pentene, 4 -Phenyl-1-pentene, 3-phenyl-1-pentene, 5- (4-methylphenyl) -1-pentene, 4- (2-methylphenyl) -1-pentene, 3- (4-methylphenyl) -1-pentene , 6-phenyl-1-hexene, 5-phenyl-1-hexene, 4-phenyl-1-hexene, 3-phenyl-1-hexene, 6- (4-methylphenyl) -1-hexene, 5- (2- Methylphenyl) -1-hexene, 4- (4-methylphenyl) -1-hexene, 3- (2-methylphenyl) -1-hexene, 7-phenyl-1-heptene, 6-phenyl-1-heptene, 5-phenyl -1-heptene, 4-phenyl-1-heptene, 8-phenyl-1-octene, 7-phenyl-1-octene, 6-phenyl-1-octene, 5-phenyl-1-octene, 4-phenyl-1 -Octene, 3-phenyl-1-octene and 10-phenyl-1-decene.

In the copolymer, the aromatic ring-containing vinyl monomers exemplified above may be used alone or in combination of two or more thereof.

Among them, allylbenzene and 4-phenyl-1-butene are preferable, and 4-phenyl-1-butene is particularly preferable.

[Non-conjugated diene]

The nonconjugated diene used by a copolymer is shown by following formula [II].

In formula [II], n is an integer of 1-5, R <^4> is an alkyl group of 1-4 carbon atoms, R <^5> and R <^6> is a hydrogen atom or an alkyl group of 1-8 carbon atoms, respectively. Provided that both R ⁵ and R ⁶ are not hydrogen atoms.

For example, non-conjugated dienes

4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1, 4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5 -Methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5 Octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6- Ethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4- Nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl -1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nona Diene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl- 1,5-decadiene, 6 -Methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6 -Decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7- Ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8- Decadiene and 9-methyl-1,8-undecadiene.

In the copolymer, non-conjugated dienes exemplified above may be used alone or in combination of two or more thereof. Other copolymerizable monomers such as ethylene, propylene, 1-butene and 4-methyl-1-pentene may be used in addition to the above non-conjugated dienes.

The molar ratio of the structural unit derived from the higher α-olefin constituting the higher α-olefin copolymer of the present invention and the structural unit derived from the aromatic ring-containing vinyl monomer is higher than that of the higher α-olefin / aromatic ring-containing vinyl monomer. 95/5, Preferably it is 40 / 60-90 / 10, More preferably, it is 50 / 50-80 / 20. The value of molar ratio was measured by 13 ^C- NMR method.

In the copolymer, the higher α-olefin is copolymerized with the aromatic ring-containing vinyl monomer, and the higher α-olefin copolymer thus obtained can improve processability, compatibility with aromatic ring-containing vinyl polymers such as SBR, and covalent vulcanization ability.

The content of the non-conjugated diene in the higher α-olefin copolymer is 0.01 to 30 mol%, preferably 0.05 to 25 mol%, particularly preferably 0.1 to 20 mol%. The iodine value of the higher α-olefin copolymer is in the range of 1 to 50, preferably 3 to 50, and more preferably 5 to 40. This value is suitable for vulcanization using sulfur or peroxides of higher α-olefin copolymers.

The higher α-olefin copolymer is measured in a decalin solution at 135 ° C. and has an intrinsic viscosity of 0.1 to 10.0 dl / g, preferably 0.1 to 7.0 dl / g.

The higher α-olefin copolymer can be produced by the following method.

The higher α-olefin copolymer copolymerizes the high α-olefin having 6 to 20 carbon atoms, the aromatic ring-containing vinyl monomer represented by the formula [I], and the nonconjugated diene represented by the formula [II] in the presence of an olefin polymerization catalyst. Can be obtained.

Here, the olefin polymerization catalyst used is formed from the solid titanium catalyst component (a), the organoaluminum compound catalyst component (b), and the electron donor catalyst component (c).

1 is a flowchart showing the processes of the olefin polymerization catalyst production method used for the preparation of the higher α-olefin copolymer.

The solid titanium catalyst component (a) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogens, and electron donors as essential components.

The titanium compound, the magnesium compound, and the electron donor described below can be prepared by contacting the solid titanium catalyst component (a) with each other.

The titanium compound used to prepare the solid titanium catalyst component (a) is, for example, a tetravalent titanium compound represented by Ti (OR) gX _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ _g ≦ ₄ ). to be.

Specific examples of the titanium compound are as follows.

Titanium tetrahalides such as TiCl ₄ TiBr ₄ and TiI ₄ , alkoxytitanium trihalides such as Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OnC ₄ H ₉ ) ₃ Cl ₃ , and Dialkoxytitanium dihalide such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OnC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , and Trialkoxy titanium monohalides such as Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OnC ₄ H ₉ ) ₃ Cl, and Ti (OC ₂ H ₅ ) Br, and Ti (OCH ₃ ) Tetraalkoxytitanium such as ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OnC ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H ₃ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalide is particularly good, and titanium tetrachloride is the best. These titanium compounds may be used alone or in combination. They can also be used after diluting them in hydrocarbons or halogenated hydrocarbons.

In the present invention, either a trivalent titanium compound or a tetravalent titanium compound may be used, but it is preferable to use a tetravalent titanium compound.

The magnesium compound used to prepare the solid titanium catalyst component (a) in the present invention includes a magnesium compound having a reducing ability and magnesium having no reducing ability.

A magnesium compound having a reducing ability is, for example, a magnesium compound having a magnesium hydrogen bond. Examples of magnesium compounds having a reducing ability include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl Magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium fluoride, butyl magnesium bromide and butyl magnesium idine.

These magnesium compounds may be used alone or may form complexes with the organoaluminum compounds described below, and these magnesium compounds may be liquid or solid.

Examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride and butoxy magnesium Alkoxy magnesium halides such as chloride and octoxy magnesium chloride, aryloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and Alkoxy magnesium, such as 2-ethylhexoxy magnesium, aryloxy magnesium, such as phenoxima magnesium and dimethyl phenoxyshima, magnesium carbonate salts, such as magnesium laurate and magnesium stearate, etc. are mentioned.

The magnesium compound having no reducing ability may be a compound derived from the above-described magnesium compound having reducing ability or a compound derived during preparation of a catalyst component. In order to induce a magnesium compound having no reducing ability from a magnesium compound having a reducing ability, a magnesium compound having a reducing ability is contacted with, for example, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. Let's do it.

In addition to magnesium compounds with or without reducing ability, the above-described complexes of magnesium compounds and other metals or mixtures of complex compounds and magnesium compounds with other metal compounds may be used. In addition, mixtures of two or more of the above compounds may also be used.

Among the various magnesium compounds described above, magnesium compounds having no reducing ability are preferable, and among them, magnesium chloride, alkoxymagnesium chloride and aryloxymagnesium chloride are particularly preferable.

Electron donors used to prepare the solid titanium catalyst component (a) include organic carbon esters (described later) and polycarboxylic acid esters.

Specific examples of the polycarboxylic acid ester are given, and examples thereof include compounds having a skeleton of the following formula.

In the above formula, R ¹ is a substituted hydrocarbon group or an unsubstituted hydrocarbon group, R ² to R ⁶ are each hydrogen or a substituted or unsubstituted hydrocarbon group, and at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be bonded to each other to form a cyclic structure.

Substituted hydrocarbons include substituted hydrocarbons containing different atoms such as N, O and S, for example -COC-, -COO-, -COOH, -OH, -SO ₃ H, -CNC- and NH ₂ And those having at least one group selected from the groups to be obtained.

Among these, as diester derived from dicarboxylic acid having the above-mentioned structure, at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms.

Examples of polycarboxylic acid esters include: diethyl succinate, dibutyl succinate, diethylmethyl succinate, diisobutyl alpha -methyl glutarate, dimethyl malonate, diethyl malonate, diethyl ethyl malo Acetate, diethylisopropylmalonate, diethylbutylmalonate, diethylphenylmalonate, diethyldiethylmalonate, diethylallylmalonate, diethyldiisobutylmalonate, diethyldinomalbutylmalonate, Dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methyl glutarate, diallyl ethyl succinate, Aliphatic polycarboxylates such as di-2-ethylhexyl fumarate, diethyl itaconate, isobutyl itaconate, diisooctyl citraconate and dimethyl citraconate, and diethylbutyl 1,2-shi Cycloaliphatic carboxylates such as lohexane carboxylate, diiso 1,2-cyclohexanecarboxylate, diethyltetrahydrophthalate and diethylnadiate, monoethylphthalate, dimethylphthalate, methylethylphthalate, monoisobutylphthalate, di Ethyl phthalate, ethyl isobutyl phthalate, mono-n-butyl phthalate, ethyl-n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didide Aromatic polycarboxylates such as silphthalate, benzylbutyl phthalate, diphenylphthalate, diethylnaphthalenedicarboxylate, dibutylnaphthalenedicarboxylate, triethyl trimellitate and dibutyl trimellitate, and 3,4-frandica There is an ester derived from a heterocyclic polycarboxylic acid such as the main acid.

Others of the polycarbon esters include, for example, diethylediate, diisobutylediate, diisobutyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate and di-2-ethylhexyl seba There is an ester derived from a long chain dicarboxylic acid such as Kate.

Of these, compounds having a skeleton represented by the above formula are preferred, esters derived from phthalic acid, maleic acid, substituted malonic acid and alcohols having 2 or more carbon atoms are preferred, and diesters obtained by reacting phthalic acid with alcohols having 2 or more carbon atoms are preferred. Especially good.

These polycarboxylic acid esters do not always need to be used as starting materials. Instead, a compound capable of inducing a polycarboxylic acid ester may be used during the preparation of the solid titanium catalyst component (a). Thereby a polycarboxylic acid ester can be produced during the production of the solid titanium catalyst component (a).

Examples of electron donors other than polycarboxylic acid esters that can be used in the preparation of the solid titanium catalyst component (a) include alcohols, amines, amides, ethers, ketones, nitriles, phosphines, stybins, arsines, phosphoamides, Organic silane compounds such as esters, thiethers, thiesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, amides and group I-IV metal salts.

In this method, the solid titanium catalyst component (a) may be prepared by contacting a magnesium compound (or metal magnesium), an electron donor, and a titanium compound with each other. In order to prepare the solid titanium catalyst component (a), a known method for producing a high active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be employed. Each component described above may be contacted in the presence of other reactants such as silicon, phosphorus and aluminum.

A method for producing the solid titanium catalyst component (a) is briefly described below by way of example.

(1) A method comprising reacting a magnesium compound or a complex compound formed from a magnesium compound and an electron donor with a liquid titanium compound. The method may be carried out in the presence of a grinding aid, and the solid compound may be ground before the reaction. In addition, each component may be pretreated with a reaction aid such as an electron donor, an organoaluminum compound, a halogen-containing silicon compound, or the like before the reaction. In this method, the electron donor is used at least once.

(2) a process of depositing a solid titanium complex by reacting a liquid magnesium compound having no reducing capacity with a liquid titanium compound in the presence of an electron donor.

(3) A method comprising the step of further reacting the titanium compound with the reaction product obtained by the method (2).

(4) A method comprising the step of further reacting the reaction product obtained by the method (1) or (2) with the electron donor and the titanium compound.

(5) a method comprising pulverizing a magnesium compound or a complex formed from a magnesium compound and an electron donor in the presence of a titanium compound to obtain a solid, and treating the obtained solid as one of a halogen, a halogen compound and an aromatic hydrocarbon, the method In the present invention, a magnesium compound or a complex compound formed from a magnesium compound and an electron donor can be ground in the presence of a grinding aid.

After grinding the magnesium compound or the complex formed from the magnesium compound and the electron donor in the presence of the titanium compound, the magnesium compound or the complex is pretreated with a reaction aid and then treated with a halogen or the like.

Examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds. In this method, the electron donor is used more than once.

(6) A method comprising the step of treating a compound obtained by one of the above methods (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method comprising contacting a reaction product of a metal acid compound, dihydrocarbyl magnesium and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method comprising reacting a magnesium compound such as magnesium salt of organic acid, alkoxymagnesium or aryloxymagnesium with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

Among the above methods (1) to (8), a method of using liquid titanium halide in the production of a catalyst and a method of using a halogenated hydrocarbon with a titanium compound or after using a titanium compound are preferable.

The amount of each component used in the preparation of the solid titanium catalyst component (a) varies depending on the method of use, but the electron donor is, for example, about 0.01 to 5 moles, preferably 0.05 to 2 moles, based on 1 mole of the magnesium compound, and the titanium compound About 0.01 to 500 moles, preferably 0.05 to 300 moles are used based on 1 mole of the silver magnesium compound.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and electron donor as essential components.

In the solid titanium catalyst component (a), the atomic ratio of halogen / titanium is about 4 to 200, preferably about 5 to 100, the molar ratio of electron donor / titanium is 0.1 to 10, preferably about 0.2 to 6, magnesium The atomic ratio of / titanium is about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component (a) contains magnesium halide having a smaller size than commercial magnesium halide, and its specific surface area is usually about 50 m 2 / g or more, preferably about 60 to 100 m 2 / g, more Preferably it is about 100-800 m <2> / g.

The solid titanium catalyst component (a) has no bloat in its composition even when washed with hexane because the above components are combined.

This solid titanium catalyst component (a) may be used alone. It may also be used after dilution with inorganic or organic compounds such as silicon compounds, aluminum compounds and polyolefins.

When using a diluent, the solid titanium catalyst component (a) exhibits high catalytic activity even if the specific surface area is smaller than that described above.

Methods for producing the high activity solid titanium catalyst (a) are described, for example, in Japanese Patent Application Laid-Open No. 108385/1975, 126590/1975, 20297/1976, 28189/1976, 64586/1976, 92885/1976, 136625/1976, 87489 / 1977, 100596/1977, 147688/1977, 104593/1977, 2580/1978, 40093/1978, 40094/1978, 43094/1978, 135102/1980, 135103/1980, 152710/1980, 811/1981, 11908/1981, 18606/1981, 83006/1983, 138705/1983, 138706/1983, 138707/1983, 138708/1983, 138709/1983, 138710/1983, 138715/1983, 23404/1985, 21109/1986, 37802/1986 and 37803 / It is disclosed in 1986.

In the present invention, as the organoaluminum compound catalyst component (b), a compound containing at least one Al-carbon bond in the molecule can be used.

Examples of such compounds include the following.

(i) an organoaluminum compound represented by the following formula:

(R ¹ ) mAl (O (R ² )) nHpXq

Wherein R ¹ and R ² are usually hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, H is a hydrogen atom, X is a halogen atom, m, m, p and q are 0 m ≦ 3, It is a number that satisfies the condition of 0≤n3, 0≤p3, 0≤q3, and m + n + p + q = 3.

(ii) Alkyl complex compounds of aluminum and group I metals represented by the following formula:

(M ¹ ) Al (R ¹ ) ₄

Wherein M ¹ is the same as Li, Na or K, R ¹ is a formula of R ¹ of the compound (i).

The organoaluminum compound (i) is, for example, as follows:

Compound of formula (R ¹ ) mAl (O (R ² )) _3-m :

Wherein R ¹ and R ² are the same as the formula of R ¹ and R ² of the compound (i), and m is number satisfying the condition of 1.5≤m≤3.

Compound of formula (R ¹ ) mAlX _3-m :

Wherein R ¹ is the same as the formula of R ¹ of the compound (i), and, X is halogen to be Im, m satisfies the condition of 0m3.

Compound of formula (R ¹ ) mAlH _3-m :

Wherein R ¹ is the same as R ¹ of the compound of formula (i), m being the number satisfying the condition of 2≤m≤3.

Compound of formula (R ¹ ) mAl (OR ² ) _n Xg:

Wherein R ¹ and R ² are the same as R ¹ and R ² in formula (i), X is halogen, m, n and q are 0m ≦ 3, 0n ≦ 3, 0 ≦ q ≦ 3 and m + It is a number that satisfies the condition of n + q = 3.

Specific examples of the aluminum compound (i) are as follows.

Trialkyl aluminum such as triethyl aluminum and tributyl aluminum, trialkenyl aluminum such as triisoprenyl aluminum, dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and dibutyl aluminum butoxide, and ethyl aluminum sesqui Alkylaluminum sesquialkoxides such as ethoxide and butylaluminum sesquibutoxide, partially alkoxylated alkylaluminums having an average composition represented by, for example, (R ¹ ) _2.5 Al (O (R ² )) _0.5 , and Dialkylaluminum halogen compounds such as aluminum chloride, dibutyl alcohol chloride and diethylaluminum bromide, alkylaluminum sesquihalides such as methylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide, and alkylaluminum Dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum di Partially hydrogenated alkylaluminum such as bromide, dialkylaluminum hydrides such as diethylaluminide and dibutylaluminum hydride, and partial hydrogenation such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Alkyl aluminum and partially alkoxylated and halogenated alkyl aluminum compounds, such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxy bromide, and the like of the aluminum compound (i), for example, two or more aluminum atoms are oxygen atoms. Or an organoaluminum compound bonded to each other by a nitrogen atom. Such compounds include, for example, (C ₂ H ₂ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and methylaluminoxane.

Examples of compound (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of these, alkylaluminum and trialkylaluminum in which two or more aluminum compounds mentioned above are bonded to each other are preferably used.

Usable as electron donors (c) are oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic or inorganic acid esters, ethers, acid amides, acid anhydrides and alkoxysilanes and ammonia, amines, nitriles and isocyanates; The same nitrogen-containing electron donor and the polycarboxylic acid ester described above.

More specifically, these electron donors (c) are methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenyl alcohol, cumyl alcohol, isopropyl alcohol. Alcohols having 1 to 18 carbon atoms such as isopropyl benzyl alcohol, and phenols having 6 to 20 carbon atoms having lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; Ketones of 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetone phenone, benzophenone and benzoquinone, and acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthaldehyde Aldehydes having 2 to 15 carbon atoms, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, and cycle Hexyl acetate, ethyl propionate, methylbutyrate, ethyl valerate, methylchloroacetate, ethyldichloroacetate, methylmethacrylate, ethyl crotonate, ethylcyclohexanecarboxylate, methylbenzoate, ethylbenzoate, propylbenzoate , Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anate, n-butyl maleate, di Isobutylmethylmaleate, di-n-hexylcyclohexene carboxylate, diethylnadiate, diisopropyltetrahydrophthalate, diethylbutyrate, diisobutylphthalate, di-n-butylphthalate, di-2- 2-30 shots such as ethylhexyl phthalate, r-butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate Organic acid esters of atomic number, acid halides of 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluphosphate chloride, anicin acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether Ethers having 2 to 20 carbon atoms, such as tetrahydrofuran, anisole and diphenyl ether, acid amides such as acetamide, benzamide and toluamide, methylamine, ethylamine, diethylamine and tri Amines such as butylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine, nitriles such as acetonitrile, benzonitrile and trinitrile, acetic anhydride, phthalic anhydride and benzoic anhydride There are acid anhydrides such as

Moreover, what can be used as an electron donor (c) is an organosilicon compound represented by following formula (1).

R and R ¹ are each a hydrocarbon group, and n is a number satisfying the condition of 0n4.

Examples of the organosilicon compound represented by the formula [1] include: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t -Butylmethyl diethoxysilane, t-amylmethyl diethoxysilane, diphenyldimethoxysilane, phenylmethyldioxysilane, diphenyl diethoxysilane, bis-O-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethylsilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyl Triethoxysilane, vinyl Liethoxysilane, t-butyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-meth Methoxyethoxysilane), vinyltriacetoxysilane, dimethyl tetraethoxysilane, and the like.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane and phenyl Methyldimethoxysilane, bis-p-tolyldimethoxysilane, phenylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane and diphenyldiethoxysilane are preferred.

Moreover, the organosilicon compound represented by following formula (2) can also be used as an electron donor (c).

Wherein R ¹ is a cyclopentyl group having a cyclopentyl group or an alkyl group, R ² is a group selected from the group consisting of a cyclopentyl group and a cyclopentyl group alkyl group having an alkyl group, R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ It is a number that satisfies the condition of 2.

In the formula [2], R ¹ is a cyclopentyl group having a cyclopentyl group or an alkyl group. Examples of the cyclopentyl group having an alkyl group include 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group and 2,3-dimethylcyclopentyl group.

In said formula [2], R <^2> is a cyclopentyl group which has an alkyl group, a cyclopentyl group, or an alkyl group. Examples thereof include an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl and hexyl, a cyclopentyl group and a cyclopentyl group having an alkyl group as mentioned for R ¹ .

In the formula (2), R ³ is a hydrogen group, for example, an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

Various organosilicon compounds of the formula [2], R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, especially those having the formula [2] in which methyl or ethyl can be preferably used.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane and cyclopentyltriethoxysilane; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane, and tricyclopentylmeth Methoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylmethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane and cyclo Monoalkoxysilanes such as pentyldimethylethoxysilane and the like.

Of these electron donors, organic carboxylates and organosilicon compounds are preferred, and of these, organic silicon compounds are particularly preferred.

The olefin polymerization catalyst used in the above method is prepared from the solid titanium catalyst component (a), the organoaluminum compound catalyst component (b) and the electron donor catalyst component (c).

In the above method, the above-mentioned higher olefins, aromatic ring-containing vinyl monomers, and nonconjugated dienes are copolymerized with each other using this olefin polymerization catalyst.

The olefin polymerization catalyst may be used to prepolymerize higher alpha olefins or alpha olefins, and then the higher alpha alpha olefins may be polymerized with aromatic ring-containing vinyl monomers and nonconjugated dienes using this catalyst.

In the preliminary polymerization, the α-olefin or higher α-olefin is prepolymerized in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, based on 1 g of the olefin polymerization catalyst.

The catalyst concentration in the prepolymerization system may be much higher than that in the polymerization system.

The amount of the solid titanium catalyst component (a) used for the prepolymerization is generally about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, more preferably 1 to 1 in terms of titanium atoms, based on 1 l of an inert hydrocarbon medium described later. Amount of 50 mmol.

The organoaluminum compound catalyst component (b) is used in an amount such that 0.1 to 500 g, preferably 0.3 to 300 g of polymer is produced per 1 g of the solid titanium catalyst component (a). Specifically, the amount of the organoaluminum catalyst component (b) is generally about 0.1 to 100 moles, preferably about 0.5 to 50 moles, more preferably 1 to 20 moles per mole of titanium atoms contained in the solid titanium catalyst component (a). to be.

The electron donor catalyst component (c) is used in an amount of 0.1 to 50 moles, preferably 0.5 to 30 moles, more preferably 1 to 10 moles per mole of titanium atoms contained in the solid titanium catalyst component (a).

Prepolymerization is carried out by adding an olefin or higher α-olefin and the above catalyst component to an inert hydrocarbon medium under mild conditions.

Examples of the inert hydrocarbon medium used here; Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, and aromatic hydrocarbons such as benzene, toluene and xylene And halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

Among these, inert hydrocarbon medium and aliphatic hydrocarbon are particularly preferably used. The olefin or higher α-olefin itself may be prepolymerized in a solvent, or may be prepolymerized in the absence of a solvent.

The higher α-olefin used in the prepolymerization may be the same or different from the higher α-olefin used in the polymerization described later.

The reaction temperature of the prepolymerization is usually about -20 to +100 占 폚, preferably about -20 to +80 占 폚, more preferably 0 to +40 占 폚.

Molecular weight regulators such as hydrogen can be used for the prepolymerization. The molecular weight regulator is used in an amount obtained by prepolymerization in a decalin solvent at 135 ° C. and having an intrinsic viscosity [η] of at least about 0.2 dl / g, preferably about 0.5 to 10 dl / g.

The prepolymerization is preferably carried out to produce about 0.1 to 500 g, preferably about 0.3 to 300 g, more preferably 1 to 100 g of polymer per 1 g of the solid titanium catalyst component (a). If the amount of polymer produced during prepolymerization is much higher, the production efficiency of the olefin polymer is often reduced.

Prepolymerization can be carried out either batchwise or continuously. An olefin formed from a solid titanium catalyst component (a) (or a prepolymerized solid titanium catalyst component (a) obtained by prepolymerization using an olefin polymerization catalyst) an organic aluminum compound catalyst component (b) and an electron donor catalyst component (c) Copolymerization of higher α-olefins, aromatic ring-containing vinyl monomers and nonconjugated dienes is carried out in the presence of a polymerization catalyst.

In the copolymerization of higher α-olefins, aromatic ring-containing vinyl monomers and non-conjugated dienes, in addition to the above olefin polymerization catalysts, components similar to those of the organic aluminum compound catalysts used in the preparation of the olefin polymerization catalysts may be used. . In addition, a component similar to the electron donor catalyst component (c) used in the preparation of the olefin polymerization catalyst may be used as the electron donor catalyst component in the copolymerization of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene. The organoaluminum compounds and electron donors used in the copolymerization of the higher α-olefins, aromatic ring-containing vinyl monomers and non-conjugated dienes are not always the same as those used in the preparation of the catalyst for olefin polymerization described above.

Copolymerization of the higher α-olefins, aromatic ring-containing vinyl monomers and nonconjugated dienes is carried out in the liquid phase.

As the reaction medium for polymerization, the above-mentioned inert hydrocarbon medium may be used, or olefin which is liquid at the reaction temperature may be used.

In the copolymerization of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene, the solid titanium catalyst component (a) is about 0.001 to 1.0 mmol, preferably about 0.005 to 0.5 mmol, in terms of titanium atoms per liter of polymerization volume. This is used. The organoaluminum compound catalyst component (b) is used in an amount such that the metal atoms contained therein are usually about 1 to 2000 moles, preferably about 5 to 500 moles, per mole of titanium atoms contained in the solid titanium catalyst component (a). The electron donor catalyst component (c) is generally used in an amount of about 0.001 to 10 mol, preferably 0.01 to 2 mol, and more preferably 0.05 to 1 mol, per mol of the metal atom contained in the organic aluminum compound catalyst component (b). do. The use of hydrogen in the copolymerization can control the molecular weight of the final polymer.

The polymerization temperature of the higher α-olefins, aromatic ring-containing vinyl monomers and non-conjugated dienes is usually about 20 to 200 ° C, preferably about 40 to 100 ° C, and the pressure is usually atmospheric pressure to 50kg / cm 2.

Copolymerization of the higher α-olefins, aromatic ring-containing vinyl monomers and nonconjugated dienes may be carried out in a batch, semicontinuous, or continuous manner. In addition, the copolymerization may be carried out in two or more steps having different reaction conditions from each other.

The higher α-olefin copolymers obtained by the above-mentioned polymerization have excellent dynamic fatigue resistance (flexible fatigue resistance), weather resistance, ozone resistance, heat aging resistance and low temperature characteristics, as well as processability and compatibility with aromatic ring-containing polymers and co-vulcanizability. Do. When applied to the resin modifiers and various rubber products, this copolymer exhibits the best properties.

The higher α-olefin copolymers can be used as resin modifiers such as polypropylene, polyethylene, polybutene, polystyrene, and modifiers for ethylene / cycloolefin copolymers. Adding higher α-olefin copolymers to those resins can significantly improve the impact resistance and the stress cracking resistance of the resin.

Rubber products are generally used in a vulcanized form, and when the higher α-olefin copolymer is used in a vulcanized form, excellent properties are shown. When the higher α-olefin copolymer is used for various rubber products, first, a non-vulcanized rubber compound may be prepared, and then the rubber compound may be molded into a desired form, and then vulcanized products may be manufactured in a vulcanized manner and a conventional method of conventional rubber.

In order to vulcanize the molded rubber compound, a method of heating the rubber compound together with a vulcanizing agent or a method of irradiating the rubber compound with an electron beam may be used.

The vulcanizing agents used for vulcanization are, for example, sulfur, sulfur containing compounds or organic peroxides.

Examples of sulfur or sulfur-containing compounds include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide and selenium dimethyldithiocarbamate. Of these, sulfur is preferably used. Sulfur or sulfur-containing compounds are used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

As the organic peroxide, those used for conventional peroxide vulcanization may be used, and examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3.3.5 Trimethylcyclohexane, t-butyl-hydroperoxide,

t-butyl cumyl peroxide, benzoyl peroxide, 2.5-dimethyl-2.5- (t-butylperoxy) hexyne-3, 2.5-dimethyl-2.5-di (benzoylperoxy) hexane, 2.5-dimethyl-2,5 mono (t-butylperoxy) hexane, and (alpha), (alpha) '-bis (t-butylperoxy m-isopropyl) benzene. Of these, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3.3.5-trimethylcyclohexane are preferably used. These organic peroxides may be used alone or in combination. The organic peroxide is used in an amount of 0.0003 to 0.05 mole, preferably 0.001 to 0.03 mole per 100 g of the higher α-olefin copolymer.

When sulfur or a sulfur-containing compound is used as a vulcanizing agent, it is preferable to use a combination of vulcanization accelerators.

Examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazolsulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-2-benzothiazolsulfinamide, 2 Mercaptobenzothiazol, 2- (2,4-dinitrophenyl) mercaptobenzothiazol, 2- (2,6-diethyl-4-morpholinothio) benzothiazol, and dibenzothiazol Thiazole compounds, such as disulfide, and guanidine compounds such as diphenylguanidine, triphenylguanidine, diortonitrileguanidine, ortonitrile biguanide and diphenylguanidine phthalate, acetaldehyde / aniline reaction products, butylaldehyde / aniline condensation Products, aldehyde / amine or ammonia reaction products such as hexamethylenetetramine and acetaldehyde ammonia, imidazole compounds such as 2-mercaptoimidazoline, thiocavanilide, diethylthiourea, dibutylthiourea, trimethyl Fuck Thiourea compounds such as urea and diorthotolylthiourea and thiuram compounds such as tetramethylchiuram monosulfide, tetramethylchiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl chiuram disulfide and pentamethylene chiuram tetrasulfide And dithioates such as zinc dimethyl dithio carbamate, zinc diethyl dithio carbamate, zinc di-n-butyl dithio carbamate, zinc ethyl phenyl dithio carbamate, and tellurium dimethyl dithio carbamate; Xanthate compounds such as zinc dibutyl xanthate and other compounds such as zincation.

The vulcanization accelerator is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

When using an organic peroxide as a vulcanizing agent, it is good to use combining a vulcanizing adjuvant. Examples of vulcanizing aids include quinone dioxime compounds such as sulfur and P-quinone dioxime, methacrylate compounds such as polyethylene glycol dimethacrylate, allyl compounds such as diallyl phthalate and triallyl cyanurate; Maleimide compounds, divinylbenzene and the like. The vulcanization aid is used in an amount of 0.5 to 2 moles, preferably about 1 mole, per mole of organic peroxide used.

In the case of vulcanization using an electron beam without using a vulcanizing agent, the unvulcanized molded rubber compound to be described later is preferably 0.1 to 10 MeV (mega electrovolt) so as to have a linear absorption of 0.5 to 35 Mrad, preferably 0.5 to 10 Mrad. Irradiation with an electron beam having an energy of 0.3 to 2MeV.

When vulcanizing using an electron beam, organic peroxides and vulcanizing aids, which are vulcanizing agents, can be used in combination, and the amount of organic peroxides used is 0.0001 to 0.1 moles per 100 g of higher alpha -olefin copolymer, preferably 0.0001 to 0.03. It's a mole.

Unvulcanized rubber compound is prepared by the following method.

In other words, higher α-olefin copolymer. The filler and softener are kneaded in a mixing apparatus such as a Banbury mixer at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and then the vulcanized mixture is added with a vulcanizing agent and, if necessary, a vulcanizing accelerator or vulcanizing aid and the resulting mixture is opened in a roll. Using a roll, such as kneading for 5 to 30 minutes at a roll temperature of 40 to 80 ℃. The mixture is then rolled to produce a rubber compound in the form of a ribbon or sheet. As described above, the rubber mixture of the high olefin copolymer, ie, the vulcanized rubber composition, is prepared by mixing the respective components by a mixing apparatus used in the conventional rubber industry such as rolls, banburic mixers, and kneaders. Rubber formulations can also be used in the conventional rubber industry as well as in steel (eg carbon black and silica), fillers (eg calcium carbonate and talc), crosslinking aids (eg triallyl isocyanurate, trimethylolpropane, Various additives, such as a triacrylate and m-phenylene bismaleimide), a plasticizer, a stabilizer, a processing aid, and a coloring agent, can be added suitably.

The rubber compound prepared as described above is then molded into the desired mold by an extruder, calendar roll or press. Vulcanization of the rubber compound is carried out simultaneously with molding. That is, a rubber compound or a molded article thereof is placed in a vulcanization vessel and heated at a temperature of 150 to 270 ° C. for 1 to 30 minutes or irradiated with an electron beam in the manner described above to obtain a vulcanized article. The vulcanization method can be carried out with or without a mold. If no mold is used, shaping and vulcanization are generally carried out continuously. In order to heat the rubber compound or the molded article thereof in the vulcanization vessel, the vessel is heated by using hot air, a glass grain fluidized bed, UHF (high frequency electromagnetic wave), steam or the like. As a matter of course, a rubber compound which does not contain a vulcanizing agent at the time of vulcanization by irradiation with an electron beam is usually used.

The vulcanized rubber product manufactured as described above can be used as automobile industry parts such as rubber dustproof tire and vibration cover material, industrial rubber products such as rubber rolls and belts, electrical insulation materials, civil engineering and building materials and rubber fabrics. If the foam is added to the non-vulcanized rubber and the rubber is heated and foamed, a foamed material can be obtained, and the foamed material can be used as a heat-resistant material, cushion material, sealing material, and the like.

[[B] diene rubber

The diene rubber [B] may be a diene rubber known in the art, and examples thereof include natural rubber, isoprene rubber, SBR, BR, CR, and NBR.

Natural rubber is generally used as standardized by the Green Book (International Quality and Package Standards for Natural Rubber Grades).

The isoprene rubber used here has a specific gravity of 0.91 to 0.94, a pattern viscosity of 30 to 120 [ML _{1 + 4} (100 ° C.)], and the SBR used here has a specific gravity of 0.91 to 0.98 and a pattern viscosity of 20 to 120 [ML. _{1 + 4} (100 ° C.)].

BR used here has a specific gravity of 0.90 to 0.95 and a pattern viscosity of 20 to 120 [ML _{1 + 4} (100 ° C.)].

In this invention, the diene rubber mentioned above can be used individually or in combination.

Among the diene rubbers, natural rubber, isoprene rubber, SBR, BR and mixtures thereof are preferably used.

[Furtherance]

The weight ratio ([A] / [B]) of the higher α-olefin copolymer [A] and the diene rubber [B] constituting the higher α-olefin copolymer rubber composition of the present invention is preferably 1/99 to 90/10. The following are 2/98 to 80/20, more preferably 3/97 to 70/30.

Rubber compositions of the present invention include reinforcing materials such as carbon black (e.g., SRF, GPF, FEF, HAF, ISAF, SAF, FT and MT) and finely divided silicic acid, and light calcium carbonate, calcium bicarbonate, talc, clay and silica. Filler may be added. The amount and type of rubber reinforcement or filler used may be suitably determined according to the use of the final rubber composition, but the amount thereof is generally 300 based on 100 parts by weight of the total of the higher α-olefin copolymer [A] and the diene rubber [B]. Parts by weight, preferably 200 parts by weight.

The rubber composition of the present invention can be used in a non-vulcanized type, but when used in a vulcanized type, properties are best shown. That is, the higher α-olefin copolymer [A] for forming the rubber composition of the present invention serves to improve weather resistance, ozone resistance, compatibility, and co-vulcanization ability of diene rubber [B] of vulcanized products. A vulcanized article excellent in adhesion to fibers as well as ozone resistance and dynamic fatigue resistance can be obtained from the rubber composition of the present invention.

The amount and type of higher α-olefin copolymer [A], diene rubber [B], reinforcing materials, fillers and softeners when obtaining the vulcanized product from the rubber composition of the present invention can be appropriately determined according to the desired use and performance of the final vulcanized product. In addition, the amount and type of compounds constituting the vulcanizing system, such as vulcanizing agents, vulcanization accelerators and vulcanizing aids, the amount and type of anti-aging and processing aids, and the method for preparing the vulcanized product may also be appropriately determined according to the desired use and performance of the final vulcanized product. Can be. The sum of the higher α-olefin copolymer [A] and the diene rubber [B] in the vulcanized product can be appropriately determined according to the desired use and performance of the vulcanized product, but usually 20% by weight or more, preferably 25% by weight or more.

As the softener, those generally used for rubber can be used. Examples of softeners include crude oil softeners such as processed oils, lubricants, paraffins, liquid paraffin, crude oil, asphalt and petrolatum, coal tar softeners such as coal tar and coal tar pitch and fatty oil softeners and facts such as castor oil, linseed oil, rapeseed oil and coconut oil. And waxes such as beeswax wax, carnauba wax and lanolin, salts such as ricinolinic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate, petroleum resins, atactic polypropylene and coumarone-indene resins Synthetic polymers such as; Of these, crude softeners are preferred, and processed oils are particularly preferred. The amount of softener used may be appropriately determined depending on the use of the final vulcanized product, but is generally 150 parts by weight, preferably 100 parts by weight, based on 100 total portions of the higher α-olefin copolymer [A] and the diene rubber [B]. Wealth is good.

In order to prepare the vulcanized article from the rubber composition of the present invention, first, a non-vulcanized rubber compound is prepared, and then the rubber compound is molded into a desired shape and then the molded rubber compound is vulcanized.

In order to vulcanize the molded rubber compound, a method of heating the vulcanizing agent rubber compound or irradiating with an electron beam may be used.

Examples of the vulcanizing agent used for vulcanization include sulfur, the aforementioned sulfur-containing compounds and organic peroxides.

In particular, the performance of rubber compositions is best demonstrated when sulfur or sulfur-containing compounds are used.

Sulfur or a sulfur-containing compound is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight in total of the higher α-olefin copolymer [A] and diene rubber [B].

When sulfur or a sulfur-containing compound is used as a vulcanizing agent, it is preferable to use a combination of the above vulcanization accelerators.

The vulcanization accelerator is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight based on 100 parts by weight in total of the higher α-olefin copolymer [A] and the diene rubber [B].

The organic peroxide is used in the amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, based on 100 g of the total of the higher α-olefin copolymer [A] and the diene rubber [B]. It is good to decide.

Organic peroxides as vulcanizing agents. When used, it is good to use the above-mentioned vulcanization aid in combination. The vulcanization aid is used 0.5 to 2 moles, preferably about 1 mole based on 1 mole of the organic peroxide used.

When vulcanizing using an electron beam without using a vulcanizing agent, the non-vulcanized molded rubber compound to be described below has an energy of 0.1 to 10 MeV, preferably 0.3 to 2 MeV, so that the linear absorption of 0.5 to 35 Mrad (megarad) is preferably 0.5 to 10 Mrad. Irradiate with an electron beam having

Unvulcanized rubber compound is prepared by the following method.

That is, the higher α-olefin copolymer [A], diene rubber [B], filler, and softener are kneaded in a mixing apparatus such as a Banbury mixer at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and then vulcanized to the resulting kneaded product. After the addition of the vulcanization accelerator or vulcanizing aid, if necessary, the mixture is kneaded at a roll temperature of 40 to 80 DEG C for 5 to 30 minutes using a roll such as an open roll. The resulting mixture is then rolled to produce a rubber compound in the form of a ribbon or sheet.

When the natural rubber is used as the diene rubber [B], by roughly kneading the natural rubber in advance, the mixed stress of the rubber reinforcement and the filler and the natural rubber is improved. Then, the rubber compound prepared as described above is molded into a desired mold by an extruder, a calendar, or a press. At the same time as or after the molding process, the rubber compound is vulcanized.

That is, the rubber compound or its molded product is placed in a vulcanization container and heated to 150 to 270 ° C for 1 to 30 minutes as described above or irradiated with an electron beam to obtain a vulcanized product.

The vulcanization process is carried out with or without a mold. If no mold is used, molding and vulcanization are generally carried out continuously. In order to heat the rubber compound or the molded article thereof in the vulcanization vessel, the vessel is heated using hot air, a glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave) steam, or the like. As a matter of course, when vulcanization is carried out by irradiation with an electron beam, a rubber compound containing no vulcanizing agent is usually used.

The vulcanized rubber products manufactured as described above can be used for automobile industry parts such as tires, rubber dustproof bodies and vibration covering materials, industrial rubber products such as rubber rolls and belts, civil engineering, building materials and rubberized fabrics. If the vulcanized product is applied to the application where the dynamic fatigue resistance is particularly necessary, it shows excellent performance and can be used for various packing of tire side wall, rubber dustproof body, rubber roll, belt, and wiper blade.

Next, the rubber composition for tire floor according to the present invention will be described in detail below.

The rubber composition for tire floors according to the present invention includes higher α-olefin copolymer [A] and diene rubber [B].

The higher α-olefin copolymer [A] used in the rubber composition for tire floors is 1.0-10.0 dl / g, preferably 1.0-7.0 dl / g, in an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. Has

The weight ratio ([A] / [B]) of the higher α-olefin copolymer [A] and the diene rubber [B] constituting the rubber bottom rubber composition according to the present invention is preferably 1/99 to 50/50, preferably 5 / 95-30 / 70.

The rubber composition for the tire floor can be produced using a conventionally known rubber-like polymer mixing method, for example, a mixer such as Banbury mixer. In the rubber compound of the present invention, conventional rubber compound components are used.

Examples of such rubber compounding active ingredients include rubber reinforcements such as carbon black and finely divided silicic acid, softeners, fillers such as calcium carbonate, calcium bicarbonate, talc, clay and silica, adhesives, waxes, binders, zinc, antioxidants and ozone. Crack inhibitors, processing aids and vulcanization enhancers. These ingredients may be used alone or in combination.

The rubber reinforcing material is used in an amount of 30 to 150 parts by weight, preferably 40 to 100 parts by weight, based on 100 parts by weight of the raw material rubber.

If the amount is too large, the braking characteristic on the wet road surface is improved, but the rotational resistance tends to decrease. On the contrary, when the amount is too small, wear resistance tends to be reduced.

In the second step of the compounding process, it is preferable to add a vulcanizing accelerator. The second step is usually performed by a Banbury mixer having a temperature of 60 ° C or less. The vulcanizing accelerator may be sulfur and a mixture of sulfur and various accelerators.

The vulcanized product of the rubber composition for tire floor according to the present invention is prepared by conventional vulcanization methods, that is, a mixture of higher α-olefin copolymer [A], diene rubber [B] and other active ingredients for 5 to 60 minutes. It can be prepared by heating and vulcanizing at a temperature of 150 ~ 200 ℃.

In addition to the above, the rubber composition using the higher α-olefin copolymer [A] has a weight ratio of 1/99 to 90/10 of the higher α-olefin copolymer [A] and the ethylene / α-olefin copolymer rubber [C]. Higher alpha-olefin copolymer rubber compositions contained in ([A] / [C]).

The ethylene / α-olefin copolymer rubber [C] is formed from ethylene and α-olefin, but may further contain a polyene component as a component thereof.

The α-olefins used here are α-olefins of 3 to 6 carbon atoms, for example propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 1-hexene, of which propylene and 1 -Butene is good. The molar ratio of ethylene and α-olefin (ethylene / α-olefin) constituting the ethylene / α-olefin copolymer rubber [C] is 50/50 to 95/5, preferably 55/45 to 93/7, more preferably The following is 60/40-91/9.

Preferred polyene components used here are non-conjugated polyenes, for example 1.4-hexadiene, 5-ethylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene Nyl and dicyclopentadiene. Of these, 5-ethylene-2-norbornene and dicyclopentadiene are preferred. The content of the non-conjugated polyene component is usually 1 to 50, preferably 4 to 40, and more preferably 6 to 30, in terms of mole%, usually 0.1 to 10 mol%, preferably 0.5 to 1, in terms of iodine value. 7 mol%, more preferably 1-5 mol%.

Ethylene α-olefin copolymer rubber [C] was measured in a decalin solvent at 135 ° C. of 0.8 to 5 dl / g, preferably 0.9 to 4 dl / g, more preferably 1.0 to 3 dl / g. Has When the ethylene / α-olefin copolymer rubber [C] having the above-mentioned intrinsic viscosity [η] is used, a higher α-olefin copolymer rubber composition capable of providing a molded article having excellent strength as well as processability can be obtained.

The weight ratio ([A] / [C]) of the higher α-olefin copolymer [A] and the ethylene / α-olefin copolymer rubber [C] in the rubber composition is 1/99 to 90/10, preferably 2 /. 98-80 / 20, More preferably, it is 2 / 98-70 / 30.

In this rubber composition, reinforcing materials such as carbon black (e.g., SRF, GPF, FEF, HAF, ISAF, SAP, FT and MT) and fine silicic acid, and fillers such as light calcium carbonate, calcium bicarbonate, talc, clay and silica Can be added. The amount and type of rubber reinforcement or filler used may be appropriately determined according to the use of the final rubber composition, but the amount thereof is 100 weight in total of the higher α-olefin copolymer [A] and the ethylene / α-olefin copolymer rubber [C]. 300 parts by weight, preferably 200 parts by weight, based on parts.

This rubber composition can be used in a non-vulcanized type, but when used in a vulcanized type, the rubber composition exhibits the best properties.

That is, the higher α-olefin copolymer [A] for forming the rubber composition of the present invention improves the weather resistance, ozone resistance, etc. of the vulcanized product, and the ethylene / α-olefin copolymer rubber [C] is the strength of the vulcanized product. Therefore, the vulcanized product excellent in strength, oscillation characteristics and dynamic fatigue resistance can be obtained from the rubber composition.

The vulcanized product of this rubber composition can be produced by the same vulcanization method as the above-mentioned higher alpha -olefin copolymer rubber composition of the present invention.

In addition, the foamed material may generally be prepared from this rubber composition by adding a foam material which may be used for rubber and a foaming aid if necessary. The foam thus obtained can be used for insulation, cushioning, sealing and the like. The foaming material is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight in total of the higher α-olefin copolymer [A] and the ethylene / α-olefin copolymer rubber [C]. By this, a foamed material having an apparent specific gravity of 0.03 to 0.7 can be produced.

Since this rubber composition contains higher α-olefin copolymer [A] and ethylene / α-olefin copolymer rubber [C] in the specific ratio as described above, the strength, heat resistance, weather resistance, dustproof characteristics, vibration blocking characteristics and dynamic resistance Excellent fatigue In addition, a vulcanized product exhibiting such excellent characteristics can be formed from this rubber composition.

The vulcanized product obtained from this rubber composition exhibits the excellent characteristics as described above, and thus, automotive industry parts such as tires, vibration shielding rubbers and vibration covering materials, industrial rubber products such as rubber rolls and belts, electrical insulation materials, civil engineering, building materials and rubberization. It can be widely used for fabrics and the like. When applied to applications where dustproofing and dynamic fatigue resistance are particularly required, it shows excellent performance of vulcanized rubber products, and also vibration-blocking rubber, rubber rolls, belts and tires. Excellent use for wiper blades, etc.

The foamed material obtained from this rubber composition can be widely applied to thermal barrier materials, cushion materials, sealing materials and the like.

In addition to those mentioned above, the rubber composition using the higher α-olefin copolymer may contain higher α-olefin copolymer [A] based on a total of 100 parts by weight of the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D]. 10 to 60 parts by weight of -40 parts by weight of the crystalline polyolefin resin [D] and a thermoplastic elastomer composition which may be partially crosslinked.

The crystalline polyolefin resin [D] suitable for use in the thermoplastic elastomer composition is prepared from a crystalline high molecular weight solid product obtained by polymerizing at least one monoolefin by a high pressure method or a low pressure method. Examples of such resins include isotactic and syndiotactic monoolefin polymer resins, and representative ones of these resins are commercially available.

Examples of suitable olefins for the crystalline polyolefin resin [D] include ethylene, propylene, 1-butene, 1-hexyne, 1-pentene, 1-heptene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-octene, 1-decene and mixtures of two or more of these olefins (mixed olefins).

The crystalline polyolefin resin [D] may be random copolymers, block copolymers and other polymers or copolymers in which they are resins.

The crystalline polyolefin resin [D] has a melt index (ASTM D 1238-65T, 230 ° C) of 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes.

Crystalline polyolefin resin [D] functions to improve fluidity and heat resistance of the final composition.

The amount of the crystalline polyolefin resin [D] in the thermoplastic elastomer composition is usually 10 to 60 parts by weight, preferably 20 to 20 parts by weight, based on 100 parts by weight of the total of the crystalline polyolefin resin [D] and the higher α-olefin copolymer [A]. 25 parts by weight is used.

If crystalline polyolefin resin [D] is used in the amount described above, an olefin thermoplastic elastomer composition excellent in both elastomeric properties and moldability can be obtained.

The thermoplastic elastomer composition may further contain a softener [E] and / or an inorganic filler [F] in addition to the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D].

Suitable as softeners [E] are those conventionally used for rubber.

Examples of emollients [E] include crude oils such as processed oils, lubricants, paraffins, liquid paraffin, crude asphalt and petrolatum, coal tars such as coal tar and coal tar pitch, and fatty oils such as castor oil, flax oil, rapeseed soy milk and coconut oil. Waxes, such as tall oil, beeswax, carnauba wax and lanolin, fatty acids and metal salts thereof, such as lysinoline acid, palmitic acid, stearic acid, barium stearate and calcium stearate, and crude oils, coumarone-intene resins and atactic polypropylenes Synthetic polymer materials, such as dioctylphthalate, dioctyl adipate and dioctyl sebacate, and other plastics such as microcrystalline wax, factis, liquid polybutadiene, modified liquid polybutadiene and liquid have.

The softening agent [E] is usually 200 parts by weight or less, preferably 2 to 200 parts by weight, based on 100 parts by weight in total of the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D].

If the amount of the softener [E] is used as described above, a thermoplastic elastomer composition excellent in heat resistance and heat aging resistance can be obtained.

Examples of inorganic fillers include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass beads And Shira Suvarun.

The inorganic filler [F] is usually 100 parts by weight or less, preferably 2 to 50 parts by weight, based on 100 parts by weight in total of the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D].

If the inorganic filler [F] is used in the above-mentioned amounts, it is possible to obtain a thermoplastic elastomer composition capable of providing a molded article having excellent elastomeric properties and moldability.

This thermoplastic elastomer composition can also be prepared by the use of an α-olefin having 3 to 5 carbon atoms in addition to the higher α-olefin copolymer [A], the crystalline polyolefin resin [D], the softener [E] and the inorganic filler [F]. Ethylene / α-olefin copolymer rubber and 3 to 5 carbon atoms may further contain ethylene / α-olefin / nonconjugated diene copolymer rubber, which may be prepared by use of α-olefin.

Examples of ethylene / α-olefin copolymer rubbers include ethylene / propylene copolymer rubber and ethylene / 1-butene copolymer rubber.

Examples of the ethylene / α-olefin / nonconjugated diene copolymer rubber include ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber and ethylene / propylene / dicyclopentadiene copolymer rubber.

Such copolymer rubber is used in an amount of 10 to 200 parts by weight based on 100 parts by weight in total of the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D].

The thermoplastic elastomer composition may further contain known heat stabilizers, anti-aging agents, climate stabilizers, antistatic agents and lubricants such as metal soaps and waxes, so long as the object of the present invention is not impaired.

The thermoplastic elastomer composition as described above is a crystalline polyolefin resin [D], a higher α-olefin copolymer [A] and optionally a component used in the presence or absence of the organic peroxide described below so as to partially crosslink, that is, a softener [ E], inorganic filler [F]. A mixture of any one of ethylene / α-olefin copolymer rubber, ethylene / α-olefin / nonconjugated diene copolymer rubber, and others can be obtained by dynamically heat treating.

In this case, the expression heat treatment dynamically means kneading in a molten state.

Examples of organic peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butyl cumyl peroxide, Benzoylperoxide, 2.5-dimethyl-2.5-di (t-butylperoxy) hexyne-3, 2.5-dimethyl-2.5-di (benzoyloxy) hexane, 2.5-dimethyl-2.5-mono (t-butylperoxy) hexane And a a'-bis (t-butylperoxy-m-isopropyl) benzene. Of these, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferred.

These organic peroxides may be used alone or in combination. The organic peroxide is usually used in an amount of 0.02 to 3.0 parts by weight, preferably 0.05 to 1.0 part by weight based on 100 parts by weight in total of the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D]. However, it is better to determine the optimum amount of organic peroxide according to the required physical property value.

In the partial crosslinking treatment with the organic peroxide, a crosslinking aid or a polyfunctional vinyl monomer is preferably used in combination. Examples include quinonedioximes such as sulfur and p-quinonedioxime, allyl compounds such as polyethylene glycol methacrylate and allylcyanurate and divinylbenzene.

Uniform and gentle crosslinking reaction can be expected by using the above-mentioned crosslinking aid or polyfunctional vinyl monomer.

The crosslinking aid or the polyfunctional monomer is usually 2.0 parts by weight, preferably 0.3-1.0 parts by weight, based on 100 parts by weight of the total of the higher α-olefin copolymer [A] and the crystalline polyolefin resin [D].

Degradation accelerators may be used to promote decomposition of organic peroxides. Examples of decomposition promoters include tersariamines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury, etc. Naphthenic acid salts; The dynamic heat treatment is preferably performed in a non-opening apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The heat treatment temperature is the melting point of the crystalline polyolefin resin [D] to 300 ° C, that is, 150 to 250 ° C, preferably 170 to 225 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The shear force applied during kneading is usually 10 to 100,000 sec ^-1 , preferably 100 to 50,000 sec ^-1 in terms of shear rate.

As a kneading apparatus, a mixing roll, a powerful mixer (eg, Banbury mixer), a kneading machine, a single screw extruder, a twin screw extruder can be used, and a non-open kneading apparatus can be preferably used.

Dynamic heat treatment results in a partially crosslinked or uncrosslinked thermoplastic elastomer composition comprising a higher α-olefin copolymer [A] and a crystalline polyolefin resin [D].

Since the thermoplastic elastomer composition contains higher α-olefin copolymer [A] and crystalline polyolefin resin [D] at a specific ratio as described above, even if the composition is not crosslinked at all, mechanical properties such as tensile strength and elongation at break are Excellent inherent properties and heat resistance of rubber such as deformation and permanent compression set.

Partially crosslinked thermoplastic elastomer compositions are superior to conventional vulcanized rubbers in mechanical properties such as tensile strength and elongation at break and inherent properties of rubber.

Higher α-olefin copolymers are suitable for use in molded articles. A high-molecular-olefin copolymer-containing rubber molded article is described.

The higher α-olefin copolymer rubber molded product is a vulcanized product of the above-mentioned high α-olefin copolymer, and the high α-olefin copolymer before vulcanization is measured in decarin at 135 ° C. and has an intrinsic viscosity of 1.0 to 10 dl / g [η. ]

The higher α-olefin copolymer rubber moldings are made from the vulcanized products of the higher α-olefin copolymers as described above, but they further contain vulcanization aids such as metal activators, compounds having an oxymethylene structure or scorch retarders. You may. In addition, the addition of additives such as rubber reinforcements, fillers, softeners, anti-aging agents and processing aids to the advanced α-olefin copolymer rubber molded articles of the present invention can further improve the properties of the product. Therefore, it is preferable to use such additives in the present invention.

The higher α-olefin copolymer rubber molded articles are preferably produced in the following manner, for example.

That is, a higher alpha-olefin copolymer rubber molded article can be obtained by adding a vulcanizing agent to the above higher alpha -olefin copolymer and vulcanizing the copolymer.

It can be vulcanized by adding a vulcanizing agent to the higher α-olefin copolymer. It is preferable to add a vulcanizing agent before the molding process. It is effective to use sulfur vulcanization and organic peroxide vulcanization to vulcanize higher α-olefin copolymers.

Examples of sulfur-containing compounds and vulcanization accelerators used for sulfur vulcanization and sulfur and their amounts are the same as those described above for higher α-olefin copolymers.

Examples and amounts of organic peroxides and vulcanization aids used for organic peroxides are the same as those described above for higher α-olefin copolymers.

It is preferable to use a combination of vulcanization aids such as metal activators, compounds having an oxymethylene structure, and anti-scorch agents in the preparation of the higher α-olefin copolymer rubber molded articles.

Examples of metal activators include magnesium oxide, zincation, zinc carbonate, higher fatty acid zinc salts, photo rosters, lead monoxide and calcium oxide. The metal activator is usually used in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer.

Compounds and scorch inhibitors having an oxymethyl structure are preferably added to cope with various rubber processing processes.

Examples of the compound having an oxymethylene structure to be used include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol.

The compound having an oxymethylene structure is usually used 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the higher α-olefin copolymer.

As the antiscoring agent, those known in the art can be used, for example maleic anhydride and salicylic acid. The antiscoring agent is usually used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer.

The performance of higher α-olefin copolymer molded parts can be further improved by adding additives such as rubber reinforcements, fillers, softeners, anti-aging agents and processing aids. These additives may be suitably mixed with higher α-olefin copolymers before or after vulcanization.

Examples of rubber reinforcements and fillers and their amounts are the same as those described above for the higher α-olefin copolymer rubber compositions.

The anti-aging agent may be used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer.

As processing aids, those commonly used for rubber can be used. The processing aid may be 10 parts by weight or less, preferably 1 to 5 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer.

Other rubbers such as natural rubbers, diene rubbers (eg SBR, IR and BR) and EPDM may also be added to the compositions for making higher α-olefin copolymer rubber molded articles.

Higher alpha -olefin copolymer rubber molded articles can be obtained, for example, by preparing rubber blends and molding the blends in the following manner. That is, high-temperature α-olefin copolymers and additives such as reinforcing agents, fillers, and softeners may be kneaded in a mixing apparatus such as a Banbury mixer at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and then vulcanized to the resulting kneaded product. And if necessary, after adding the vulcanization accelerator and the vulcanization aid, the mixture is kneaded for 5 to 30 minutes at a roll temperature of 40 to 80 ° C using a roll such as an open roll. The resulting mixture is then rolled to produce a rubber compound in the form of a ribbon or sheet.

If the higher α-olefin copolymer and the additive are directly supplied to an extruder heated to about 80 to 100 ° C. and then held for about 0.5 to 5 minutes, the rubber compound may be prepared in pellet form.

Then press molding machine transfer molding machine, injection molding machine, roller machine, calender machine, extruder, etc. are used according to the end product's use to form and vulcanize the rubber compound to obtain a high quality α-olefin copolymer rubber molded product. High-quality α-olefin copolymer rubber molded articles are, for example, molded articles for blades, rolls, belts, and vibration shielding materials.

Wiper blade rubber moldings can be obtained by molding and vulcanizing the rubber formulations prepared above using press molding machines, transfer molding machines, injection molding machines and the like.

Rubber molded articles for rolls can be produced by the following method.

The rubber compound prepared as described above is rolled by a roller calendering machine, an extruder, and the like, and then the rubber compound is spirally wound around the metal core coated with an adhesive to prepare a rubber compound roll. Then roll the roll tightly with a cloth and apply the appropriate plates to both ends of the roll. In some cases, the wire can be wound tightly on the fabric.

The wire thus treated is then placed in a vulcanizer and heated to 130-220 ° C. to vulcanize. Completely cool the vulcanized rolls, remove the fabric and wires from the rolls, and then roll finish the machine.

The obtained rubber molded article for roll is excellent in both heat aging resistance and dynamic fatigue resistance, and has a small variation in elastic modulus at a wide temperature from low temperature to high temperature.

A rubber belt molded article can be obtained by molding a rubber compound prepared above by a roller machine, a calendering machine, an extruder or the like to obtain a belt-shaped molded article, and then heating and vulcanizing at 130 to 220 ° C. for 1 to 60 minutes. The rubber belt molded article can also be obtained by molding and vulcanizing a rubber compound in a mold by a press molding machine or an injection molding machine. In this case, the mold temperature is generally 130 to 220 캜, and the period required for vulcanization is 1 to 60 minutes.

The rubber belt molded article thus obtained is excellent in heat aging resistance and dynamic fatigue resistance, and has a small variation in elastic modulus over a wide temperature range from low temperature to high temperature.

The vibration blocking rubber molded article can be obtained by vulcanizing the rubber compound obtained above using a press molding machine, a transfer molding machine, an injection molding machine, or the like.

The vibration blocking rubber molded product thus obtained has excellent heat aging resistance and dynamic fatigue resistance.

The molded article is made of only a rubber compound or a higher α-olefin copolymer as described above. The rubber compound may also be laminated with conventionally used materials to obtain a composite of higher α-olefin copolymer rubber molded articles which further improves heat aging and dynamic fatigue resistance.

For example, a composite rubber belt can be obtained by combining a rubber belt molded article as prepared above with a reinforcing material such as synthetic fabric, natural fabric, steel cord or glass cord.

Wiper blade molded products as prepared above may be subjected to surface treatment such as chlorination, bromination, fluorination, etc. to reduce the coefficient of friction, and the surface of the molded article may be filled with a coating or short fiber with a resin such as polyethylene to reduce the coefficient of friction. In this way, the performance of the wiper blade can be greatly improved.

Progressive block moldings are often used in combination with iron. When it is necessary to bond iron to vibration-resistant rubber molded parts, commercial adhesives can be used to achieve sufficient adhesion between them. Among the adhesives, Chemlock 250 and 253 manufactured by Roadpist are preferred.

In addition to the above-described high α-olefin copolymer rubber molded articles, the rubber molded article may include a rubber composition including 100 parts by weight of the high quality α-olefin copolymer used for the high quality α-olefin copolymer rubber molded article and 5 to 200 parts by weight of a conductivity-imparting agent. There is a conductive rubber molded article formed from a vulcanized article.

Examples of conductivity-imparting agents include those known in the art such as carbon black, carbon fiber, metal powder and metal fiber.

These can be used individually or in combination.

In the present invention, carbon black is preferable.

The use amount of the conductivity giving agent is usually 5 to 200 parts by weight, preferably 40 to 200 parts by weight per 100 parts by weight of the higher α-olefin copolymer.

The conductive rubber molded article may further contain a preparation which can be used for the vulcanization reaction, for example, the above-described activator, a compound having an oxymethyl structure, and an antiscoring agent.

If additives such as rubber reinforcements, fillers, softeners, anti-aging agents and processing aids as mentioned in the conductive rubber molded article are included, their manufacturability can be further improved. It is therefore advisable to use such additives.

That is, the compound is vulcanized by adding a vulcanizing agent to a rubber compound containing a higher α-olefin copolymer and a conductivity imparting agent.

The vulcanization is carried out by adding a vulcanizing agent to a rubber compound containing a higher α-olefin copolymer and a conductivity imparting agent as described above, and adding the vulcanizing agent before the molding step. The sulfur vulcanization and organic peroxide vulcanization described above are used effectively to vulcanize higher α-olefin copolymers.

It is good to add the vulcanizing adjuvant mentioned later at the time of manufacture of an electroconductive rubber to higher alpha-olefin copolymer simultaneously with addition of a vulcanizing agent.

Vulcanization aids used in combination with vulcanizing agents include, for example, metal activators, compounds having an oxymethylene structure, and anti-scoring agents, as described above.

It is preferable to add a compound having an oxymethylene structure and an anti-scorch agent to various rubber processes.

The amounts of the metal activator, the compound having an oxymethylene structure and the anti-scoring agent are the same as those described above for the higher α-olefin copolymer rubber molded article.

If the conductive rubber molded article contains additives such as rubber reinforcements, fillers, softeners, anti-aging agents and processing aids, the properties of the conductive rubber molded articles may be further improved. These additives can be appropriately mixed with higher α-olefin copolymers before or after vulcanization.

Examples of rubber reinforcing materials include finely divided silicic acid and short fibers, polyester, nylon, aramid and glass.

Examples of fillers include light calcium carbonate, calcium bicarbonate, talc, clay and silica. Reinforcing materials and fillers are usually used in an amount of 300 parts by weight, preferably 200 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

As the softener, the above-mentioned softener [E] which can be used for the thermoplastic elastomer composition can be used, if necessary. The amount may be appropriately selected depending on the use of the vulcanized product, but is generally 100 parts by weight, preferably 70 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

If the anti-aging agent is added to the higher α-olefin copolymer, the service life of the final conductive rubber molded article can be extended. This is usually the same as rubber.

Examples of the anti-aging agent used herein include aromatic second amine stabilizers such as N, N'-di-2-naphthylphenylenediamine and phenylnaphthylamine;

Phenolic stabilizers such as dibutylhydroxytoluene and tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane,

Thiether ether stabilizers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide,

Dithiocarbamate-based stabilizers such as nickel dibutyl dithiocarbamate.

These anti-aging agents are used alone or in combination.

The usage-amount is 0.1-5 weight part with respect to 100 weight part of higher alpha-olefin copolymers, Preferably it is 0.5-3 weight part.

As processing aids, those used in ordinary rubber processing can be used. Examples include ricinolic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, esters of these acids, salts and esters of higher fatty acids.

Its use amount is 10 parts by weight or less, preferably 1 to 5 parts by weight per 100 parts by weight of the higher α-olefin copolymer.

In this mold, other types of rubbers such as natural rubber, diene rubbers (e.g., SBR, IR and BR), EPDM, and polyethylenechloro sulfonate can be added to the composition for producing a conductive rubber molded article.

The conductive rubber molded article of the present invention can be obtained by, for example, preparing a rubber compound in the following manner and then molding.

That is, the higher α-olefin copolymer and, if necessary, additives such as reinforcing materials, fillers and softeners are kneaded in a mixing apparatus such as a Benbury mixer for 3 to 10 minutes at a temperature of 80 to 170 ° C., and then vulcanizing agent, if necessary. And further adding a vulcanizing aid, and kneading for 5 to 30 minutes at a roll temperature of 40 to 80 ° C. using a roll such as an open roll. The obtained mixture is then rolled to obtain a ribbon or sheet rubber compound.

The rubber compound thus obtained is then molded into a roll machine, calendering machine, extruder or the like, and then the molded article is heated and vulcanized at 130 to 220 ° C. for 1 to 60 minutes to produce a conductive rubber molded article.

In addition, the conductive rubber molded article can be obtained by molding and vulcanizing the conductive rubber obtained above in a mold by a press molding machine or an injection molding machine. In this case, the molding temperature is 130 to 220 ° C and the vulcanization time is 1 to 60 minutes.

The conductive rubber molded article thus obtained is excellent in both dynamic fatigue resistance and conductivity.

Since the conductive rubber molded article is formed from a vulcanized article containing a specific higher α-olefin copolymer and a conductivity imparting agent at a specific ratio, both the dynamic fatigue resistance and the conductivity are excellent.

Since the higher α-olefin copolymer rubber composition of the present invention contains the specific high α-olefin copolymer [A] and the specific diene rubber [B] at a specific ratio, it is not only processability, strength, weather resistance, ozone resistance and dynamic fatigue resistance, Excellent adhesion to the fibers. From this higher α-olefin copolymer rubber composition, a vulcanized product having excellent characteristics as described above can be obtained.

Since the vulcanized product obtained from the high-quality α-olefin copolymer rubber composition of the present invention exhibits excellent properties as described above, automobile industry parts such as tires, rubber vibration barrier materials and vibration cover parts, rubber rolls, belt civil engineering and building materials, rubberized fibers And industrial rubber products such as electrical insulation materials.

The rubber composition for tire floors according to the present invention contains a specific higher α-olefin copolymer [A] and a specific diene rubber [B] at a specific ratio, thereby providing excellent strength, abrasion resistance and braking ability on wet roads, and low rotational resistance. Have

From this rubber composition, a vulcanized product having excellent characteristics as described above can be obtained.

EXAMPLE

The invention is further described below with reference to the embodiments. However, the present invention is not limited to these embodiments.

Example 1

[Preparation of solid titanium catalyst component (a)]

After stirring 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol at 130 ° C. for 2 hours to obtain a homogeneous solution, 21.3 g of phthalic anhydride was added to the solution and mixed and stirred at 130 ° C. for 1 hour. Phthalic anhydride was dissolved in the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, 75 ml of the solution was added dropwise to 200 ml of titanium tetrachloride maintained at -20 캜 for 1 hour, and then the temperature of the mixed solution was raised to 110 캜 over 4 hours. 5.22 g of diisobutyl phthalates were added when it reached 110 degreeC, and it stirred at the same temperature for 2 hours. Thereafter, the solids were collected by heat filtration, and the collected solids were suspended in 275 ml of titanium tetrachloride and reacted under heating at 110 ° C. for 2 hours. Thereafter, the suspension was again filtered by heat filtration to collect the solids, and then sufficiently washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.

The titanium catalyst component (a) produced through the above process was dried as a part of the decancer slurry although it was dried to examine the catalyst composition. The solid titanium catalyst component (a) thus obtained had 2.5 wt% titanium, 65 wt% chlorine, 19 wt% magnesium, and 13.5 wt% diisobutyl phthalate.

[polymerization]

Copolymerization of 1-hexene, 4-phenyl-1-butene and 7-methyl-1.6-octadiene was carried out continuously in a 4-liter glass polymerizer with a stirring vane.

Specifically, the concentration of 1-hexene in the polymerization reactor is 132 g / l, the concentration of 4-phenyl-1-butene is 39 g / l, and the concentration of 7-methyl-1.6-octadiene is 10 g / l at the top of the polymerization reactor. 1-hexane, 4-phenyl-1-butene and 7-methyl-1.6-octadiene and hexane solution were added at a feed rate of 2.1 l / hr so that the concentration of titanium catalyst component (a) was 0.04 mmol / L. Trimethylbutylsilane with hexane slurry at a feed rate of 0.4 l / hr to a concentration of 4 mmol / l of aluminum in a hexane solution of triisobutyl aluminum at a feed rate of 1 l / hr and a concentration of 1.3 mmol / l of silane. Hexane solution was fed continuously at a feed rate of 0.5 L / hr. At the same time, the final polymer solution is continuously withdrawn from the bottom of the polymerizer such that the amount of polymer solution in the polymerizer is always 2 liters. The polymerization reactor was also fed continuously at the top at a feed rate of 0.8 l / hr and nitrogen at a feed rate of 50 l / hr.

The copolymerization reaction was carried out at 50 ° C. by circulating hot water in a jackel provided outside the polymerization reactor.

Then, a small amount of methanol was added to the polymer solution extracted from the bottom of the polymerization reactor to terminate the copolymerization reaction, and then a large amount of methane was introduced into the polymer to precipitate the copolymer. The obtained copolymer was washed with methanol and then dried at 130 ° C. for 24 hours under reduced pressure to obtain a 1-hexene / 4-phenyl-1-butene / 7-methyl-1.6-octadiene copolymer at a rate of 122 g / hr.

The copolymer thus obtained was measured in a molar ratio of 75/25 of (1-hexene / 4-phenyl-1-butene) and 3.6% of 7-methyl-1.6-octadiene, an iodine value of 9.4, and decarin at 135 ° C. to 5.7. The intrinsic viscosity of dl / g also had [η].

Example 2-6

The procedure of Example 1 was repeated but the copolymers shown in Table 1 were prepared by changing the higher α-olefins and polymerization conditions to those shown in Table 1.

Example 7

The 1-hexene / 4-phenyl-1-butene / 7-methyl-1.6-octadiene copolymer prepared in Example 1 was kneaded with the additives shown in Table 2 using an 8-inch open roll to prepare a non-vulcanized rubber compound. Got it. Unvulcanized rubber compound was evaluated for processing performance. The results are shown in Table 2.

1) Trade name: Asahi # 80. manufactured by Asahi Kabon Co., Ltd.

2) Brand Name: Sun Seller M

3) Brand Name: Sun Seller TT. Sanshin Family Care Teacher

In addition, the above-described rubber compound is heated for 20 minutes by a press heated to 160 ° C to prepare a vulcanized sheet. The vulcanization sheet was tested. The test items are as follows.

[Test Items]

Tensile tests, hardness tests, ozone resistance tests, and flexibility tests were conducted.

[Test Methods]

Tensile test, hardness test, ozone resistance test and flexibility test were carried out according to JISK 6301.

That is, tensile strength (T) and elongation (E) were measured by the tensile test, and JISA hardness (H) was measured by the hardness test.

The ozone resistance test was carried out in an ozone test vessel (static test, ozone concentration: 50pphm, elongation: 20%, temperature: 40 ° C, time: 200 hours) to test the surface degradation of the vulcanized sheet (with or without cracks).

In the flexibility test, resistance to crack growth was tested by Dmatia flexometi. Specifically, the vulcanized sheet was repeatedly bent until the crack length was 15 mm, and the number of bends was counted. The results are shown in Table 3.

Example 8

The procedure of Example 7 was repeated, but the 1-hexene / 4-phenyl-1-butene / 7-methyl-1,6-octadiene copolymer prepared in Example 2 was prepared in Example 1 1-hexene / It was used instead of the 4-phenyl-1-butene / 7-methyl-1,6-octadiene copolymer. The results are shown in Table 3.

Comparative Example 1

The procedure of Example 1 was repeated but copolymerized under the polymerization conditions shown in Table 1 without using 4-phenyl-1-butene to prepare a 1-hexene / 7-methyl-1,6-octadiene copolymer. The procedure of Example 7 was then repeated. However, the 1-hexene / 7-methyl-1,6-octadiene copolymer obtained above was used instead of the copolymer of Example 1. The results are shown in Table 3.

5: Cutting tailing and rounding of the vulcanized sheet is easily made during the roll kneading process.

4: Cutting of vulcanized sheet is difficult, but tailing and rounding are easily made during roll kneading process.

3: Cutting tailing of the vulcanized sheet is difficult but rounding is easily made during the roll kneading process.

2: The cutting tailing of the vulcanized sheet is difficult but is made during the rounding roll kneading process.

1: The cutting tailing rounding of the vulcanized sheet is difficult in the roll kneading process.

Example 9-11

The 1-hexene / 4-phenyl-1-butene / 7-methyl-1,6-octadiene copolymer prepared in Example 1 was opened 8-inch with SBR (manufactured by Nippon Zeon) and the additives shown in Table 4. The mixture was kneaded using a rolling roll to obtain an unvulcanized rubber compound. The non-vulcanized rubber compound obtained is heated for 20 minutes by a press heated to 60 캜, and then evaluated for vulcanization characteristics. The results are shown in Table 4.

1) Trade name: Nipole 1502. manufactured by Dixeon

2) Trade Name: Asahi # 80. Asahi Car Corporation

3) Trade name: Sunsen 4240. Nippon Sun Petroleum

4) Brand Name: Sun Seller CN. Sanshin Furniture High School

Value units in Table 4 are parts by weight.

Comparative Example 2-4

The procedure of one of Examples 9-11 was repeated but the 1-hexene / 7-methyl-1,6-octadiene copolymer of Comparative Example 1 was used instead of the copolymer used in Examples 9-11. The results are shown in Table 5.

Example 12

The polymerization was carried out under the same conditions as in Example 1 to obtain 1-hexene / 4-phenyl-1-butene / 7-methyl-1,6-octadiene copolymer at a rate of 122 g / hr.

The copolymer thus obtained had an intrinsic viscosity [η] of 5.7 L / g as measured in decarin at 1-hexene / 4-phenyl-1-butene molar ratio 75/25, iodine value 9.4 and 135 ° C. The polymerization conditions are shown in Table 6.

[Manufacture of Vulcanized Rubber]

As higher α-olefin copolymer rubber [A], 1-hexene / 4-phenyl-1-butene / 7-methyl-1,6-octadiene copolymer (1-a) and diene rubber [B] prepared above Commercial natural rubber (RSSI, Malaysia) was mixed with the additives shown in Table 7 to obtain an unvulcanized rubber compound.

In the above procedure, the natural rubber is roughly kneaded by an open roll adjusted at 40 ° C. in a conventional manner to have a pattern viscosity [ML] (100 ° C.) 60, followed by copolymer (1-a), roughly kneaded natural rubber (2 -a), zincated, stearic acid, HAF carbon and naphthenin oil were kneaded in a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.) for 4 minutes and then the mixture was allowed to stand at room temperature for 1 day.

Sulfur and vulcanization accelerators (DPG, CBZ) were added to the kneaded mixture thus obtained, followed by kneading with an open roll (front roll / rear roll: 50/60 ° C., 16/18 rpm) to obtain a rubber compound.

1) Brand Name: SHEST H. Togaikabon Co., Ltd.

2) Trade name: Sunsen 4240.

3) Brand Name: Sun Seller D. Sanshin Furniture High School

4) Trade name: Sun Seller CM. Sanshin Furniture High School

The rubber compound obtained above was heated for 20 minutes by a press heated to 160 ° C. to prepare a vulcanized sheet. The vulcanization sheet was tested below. The test items are as follows.

[Test Items]

Tensile tests, hardness tests, ozone resistance tests, flexibility tests, and adhesion tests on polyester cords were conducted.

[Test Methods]

The tensile test, the hardness test, the ozone resistance test, and the flexibility test were conducted in accordance with the above-described method of JISK6301.

The adhesion test was performed according to the test described in Japanese Patent Laid-Open No. 13779/1983. Specifically, the adhesive strength of H was measured according to ASTMD 2138, and measured as the adhesive force to the length of 100 mm of the drawn polyester cord.

The results are shown in Table 8.

Example 13

The procedure of Example 12 was repeated but the amounts of copolymer (1-a) and natural rubber (2-a) were changed to 50 parts by weight, respectively. The results are shown in Table 8.

Example 14

The procedure of Example 12 was repeated but the amounts of copolymer (1-a) and natural rubber (2-a) were changed to 70 parts by weight and 30 parts by weight, respectively. The results are shown in Table 8.

[Comparative Example 5]

The procedure of Example 12 was repeated, but 100 parts by weight of natural rubber (2-a) was used alone without using copolymer (1-a). The results are shown in Table 8.

Comparative Example 6

The procedure of Example 12 was repeated but 100 parts by weight of copolymer (1-a) was used alone, without using natural rubber (2-a). The results are shown in Table 9.

Comparative Example 7

Example 13 was repeated but ethylene / propylene / 5-ethylidene-2-norbornene (EPDM, ethylene content: 70 mol% [η]: 2.5 dl / g, iodine value instead of copolymer (1-a) : 20) was used. The results are shown in Table 9.

Example 15

The procedure of Example 12 was repeated, but SBR [(2-b), trade name: Nipol 1502, manufactured by Nippon Zeon] was used instead of natural rubber (2-a). The results are shown in Table 9.

Comparative Example 8

The procedure of Example 12 was repeated but 100 parts by weight of SBR (2-b) was used alone, without using copolymer (1-a). The results are shown in Table 9.

Example 16

The procedure of Example 12 was repeated, but isoprene rubber ((2-c), trade name: Nipol IR2200, manufactured by Nippon Zeon) was used instead of natural rubber (2-a). The results are shown in Table 10.

Comparative Example 9

The procedure of Example 16 was repeated but 100 parts by weight of isoprene rubber (2-c) alone was used without using the copolymer (1-a). The results are shown in Table 10.

Example 17

The procedure of Example 12 was repeated, but BR [(2-d), trade name: Nipol BR1200, manufactured by Nippon Zeon Co., Ltd.] was used instead of natural rubber (2-a). The results are shown in Table 10.

Comparative Example 10

The procedure of Example 17 was repeated but 100 parts by weight of BR (2-d) alone was used without using the copolymer (1-a). The results are shown in Table 10.

Example 18

The procedure of Example 12 was repeated, but 1-hexene / 4-phenyl-1-butene obtained by the copolymerization of Example 12 was changed except that the polymerization conditions were changed as shown in Table 6 instead of the copolymer (1-a). / 7-methyl-1,6-octadiene copolymer (1-b) was used. The results are shown in Table 11.

Example 19

The procedure of Example 12 was repeated but 1-octene / 4- obtained by the copolymerization of Example 12, except that the polymerization conditions and higher α-olefins were changed as shown in Table 6 instead of copolymer (1-a). Phenyl-1-butene / 7-methyl-1,6-octadiene copolymer (1-c) was used. The results are shown in Table 11.

Example 20

The procedure of Example 12 was repeated but instead of 70 parts by weight of natural rubber (2-a), 50 parts by weight of natural rubber (2-a) and 20 parts by weight of SBR (2-b) were used. The results are shown in Table 11.

Example 21

The procedure of Example 12 was repeated but mixed diene rubber was used instead of 70 parts by weight of natural rubber (2-a), 50 parts by weight of natural rubber (20 parts) and 20 parts by weight of BR (2-d). The results are shown in Table 11.

[Examples 22-27, Comparative Examples 11 and 12]

The copolymers (1-a), (1-b) and (1-c) used in Examples 12, 18 or 19, respectively, were mixed with the additives shown in Table 12, each of the resulting mixtures being 8-inch open. Kneaded with a roll and vulcanized at 150 ° C. for 20 minutes to obtain a vulcanized product. The physical properties of the obtained vulcanized product were measured.

The amount of the rubber composition in Table 12 is parts by weight. Rubber properties were evaluated by the following test method.

In other words, the strength was evaluated by the tensile strength (TB), the wear resistance by the Lambbourne method, the braking characteristics on the wet road surface by the tanδ value measured by the spectrometer at 0 ℃, the rotation resistance by the spectrometer of 50 ℃ It evaluated by the measured tan-delta value.

[Test Methods]

(1) Tensile strength (T) was measured according to JISK 6301,

(2) Lambbourne wear is measured by a Lamborghane wear tester manufactured by Iwamoto Seisakusho Co., Ltd. under the following conditions.

Measuring conditions :

Load: 3kg

Ambient Speed of Sample: 150m / min

Ambient speed of abrasive wheel: 100m / min

(3) The tan δ value was measured by a dynamic spectrometer manufactured by Rheometric Corporation under the following conditions.

Measuring conditions :

Shear Strain: 0.5%

Frequency: 15 Hz

[Wiper Blade Rubber Molded Products]

Example 28

The copolymer (1-a) used in Example 12 was mixed with the additives shown in Table 14 to obtain an unvulcanized rubber blend.

In the above procedure, the higher α-olefin copolymer (1-a), zincated, stearic acid and ISAF carbon were kneaded in a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.) for 5 minutes, and the resulting mixture was left at room temperature for 1 day. .

A vulcanization accelerator and sulfur were added to the kneaded product thus obtained and kneaded by an open roll to obtain a rubber compound.

The roll used here had a front roll surface temperature of 50 ° C and a rear roll surface temperature of 60 ° C. The rotation speed of the front roll was 16 rpm, and the rotation speed of the rear roll was 18 rpm.

The rubber compound obtained above was heated for 30 minutes by a press heated to 160 ° C. to prepare a vulcanized sheet. The obtained vulcanized sheet was tested below. The test items are as follows.

[Test Items]

Tensile test, hardness test, aging test, ozone resistance test, flexibility test and weather resistance test were performed according to JISK 6301.

Specifically, the tensile strength (T), elongation (E), shear strength (T) is measured in the tensile test, JISA hardness (H) is measured by the hardness test.

The aging test was carried out by heating the vulcanized sheet obtained with hot air at 100 ° C. for 70 hours. In this test, the holding force of physical properties of the vulcanized product before aging, that is, the holding force of tensile strength A (E) and the elongation of elongation A (E) are measured. The ozone resistance test was carried out in an ozone test vessel (static test, ozone concentration: 50pphm, elongation: 20%, temperature: 40 ° C, time: 200 hours) and the end time of crack generation was measured. In the flexibility test, resistance to crack growth was tested by a Dmatia flexometer. Specifically, the vulcanized sheet was repeatedly bent until the crack length was 15 mm, and the number of the vulcanized sheets was counted. The aged samples were also tested in the same manner by heating for 70 hours with hot air at 120 ° C.

The weathering test was carried out in accordance with JISB 7753, and the vulcanizing sheet measured the holding force of tensile strength A (T) and the holding force of elongation A (E) after exposure to mater by 1000 hours of sunshine weather. The results are shown in Table 17.

Example 29

The procedure of Example 28 was repeated but the copolymer (1-b) used in Example 18 was used instead of copolymer (1-a). The results are shown in Table 17.

Example 30

The procedure of Example 28 was repeated but the copolymer (1-c) used in Example 19 was used instead of copolymer (1-a). The results are shown in Table 17.

Comparative Example 13

The procedure of Example 28 was repeated, but ethylene / propylene / 5-ethyl having a molar ratio of 67/33, a pattern viscosity [ML (121 ° C.)] of 63, and an iodine value of 20 instead of copolymer (a-1). Liden-2-norbornene copolymer was used and the components used and their amounts were changed to those shown in Table 15. The results are shown in Table 17.

Comparative Example 14

The procedure of Example 28 was repeated but natural rubber (RSS # 3) and chloroprene rubber (trade name: Neoprene WRT, manufactured by Dupont) were used instead of the copolymer (a-1). Changed.

The results are shown in Table 17.

Example 31

The rubber compound obtained in the same manner as in Example 28 was extruded into a wiper blade type molded article and then vulcanized in a steam under a pressure of 6.5 kg / cm 2 for 30 minutes to obtain a wiper blade molded article.

The wiper blade molded article thus obtained was evaluated for friction characteristics and ozone resistance by the following test.

The results are shown in Table 18.

[Test Methods]

(1) friction characteristics

(a) coefficient of friction

The wiper blade molded article was subjected to a durability test using a flat glass plate under the following conditions, and the coefficient of friction of the rubber molded article was measured in a dry phase.

Wiper Blade Torture Length: 100mm

Dark load: 155g

Round trip length: 150mm

Speed: 45 round trips per second

Water spray cycle: 1 minute water spray and 4 minutes water stop

(b) Friction coefficient after weathering test

Samples exposed by the Sunshine Weatherometer for 1000 hours were measured for the coefficient of friction in the same manner as in test (a) above.

(2) ozone resistance

The ozone resistance test was carried out in an ozone test vessel (static test, ozone concentration: 50pphm, elongation: 20%, temperature: 40 ° C, time: 200 hours), and the end time of crack generation was measured.

Example 32

The rubber compound obtained in the same manner as in Example 28 and the rubber compound for wiper blades obtained in Comparative Example 2 were extruded in two layers to prepare a wiper blade, and then the surface thereof was coated with the rubber compound of Example 28, followed by 6.5 kg / cm 2. Vulcanized in steam under pressure of 30 minutes to obtain a wiper blade rubber molded article.

The thus obtained wiper blade molded article was evaluated for friction characteristics and ozone resistance in the same manner as in Example 31.

The results are shown in Table 18.

Comparative Example 15

The procedure of Example 32 was repeated, but a rubber compound obtained in the same manner as in Example 13 was used instead of the rubber compound obtained in the same manner as in Example 28.

The results are shown in Table 18.

[Comparative Example 16]

The procedure of Example 32 was repeated but the surface of the rubber compound obtained in the same manner as in Example 28 was coated with a rubber compound for wiper blade obtained in Comparative Example 14 to prepare a wiper blade by two-layer extrusion.

The results are shown in Table 18.

[Rubber Molded Products]

Example 33

The same copolymer (1-a) used in Example 1 was mixed with the additives shown in Table 19 to obtain an unvulcanized rubber compound.

In the above procedure, the higher α-olefin copolymer (a-1), zincated, stearic acid, FEF carbon and process oil were kneaded with each other for 5 minutes using a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.). Leave at room temperature for 1 day. After adding the vulcanization accelerator and sulfur to the kneaded product thus obtained, it was kneaded by an open roll to obtain a rubber compound sheet having a thickness of about 2 mm. The surface temperatures of the front and rear rolls were 50 ° C and 60 ° C, respectively, and their rotation speeds were 16rpm and 18rpm, respectively.

The rubber sheet obtained above is wound on a metal cord around a hollow pipe type (SUS 304) having an outer diameter of 60 mm, and then vulcanized at 160 ° C. for 30 minutes. After vulcanization is completed, the vulcanized rubber is cooled and separated from the metal core. Vulcanized rubber was measured with respect to fracture stress T (1), fracture elongation E (1) and JISA hardness H (1) according to JISK6301.

The sample was then aged for 3 days in air at 150 ° C. and the aged sample was measured for fracture stress T (2), fracture elongation E (2) and JISA hardness H (2) in the same manner as described above. .

Fracture energy can be approximated by tensile force (T × E), and the ratio (TE) between the tension before and after aging (TE) and the difference between JISA hardness before and after JISA hardness after aging (ΔH) It was calculated by the following formula, and the value thus obtained was taken as a measure of heat aging resistance.

TE (%) = {[(after T old) × (E after old)] / [(before T old) × (before E old)]} × 100 = {[T (2) × E (2)] / [T (1) × E (1)]} × 100

ΔH = H (2)-H (1)

The permanent compression set test was also conducted according to JISK 6301 under conditions of a temperature of 100 ° C or -10 ° C and a period of 70 hours.

In addition, the picopolishing test was carried out in accordance with ASTM D 2228 using a vulcanized sample obtained by booting from the rubber compound described above to measure the polishing rate of the sample.

Then, a non-vulcanized sheet of rubber compound having a thickness of 2 mm was punched out to obtain a dumbbell sample of No1 type according to JISK6301. The obtained sample was subjected to a tensile test at a tensile rate of 100 mm / min and a temperature of 23 ° C. to measure the tensile strength at yield, and then the measured value was taken as the shape holding force value of the unvulcanized rubber compound.

The results are shown in Table 21.

Example 34

The procedure of Example 33 was repeated, but the copolymer (1-b) used in Example 18 was used instead of copolymer (1-a).

The results are shown in Table 21.

Example 35

The procedure of Example 33 was repeated, but the copolymer (1-c) used in Example 19 was used instead of the copolymer (1-a).

The results are shown in Table 21.

[Comparative Example 17]

Example 33 was repeated, but ethylene / propylene / 5-ethyl having a molar ratio of ethylene / propylene instead of copolymer (1-a), 80/20, pattern viscosity [ML (100 ° C.)] 120, iodine value 10 Liden-2-norbornene copolymer (EPDM) was used, and the components used and their amounts were changed to those shown in Table 20.

The results are shown in Table 21.

[Rubber belt molding]

Example 36

The copolymer (1-a) used in Example 12 was mixed with the additives shown in Table 22 to obtain an unvulcanized rubber composition.

In the above procedure, a kneaded product obtained by kneading each of the high α-olefin copolymer (1-a), zincated, stearic acid and ISAF carbon using 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.) for 5 minutes at room temperature for 1 day I left it. After adding the vulcanization accelerator and sulfur to the kneaded product thus obtained, it was kneaded by an open roll to obtain a rubber compound. The surface temperatures of the front and rear rolls were 50 ° C and 60 ° C, respectively, and their rotation speeds were 16rpm and 18rpm, respectively.

The rubber compound obtained above was filled into a mold for manufacturing a belt and a sample for manufacturing a flexibility test, and the vulcanized product obtained by vulcanizing the rubber compound in each mold for 20 minutes by a press heated to 160 ° C was tested as follows. The test items are as follows.

[Test Items]

Tensile test, hardness test, aging test, flexibility test and modulus of elasticity were measured.

[Test Methods]

Tensile test, hardness test, aging test and flexibility test were conducted according to JISK 6301. That is, the tensile test (T) and the elongation (E) were measured in the tensile test, and the JISA hardness (H) was measured in the hardness test.

The aging test was carried out by heating the vulcanized product for 70 hours with hot air at 135 ° C. In this test, the holding force of the physical properties of the vulcanized product before aging, that is, the holding force of the tensile strength A (T), the holding force of the elongation A (E) and the hardness (ΔH) were measured.

Resistance to crack growth in the softness test was tested by Dmatia flexometer. Specifically, the sample was repeatedly bent until the crack length became 15 mm, and the number of bends was counted.

The composite modulus of elasticity (G *) was measured at 10 Hz using a dynamic spectrometer (manufactured by Leometric) as a variation of the modulus of elasticity with temperature.

The results are shown in Table 24.

Example 37

The procedure of Example 36 was repeated, but the copolymer (1-b) used in Example 18 was used instead of the copolymer (1-a). The results are shown in Table 24.

Example 38

The procedure of Example 36 was repeated, but the copolymer (1-c) used in Example 19 was used instead of the copolymer (1-a). The results are shown in Table 24.

[Comparative Example 18]

The procedure of Example 36 was repeated, but chloroprene rubber (trade name: Neoprene WRT, manufactured by DuPont) was used and the ingredients and amounts used were changed to those shown in Table 23. The results are shown in Table 24.

Example 39

The copolymer (1-a) used in Example 12 was mixed with the additives shown in Table 25 to prepare an unvulcanized rubber compound.

1) Trade name: SESTSO, manufactured by Tokai Carbon Co., Ltd.

2) Brand Name: Nokseller M, Ouchi Shinkogagaku Teacher

3) Brand Name: Nokseller TT, Ouchi Shinkogagaku Co., Ltd.

In the above procedure, the higher α-olefin copolymer (1-a), zincated, stearic acid and FEF carbon were kneaded with each other for 6 minutes in a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.), and then allowed to stand at room temperature for 1 day, followed by vulcanization. Accelerator and sulfur were added and kneaded by an open roll to obtain a rubber compound. The surface temperatures of the front roll and the rear roll were 50 ° C and 60 ° C, respectively, and their rotation speeds were 16rpm and 18rpm, respectively.

The rubber compound obtained above was heated for 20 minutes by a press heated to 160 ° C. to obtain a vulcanized sheet. The obtained vulcanized sheet was tested below. The test items are as follows.

[Test Items]

Flexibility test and polishing test were performed.

[Test Methods]

Resistance to crack growth in the flexibility test was tested by a Dematia flexometer according to JISK6301. Specifically, the vulcanized sheet was repeatedly bent and cracked until the crack length became 15 mm. Continued flexural recovery was taken as the value of dynamic fatigue resistance. Moreover, the same flexibility test was carried out for the aged sample heated by 120 degreeC hot air for 70 hours.

The vulcanized sheet for the metal in the polishing test was tested according to Method A of ASTM D 429. Chemlock 253 (manufactured by Roadfist) was used as the adhesive.

The results are shown in Table 28.

Example 40

The procedure of Example 39 was repeated but the copolymer (1-b) used in Example 18 was used instead of copolymer (1-a).

The results are shown in Table 28.

Example 41

The procedure of Example 39 was repeated but the copolymer (1-c) used in Example 19 was used instead of copolymer (1-a).

The results are shown in Table 28.

Comparative Example 19

Natural rubber (RSS # 3) was roughly kneaded by a 14-inch open roll to a pattern viscosity [ML (100 ° C)] 60. The roughly kneaded natural rubber was kneaded with an open roll after mixing with the additives shown in Table 26 to obtain a non-vulcanized rubber compound.

The rubber compound was then heated for 60 minutes by a press heated to 140 ° C., and the vulcanized sheet was then subjected to the same test as in Example 39.

The results are shown in Table 29.

Claims (13)

[A] higher α-olefins composed of monomers derived from higher α-olefins having 6 to 20 carbon atoms, aromatic ring-containing vinyl monomers represented by the following formula [I], and nonconjugated dienes represented by the following formula [II]: Higher α-olefin copolymer comprising a copolymer and [B] diene rubber, wherein the weight ratio ([A] / [B]) of the components [A] and [B] is 1 / 99-90 / 100. Rubber composition comprising a. N is an integer of 0-5, R <^1> , R <^2> , R <^3> is respectively independently a hydrogen atom or an alkyl group of 1-8 carbon atoms. Wherein n is an integer of 1 to 5, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Provided that both R ⁵ and R ⁶ are not hydrogen atoms. The molar ratio (higher alpha -olefin / aromatic ring-containing vinyl monomer) of the higher alpha -olefin and the aromatic ring-containing vinyl monomer in the higher alpha -olefin copolymer [A] is 95 / 5-30 / 70. A rubber composition comprising the characteristic higher α-olefin copolymer. The higher α-olefin copolymer [A] is a higher α-olefin copolymer according to claim 1 or 2, wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 10.0 dl / g. Rubber composition containing. The rubber composition according to claim 1 or 2, wherein the higher α-olefin copolymer [A] has an iodine value of 1 to 50. The rubber composition according to claim 1 or 2, wherein the diene rubber [B] is a natural rubber, isoprene rubber, SBR, BR or a mixture thereof. 4. The rubber composition according to claim 3, wherein the higher α-olefin copolymer [Al] has an iodine value of 1 to 50. The rubber composition according to claim 3, wherein the diene rubber [B] is a natural rubber, isoprene rubber, SBR, BR or a mixture thereof. The rubber composition according to claim 4, wherein the diene rubber [B] is a natural rubber, isoprene rubber, SBR, BR or a mixture thereof. [A] higher α-olefins composed of monomers derived from higher α-olefins having 6 to 20 carbon atoms, aromatic ring-containing vinyl monomers represented by the following formula [I], and nonconjugated dienes represented by the following formula [II]: A rubber composition for tire floors, comprising coalescing and [B] diene rubber, wherein the weight ratio ([A] / [B]) of the components [A] and [B] is 1 / 99-50 / 50. N is an integer of 0-5, R <^1> , R <^2> , R <^3> is respectively independently a hydrogen atom or an alkyl group of 1-8 carbon atoms. Wherein n is an integer of 1 to 5, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Provided that both R ⁵ and R ⁶ are not hydrogen atoms. The rubber composition for tire floors according to claim 9, wherein the higher α-olefin copolymer [A] has an intrinsic viscosity [η] of 0.1 to 10.0 dl / g as measured in decarin at 135 ° C. The rubber composition for tire floors according to claim 9 or 10, wherein the higher α-olefin copolymer [A] has an iodine value of 1 to 50. The rubber composition for tire floors according to claim 9 or 10, wherein the diene rubber [B] is natural rubber, isoprene rubber, SBR, BR or a mixture thereof. The rubber composition for tire floors according to claim 11, wherein the diene rubber [B] is natural rubber, isoprene rubber, SBR, BR or a mixture thereof.