RU2383565C2 - Rubber composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: rubber composition contains 100 pts. wt rubber component [(a)+(b)] obtained from 20-80 wt % vinyl-cis-butadiene rubber (a) containing three components: 1,2 polybutadiene with melting point equal to above 170°C, high molecular substance with at least one unsaturated double bond on one repeating unit and which is a substance selected from at least one: polyisoprene, crystalline polybutadiene with melting point equal to or below 150°C, liquid polybutadiene and derivatives thereof, and a third component as a matrix component - cis-polybutadiene and (b) from 80 to 20 wt % rubber on a diene base, different from (a); and (c) from 40 to 100 pts. wt rubber reinforcement agent containing 40% or more silicon dioxide. (a) is obtained through cis-1,4-polymerisation of 1,3-butadiene in a solution on a hydrocarbon base using a catalyst with addition of a high-molecular substance after cis-polymerisation with subsequent 1,2-polymerisation. 1,2-polybutadiene is dispersed in short crystalline fibre state, just as the high-molecular substance is dispersed in cis-polybutadiene rubber separately, or in a state where they are linked to each other.

EFFECT: improvement of the rubber composition during extrusion with retention of good operational characteristics for skidding on a wet road, exothermal characteristics and resistance to abrasive wear.

12 cl, 4 dwg, 8 tbl, 52 ex

Description

The present invention relates to a silica-filled rubber composition for use in the manufacture of tire treadmills, which is characterized by low swelling of the extrudable stream and excellent processability during extrusion while maintaining excellent wet slippage performance, exothermic performance and abrasion resistance required for tire operation such as safety and economy.

In addition, the invention relates to a rubber composition for the manufacture of sidewalls obtained from the new vinyl-cis-polybutadiene, which is characterized by low swelling of the extrudable stream and excellent processability during extrusion, and which is able to improve low fuel consumption in relation to its vulcanizate.

In addition, the invention relates to a tire for a passenger car, where a rubber composition is used as a treadmill rubber, characterized by low swelling of the extrudable stream and excellent processability during extrusion while maintaining a high modulus of elasticity.

In addition, the invention relates to a rubber composition for a large-sized vehicle, where a rubber composition characterized by a low swelling of the extrudable stream and excellent processability during extrusion while maintaining a high modulus of elasticity are used as the treadmill rubber.

In addition, the invention relates to a high-hardness filled rubber composition, and more particularly to a rubber composition for use in the manufacture of flanges and bead ribbons, which improves the dimensional stability (swelling of the extrudable stream is small) during extrusion or durability while maintaining high hardness.

In addition, the invention relates to a rubber composition intended for the manufacture of tread layers of treads, and more particularly, to a rubber composition intended for the manufacture of trench layers of treads obtained from a new vinyl cis-polybutadiene capable of providing both internal exothermic characteristics of the tire and processability when extruded, compatible with each other with good balance.

In addition, the invention relates to a rubber composition for the manufacture of internal tire elements, such as tire lining rubber, including carcasses and breakers, which is characterized by low swelling of the extrudable stream, excellent processability during extrusion, and satisfactory adhesion to metals.

The rubber composition of the invention can be used for the manufacture of tire elements such as tire sidewalls, tread tracks, reinforcing sidewall layers of a deflated tire, carcasses, breakers, side ribbons, undercut layers of treads, flanges, stiffeners and inner shells; industrial products such as rubber vibration dampers, hoses, belts, rubber rollers, rubber fans and rubber shoe soles; and other composites, adhesives, plastic modifiers, and the like.

State of the art

Polybutadiene is characterized by the presence of the so-called microstructure, in which a linking segment formed during polymerization in 1,4-positions (1,4-structure) and a linking segment formed during polymerization in 1,2-positions are simultaneously present in the molecular chain (1, 2-structure). The 1,4 structure is further subdivided into categories of cis structure and trans structure. On the other hand, the 1,2-structure forms a structure having a vinyl group as a side chain.

To date, a method for producing a vinyl-cis-polybutadiene rubber composition has been implemented in a solvent based on an aromatic hydrocarbon such as benzene, toluene and xylene. Since in the case of using such a solvent, the viscosity of the polymerization solution is high, there were problems with mixing, heat transfer, transportation, and the like, and excess energy was required to extract the solvent.

As the aforementioned production method, a method is known in which 1,3-butadiene is subjected to cis-1,4 polymerization in the aforementioned inert organic solvent using a catalyst obtained from water, a soluble cobalt compound and organoaluminium halide described by the general formula AlR _n X _{3- n} (where R represents an alkyl group containing from 1 to 6 carbon atoms, a phenyl group or a cycloalkyl group; X represents a halogen atom; n represents a number in the range from 1.5 to 2), to obtain BR (butadiene rubber), and then 1,3-butadiene is subjected to syndiotactic 1,2-polymerization (hereinafter abbreviated as "1,2-polymerization") in the presence of a catalyst obtained from a soluble cobalt compound, an organoaluminum compound, described by the general formula AlR ₃ (where R represents an alkyl group containing from 1 to 6 carbon atoms, a phenyl group or a cycloalkyl group), and carbon disulfide, with the addition or non-addition of 1,3-butadiene to this polymerization system and / or the aforementioned solvent (see, for example, JP-B-49-17666 (Patent Document 1) and JP-B-49-17667 (Patent Document 2)).

In addition, for example, in documents JP-B-62-171 (patent document 3), JP-B-63-36324 (patent document 4), JP-B-2-37927 (patent document 5), JP-B- 2-38081 (Patent Document 6) and JP-B-3-63566 (Patent Document 7) describe a process in which the preparation is carried out by cis-1,4 polymerization of 1,3-butadiene in the presence or absence of carbon disulfide or, after production of 1,3-butadiene and carbon disulfide, they are separated and recovered, thereby circulating 1,3-butadiene essentially free of carbon disulfide or the aforementioned inert organic of solvent. In addition, JP-B-4-48815 (Patent Document 8) describes a rubber composition exhibiting excellent tensile stress and resistance to crack propagation in bending, in which its filled material has a low coefficient of swelling of the extrudable stream and its vulcanizate is suitable for use as sidewall tires.

In addition, JP-A-2000-44633 (Patent Document 9) describes a preparation process which is carried out in an inert organic solvent containing, as a main component, a C4 fraction such as n-butane, cis-2-butene, trans-2-butene and butene-1. It is desirable that in this method, the 1,2-polybutadiene contained in the rubber composition would be a crystal formed by a short fiber, and the distribution of the length of the major axis of the crystal formed by a short fiber would be such that for 98% or more of the fiber length a value less than 0.6 μm would take place, and for 70% or more of it a value less than 0.2 μm would take place. In addition, it is described that the resulting rubber composition improves moldability, tensile stress, tensile strength and crack propagation resistance when bending cis-1,4-polybutadiene rubber (hereinafter abbreviated as "BR" ) However, depending on the scope of application, rubber compositions were required in which various characteristics would be improved.

Patent Document 1: JP-B-49-17666.

Patent Document 2: JP-B-49-17667.

Patent Document 3: JP-B-62-171.

Patent Document 4: JP-B-63-36324.

Patent Document 5: JP-B-2-37927.

Patent Document 6: JP-B-2-38081.

Patent Document 7: JP-B-3-63566.

Patent Document 8: JP-B-4-48815.

Patent Document 9: JP-A-2000-44633.

In general, with regard to the performance characteristics of a car tire, excellent wet slippage as a braking characteristic and excellent rolling resistance (tan δ) or abrasion resistance as a fuel consumption characteristic are required. However, it is known that these characteristics are in a relationship of contradiction with each other. Despite the fact that in recent years, silicon dioxide filling has been proposed, demonstrating excellent wet slippage performance, which thus ensures a very good balance between the above characteristics, this option is still not satisfactory. It is known that, although silica filling results in excellent wet slippage and fuel economy characteristics, abrasion resistance and processability are reduced. While the abrasion resistance is improved due to the use of BRs with a high level of cis structure, there is a certain possibility that wet slippage performance will be degraded, and therefore improvements are needed.

In addition, it is generally known that the proportion of tire rolling resistance in running resistance, which has a significant negative effect on car fuel consumption, is large, and that the negative impact due to energy losses in the sidewall rubber is relatively large. For this reason, to date, rubbers having a low loss tangent, such as natural rubbers, isoprene rubbers, butadiene rubbers, and mixtures thereof have been used in the sidewall part. However, an additional improvement in tire rolling resistance is required.

As a way to reduce the loss tangent of the sidewall rubber, one can imagine the use of carbon black, which demonstrates low reinforcement characteristics, or a decrease in the degree of filling with carbon black. However, a problem such as the following occurs: the swelling of the extrudable stream during processing during extrusion becomes large, and therefore it becomes difficult to obtain a small thickness of the sidewall element or to realize an improvement in tire uniformity. For this reason, a method for realizing low fuel consumption while maintaining a small swelling of the extrudable stream with respect to its extrudate is required.

In addition, in general, tires are required that demonstrate excellent road performance and durability and the like. In particular, from a safety point of view, tires are required which on the wet surface exhibit excellent slippage resistance on wet roads. In addition, based on social needs for the implementation of the conservation of natural resources, in recent years, research and development of tires characterized by low rolling resistance, namely tires exhibiting low energy losses, has been carried out. While the tire’s energy loss resulting from free rotation varies depending on the design of the tire and the like, approximately half of all energy is consumed in the tread part. Accordingly, if the energy loss in the tread rubber is reduced, then a tire having a low energy loss during rolling will be obtained.

Thus, an attempt is made to modify the tread rubber so that the energy loss would be small. However, such a modification of the rubber tends to lead to a deterioration in wet slip performance. Since the improvement in rolling resistance and the improvement in wet slippage are generally contradictory, attempts are being made to implement various developmental options to improve the tire design in order to make them compatible with each other. As one of the development options, a method for manufacturing a tread in the form of two layers consisting of a treadmill and a trench layer of a tread is provided. That is, this method consists in the manufacture of a tread in the form of two layers - a treadmill with excellent wet slippage characteristics, and a trench layer with low energy loss, which only provides an improvement in wet slippage for tires in general, but also a reduction in energy loss.

For rubber intended for the manufacture of a treadmill, in addition to wet slippage characteristics, a high modulus of elasticity and molding stability resulting from abrasion resistance and high-speed motion characteristics are required. As a method of producing rubber, characterized by a high modulus of elasticity, to date, they tried to offer various methods. The method of filling with a large amount of carbon black is not preferable, since the rubber unification is unsatisfactory at the processing stage, the load per unit of electric power increases during kneading or extrusion, and the ML value for the filled material becomes large, which makes difficulties during extrusion molding. The method of filling with a large amount of sulfur has such disadvantages as the following: sulfur leads to sweating, and due to an increase in the degree of crosslinking, the crack propagates quickly. Regarding the addition of thermosetting resin, since the thermosetting resin exhibits poor compatibility with commonly used natural rubbers or diene-based rubbers, satisfactory dispersion can hardly be achieved if a large amount of thermosetting resin is filled. In addition, since this filled mixture is solid even in an unvulcanized state, a heavy load may be caused by kneading or extrusion, or processability during molding of the tire may deteriorate, and since in the method of simply mixing with the elementary fiber before filling it, the adhesion between short fibers and rubber is insufficient , creep can increase or decrease the service life under fatigue loads.

As the rubber intended for the manufacture of the undercut groove of the tread, a rubber exhibiting low exothermic characteristics is required. Examples of rubbers exhibiting low exothermic characteristics include natural rubbers, isoprene rubbers and cis-1,4-polybutadiene rubbers, and filled materials formed from such rubber and carbon black are used. To identify low exothermic characteristics of materials other than rubbers, one could assume to use carbon black having a large particle size and low reinforcement characteristics, or to reduce the amount of carbon black. However, these methods are inherent in problems such as the following: the elastic modulus or fatigue strength of rubber is reduced, and the swelling of the extrudable stream becomes large. In addition, there is a method for the manifestation of low exothermic characteristics as a result of filling with short fibers of nylon or vinylon, thereby obtaining a rubber having a high modulus of elasticity. However, since these short fibers exhibit insufficient adhesion to rubbers, there is a problem in that the service life under fatigue loads will be short.

On the other hand, when the treadmill / undercut system is used in passenger car tires during joint extrusion of the tread track and undercut layer, the problem arises of warping the extrudate due to the difference between the swelling of the extrudable flows of both elements. If the swelling of the extrudable flow for the rubber of the trench layer of the tread is small, then this problem is likely to be solved. If there will be a filling with a large amount of carbon black, demonstrating high characteristics of reinforcement, then, despite the decrease in swelling of the extrudable stream, the heat generation will become large. Thus, a method is desirable that simultaneously satisfies the requirements for swelling of the extrudable stream and low heat.

In addition, highly hard rubbers are used as rubber elements located in the vicinity of the tire edge. Examples thereof include a rubber composition characterized by a high degree of carbon black filling, and a rubber composition characterized by filling with a novolac type phenolic resin (see JP-B-57-30856), and a rubber composition characterized by filling with short fibers and an olefin based resin ( see document JP-A-7-315014).

As for the method of producing a high hard rubber composition, in the general case, the amount of carbon black is increased or fiber, resin, and the like are filled. However, in all these methods, there may be a case when during multiple deformation the heat generation becomes large, as a result of which the durability and fatigue strength are reduced. Therefore, improvements are required.

In addition, in terms of durability at high speeds and road qualities at high speeds, radial tires generally use steel cord. In the case of using a steel cord, it is likely that very large stresses will build up in the rubber in the vicinity of the steel cord during tire movement. Accordingly, a rubber suitable for use with a steel cord is required to exhibit a high modulus of elasticity and excellent adhesion to metals. Even in radial tires or diagonal tires using organic fiber cords, rubber having a high modulus of elasticity is preferred as rubber suitable for use with the cord in terms of durability.

As a method of producing rubber, characterized by a high modulus of elasticity, to date, they tried to offer various methods. The method of filling with a large amount of carbon black is not preferable, since the rubber unification is unsatisfactory at the processing stage, the load per unit of electric power increases during kneading or extrusion, and the ML value for the filled material becomes large, which makes difficulties during extrusion molding. The method of filling with a large amount of sulfur has such disadvantages as the following: sulfur leads to sweating and due to an increase in the degree of crosslinking, the crack propagates quickly. Regarding the addition of thermosetting resin, since the thermosetting resin shows poor compatibility with natural rubbers or diene-based rubbers commonly used as lining rubber for the cord, it is likely that dispersion cannot be obtained and the crack propagation resistance worsens. In addition, conventional known rubber compositions for the manufacture of tire casing linings exhibit low cohesive strength in an unvulcanized state. Thus, in terms of processability, molding requires materials exhibiting greater cohesive strength in the unvulcanized state.

Description of the invention

The tasks solved by the invention

The objective of the invention is the creation of a silicon dioxide-filled rubber composition intended for the manufacture of a tire characterized by excellent processability during extrusion and demonstrating satisfactory wet slippage and abrasion resistance while maintaining a high modulus of elasticity.

In addition, the objective of the invention is to obtain a rubber composition intended for the manufacture of sidewalls, characterized by low fuel consumption in relation to its vulcanizate and showing a small swelling of the extrudable stream.

In addition, the object of the invention is to provide tires for a passenger car characterized by excellent processability during extrusion molding and exhibiting good high-speed motion characteristics, wet grip characteristics and abrasion resistance due to the use of a rubber composition for the manufacture of a treadmill showing excellent extrusion processability while maintaining injury to a high modulus of elasticity.

In addition, the object of the invention is to provide a rubber composition for a large vehicle characterized by excellent formability and exhibiting good high-speed performance, wet slippage and abrasion resistance due to the use of a rubber composition for the manufacture of a treadmill exhibiting small swelling of the extrudable flow and superior extrusion processability while keeping a high elastic modulus.

In addition, the objective of the invention is to create a rubber composition capable of improving the stability of geometric dimensions during extrusion and the durability of the tire obtained from it while maintaining high hardness.

In addition, the objective of the invention is to obtain a rubber composition intended for the manufacture of the undercut groove of the tread, showing low exothermic characteristics with respect to the vulcanizate from it and characterized by a small swelling of the extrudable stream.

In addition, the object of the invention is to provide a rubber composition for the manufacture of tire cord linings in the case of carcasses, side ribbons, flanges and the like, characterized by low swelling of the extrudable stream, high cohesive strength in the unvulcanized state and excellent processability during molding and exhibiting a large modulus elasticity in relation to its vulcanizate.

Means for solving problems

(1) The invention relates to a rubber composition, which is a silica-filled rubber composition for the manufacture of tires containing 100 parts by weight of a rubber component obtained from (a) from 20 to 80% by weight of vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene with a melting point of 170 ° C. or higher, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one element selected from liizoprena, crystalline polybutadiene having a melting point not exceeding 150 ° C, liquid polybutadiene and derivatives thereof and (b) from 80 to 20% by weight of the diene-based rubber other than (a).; and (c) from 40 to 100 mass parts of a rubber reinforcing filler containing 40% or more silicon dioxide, which is characterized in that 1,2-polybutadiene is dispersed in a state of short crystalline fiber, and a high molecular weight substance is dispersed in a granular state in cis polybutadiene rubber, which is a matrix component of the considered vinyl-cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(2) In addition, the invention relates to a rubber composition, which is a rubber composition intended for the manufacture of a sidewall, containing 100 mass parts of a rubber component obtained from (a) from 20 to 80 wt.% Vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene with a melting point of 170 ° C. or more, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one element selected from polyisoprene, ristallicheskogo polybutadiene having a melting point not exceeding 150 ° C, liquid polybutadiene and derivatives thereof and (b) from 80 to 20% by weight of the diene-based rubber other than (a).; and (c) from 25 to 60 parts by weight of a rubber reinforcing filler, which is characterized in that 1,2-polybutadiene is dispersed in a state of short crystalline fiber, and a high molecular weight substance is dispersed in a granular state in cis-polybutadiene rubber, which is a matrix component the subject vinyl cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(3) In addition, the invention relates to a rubber composition, which is a rubber composition for manufacturing a passenger car tire, containing 100 parts by weight of a rubber component obtained from (a) from 10 to 50% by weight of vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene with a melting point of 170 ° C. or more, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one element, select made of polyisoprene, crystalline polybutadiene with a melting point not exceeding 150 ° C, liquid polybutadiene and their derivatives, (f) 30 to 70 wt.% styrene-butadiene rubber and (b) 0 to 60 wt.% rubber on a diene basis, different from (a) and (e); and (d) from 40 to 100 parts by weight of a rubber reinforcing filler, which is characterized in that 1,2-polybutadiene is dispersed in a state of short crystalline fiber and the high molecular weight substance is dispersed in a granular state in cis-polybutadiene rubber, which is a matrix component the subject vinyl cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(4) In addition, the invention relates to a rubber composition, which is a rubber composition intended for the manufacture of a tire of a large-sized vehicle, containing 100 mass parts of a rubber component obtained from (a) from 10 to 60 wt.% Vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene with a melting point of 170 ° C. or more, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one member selected from polyisoprene, crystalline polybutadiene having a melting point not exceeding 150 ° C, liquid polybutadiene and derivatives thereof and (b) from 90 to 40% by weight of the diene-based rubber other than (a).; and (c) from 45 to 70 parts by weight of a rubber reinforcing filler, which is characterized in that 1,2-polybutadiene is dispersed in a state of short crystalline fiber and the high molecular weight substance is dispersed in a granular state in cis-polybutadiene rubber, which is a matrix component the subject vinyl cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(5) In addition, the invention relates to a rubber composition, which is a highly hard filled rubber composition containing 100 mass parts of a rubber component obtained from (a) from 20 to 80 wt.% Vinyl-cis-polybutadiene rubber containing 1.2 polybutadiene with a melting point of 170 ° C. or more, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one element selected from polyisoprene, crystalline polybutadiene with a melting point not exceeding 150 ° C, liquid polybutadiene and their derivatives, and (b) from 80 to 20 wt.% rubber on a diene basis, other than (a); and (c) from 60 to 100 parts by weight of a rubber reinforcing filler, which is characterized by the fact that 1,2-polybutadiene is dispersed in a state of short crystalline fiber, and the high molecular weight substance is dispersed in a granular state in cis-polybutadiene rubber, which is a matrix component the subject vinyl cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(6) In addition, the invention relates to a rubber composition, which is a rubber composition intended for the manufacture of a groove tread layer containing 100 parts by weight of a rubber component obtained from (a) from 20 to 80 wt.% Vinyl-cis-polybutadiene rubber containing 1,2-polybutadiene with a melting point of 170 ° C or more, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one element, select emy from polyisoprene, crystalline polybutadiene having a melting point not exceeding 150 ° C, liquid polybutadiene and derivatives thereof and (b) from 80 to 20% by weight of the diene-based rubber other than (a).; and (c) from 22 to 55 parts by weight of a rubber reinforcing filler, characterized in that 1,2-polybutadiene is dispersed in a state of short crystalline fiber, and a high molecular weight substance is dispersed in a granular state in cis-polybutadiene rubber, which is a matrix component the subject vinyl cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(7) In addition, the invention relates to a rubber composition which is a rubber composition for the manufacture of a tire cord liner containing 100 parts by mass of a rubber component obtained from (a) from 10 to 60% by weight of vinyl cis-polybutadiene rubber containing 1,2-polybutadiene with a melting point of 170 ° C. or more, and a high molecular weight substance having at least one unsaturated double bond per repeating unit and containing at least one element selected from the floor isoprene, crystalline polybutadiene having a melting point not exceeding 150 ° C, liquid polybutadiene and derivatives thereof and (b) from 90 to 40% by weight of the diene-based rubber other than (a).; and (c) from 30 to 80 parts by weight of a rubber reinforcing filler, which is characterized in that 1,2-polybutadiene is dispersed in a state of short crystalline fiber and the high molecular weight substance is dispersed in a granular state in cis-polybutadiene rubber, which is a matrix component the subject vinyl cis-polybutadiene rubber (a); and the fact that a short crystalline fiber of 1,2-polybutadiene is dispersed in particles of a high molecular weight substance.

(8) The invention relates to a rubber composition as proposed above in any one of the positions (1) to (7), which is characterized in that the vinyl-cis-polybutadiene rubber in question (a) is produced by the method for producing vinyl-cis-polybutadiene rubber as a result of cis-1,4 polymerization for 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4 polymerization catalyst, followed by 1,2-polymerization of the obtained reaction polymerization mixture in the presence of 1,2- cocatalyst polymerization to n irradiating, therefore, 1,2-polybutadiene with a melting point of 170 ° C. or more, and then separating, extracting and obtaining vinyl-cis-polybutadiene rubber formed in the resulting polymerization reaction mixture, which is characterized by inclusion in the production system vinyl-cis-polybutadiene rubber of the step of adding a high molecular weight substance having at least one unsaturated double bond to one repeating unit.

(9) In addition, the invention relates to a rubber composition as proposed above in any one of the positions (1) to (8), which is characterized in that at the stage of production of vinyl-cis-polybutadiene rubber (a) an unsaturated high molecular weight substance is contained in amount in the range from 0.01 to 50 wt.% when calculating the total amount of amounts of crystalline fiber from 1,2-polybutadiene and cis-polybutadiene rubber.

(10) In addition, the invention relates to a rubber composition proposed above in any one of the positions (1) to (9), which is characterized in that a short fiber of 1,2-polybutadiene in the vinyl-cis-polybutadiene rubber in question ( a) is also dispersed in cis-polybutadiene rubber, which acts as a matrix component, not contained in particles of a high molecular weight substance; the fact that the length of the major axis of the short crystalline fiber dispersed in the matrix in question is in the range from 0.2 to 1000 microns; and the fact that the length of the major axis of the short crystalline fiber of 1,2-polybutadiene dispersed in the particles of the considered high molecular weight substance is in the range from 0.01 to 0.5 μm.

(11) In addition, the invention relates to a rubber composition proposed above in any one of the positions (1) to (10), which is characterized in that the vinyl-cis-polybutadiene rubber in question (a) exhibits the following characteristics:

(1) cis-polybutadiene rubber, which is the matrix component of the subject vinyl cis-polybutadiene rubber, has a Mooney viscosity in the range of 10 to 50;

(2) cis-polybutadiene rubber, which is the matrix component of the considered vinyl-cis-polybutadiene rubber, is characterized by viscosity in a toluene solution at 25 ° C in the range from 10 to 150;

(3) cis-polybutadiene rubber, which is the matrix component of the subject vinyl cis-polybutadiene rubber, is characterized by a value [η] in the range from 1.0 to 5.0;

(4) cis-polybutadiene rubber, which is a matrix component of the subject vinyl cis-polybutadiene rubber, is characterized by a 1,4-cis structure in the range of 80% or more;

(5) 1,2-polybutadiene and a high molecular weight substance are dispersed in a physically and / or chemically adsorbed state in cis-polybutadiene rubber, which is a matrix component of the vinyl-cis-polybutadiene rubber in question; and

(6) The high molecular weight substance in the considered vinyl cis-polybutadiene rubber is a substance insoluble in boiling n-hexane.

(12) In addition, the invention relates to a rubber composition as proposed in (1) above, which is characterized in that the diene-based rubber (b) other than (a) is natural rubber and / or polyisoprene, and / or styrene butadiene rubber.

(13) In addition, the invention relates to a rubber composition proposed above in any one of the positions (2) to (7), which is characterized in that the diene-based rubber (b) other than (a) is natural rubber and / or polyisoprene.

(14) In addition, the invention relates to a rubber composition proposed above in any one of the positions (2) to (7), which is characterized in that the rubber reinforcing filler is carbon black.

Advantages of the Invention

The silica-filled rubber composition for making a tire used in the invention is characterized by low swelling of the extrudable stream and excellent processability during extrusion and formability while maintaining high slippage characteristics on wet roads, improves the manufacturability of the tire and demonstrates excellent abrasion resistance and low fuel consumption.

The rubber composition of the invention, intended for the manufacture of sidewalls, shows low fuel consumption in relation to its vulcanizate and is characterized by a small swelling of the extrudable stream.

The rubber composition according to the invention and intended for the manufacture of a passenger car tire is capable of realizing a high modulus of elasticity and high abrasion resistance while maintaining slippage characteristics on wet roads.

The rubber composition according to the invention and intended for the manufacture of a tire of a large-sized vehicle is characterized by low swelling of the extrudable stream and excellent processability during extrusion while maintaining a high modulus of elasticity and is able to achieve a very good balance between wet slippage and abrasion resistance.

The high-hardness filled rubber composition according to the invention at the same time improves the dimensional stability during processing and the tire durability while maintaining high hardness and is able to ensure that both performance characteristics are compatible with each other with good balance.

The rubber composition according to the invention and intended for the manufacture of a groove tread layer at the same time improves the swelling of the extrudable stream and low fuel consumption and is able to ensure compatibility of both performance characteristics with each other with good balance.

The rubber composition according to the invention and intended for the manufacture of tire lining is characterized by low swelling of the extrudable stream, high cohesive strength in the unvulcanized state and excellent processability during extrusion and formability while maintaining a high modulus of elasticity, demonstrates excellent adhesion to metals and is able to achieve a very good balance between the corresponding characteristics.

Brief Description of the Drawings

Figure 1 shows an embodiment in which a crystal fiber 2 of 1,2-polybutadiene with a melting point of 170 ° C. or more and fine particles 3 of an unsaturated high molecular weight substance are individually dispersed in a matrix 1.

Figure 2 shows an embodiment in which small particles 3 of unsaturated high molecular weight substance are dispersed in a matrix 1 in a state in which they adhere to a crystalline fiber 2 of 1,2-polybutadiene.

Figure 3 shows an embodiment in which a crystalline fiber 2 of 1,2-polybutadiene is dispersed in a matrix 1 in a state in which it adheres to the fine particles 3 of an unsaturated high molecular weight substance.

Figure 4 shows an embodiment in which a crystalline fiber 2 of 1,2-polybutadiene is dispersed in a matrix 1 in a state in which it is incorporated and dispersed in fine particles 3 of an unsaturated high molecular weight substance.

The best ways to implement the invention

In general, the vinyl cis-polybutadiene rubber (a) of the invention is formed as follows. That is, it consists of (1) from 1 to 50 mass parts of 1,2-polybutadiene with a melting point of 170 ° C or more, (2) 100 mass parts of cis-polybutadiene rubber and (3) from 0.01 to 50 wt.%, based on the total number of the above items (1) and (2), unsaturated high molecular weight substances. In addition, 1,2-polybutadiene with a melting point of 170 ° or more, which is component (1), forms a crystalline fiber in a short fiber state, in which the minor axis of the crystals formed by the middle monodisperse fiber does not exceed 0, 2 μm, the aspect ratio does not exceed 10, and the number of crystals formed by the middle monodisperse fiber is 10 or more.

It is desirable that the crystalline fiber of 1,2-polybutadiene, which is the aforementioned component (1), be in the state of a short fiber, in which the minor axis of the crystals formed by the middle monodisperse fiber does not exceed 0.2 μm, and preferably not exceeds 0.1 μm, the aspect ratio does not exceed 10, and preferably does not exceed 8, and the number of crystals formed by the middle monodisperse fiber is 10 or more, and preferably 15 or more, and would have a plat temperature a phenomenon of 170 ° C or more, and preferably in the range of 190 to 220 ° C.

Then, with regard to the vinyl-cis-polybutadiene rubber (a) of the invention, 1,2-polybutadiene with a melting point of 170 ° C. or more, which is the aforementioned component (1), is present in a state of short crystalline fiber, and the unsaturated macromolecular substance, which is the aforementioned component (3), is present in a granular state in cis-polybutadiene, which is the aforementioned component (2) and plays the role of a matrix component. In addition, particles of unsaturated macromolecular substance dispersed in cis-polybutadiene, which is the aforementioned component (2) and plays the role of a matrix component, are characterized by a major axis size in the range from 0.2 to 1000 μm, and a short crystalline fiber of 1.2 -polybutadiene dispersed in the particles of the considered high molecular weight substance is characterized by the length of the major axis in the range from 0.01 to 0.5 microns.

It is desirable that cis-polybutadiene rubber, which is the aforementioned component (2), exhibits the following characteristics. That is, the Mooney viscosity (ML _{1 + 4} at 100 ° C, hereinafter abbreviated as “ML”) is preferably in the range from 10 to 50, and more preferably from 10 to 40. Thus, such effects like: manufacturability during mixing during the preparation of the filled mixture is improved, and the dispersibility of the aforementioned component (1) in the component (2) is improved. In addition, it is desirable that cis-polybutadiene rubber, which is a component (2), exhibits the following characteristics. That is, it is desirable that the viscosity in the toluene solution (centipoise at 25 ° C, hereinafter abbreviated as "T-cp") is preferably in the range from 10 to 150, and more preferably from 10 to 100; and that the value [η] (intrinsic viscosity) would be in the range from 1.0 to 5.0, and preferably from 1.0 to 4.0. In addition, it is desirable that the content of the 1,4-cis structure is 80% or more, and preferably 90% or more; and that the gel-like substance would essentially be absent. In this case, essentially the absence of a gel-like substance means that the content of a substance insoluble in toluene does not exceed 0.5 wt.%.

“Insoluble in toluene” referred to herein means a gel-like substance adhering to a wire mesh with a mesh number of 200 after loading 10 g of a rubber sample and 400 ml of toluene into an Erlenmeyer flask, completely dissolved at room temperature (25 ° C.), and after this filtering the solution using a filter on which to place a wire mesh. The aforementioned proportion denotes a value defined as the percentage of rubber in the sample, which is obtained by drying in a vacuum a wire mesh with adhering gel and measuring the adhering amount.

In addition, the value [η] (intrinsic viscosity) is the value [η] determined in accordance with the following expressions after loading 0.1 g of a rubber sample and 100 ml of toluene into an Erlenmeyer flask, completely dissolved at 30 ° C, loading 10 ml of the solution into a Cannon-Fenske dynamic viscometer in a tank of water at a constant temperature, controlled at a temperature of 30 ° C, and measuring the dripping time (T) of the solution.

ηsp = T / T ₀ -1 (T ₀ - dripping time of only toluene).

ηsp / c = [η] + k '[η] ² c.

(ηsp is the relative viscosity, k 'is the Huggins constant (0.37), and s is the concentration of the sample (g / ml)).

It is advisable that, if we talk about the proportion of the amount of 1,2-polybutadiene crystalline fiber, which is the aforementioned component (1), relative to the amount of cis-polybutadiene rubber, which is a component (2), then the proportion of the amount of 1,2- polybutadiene crystalline fiber, which is the aforementioned component (1), would be a value in the range from 1 to 50 mass parts, and preferably from 1 to 30 mass parts, referred to 100 mass parts of cis-polybutadiene auchuka, which is the component (2) described earlier. If the fraction falls within the aforementioned range, then it will be possible to avoid inconvenience such as the following: if the fraction is large, exceeding 50 mass parts, then a short-fiber crystal formed from 1,2-polybutadiene crystal fiber in cis polybutadiene rubber is likely to become large, leading to poor dispersibility, and if the proportion is small, not reaching 1 mass part, then the characteristics of the reinforcement due to the presence of crystal and formed by short fiber will deteriorate. Accordingly, it is unlikely that problems will arise in the unlikely manifestation of the modulus of elasticity, processability during extrusion, moldability, and the like as characteristic features and in the deterioration of processability, and therefore this option is preferred. In addition, it is desirable that the proportion of the amount of unsaturated macromolecular substance, which is component (3), be in the range from 0.01 to 50 wt.%, And preferably from 0.01 to 30 wt.%, Based on the amount previously described vinyl cis-polybutadiene rubber. Falling within the aforementioned range is preferable in terms of improving dispersibility due to coagulation of the 1,2-polybutadiene crystalline fiber, which is the aforementioned component (1), and suppressing the deterioration of various associated physical properties that are characteristic of vinyl-cis-polybutadiene rubber, and the like.

For example, the aforementioned vinyl cis-polybutadiene rubber is suitably prepared in accordance with the following manufacturing method.

In general, in the preparation of the vinyl-cis-polybutadiene rubber of the invention, the polymerization of 1,3-butadiene is carried out using a hydrocarbon-based solvent. As this hydrocarbon-based solvent, a hydrocarbon-based solvent characterized by a solubility parameter (hereinafter, abbreviated as “SP value”) not exceeding 9.0 is preferred, and a hydrocarbon-based solvent characterized by solubility not exceeding 8.4. Examples of a hydrocarbon-based solvent having a solubility parameter not exceeding 9.0 include aliphatic hydrocarbons and alicyclic hydrocarbons such as n-hexane (SP value: 7.2), n-pentane (SP value: 7.0), n octane (SP value: 7.5), cyclohexane (SP value: 8.1) and n-butane (SP value: 6.6). Among them, cyclohexane and the like are preferable.

SP values for these solvents are known from documents such as the Rubber Industry Handbook (Fourth Edition, The Society of Rubber Industry, Japan, issued January 20, 1994, page 721).

As a result of using a solvent characterized by an SP value of not more than 9.0, a dispersed state is formed of short-fiber crystals formed from 1,2-polybutadiene crystal fiber in cis-polybutadiene rubber, as is expected in the invention, and exhibit excellent swelling characteristics of the extrudable flow and high modulus of elasticity and tensile strength, and therefore this option is preferred.

First of all, 1,3-butadiene and the aforementioned solvent are mixed, and then the water content in the resulting solution is controlled. The water level is preferably in the range from 0.1 to 1.0 mol, and particularly preferably from 0.2 to 1.0 mol per mole of organoaluminium chloride used in the above solution as the cis-1,4- catalyst mentioned below polymerization. Entering the water content within this range is preferable since sufficient catalytic activity can be obtained; preferred levels of cis-1,4 structure and molecular weight can be obtained; gelation during the polymerization can be suppressed, so that sticking of the gel to the polymerization tank and the like can be prevented; and in addition to this, the continuous polymerization time may be extended. As a method of controlling the level of water content, known methods can be used. Also effective is the method of adding and dispersing as a result of passing through a porous filter material (see document JP-A-4-85304).

Organoaluminium chloride is added as a catalyst for cis-1,4 polymerization to the solution obtained by controlling the water content. As organoaluminium chloride, a compound described by the general formula AlR _n X _{3-n is} preferably used. As specific examples thereof, diethylaluminum monochloride, diisobutylaluminum monochloride, dicyclohexylaluminum monochloride, diphenylaluminium monochloride, diethylaluminium sesquichloride and the like can be listed. The amount of organoaluminum chloride used is preferably 0.1 mmol or more, and more preferably is in the range of 0.5 to 50 mmol, per mole of the total amount of 1,3-butadiene.

Thereafter, a soluble cobalt compound is added to the mixed solution containing the organoaluminum chloride added to it as one of the other cis-1,4 polymerization catalysts, thereby subjecting 1,3-butadiene to cis-1,4 polymerization. The soluble cobalt compound is a cobalt compound that is soluble in the hydrocarbon-based solvent used, or soluble in liquid 1,3-butadiene, or capable of forming a uniform dispersion. Examples thereof include complexes derived from β-diketone and cobalt, such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; complexes derived from β-keto acid and cobalt ester, such as cobalt ethyl acetate-acetate complex; cobalt salts of an organic carboxylic acid containing 6 or more carbon atoms, such as cobalt octanoate, cobalt naphthenate and cobalt benzoate; and halogenated cobalt complexes, such as a complex derived from cobalt chloride and pyridine, and a complex derived from cobalt chloride and ethyl alcohol. The amount of soluble cobalt compound used is 0.001 mmol or more, and particularly preferably 0.005 mmol or more, based on one mole of 1,3-butadiene. In addition, the molar ratio between organoaluminum chloride and the soluble cobalt compound (Al / Co) is 10 or more, and particularly preferably 50 or more. In addition, in addition to the soluble cobalt compound, an organic nickel salt of an organic carboxylic acid, an organic nickel complex salt, an organolithium compound, an organic carboxylic acid neodymium salt and an organic neodymium complex salt can be used.

The temperature at which cis-1,4 polymerization is carried out generally ranges from a temperature in excess of 0 ° C to 100 ° C, preferably from 10 to 100 ° C, and more preferably from 20 to 100 ° C. The polymerization time (average residence time) is preferably in the range from 10 minutes to 2 hours. The cis-1,4 polymerization is preferably carried out so that the polymer concentration after cis-1,4 polymerization is in the range of 5 to 26% by weight. A single tank is used as the polymerization tank, or two or more tanks are combined and used. The polymerization is carried out as a result of mixing and mixing the solution in a polymerization tank (polymerization unit). As the polymerization tank used for the polymerization, you can use a polymerization tank equipped with a device for mixing a highly viscous solution, for example, the device described in JP-B-40-2645.

In the preparation of the vinyl-cis-polybutadiene rubber of the invention during the cis-1,4 polymerization, a known regulator of the degree of polymerization can be used, for example, non-conjugated dienes such as cyclooctadiene, allen and methylallen (1,2-butadiene); and α-olefins such as ethylene, propylene and butene-1. In addition, in order to further suppress gelation during the polymerization, a known gelation preventing additive can be used. In addition, in the General case, the level of cis-1,4-structure in the polymerization product is 80% or more, and preferably 90% or more, and the ML value is in the range from 10 to 50, and preferably from 10 to 40. Gel the substance is essentially absent.

Thereafter, as a result of the addition of the cis-1,4-polymerization reaction of the organoaluminum compound described by the general formula AlR ₃ to the thus obtained mixture, the carbon disulfide and optionally the above-mentioned soluble cobalt compound, 1,3-butadiene is subjected to 1-polymerization catalysts 1 , 2-polymerization, thereby providing vinyl-cis-polybutadiene rubber. In this situation, unreacted 1,3-butadiene can react when 1,3-butadiene is added or not added to the mixture of the polymerization reaction in question. Suitable examples of the organoaluminum compound described by the general formula AlR ₃ include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and triphenylaluminum. The amount of the organoaluminum compound is 0.1 mmol or more, and in particular is in the range from 0.5 to 50 mmol per mole of 1,3-butadiene. Although there are no particular restrictions on the brand of carbon disulfide, anhydrous carbon disulfide is preferred. The carbon disulfide concentration does not exceed 20 mmol / L, and in particular is preferably in the range from 0.01 to 10 mmol / L. As a substitute for carbon disulfide, known phenylisothiocyanate and xanthogenic acid derivatives can be used.

The temperature at which the 1,2-polymerization is carried out is generally in the range from 0 to 100 ° C., preferably from 10 to 100 ° C., and more preferably from 20 to 100 ° C. As a result of adding to the polymerization system during 1,2-polymerization from 1 to 50 parts by weight, and preferably from 1 to 20 parts by weight of 1,3-butadiene, based on 100 parts by weight of the above cis-1,4-polymerization reaction mixture the yield of 1,2-polybutadiene during 1,2-polymerization can be increased. The polymerization time (average residence time) is preferably in the range from 10 minutes to 2 hours. It is preferable to carry out 1,2-polymerization in such a way that, upon completion of 1,2-polymerization, the polymer concentration is in the range from 9 to 29 wt.%. A single tank is used as the polymerization tank, or two or more tanks are combined and used. The polymerization is carried out as a result of mixing and mixing the polymerization solution in the polymerization tank (polymerization unit). As for the polymerization tank, which is used for 1,2-polymerization, since during the 1,2-polymerization the viscosity becomes so high that the polymer will tend to adhere to it, it will be possible to use a polymerization tank equipped with a device for mixing highly viscous solution, for example, with the device described in JP-B-40-2645.

If upon receipt of the vinyl-cis-polybutadiene rubber of the invention, the vinyl-cis-polybutadiene rubber will be obtained by cis-1,4-polymerization and then 1,2-polymerization, as described above, then the vinyl-cis production system β-polybutadiene rubber will include the step of adding a high molecular weight substance having at least one unsaturated double bond to one repeating unit and containing at least one element selected from polyisoprene, crystalline polybutadiene melting point not exceeding 150 ° C, liquid polybutadiene and derivatives thereof. Even if, for example, such a substance will be added during mixing during the preparation of the filled mixture after obtaining vinyl-cis-polybutadiene rubber, the effects of the invention of this application will not be obtained. With regard to the addition of this unsaturated high molecular weight substance to the production system, the addition of the polymerization reaction to the mixture is preferably carried out at an arbitrary point in time from cis-1,4-polymerization to 1,2-polymerization, and more preferably during 1,2- polymerization.

As the aforementioned unsaturated macromolecular substance, at least one element selected from polyisoprene, crystalline polybutadiene with a melting point less than 170 ° C, linear polybutadiene and their derivatives is preferred.

Examples of polyisoprene typically include synthetic polyisoprene (e.g., cis-1,4-polyisoprene, in which the cis structure is 90% or more), liquid polyisoprene, trans-polyisoprene and other modified polyisoprene.

Crystalline polybutadiene with a melting point less than 170 ° C. is preferably crystalline polybutadiene with a melting point in the range of 0 to 150 ° C., and examples thereof include low melting 1,2-polybutadiene and trans-polybutadiene.

Examples of liquid polybutadiene include extremely low molecular weight polybutadiene exhibiting an intrinsic viscosity [η] not exceeding 1.

In addition, examples of these derivatives include isoprene / isobutylene copolymer, isoprene / styrene copolymer, styrene / isoprene / styrene block copolymer, liquid epoxidized polybutadiene, liquid carboxyl-modified polybutadiene and hydrogenation products of these derivatives.

Among the aforementioned corresponding unsaturated macromolecular substances, it is preferable to use polyisoprene, a block copolymer of styrene / isoprene / styrene and 1,2-polybutadiene with a melting point in the range from 70 to 110 ° C. In addition, the aforementioned corresponding unsaturated macromolecular substances can be used individually in a mixture of two or more types thereof.

As described previously, when the aforementioned unsaturated high molecular weight substance is added to the resulting vinyl cis-polybutadiene rubber, the dispersibility of 1,2-polybutadiene with a melting point of 170 ° C. or more in cis-polybutadiene rubber acting as a matrix component significantly increase due to the compatibilizing effect of unsaturated high molecular weight substances. As a result, the characteristics of the resulting vinyl cis-polybutadiene rubber become excellent.

The added amount of unsaturated macromolecular substance is preferably in the range from 0.01 to 50 wt.%, And more preferably from 0.01 to 30 wt.%, Based on the amount of vinyl-cis-polybutadiene rubber produced. In addition, with regard to the addition at any time, after the addition, stirring is preferably carried out over a period of time from 10 minutes to 3 hours, and more preferably from 10 minutes to 30 minutes.

After the polymerization reaction reaches a predetermined polymerization rate, a known antioxidant may be added in accordance with normal practice. Representative examples of the antioxidant include phenol-based antioxidants such as 2,6-di-tert-butyl-p-cresol (BHT); phosphorus-based antioxidants such as trinonyl phenyl phosphite (TNP); and sulfur-based antioxidants such as 4,6-bis (octylthiomethyl) -o-cresol and dilauryl-3,3'-thiodipropionate (TPL). An antioxidant can be used individually or in combination of two or more types. The amount of antioxidant added is in the range of 0.001 to 5 parts by weight, based on 100 parts by weight of vinyl-cis-polybutadiene rubber. After that, an inhibitor is added to the polymerization system, thereby stopping the polymerization. This is carried out in accordance with a method which is itself known, for example, by a method in which, after the completion of the polymerization reaction, the polymerization reaction mixture is fed to the reaction inhibition tank and a large amount of a polar solvent, such as alcohols, such as methanol and ethanol and water; and by a method in which an inorganic acid, such as hydrochloric acid and sulfuric acid, an organic acid, such as acetic acid and benzoic acid, or hydrogen chloride gas, are introduced into the mixture of the polymerization reaction. Thereafter, the obtained vinyl cis-polybutadiene rubber, in accordance with conventional practice, is separated, recovered, washed and dried to obtain the desired vinyl cis-polybutadiene rubber.

In the General case, the thus obtained vinyl-cis-polybutadiene rubber according to the invention, the ratio between the quantities of the respective components, namely the ratio between the quantities of 1,2-polybutadiene with a melting point of 170 ° C or more, cis-polybutadiene rubber and unsaturated high molecular weight substance represents what is described above. In addition, in the microstructure of cis-polybutadiene rubber, cis-1,4-polybutadiene is 80% or more of it, and the remainder consists of trans-1,4-polybutadiene and vinyl-1,2-polybutadiene. This cis-polybutadiene rubber and unsaturated macromolecular substance are soluble in boiling n-hexane, and 1,2-polybutadiene with a melting point of 170 ° C or more is a substance insoluble in boiling n-hexane (here and hereinafter abbreviated as “HI”). In the General case, this 1,2-polybutadiene with a melting point of 170 ° C or more, detects a melting point in the range from 170 to 220 ° C and is a crystalline fiber in the state of a short fiber, as described previously. In addition, as described previously, the ML value of cis-polybutadiene rubber is in the range from 10 to 50, and preferably from 20 to 40.

In addition, as previously described, in the vinyl cis-polybutadiene rubber of the invention, 1,2-polybutadiene with a melting point of 170 ° C or more, and the unsaturated high molecular weight substance are uniformly dispersed in the cis-polybutadiene rubber matrix.

In the general case, as previously described, in the vinyl-cis-polybutadiene rubber of the invention, 1,2-polybutadiene with a melting point of 170 ° C. or more is dispersed as a crystalline fiber. In addition, the unsaturated high molecular weight substance can be dispersed in an embodiment of any type related to a 1,2-polybutadiene crystal fiber with a melting point of 170 ° C. or more. Examples of this dispersion embodiment include an embodiment in which a crystalline fiber 2 of 1,2-polybutadiene with a melting point of 170 ° C. or more and small particles 3 of an unsaturated high molecular weight substance are individually dispersed in matrix 1, as conceptually illustrated in FIG. .one; an embodiment in which the fine particles 3 of an unsaturated high molecular weight substance are dispersed in the matrix 1 in a state in which they adhere to the crystal fiber 2 of 1,2-polybutadiene, as conceptually illustrated in FIG. 2; an embodiment in which a crystalline fiber 2 of 1,2-polybutadiene is dispersed in a matrix 1 in a state in which it adheres to the fine particles 3 of an unsaturated high molecular weight substance, as conceptually illustrated in FIG. 3; and an embodiment in which a crystalline fiber 2 of 1,2-polybutadiene is dispersed in a matrix 1 in a state in which it is incorporated and dispersed in fine particles 3 of an unsaturated high molecular weight substance, as conceptually illustrated in FIG. 4. Embodiments may also be used in which two or more types of dispersed conditions coexist, shown in FIG. from 1 to 4. In Figs. 1-4, 1 denotes a matrix; 2 denotes a crystalline fiber of 1,2-polybutadiene with a melting point of 170 ° C. or more; and 3 denotes small particles of unsaturated macromolecular substance.

In the method for producing vinyl cis-polybutadiene rubber of the invention, 1,3-butadiene and a hydrocarbon-based solvent are usually separated by distillation from the mother liquor of the polymerization reaction mixture, which remains after separation and preparation of the resulting vinyl-cis-polybutadiene rubber, which contains unreacted 1,3-butadiene, a hydrocarbon-based solvent and carbon disulfide, and the like; and carbon disulfide is separated and removed as a result of adsorption and separation treatment of carbon disulfide or separation treatment of a carbon disulfide adduct, thereby ensuring the recovery of 1,3-butadiene and a hydrocarbon-based solvent that are substantially free of carbon disulfide. In addition, 1,3-butadiene and a hydrocarbon-based solvent that are substantially free of carbon disulfide can also be recovered by removing the three components from the above mother liquor of the polymerization reaction mixture by distillation, and then separating and removing carbon disulfide by using the aforementioned adsorption and separation or separation treatment of a carbon disulfide adduct. Thus, the recovered carbon disulfide and the hydrocarbon-based solvent are mixed with 1,3-butadiene, again supplied to fill the flow, and then sent for reuse.

According to the aforementioned method for producing vinyl cis-polybutadiene rubber, the vinyl cis-polybutadiene rubber of the invention can be advantageously continuously produced on an industrial scale with excellent performance of the catalytic component and with high catalytic efficiency. In particular, vinyl-cis-polybutadiene rubber can advantageously be continuously produced on an industrial scale with a high degree of conversion without consequences in the form of sticking to the inner wall in a polymerization tank, mixing blades and other parts where mixing is slow.

Thus, in order for the thus obtained vinyl-cis-polybutadiene rubber to exhibit excellent desirable characteristics, it is preferred that the 1,2-polybutadiene crystal fiber dispersed in the vinyl-cis-polybutadiene rubber be partially dispersed in a monodisperse state in as small crystals in a matrix of cis-polybutadiene rubber and would coexist with a large 1,2-polybutadiene crystalline fiber, showing the presence of a coagulation structure. That is, it is preferable that the monodisperse 1,2-polybutadiene crystalline fiber in the cis-polybutadiene rubber matrix is in a state of short fiber, in which the minor axis of the crystals formed by the middle monodisperse fiber does not exceed 0.2 μm, the aspect ratio does not exceed 10, and the number of crystals formed by the middle monodisperse fiber is 10 or more, and would have a melting point of 170 ° C. or more. In addition, in addition to a 1,2-polybutadiene crystalline fiber having a melting point of 170 ° C. or more, it is preferable that an unsaturated high molecular weight substance be dispersed in a matrix of cis-polybutadiene rubber. It is preferable that this unsaturated high molecular weight substance exhibits a high affinity for a 1,2-polybutadiene crystalline fiber and is dispersed in a physically or chemically adsorbed state in the vicinity of the crystalline fiber in question in a cis-polybutadiene rubber matrix (dispersion embodiments of Figs. 2 to four). If, as previously described, a 1,2-polybutadiene crystalline fiber having a melting point of 170 ° C or more and an unsaturated high molecular weight substance coexist and are dispersed in a matrix of cis-polybutadiene rubber, then the above various physical properties will become excellent , and therefore, this option is preferred.

Thereafter, as a result of mixing in the preparation of the filled mixture (a) of the aforementioned vinyl-cis-polybutadiene rubber, (b) a diene-based rubber other than (a), and (c) a reinforcing rubber filler containing 40% or more silicon dioxide, a silica-filled rubber composition is prepared for the manufacture of a tire that is used in the invention.

In addition, as a result of mixing during the preparation of the filled mixture (a) of the aforementioned vinyl-cis-polybutadiene rubber, (e) styrene-butadiene rubber, (b) diene-based rubber other than (a) and (e), and (d) a filler reinforcing rubber, receive a rubber composition intended for the manufacture of a treadmill tread of a passenger car tire, which is used in the invention.

In addition, as a result of mixing in the preparation of the filled mixture (a) of the aforementioned vinyl-cis-polybutadiene rubber, (b) a diene-based rubber other than (a), and (c) a filler reinforcing the rubber, each representative selected from a rubber composition intended for the manufacture of a sidewall, a rubber composition intended for the manufacture of a tire of a large-sized vehicle, a high hardness filled rubber composition, a rubber composition intended for the manufacture of anavochnogo tread and a rubber composition for tire cord coating which are used in the invention.

Examples of the aforementioned diene-based rubber (b) include a high cis structure polybutadiene rubber, a low cis structure polybutadiene rubber (BR), natural rubber, polyisoprene rubber, emulsion polymerised or SB polymerised (SBR rubber). ), rubber based on a copolymer of ethylene, propylene and diene monomer (EPDM), butadiene acrylonitrile rubber (NBR), butyl rubber (IIR) and chloroprene rubber (CR).

In addition, derivatives of these rubbers, for example polybutadiene rubbers modified with a tin compound, and the aforementioned rubbers, which are modified with epoxide, modified with silane or modified with maleic acid, can also be used. These rubbers can be used individually or in combination of two or more types.

As the rubber reinforcing filler, which is component (c) of the invention, mention may be made of carbon black having a particle size not exceeding 90 nm and exhibiting a dibutyl phthalate (DBP) oil absorption of 70 ml / 100 g or more, and examples thereof include FEF, FF, GPF, SAF, ISAF, SRF and HAF. In addition, examples of silica include silicic anhydride obtained by the dry process and hydrated silicic acid and synthetic silicates obtained by the wet process. In addition, examples of a rubber reinforcing filler, in addition to various carbon black grades, include inorganic reinforcing fillers such as carbon black, activated calcium carbonate, and ultrafine magnesium silicate; and organic reinforcing agents such as syndiotactic 1,2-polybutadiene resin, polyethylene resin, polypropylene resin, high impact polystyrene resin, phenolic resin, lignin, modified melamine resin, coumaronindene resin and petroleum resin.

In a tire-filled rubber composition of the invention for manufacturing a tire, the above-mentioned respective components are mixed to formulate the filled mixture in such a way as to satisfy the condition of 100 parts by mass of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range of 20 up to 80 wt.% and diene-based rubber (b) other than (a) in an amount in the range from 80 to 20 wt.%, and from 40 to 100 mass parts of a rubber reinforcing filler containing 40% or more e silicon dioxide (s).

If the amount of the aforementioned vinyl-cis-polybutadiene is less than the aforementioned lower limit, then the swelling of the extrudable stream will be large, and a rubber composition exhibiting low exothermic characteristics with respect to its vulcanizate will not be obtained, while if the amount of vinyl-cis-cis-polybutadiene is not If the polybutadiene content is greater than the aforementioned upper limit, then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the elastic modulus of its vulcanizate will be reduced, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high, so that the formability of the tire, likely to get worse. In addition, if the proportion of rubber goes beyond the aforementioned range, then the resistance to abrasive wear of its vulcanizate and the like will be reduced.

In the rubber composition of the invention intended for the manufacture of sidewalls, the aforementioned corresponding components are mixed in the preparation of the filled mixture in such a way as to satisfy the condition of 100 mass parts of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range from 20 to 80 wt. % and diene-based rubber (b), other than (a), in an amount in the range from 80 to 20 wt.%, and from 25 to 60 parts by weight of a rubber reinforcing filler, (c).

If the amount of the aforementioned vinyl-cis-polybutadiene is less than the aforementioned lower limit, then the swelling of the extrudable stream will be large and a rubber composition exhibiting low fuel consumption in relation to its vulcanizate will not be obtained, while if the amount of the aforementioned vinyl-cis If the polybutadiene content is greater than the aforementioned upper limit, then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the swelling of the extrudable stream will become large, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high so that kneading becomes difficult. and therefore, this option is not preferred.

In the rubber composition of the invention intended for the manufacture of a passenger car tire, the aforementioned respective components are mixed in the preparation of the filled mixture in such a way as to satisfy the condition of 100 mass parts of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range from 10 to 50 wt.%, Styrene butadiene rubber (b) in an amount in the range from 30 to 70 wt.% And diene-based rubber (c) other than (a) and (b), in an amount in the range from 0 to 60 wt. %, and from 40 to 100 ma osovye parts of the filler, reinforcing rubber, (d).

If the amount of the aforementioned vinyl cis-polybutadiene is less than the aforementioned lower limit, then a rubber composition exhibiting a high modulus of elasticity with respect to its vulcanizate will not be obtained, while if the amount of vinyl-cis-polybutadiene is greater than the aforementioned upper limit, then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the elastic modulus of its vulcanizate will be reduced, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high, so that the formability of the tire, likely to get worse. In addition, if the proportion of rubber goes beyond the aforementioned range, then the resistance to abrasive wear of its vulcanizate and the like will be reduced.

In the rubber composition of the invention intended for the manufacture of a large-sized vehicle tire, the aforementioned respective components are mixed in the preparation of the filled mixture in such a way as to satisfy the condition of 100 mass parts of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range of 10 up to 60 wt.% and diene-based rubber (b), other than (a), in an amount in the range of 90 to 40 wt.%, and from 45 to 70 mass parts of the rubber reinforcing filler, (c).

If the amount of the aforementioned vinyl cis-polybutadiene is less than the aforementioned lower limit, then a rubber composition exhibiting a high modulus of elasticity with respect to its vulcanizate will not be obtained, while if the amount of vinyl-cis-polybutadiene is greater than the aforementioned upper limit, then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the elastic modulus of its vulcanizate will be reduced, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high, so that the formability of the tire, likely to get worse. In addition, if the proportion of rubber goes beyond the aforementioned range, then the elastic modulus of its vulcanizate and the like will be degraded.

In the highly hard filled rubber composition of the invention, the aforementioned respective components are mixed in the preparation of the filled mixture in such a way as to satisfy the condition of 100 parts by mass of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range from 20 to 80% by weight and rubber on a diene base (b) other than (a), in an amount in the range from 80 to 20 wt.%, and from 40 to 100 mass parts of a rubber reinforcing filler, (c).

If the amount of the aforementioned vinyl-cis-polybutadiene is less than the aforementioned lower limit, then the swelling of the extrudable stream will be large, and a rubber composition exhibiting low exothermic characteristics with respect to its vulcanizate will not be obtained, while if the amount of vinyl-cis-cis-polybutadiene is not If the polybutadiene content is greater than the aforementioned upper limit, then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the swelling of the extrudable stream will become large, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high so that kneading becomes difficult. and therefore, this option is not preferred.

In the rubber composition of the invention intended for the manufacture of a groove tread layer, the aforementioned respective components are mixed in the preparation of the filled mixture in such a way as to satisfy the condition of 100 parts by mass of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range from 20 to 80 wt.% And diene-based rubber (b), other than (a), in an amount in the range from 80 to 20 wt.%, And from 25 to 55 parts by weight of a rubber reinforcing filler, (c).

If the amount of the aforementioned vinyl-cis-polybutadiene is less than the aforementioned lower limit, then the swelling of the extrudable stream will be large, and a rubber composition exhibiting low exothermic characteristics with respect to its vulcanizate will not be obtained, while if the amount of vinyl-cis-cis-polybutadiene is not If the polybutadiene content is greater than the aforementioned upper limit, then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the swelling of the extrudable stream will become large, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high so that kneading becomes difficult. and therefore, this option is not preferred.

In the rubber composition of the invention intended for the manufacture of tire tire linings, the aforementioned respective components are mixed to formulate the filled mixture in such a way as to satisfy the condition of 100 parts by mass of the rubber component formed by vinyl-cis-polybutadiene (a) in an amount in the range from 10 to 60 wt.% And diene-based rubber (b), other than (a), in an amount in the range from 90 to 40 wt.%, And from 30 to 80 parts by weight of a rubber reinforcing filler, (c).

If the amount of the aforementioned vinyl cis-polybutadiene is less than the aforementioned lower limit, then a rubber composition exhibiting a high modulus of elasticity with respect to its vulcanizate will not be obtained, while if the amount of vinyl-cis-polybutadiene is greater than the aforementioned upper limit, then then the Mooney viscosity of the composition will be excessively high, so that the formability will become worse. If the amount of the aforementioned rubber reinforcing filler is less than the aforementioned lower limit, then the elastic modulus of its vulcanizate will be reduced, while if it is greater than the aforementioned upper limit, then the Mooney viscosity will be excessively high, so that the formability of the tire, likely to get worse. In addition, if the proportion of rubber goes beyond the aforementioned range, then the elastic modulus of its vulcanizate and the like will be reduced, and the adhesion to metals will be reduced.

The rubber composition of the invention is obtained by kneading the aforementioned respective components in a conventional manner using a Banbury mixer, open rollers, a plasticizer, a twin screw kneading machine and the like. The kneading temperature is required to be lower than the melting temperature of the 1,2-polybutadiene crystalline fiber that is contained in the subject vinyl cis-polybutadiene. If kneading is carried out at a temperature above a given melting point of a 1,2-polybutadiene crystalline fiber, then the small short fibers in vinyl-cis-polybutadiene will melt and deform to become spherical particles and the like, and therefore this option is not preferred.

If desired, components for making a filled mixture that are commonly used in the rubber industry, such as a vulcanizer, vulcanization activator, antioxidant, filler, process oil, zinc white and stearic acid, can be mixed into the rubber composition of the invention.

As a vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin-based vulcanizing agents and metal oxides such as magnesium oxide are suitable for use.

As a vulcanization activator, known vulcanization activators such as aldehydes, ammonia brands, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates and xanthates are suitable for use.

Examples of the antioxidant include amine / ketone based antioxidants, imidazole based antioxidants, amine based antioxidants, phenol based antioxidants, sulfur based antioxidants and phosphorus based antioxidants.

Examples of filler include inorganic fillers such as calcium carbonate, basic magnesium carbonate, clay, lead acid and diatomaceous earth; and organic fillers such as regenerated rubbers and powdered rubbers.

Suitable process oils are all aromatic process oils, naphthenic-based process oils and paraffin-based process oils.

A silicon dioxide-filled rubber composition of the invention for manufacturing a tire can be developed to provide improved performance for swelling of the extrudable stream, performance for abrasion resistance and performance for low fuel consumption while maintaining slippage characteristics on wet roads, and it is suitable for use in applications such as the tread or sidewall of a tire, When even good balance performance.

The rubber composition of the invention, intended for the manufacture of a sidewall, is characterized by a small swelling of the extrudable stream and exhibits low exothermic characteristics with respect to its vulcanizate. Thus, it can be used as a tire element of a passenger car, bus, truck, plane, tire with a flat tire and the like in combination with another tire element (for example, a treadmill, a sidewall, a reinforcing layer of a sidewall, a trench layer of a tread, frame, breaker and edge) instead of the commonly known rubber compositions intended for the manufacture of sidewalls.

The rubber composition of the invention for manufacturing a passenger car tire is characterized by excellent processability during extrusion molding and shows satisfactory properties with respect to high-speed motion, wet grip characteristics and abrasion resistance. Thus, it can be used as a tire element of a passenger car, bus, truck, plane, tire with a flat tire and the like in combination with another tire element (for example, a treadmill, a sidewall, a reinforcing layer of a sidewall, a trench layer of a tread, frame, breaker and flange) instead of the commonly known rubber compositions intended for the manufacture of a treadmill.

The rubber composition of the invention, intended for the manufacture of a tire of a large-sized vehicle, is characterized by a small swelling of the extrudable stream and demonstrates excellent processability during extrusion while maintaining a high modulus of elasticity. Thus, it can be used as a tire element of a passenger car, bus, truck, plane, tire with a flat tire and the like in combination with another tire element (for example, a treadmill, a sidewall, a reinforcing layer of a sidewall, a trench layer of a tread, frame, breaker and flange) instead of the commonly known rubber compositions intended for the manufacture of a treadmill.

The highly hard filled rubber composition of the invention is characterized by low swelling of the extrudable stream and exhibits low exothermic characteristics with respect to its vulcanizate. Thus, it can be used as a tire element of a passenger car, bus, truck, plane, tire with a flat tire and the like in combination with another tire element (for example, a treadmill, a sidewall, a reinforcing layer of a sidewall, a trench layer of a tread, frame, breaker and flange) instead of the commonly known high hard filled rubber compositions.

The rubber composition of the invention, intended for the manufacture of the undercut groove of the tread, is characterized by a small swelling of the extrudable stream and exhibits low exothermic characteristics with respect to its vulcanizate. Thus, it can be used as a tire element of a passenger car, bus, truck, plane, tire with a flat tire and the like in combination with another tire element (for example, a treadmill, a sidewall, a reinforcing layer of a sidewall, a trench layer of a tread, frame, breaker and rim) instead of the commonly known rubber compositions intended for the manufacture of the undercut groove of the tread.

The rubber composition of the invention, intended for the manufacture of tire casing linings, is characterized by low swelling of the extrudable flow and high cohesive strength in the unvulcanized state and demonstrates excellent processability during molding during extrusion and formability while maintaining a high modulus of elasticity. Thus, it can be used as a tire element of a passenger car, bus, truck, plane, tire with a flat tire and the like in combination with another tire element (for example, a treadmill, a sidewall, a reinforcing layer of a sidewall, a trench layer of a tread, carcass, breaker and rim) instead of the commonly known rubber compositions intended for the manufacture of tire lining.

Example 1

Next, examples based on the invention and comparative examples will be specifically described. In the examples and comparative examples, the physical properties of the crude rubber formed by the resulting vinyl cis-polybutadiene rubber, the physical properties of the filled material formed by the resulting rubber composition, and the physical properties of its vulcanizate were measured as follows.

(1) Level of 1,2-polybutadiene crystalline fiber.

The amount of extraction residue resulting from 2 g of vinyl-cis-polybutadiene rubber extraction in boiling medium using 200 ml of n-hexane for 4 hours using a Soxhlet extraction apparatus was expressed in parts by weight.

(2) Melting point of a 1,2-polybutadiene crystalline fiber.

For the residue after extraction in boiling n-hexane, a determination was made of the peak temperature on the endothermic curve obtained using a differential scanning calorimeter (DSC).

(3) A form of crystalline fiber.

Vinyl-cis-polybutadiene rubber in which 1,2-polybutadiene with a melting point of 170 ° C or more is present in a state of short crystalline fiber and an unsaturated high molecular weight substance is present in a granular state in cis-polybutadiene, which plays the role of a matrix component moreover, particles of unsaturated macromolecular substance dispersed in cis-polybutadiene, which is the aforementioned component (2) and plays the role of a matrix component, are characterized by a larger size a major axis in the range from 0.2 to 1000 microns, and a short crystalline fiber of 1,2-polybutadiene dispersed in the particles of the high molecular weight substance is characterized by a major axis length in the range from 0.01 to 0.5 microns, vulcanized using monochloride sulfur and carbon disulfide; the vulcanizate was cut into ultrafine sections; and for the double bond of the rubber segment of vinyl-cis-polybutadiene, staining was carried out using osmium tetrachloride vapors and determined by observation using a transmission electron microscope.

(4) Microstructure of the rubber segment in vinyl-cis-polybutadiene rubber.

The infrared absorption spectra were analyzed. The microstructure was calculated from the ratio between the absorption intensities for the cis structure in the region of 740 cm ⁻¹ , for the transformation in the region of 967 cm ⁻¹ and for the vinyl structure in the region of 910 cm ⁻¹ .

(5) Viscosity in toluene solution for rubber segment in vinyl cis-polybutadiene rubber.

Viscosity was measured in a toluene solution with a concentration of 5 wt.% At 25 ° C and expressed in centipoises (centipoise).

(6) The value [η] for the rubber segment in vinyl-cis-polybutadiene rubber.

As a result of drying, a soluble substance in boiling n-hexane was collected, and a measurement was carried out for it in a toluene solution at a temperature of 30 ° C.

(7) Mooney viscosity.

The value measured at 100 ° C in accordance with JIS K6300.

(8) Swelling of the extrudable stream.

As an estimate of the processability of the filled material during extrusion, the ratio between the size of the filled material and the size of the outlet portion of the forming channel of the extruder head (where L / D = 1.5 mm / 1.5 mm) was measured and the determination was carried out during extrusion at 100 ° C and at a shear rate of 100 s ^-1 using a processability analyzer (MRI manufactured by Monsanto).

(9) Tensile modulus.

The tensile modulus M300 was measured in accordance with JIS K6301.

(10) Pico abrasion.

The Pico abrasion index was measured in accordance with D2228.

(11) Wet slippage performance.

They were measured using a portable wet slippage test device and 3M Safety-Walk device (Type B).

(12) Low fuel consumption (low exothermic characteristics or exothermic characteristics).

The heat release for the rubber composition was measured in a fixed voltage mode with a static load of 196 n at a temperature of 40 ° C and a frequency of 10 Hz. The lower the index, the more excellent the fuel consumption.

(13) Hardness.

It was measured at room temperature using a Type A hardness tester in accordance with JIS K6253.

(14) The modulus of elasticity in an unvulcanized state.

Carrying out cutting from unvulcanized rubber using a double-blade stamp No. 3, a sample was obtained, for which measurements were then taken at room temperature at a drawing speed of 200 mm / min.

(15) Adhesive bond strength with metal.

It was measured in accordance with ASTM D2229.

Obtaining a sample of vinyl-cis-polybutadiene 1.

A solution in the form of 1.6 kg of 1,3-butadiene dissolved in 18 kg of absolute cyclohexane, to which 4 mmol of octanoate was added, was then loaded into a reaction vessel equipped with a stirrer made of stainless steel, having an internal volume of 30 L and purged with nitrogen gas. cobalt, 84 mmol of diethylaluminium chloride and 70 mmol of 1,5-cyclooctadiene, and the mixture was stirred at 25 ° C. for 30 minutes, thereby allowing cis polymerization to proceed. The resulting polymer showed ML 33 and T-cp 59 values and was characterized by the presence of a microstructure consisting of 0.9% 1,2-structure, 0.9% trans-1,4-structure and 98.2% cis-1, 4-structure. At the end of the cis polymerization, 5% by weight (percentage based on the amount of the resulting vinyl cis polybutadiene rubber) of an unsaturated high molecular weight substance consisting of polyisoprene (IR) was added to the resulting polymerization product solution (ML: 87, cis -1,4-structure: 98%), and the mixture was stirred at 25 ° C for one hour. Immediately after this, 90 mmol of triethylaluminium and 50 mmol of carbon disulfide were added to the polymerization solution, and the mixture was stirred at 25 ° C. for 60 minutes, thereby allowing the passage of 1,2 polymerization. Upon completion of the polymerization, a solution of the polymerization product was added to 18 L of methanol containing 1 wt.% Of 4,6-bis (octylthiomethyl) -o-cresol, thereby allowing the formation of deposits and precipitation of the rubber polymer. This rubber polymer was separated, washed with methanol, and then dried in vacuum at normal temperature. Thus obtained vinyl-cis-polybutadiene rubber showed a percentage yield of 80%. After that, this vinyl-cis-polybutadiene rubber was treated with boiling n-hexane, and the insoluble matter and soluble material were separated and dried. The resulting boiling n-hexane soluble polymer exhibited ML 31, T-cp 57 and a T-cp / ML ratio of approximately 1.8, and was characterized by the presence of a microstructure consisting of 1.0% 1.2- structure, 0.9% trans-1,4 structure and 98.1% cis-1,4 structure. In addition, the value [η] was equal to 1.7. The number of crystals formed by monodisperse fiber, characterized by a minor axis length not exceeding 0.2 μm, contained in vinyl-cis-polybutadiene rubber was 100 or more, the aspect ratio did not exceed 10, and the melting point was 202 ° C.

Obtaining a sample of vinyl-cis-polybutadiene 2.

Vinyl-cis-polybutadiene was obtained in the same manner as in the method for producing sample 1, except that no unsaturated high molecular weight substance (additive) was added.

The physical properties of the aforementioned sample 1 and sample 2 are shown in table 1.

Table 1 Sample Name Sample 1 Sample 2 High molecular weight substance (Add quantity) IR Absent (10 wt.%) Polymerization Solvent (SP value for polymerization solvent) Cyclohexane 1.4 8.1 1.4 Characteristics of a Matrix in Vinyl-CIS-Polybutadiene Rubber Mooney Viscosity 31 1.4 [η] 1.7 1.4 Viscosity in toluene solution (cP) 57 four Microstructure (%) Cis 98.1 four Trance 0.9 four Vinyl 1,0 four Characteristics of 1,2-polybutadiene crystalline fiber The melting temperature of the crystal formed by the fiber, (° C) 202 four The number of crystals formed by monodisperse fiber: (The number of crystals characterized by a small axis length not exceeding 0.2 microns per 400 microns ² ) 100 or more four Aspect ratio for monodisperse crystals No more than 10 20 or more The size of the major axis for crystalline fiber dispersed in the matrix 0.2 to 0.5 1 or more The major axis size for a crystalline fiber dispersed in a high molecular weight substance No more than 0.1 - wt.% 1,2-polybutadiene 12 Small The number of crystals formed by monodisperse fiber Big Small

Examples 1-1 to 1-4 and comparative examples 1-1 to 1-3

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2 of components for the composition of the filled mixture, other than the vulcanization accelerator and sulfur, from the formulation for the composition of the filled mixture shown in Table 2, such thus, obtaining a kneaded material, which is a silicon dioxide-filled rubber composition for manufacturing a tire. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. After that, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10-inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 2.

The compositions of the examples realize a small swelling of the extrudable stream, high abrasion resistance and low fuel consumption while maintaining wet slippage characteristics in comparison with the case of using commercially available polybutadiene with a high level of cis structure, as in comparative examples. On the other hand, when vinyl cis-polybutadiene is used in the compositions of comparative examples, which does not meet the characteristics of the invention, or the amount of added silicon dioxide is small, then, despite the implementation of a small swelling of the extrudable stream and high resistance to abrasive wear, there is a significant deterioration in performance slipping on wet roads, so that the desired characteristics cannot be obtained.

table 2 Table for compiling a filled mixture Example Comparative example 1-1 1-2 1-3 1-4 1-1 1-2 1-3 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 Sample 1 - Sample 2 Sample 1 Quantity (parts) 35 35 45 35 - 35 35 NR (Natural Rubber) (Note 1) - 25 fifteen - - - - BR (note 2) - - - - 35 - - SRB1500 65 40 40 65 65 65 65 Carbon black N330 27 27 27 21.5 27 27 60 Silica (Note 3) thirty thirty thirty 35 thirty thirty - Silane Sizing (Note 4) 6 6 6 7 6 6 - Aromatic oil fifteen fifteen fifteen fifteen fifteen fifteen fifteen Zinc oxide 5 5 5 5 5 5 3 Stearic acid 2 2 2 2 2 2 2 Antioxidant (note 5) one one one one one one one Vulcanization Accelerator (Note 6) 1.3 1.3 1.3 1.4 1.3 1.3 one Vulcanization Accelerator (Note 7) 0.7 0.7 0.7 0.9 0.7 0.7 - Sulfur 2 2 2 21 2 2 1.8 Physical properties of the filled material: Extruded Flow Swell Index 73 79 77 78 one hundred 92 68 Physical properties of the vulcanizate: Pico Abrasion (Index) 172 160 180 163 one hundred 160 185 Wet slippage performance (index) 99 98 98 one hundred one hundred 91 90 Low fuel consumption (index) 89 89 79 83 one hundred 103 110

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Ultrasil VN3 GR (manufactured by Degussa).

(Note 4) X50S (a mixture of equal amounts of N330 and Si69, manufactured by Degussa).

Si69: Bis (3-triethoxysilylpropyl) tetrasulfide.

(Note 5) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 6) Vulcanization accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide).

(Note 7) Vulcanization accelerator: NOCCELER D (N, N'-diphenylguanidine).

Examples 2-1 to 2-5 and comparative examples 2-1 to 2-4

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2 of components for preparing the filled mixture other than the vulcanization accelerator and sulfur from the filled mixture formulation shown in Table 3, such thus, getting mixed material, which is a rubber composition intended for the manufacture of sidewalls. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. Thereafter, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10 inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 3.

The compositions of the examples are significantly improved in terms of modulus of elasticity and show a very good balance between the swelling of the extrudable stream and the exothermic characteristics in comparison with the case of using commercially available polybutadiene with a high level of cis structure, as in comparative examples. On the other hand, when commercially available BR is used in the compositions of comparative examples, then the swelling of the extrudable stream is large; and when the amount of carbon black is large when compiling the filled mixture, then the exothermic characteristics deteriorate. In addition, when vinyl-cis-polybutadiene is used that is not in accordance with the invention, or the amount of vinyl-cis-polybutadiene used is small, then the improvement effects do not reach the expected levels.

Table 3 Table for compiling a filled mixture Example Comparative example 2-1 2-2 2-3 2-4 2-5 2-1 2-2 2-3 2-4 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 Sample 1 Sample 1 - Sample 2 Sample 1 Sample 1 Quantity (parts) 60 60 60 80 40 - 60 60 10 NR (note 1) 40 40 40 twenty 60 40 40 40 90 BR (note 2) - - - - - 60 - - - Carbon black N330 40 55 thirty 40 40 40 40 70 40 Aromatic oil 10 10 10 10 10 10 10 10 10 Zinc oxide 3 3 3 3 3 3 3 3 3 Stearic acid 2 2 2 2 2 2 2 2 2 Antioxidant (Note 3) one one one one one one one one one Vulcanization Accelerator (Note 4) 1,0 1,0 1,0 0.9 0.8 1,0 1,0 1,0 0.7 Sulfur 1,5 1,5 1,5 1.7 2.0 1,5 1,5 1,5 2.2 Physical properties of the filled material: Extruded Flow Swell Index 73 64 84 68 83 one hundred 90 58 98 Physical properties of the vulcanizate: 300% tensile modulus (index) 190 240 160 165 185 one hundred 135 269 104 Exothermic Characteristics (Index) 80 90 69 75 86 one hundred 104 107 101

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 4) Vulcanization Accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide)

Examples 3-1 to 3-4 and comparative examples 3-1 to 3-5.

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2, components for composing the filled mixture, other than the vulcanization accelerator and sulfur, from the formulation for compiling the filled mixture shown in Table 4. thus, getting mixed material, which is a rubber composition intended for the manufacture of a treadmill tread tires of a passenger car. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. Thereafter, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10 inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 4.

The compositions of the examples realize a high modulus of elasticity and high resistance to abrasive wear while maintaining wet slippage characteristics in comparison with the case of using commercially available polybutadiene with a high level of cis structure, as in comparative examples. On the other hand, when vinyl cis-polybutadiene is used in the compositions of the comparative examples, which does not meet the characteristics of the invention, or the amount of SBR added is small, then, despite the high modulus of elasticity and high abrasion resistance being realized, there is a significant decrease in slippage performance by wet roads, so that the desired characteristics cannot be obtained.

Table 4 Table for compiling a filled mixture Example Comparative example 3-1 3-2 3-3 3-4 3-1 3-2 3-3 3-4 3-5 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 Sample 1 - Sample 2 - Sample 1 Sample 1 Quantity (parts) 35 35 45 twenty - 35 - 35 65 NR (note 1) - 25 fifteen 40 35 - - 55 - BR (note 2) - - - - - - 35 - - SBR1500 65 40 40 40 65 65 65 10 35 Carbon black N330 60 60 60 60 60 60 60 60 60 Aromatic oil fifteen fifteen fifteen fifteen fifteen fifteen fifteen fifteen fifteen Zinc oxide 3 3 3 3 3 3 3 3 3 Stearic acid 2 2 2 2 2 2 2 2 2 Antioxidant (Note 3) one one one one one one one one one Vulcanization Accelerator (Note 4) 1,5 1,2 1.3 1,2 1.4 1,5 1,5 1,0 1.3 Sulfur 1.8 1.9 1.8 2.0 2.1 1.8 1.8 2.0 1.7 Physical properties of the filled material: Extruded Flow Swell Index 73 80 72 87 one hundred 92 105 90 62 Physical properties of the vulcanizate: 300% tensile modulus (index) 183 174 190 151 one hundred 126 88 160 215 Pico Abrasion (Index) 177 163 183 152 one hundred 164 146 138 201 Wet slippage performance (index) 99 97 96 98 one hundred 91 88 94 93

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 4) Vulcanization Accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide)

Examples 4-1 to 4-3 and comparative examples 4-1 to 4-2.

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2, components for composing the filled mixture other than the vulcanization accelerator and sulfur, from the formulation for compiling the filled mixture shown in Table 5. thus, obtaining a kneaded material, which is a rubber composition intended for the manufacture of a treadmill tire tread of a large vehicle. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. Thereafter, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10 inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 5.

The compositions of the examples realize small swelling of the extrudable flow and excellent wet slippage and abrasion resistance while maintaining a high modulus of elasticity in comparison with the case of using commercially available polybutadiene with a high cis structure content, as in comparative examples. On the other hand, since vinyl cis-polybutadiene is used in the compositions of the comparative examples, which does not meet the characteristics of the invention, the abrasion resistance does not improve, or the slippage performance deteriorates on wet roads, so that the desired characteristics cannot be obtained.

Table 5 Table for compiling a filled mixture Example Comparative example 4-1 4-2 4-3 4-1 4-2 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 - Sample 2 Quantity (parts) thirty twenty thirty - thirty NR (note 1) 70 80 70 70 70 BR (note 2) - - - thirty - Carbon black N330 60 60 fifty 60 60 Aromatic oil 10 10 10 10 10 Zinc oxide 3 3 3 3 3 Stearic acid 2 2 2 2 2 Antioxidant (Note 3) one one one one one Vulcanization Accelerator (Note 4) 0.8 0.8 0.8 0.8 0.8 Sulfur one one one one one Physical properties of the filled material: Extruded Flow Swell Index 74 82 80 one hundred 95 Physical properties of the vulcanizate: 300% tensile modulus (index) 173 154 127 one hundred 128 Pico Abrasion (Index) 163 144 125 one hundred 133 Wet slippage performance (index) 105 104 105 one hundred 94

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 4) Vulcanization Accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide)

Examples 5-1 to 5-5 and comparative examples 5-1 and 5-2.

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2, components for composing the filled mixture other than the vulcanization accelerator and sulfur, from the formulation for compiling the filled mixture shown in Table 6. thus, obtaining a kneaded material that is a highly hard filled rubber composition. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. Thereafter, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10 inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 6.

The compositions of the examples are significantly improved in terms of modulus of elasticity and exhibit a very good balance between swelling of the extrudable stream and low exothermic characteristics. On the other hand, when commercially available BR is used in the compositions of comparative examples, then the swelling of the extrudable stream is large; and when the amount of carbon black is large when compiling the filled mixture, then the exothermic characteristics deteriorate. In addition, when vinyl-cis-polybutadiene is used that is not in accordance with the invention, or the amount of vinyl-cis-polybutadiene used is small, then the improvement effects do not reach the expected levels.

Table 6 Table for compiling a filled mixture Example Comparative example 5-1 5-2 5-3 5-4 5-5 5-1 5-2 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 Sample 1 Sample 1 - Sample 1 Quantity (parts) fifty 70 thirty fifty fifty - fifty NR (note 1) fifty thirty 70 fifty fifty fifty fifty BR (note 2) - - - - - fifty - Carbon black N330 70 70 70 60 80 70 70 Aromatic oil 5 5 5 10 10 5 5 Zinc oxide 5 5 5 3 3 5 5 Stearic acid 2 2 2 2 2 2 2 Antioxidant (Note 3) one one one one one one one Vulcanization Accelerator (Note 4) 1,0 1,2 0.8 1,0 1,0 1,0 1,0 Sulfur 3.0 2,8 3.2 3.0 3.0 3.0 3.0 Physical properties of the filled material: Extruded Flow Swell Index 75 68 85 83 65 one hundred 89 Physical properties of the vulcanizate: Hardness (index) 124 134 16 116 130 one hundred 109 Low exothermic characteristics (index) 80 73 87 68 84 one hundred 104

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 4) Vulcanization Accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide)

Examples 6-1 to 5-5 and comparative examples 6-1 to 6-5.

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2, components for preparing the filled mixture, other than the vulcanization accelerator and sulfur, from the formulation for preparing the filled mixture shown in Table 7. thus, obtaining a kneaded material that is a highly hard filled rubber composition. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. Thereafter, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10 inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 7.

The compositions of the examples are significantly improved in terms of modulus of elasticity and show a very good balance between swelling of the extrudable stream and exothermic characteristics. On the other hand, when commercially available BR is used in the compositions of comparative examples, then the swelling of the extrudable stream is large; and when the amount of carbon black is large when compiling the filled mixture, then the exothermic characteristics deteriorate. In addition, when vinyl-cis-polybutadiene is used that is not in accordance with the invention, or the amount of vinyl-cis-polybutadiene used is small, then the improvement effects do not reach the expected levels.

Table 7 Table for compiling a filled mixture Example Comparative example 6-1 6-2 6-3 6-4 6-5 6-1 6-2 6-3 6-4 6-5 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 Sample 1 Sample 1 - Sample 2 Sample 1 Sample 1 Sample 1 Quantity (parts) fifty 70 thirty fifty fifty - fifty fifty fifty 10 NR (note 1) fifty thirty 70 fifty fifty fifty fifty fifty fifty 90 BR (note 2) - - - - - fifty - - - - Carbon black N330 40 40 40 fifty 35 40 40 60 twenty 40 Aromatic oil 10 10 10 10 10 10 10 10 10 10 Zinc oxide 5 5 5 5 5 5 5 5 5 5 Stearic acid 2 2 2 2 2 2 2 2 2 2 Antioxidant (Note 3) one one one one one one one one one one Vulcanization Accelerator (Note 4) 1,0 0.9 0.8 1,0 1,0 1,0 1,0 1,0 1,0 0.7 Sulfur 1,5 1.7 2.0 1,5 1,5 1,5 1,5 1,5 1,5 2.2 Physical properties of the filled material: Extruded Flow Swell Index 71 63 85 62 78 one hundred 88 55 103 94 Physical properties of the vulcanizate: 300% tensile modulus (index) 210 234 160 233 190 one hundred 138 260 113 120 Exothermic Characteristics (Index) 83 79 88 96 75 one hundred 106 110 87 99

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 4) Vulcanization Accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide)

Examples 7-1 to 7-3 and comparative examples 7-1 to 7-2.

When using a 1.7 L Banbury mixer for testing, kneading was carried out using each of the aforementioned Sample 1 and Sample 2, components for composing the filled mixture other than the vulcanization accelerator and sulfur, from the formulation for compiling the filled mixture shown in Table 8. thus, getting mixed material, which is a rubber composition intended for the manufacture of the lining of the tire cord. In this case, the maximum kneading temperature was controlled, keeping in the range from 170 to 180 ° C. Thereafter, this kneaded material was kneaded together with a vulcanization accelerator and sulfur on 10 inch rollers, and the mixture was rolled in sheet form and then loaded into a mold for vulcanization, thereby obtaining a vulcanizate. Vulcanization was carried out at 150 ° C for 30 minutes. The results are summarized and shown in table 8.

The compositions of the examples exhibit a small swelling of the extrudable flow, are significantly improved with respect to the elastic modulus in the unvulcanized state while maintaining a high elastic modulus, and are characterized by excellent adhesion to metals. On the other hand, since vinyl cis-polybutadiene, which does not meet the characteristics of the invention, or commercially available polybutadiene with a high level of cis-content is used in the compositions of the comparative examples, the desired characteristics cannot be obtained.

Table 8 Table for compiling a filled mixture Example Comparative example 7-1 7-2 7-3 7-1 7-2 Type of vinyl-cis-polybutadiene Sample 1 Sample 1 Sample 1 - Sample 2 Quantity (parts) 35 twenty 35 - 35 NR (note 1) 65 80 65 65 65 BR (note 2) - - - 35 - Carbon black N330 60 60 fifty 60 60 Zinc oxide 7 7 7 7 7 Stearic acid 2 2 2 2 2 Cobalt stearate 3 3 3 3 3 Antioxidant (Note 3) 2 2 2 2 2 Vulcanization Accelerator (Note 4) 0.8 0.8 0.8 0.8 0.8 Sulfur 1,5 1,5 1,5 1,5 1,5 Physical properties of the filled material: Extruded Swelling (Index) 72 81 80 one hundred 96 100% modulus of elasticity in an unvulcanized state (index) 136 124 113 one hundred 105 Physical properties of the vulcanizate: 300% tensile modulus (index) 174 150 128 one hundred 126 Tensile Strength (Index) 163 144 125 one hundred 138 Adhesive adhesion to metal (index) 107 106 105 one hundred 93

(Note 1) NR: RSS # 1.

(Note 2) BR: Polybutadiene (UBEPOL-BR150, manufactured by Ube Industries, Ltd.).

(Note 3) Antioxidant: ANTAGE AS (reaction product between amine and ketone).

(Note 4) Vulcanization Accelerator: NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide)

Industrial applicability

The silica-filled rubber composition for making a tire used in the invention is characterized by low swelling of the extrudable stream and excellent processability during extrusion and formability while maintaining high slippage characteristics on wet roads, improves the manufacturability of the tire and demonstrates excellent abrasion resistance and low fuel consumption.

The rubber composition of the invention, intended for the manufacture of sidewalls, shows low fuel consumption in relation to its vulcanizate and is characterized by a small swelling of the extrudable stream.

The rubber composition according to the invention and intended for the manufacture of a passenger car tire is capable of realizing a high modulus of elasticity and high abrasion resistance while maintaining slippage characteristics on wet roads.

The rubber composition according to the invention and intended for the manufacture of a tire of a large-sized vehicle is characterized by low swelling of the extrudable stream and excellent processability during extrusion while maintaining a high modulus of elasticity and is able to achieve a very good balance between wet slippage and abrasion resistance.

The high-hardness filled rubber composition according to the invention at the same time improves the dimensional stability during processing and the tire durability while maintaining high hardness and is able to ensure that both performance characteristics are compatible with each other with good balance.

The rubber composition according to the invention and intended for the manufacture of a groove tread layer at the same time improves the swelling of the extrudable stream and low fuel consumption and is able to ensure compatibility of both performance characteristics with each other with good balance.

The rubber composition according to the invention and intended for the manufacture of tire lining is characterized by low swelling of the extrudable stream, high cohesive strength in the unvulcanized state and excellent processability during extrusion and formability while maintaining a high modulus of elasticity, demonstrates excellent adhesion to metals and is able to achieve a very good balance between the corresponding characteristics.

Claims (12)

1. The rubber composition, which is a silicon dioxide-filled rubber composition for making a tire, containing 100 parts by weight the rubber component [(a) + (b)] obtained from 20 to 80 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C. or higher , high molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives, and the third component as a matrix component is is-polybutadiene, and (b) - from 20 to 80 wt.% rubber on a diene basis, other than (a), and from 40 to 100 wt.h. a rubber reinforcing agent (c) containing 40% or more silicon dioxide, wherein the vinyl-cis-butadiene rubber (a) is obtained by cis-1,4 polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis catalyst -1,4-polymerization, with the addition of a high molecular weight substance after the cis-polymerization step, followed by 1,2-polymerization of 1,3-butadiene in the resulting reaction polymerization mixture together with the 1,2-polymerization catalyst, to thereby obtain 1,2-polybutadiene with a melting point equal to 170 ° C or more, and then with separation, extraction of the resulting vinyl-cis-butadiene rubber from the resulting polymerization reaction mixture, where
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, while for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0 , 2 to 1000 microns, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 microns
while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals does not exceed 0.2 μm, the aspect ratio does not exceed 10, and the number of monodisperse fiber crystals per 400 μm ² is 10 or more. 2. The rubber composition, which is a rubber composition intended for the manufacture of sidewalls containing 100 parts by weight the rubber component, [(a) + (b)], obtained from 20 to 80 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C or higher molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives , and the third component as the matrix component is cis-polybutadiene, and (b) - from 20 to 80% by weight of the diene-based rubber other than (a) and from 25 to 60 parts by weight. a rubber reinforcing agent (c), wherein the vinyl-cis-butadiene rubber (a) was obtained by cis-1,4-polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4-polymerization catalyst, s adding a high molecular weight substance after the cis-polymerization step followed by 1,2-polymerization of 1,3-butadiene in the obtained reaction polymerization mixture together with the 1,2-polymerization catalyst to thereby obtain 1,2-polybutadiene with a melting point of 170 ° C or more, and then with the unit, removed the resulting vinyl cis-butadiene rubber from the resulting polymerization reaction mixture, where
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, while for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0 , 2 to 1000 microns, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 μm, while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals and not more than 0.2 micron, the aspect ratio does not exceed 10, and the number of monodispersed fiber crystals 400 microns ² is 10 or more. 3. The rubber composition, which is a rubber composition intended for the manufacture of tires of a passenger car, containing 100 wt.h. the rubber component, [(a) + (b)], obtained from 10 to 50 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C or higher molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives , and the third component as the matrix component is is-polybutadiene, (e) from 30 to 70 wt.% styrene-butadiene rubber and (b) from 0 to 60 wt.% diene-based rubber, different from (a) and (e), and from 40 to 100 wt. hours a rubber reinforcing agent (d), wherein the vinyl-cis-butadiene rubber (a) is obtained by cis-1,4-polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4-polymerization catalyst, with adding a high molecular weight substance after the cis-polymerization step followed by 1,2-polymerization of 1,3-butadiene in the obtained reaction polymerization mixture together with the 1,2-polymerization catalyst to thereby obtain 1,2-polybutadiene with a melting point of 170 ° C or more, and then with the unit, removed Niemi resulting vinyl-cis-polybutadiene rubber from the resultant polymerization reaction mixture, wherein
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, while for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0 , 2 to 1000 microns, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 μm, while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals and not more than 0.2 micron, the aspect ratio does not exceed 10, and the number of monodispersed fiber crystals 400 microns ² is 10 or more. 4. The rubber composition, which is a rubber composition intended for the manufacture of tires of a large vehicle, containing 100 wt.h. the rubber component [(a) + (b)] obtained from 10 to 60 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C. or higher , high molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives, and the third component as a matrix component is is-polybutadiene, and (b) - from 40 to 90 wt.% rubber on a diene basis, other than (a), and from 45 to 70 wt.h. a rubber reinforcing agent (c), wherein the vinyl-cis-butadiene rubber (a) was obtained by cis-1,4-polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4-polymerization catalyst, s adding a high molecular weight substance after the cis-polymerization step followed by 1,2-polymerization of 1,3-butadiene in the obtained reaction polymerization mixture together with the 1,2-polymerization catalyst to thereby obtain 1,2-polybutadiene with a melting point of 170 ° C or more, and then with the unit, removed the resulting vinyl cis-butadiene rubber from the resulting polymerization reaction mixture, where
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, while for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0 , 2 to 1000 microns, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 μm, while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals and not more than 0.2 micron, the aspect ratio does not exceed 10, and the number of monodispersed fiber crystals 400 microns ² is 10 or more. 5. The rubber composition, which is a highly hard filled rubber composition for the manufacture of flanges and side ribbons of tires, containing 100 wt.h. the rubber component, [(a) + (b)], obtained from 20 to 80 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C or above, a high molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives, and the third component as a matrix component is c-polybutadiene, and (b) - from 20 to 80% by weight of the diene-based rubber other than (a) and from 60 to 100 parts by weight. a rubber reinforcing agent (c), wherein the vinyl-cis-butadiene rubber (a) was obtained by cis-1,4-polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4-polymerization catalyst, s adding a high molecular weight substance after the cis-polymerization step followed by 1,2-polymerization of 1,3-butadiene in the obtained reaction polymerization mixture together with the 1,2-polymerization catalyst to thereby obtain 1,2-polybutadiene with a melting point of 170 ° C or more, and then with the unit, removed the resulting vinyl cis-butadiene rubber from the resulting polymerization reaction mixture, where
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, while for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0 , 2 to 1000 microns, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 μm, while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals and not more than 0.2 micron, the aspect ratio does not exceed 10, and the number of monodispersed fiber crystals 400 microns ² is 10 or more. 6. The rubber composition, which is a rubber composition intended for the manufacture of the undercut groove of the tread, containing 100 wt.h. the rubber component, [(a) + (b)], obtained from 20 to 80 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C or higher molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives , and the third component as the matrix component is cis-polybutadiene, and (b) - from 20 to 80% by weight of the diene-based rubber other than (a) and from 22 to 55 parts by weight. a rubber reinforcing agent (c), wherein the vinyl-cis-butadiene rubber (a) was obtained by cis-1,4-polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4-polymerization catalyst, s adding a high molecular weight substance after the cis-polymerization step followed by 1,2-polymerization of 1,3-butadiene in the obtained reaction polymerization mixture together with the 1,2-polymerization catalyst to thereby obtain 1,2-polybutadiene with a melting point of 170 ° C or more, and then with the unit, removed the resulting vinyl cis-butadiene rubber from the resulting polymerization reaction mixture, where
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, wherein
for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.2 to 1000 μm, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 μm, while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals and not more than 0.2 micron, the aspect ratio does not exceed 10, and the number of monodispersed fiber crystals 400 microns ² is 10 or more. 7. The rubber composition, which is a rubber composition intended for the manufacture of the lining of the tire cord containing 100 parts by weight of the rubber component, [(a) + (b)], obtained from 10 to 60 wt.% vinyl-cis-butadiene rubber (a) containing three components: 1,2-polybutadiene with a melting point of 170 ° C or higher molecular weight substance having at least one unsaturated double bond per repeating unit and being a substance selected from at least one: polyisoprene, crystalline polybutadiene with a melting point of 150 ° C or lower, liquid polybutadiene and their derivatives , and the third component as the matrix component is cis-polybutadiene, and (b) - from 40 to 90% by weight of the diene-based rubber other than (a) and from 30 to 80 parts by weight. a rubber reinforcing agent (c), wherein the vinyl-cis-butadiene rubber (a) was obtained by cis-1,4-polymerization of 1,3-butadiene in a hydrocarbon-based solvent using a cis-1,4-polymerization catalyst, s adding a high molecular weight substance after the cis-polymerization step followed by 1,2-polymerization of 1,3-butadiene in the obtained reaction polymerization mixture together with the 1,2-polymerization catalyst to thereby obtain 1,2-polybutadiene with a melting point of 170 ° C or more, and then with the unit, removed the resulting vinyl cis-butadiene rubber from the resulting polymerization reaction mixture, where
(1) each of the short crystalline fibers of 1,2-polybutadiene and particles of an unsaturated high molecular weight substance are dispersed separately in the cis-polybutadiene matrix, or
(2) particles of an unsaturated high molecular weight substance are dispersed in a cis-polybutadiene matrix in an attached state to the short crystalline fibers of 1,2-polybutadiene, or
(3) short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix attached to particles of an unsaturated high molecular weight substance, while for (1) - (3) the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0 , 2 to 1000 microns, or
(4) the short crystalline fibers of 1,2-polybutadiene are dispersed in a cis-polybutadiene matrix and are incorporated and dispersed in particles of an unsaturated high molecular weight substance, while the particle size of the unsaturated high molecular weight substance, measured along the major axis, is in the range from 0.01 to 0 5 μm, while 1,2-polybutadiene with a melting point of 170 ° C or more is in a state of crystalline or short fiber, in which the average length of the minor axis of monodisperse fiber crystals and not more than 0.2 micron, the aspect ratio does not exceed 10, and the number of monodispersed fiber crystals 400 microns ² is 10 or more. 8. The rubber composition according to claim 2, characterized in that at the stage of obtaining vinyl-cis-butadiene rubber, unsaturated high molecular weight substance is contained in an amount in the range from 0.01 to 50 wt.% Based on the total amount of amounts of crystalline fiber from 1 , 2-polybutadiene and cis-polybutadiene. 9. The rubber composition according to claim 2, characterized in that the said vinyl-cis-butadiene rubber (a) has the following characteristics:
(1) cis-polybutadiene, which is the matrix component of said vinyl cis-butadiene rubber, has a Mooney viscosity in the range of 10 to 50;
(2) cis-polybutadiene, which is the matrix component of said vinyl-cis-butadiene rubber, has a viscosity in a toluene solution at 25 ° C. in the range of 10 to 150;
(3) cis-polybutadiene, which is the matrix component of said vinyl-cis-butadiene rubber, has a [η] value in the range of 1.0 to 5.0;
(4) cis-polybutadiene, which is a matrix component of said vinyl-cis-butadiene rubber, contains a 1,4-cis structure in the range of 80% or more;
(5) 1,2-polybutadiene and a high molecular weight substance are dispersed in a physically and / or chemically adsorbed state in cis-polybutadiene, which is a matrix component of said vinyl-cis-butadiene rubber. 10. The rubber composition according to claim 2, characterized in that the diene-based rubber (b) other than (a) is natural rubber and / or polyisoprene and / or styrene butadiene rubber. 11. The rubber composition according to claim 2, characterized in that the diene-based rubber (b) other than (a) is natural rubber and / or polyisoprene. 12. The rubber composition according to claim 2, characterized in that the rubber reinforcing agent is carbon black.

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