Patent Application
20070155902
This invention relates to a rubber composition containing an aromatic vinyl compound-diene compound copolymer and a pneumatic tire using such a rubber composition in a ground contact part of a tread portion.
At the present time, liquid styrene-butadiene copolymer rubber (hereinafter may be referred to as “SBR” simply) having mainly a molecular weight of about 10,000 is widely used (see, for example, Patent Article 1). Also, the liquid SBR is used for the wear resistance (see, for example, Patent Article 2). As a technique of improving the storage modulus, there is the compounding of polyethylene glycol polymaleate (PEGM) (see, for example, Patent Article 3).
Problems to be Solved by the Invention
The inventor has found that the conventional compounding technique is insufficient in the workability such as processing or the like of rubber composition, and the storage modulus and loss factor of the rubber composition.
It is, therefore, an object of the invention to provide a rubber composition having a high storage modulus and a low loss factor without damaging the workability such as compounding, milling, processing or the like.
It is another object of the invention to provide a rubber composition having a high storage modulus and a low loss factor without damaging the workability such as compounding, milling, processing or the like and stably providing an improvement of fracture strength.
Means for Solving Problems
The invention is concerned with a rubber composition characterized by containing 5-60 parts by mass of an aromatic vinyl compound-diene compound copolymer (B) having a weight average molecular weight of 5,000-300,000 (conversion to polystyrene through gel permeation chromatography) based on 100 parts by mass of a rubber component comprising at least one rubber of natural rubber and synthetic diene-based rubbers in which the copolymer (B) comprises 5-80 mass % of the aromatic vinyl compound and a vinyl bond content in diene compound portion is 10-80 mass % as well as a pneumatic tire using such a rubber composition.
The inventor has variously examined the conventional compounding means for solving the above problems. In this regard, the inventor has found that in the compounding means described in Patent Article 1, the amount of carbon black (hereinafter abbreviated to as “C/B”) is increased and hence not only G′ (storage modulus) but also tan δ (loss factor) are increased to cause the Mooney viscosity (hereinafter abbreviated to as “ML”) of the compounding mass and the processability is deteriorated.
Also, the inventor has found that in the rubber composition having a styrene composition distribution in SBR as a high molecular weight matrix through an increment process as disclosed in Patent Article 2, the composition has a tapered structure and such a matrix polymer has a broad tan δ temperature dispersion and the loss factor becomes insufficient. Moreover, it has been found that when a liquid emulsion-polymerized SBR is combined as described in patent Article 2, it is disadvantageous in the loss factor because such a SBR tends to have a broad molecular weight distribution.
Further, the inventor has found that the compounding of PEGM described in Patent Article 3 increases G′ but is lacking in the improving the loss factor because tan δ is on a level with the above.
The inventor has thought that the compounding described the above patent articles is insufficient in the improvement of the loss factor, made the examination of the tire tread compounding under the above knowledge, examined aromatic vinyl compound-diene compound copolymers having various molecular structures, and found that the improvements of the storage modulus and the loss factor can be established by using a copolymer having a relatively high molecular weight (about 100,000) and a given molecular structure without damaging the workability, and as a result, the invention has been accomplished.
Also, the inventor has found that the matrix having an excellent compatibility in the above rubber composition enhances the fracture strength of the rubber composition and brings about the excellent storage modulus and the stability in the improvement of the loss factor.
The above rubber composition is possible to establish and improve high G′ and low tan δ in a pneumatic tire and can be general-purpose and high performance tread compounding for a passenger car tire (PSR) using a liquid SBR having a relatively high molecular weight. However, if the matrix becomes non-compatible, there is a possibility of lowering the fracture strength (which may be referred to as “TB” hereinafter).
Under the above knowledge, the inventor has made further examinations on the microscopically molecular structure of the matrix for providing the stable compatibility in detail. Although there are considered various means for enhancing the compatibility, the utility of the rubber composition can be enhanced by examining the microstructures of the matrix and the liquid copolymer without essentially changing the construction of the rubber composition.
As a result, the inventor has found out that in a rubber composition comprising a rubber component (A) containing a copolymer (C) having predetermined aromatic vinyl compound content and vinyl bond content and a given copolymer (B) such as a liquid SBR, the compatibility between the rubber component (A) as a matrix and the copolymer (B) can be enhanced by making a difference in the aromatic vinyl compound content between the copolymer (C) and the copolymer (B) to not more than 30 mass %, and the invention ha been accomplished.
Effect of the Invention
According to the invention, the storage modulus and loss factor can be considerably improved without the damage of the workability by compounding the aromatic vinyl compound-diene compound copolymer having a predetermined molecular structure instead of a usual softening agent such as aromatic oil.
Also, according to the invention, the predetermined copolymer (C) and the predetermined copolymer (B) are used by making the difference in the aromatic vinyl compound content between the copolymer (C) and the copolymer (B) to not more than 30 mass %, whereby the compatibility between the rubber component (A) as a matrix and the copolymer (B) is ensured and the improvement of TB, G′ and tan δ can be stably obtained.
(1) Rubber composition
It comprises 5-60 parts by mass of a predetermined copolymer (B) based on 100 parts by mass of a rubber component (A).
(2) Rubber component (A)
The rubber component comprises at least one rubber of natural rubber and synthetic diene-based rubbers. Although various ones are applicable, emulsion-polymerized or solution-polymerized rubber is preferable. Also, a glass transition temperature Tg is preferable to be not lower than −60° C. in view of the wear resistance, heat resistance and the like.
As the synthetic diene-based rubber may be mentioned cis-1,4-polyisoprene, styrene-butadiene copolymer, low cis-1,4-polybutadiene, high cis-1,4-polybutadiene, ethylene-propylene-diene copolymer, chloroprene, halogenated butyl rubber, acrylonitrile-butadiene rubber and the like. The natural rubber and synthetic diene-based rubbers may be used alone or in a blend thereof.
The preferable rubber component (A) is natural rubber, cis-1,4-polyisoprene, SBR and polybutadiene. Moreover, it is preferable that not less than 50 mass % of SBR is included in the rubber component (A) in a point that the improving effect by a combination with the predetermined copolymer (B) is clear.
Preferably, the rubber component (A) contains not less than 50 mass % of styrene-butadiene copolymer (C) having a weight average molecular weight of 300,000-1,500,000. Also, the copolymer (C) is preferable to comprise 20-60 mass % of an aromatic vinyl compound and have a vinyl bond content in diene compound portion of 10-80 mass %. Such a rubber component (A) can ensure the compatibility within a given range and provides stably the improvement of TB, G′ and tan δ. Moreover, a rubber component compounded with bismaleimide (BMI) (JP-A-2001-131343) increases G′ though it does not contain the predetermined copolymer (B), but tan δ is the same and the improving effect of the loss factor is lacking, and also the compatibility with the copolymer (B) does not come into problem.
Preferably, the copolymer (C) is an emulsion-polymerized styrene-butadiene copolymer comprising not less than 20 mass % of an aromatic vinyl compound, or a solution-polymerized styrene-butadiene copolymer comprising not less than 20 mass % of an aromatic vinyl compound and having not less than 10 mass % of a vinyl bond content in diene compound portion.
(2) Aromatic vinyl compound-diene compound copolymer (B)
It is a copolymerized compound of an aromatic vinyl compound and a diene compound as a monomer. It has a weight average molecular weight of 5,000-200,000 or 5,000-300,000 (conversion to polystyrene through a gel permeation chromatography). The copolymer (B) comprises 5-80 mass % of an aromatic vinyl compound and has a vinyl bond content in diene compound portion of 10-80 mass %.
The copolymer (B) has preferably a weight average molecular weight of 20,000-150,000 or 20,000-200,000, more preferably a weight average molecular weight of 50,000-150,000. As the molecular weight becomes further higher, the storage modulus and loss factor become excellent, but the workability lowers at the molecular weight of more than 150,000 or 200,000. Also, the molecular weight distribution is preferable to be narrow. If it is wide, the loss factor tends to be deteriorated.
The copolymers comprising less than 5 mass % or more than 80 mass % of the aromatic vinyl compound and the diene compound having a vinyl bond content of less than 10 mass % or more than 80 mass % are insufficient in the desired workability and the establishment between the storage modulus and the loss factor. Moreover, the vinyl bond content used herein means the amount of vinyl bond in the constitutional unit inherent to the diene compound and shows a ratio of vinyl bond content occupied in the amount of all bonds including other bonds represented by cis bond and trans bond.
As the aromatic vinyl compound are mentioned styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like. Preferably, styrene, p-methylstyrene and α-methylstyrene are mentioned. Particularly, styrene is preferable.
As the diene compound are used butadiene, isoprene, pentadiene, 2,3-dimethyl butadiene and the like. Particularly, butadiene is preferable.
Preferably, the copolymer (B) has a weight average molecular weight of 5,000-200,000. Also, the copolymer (B) is preferable to comprise 10-70 mass % of the aromatic vinyl compound. Further, it is preferable that the difference in the aromatic vinyl compound content between the copolymer (C) and the copolymer (B) is not more than 30 mass %. When the difference in the aromatic vinyl compound content exceeds 30 mass %, there is a possibility that the compatibility easily lowers and the sufficient fracture strength is not obtained.
The copolymer (B) can be obtained by various production methods as far as the predetermined molecular structure is provided. As the copolymer (B) are applicable various liquid or low molecular weight polymers or rubbers, but the copolymer is preferably produced by solution polymerization of styrene and butadiene. Particularly, the copolymer (B) is preferable to be a solution-polymerized styrene-butadiene copolymer rubber.
As an industrial example of the above method, there is a method of copolymerizing given monomers in a hydrocarbon solvent using an organolithium compound as an initiator. For example, the copolymer (B) can be obtained by copolymerizing a diene compound such as 1,3-butadiene containing a small amount of 1,2-butadiene with an aromatic vinyl compound in a hydrocarbon solvent using an organolithium compound initiator in the presence of ether or a tertiary amine in a tank-type or tower-type reaction vessel.
Although the liquid SBR having a molecular weight of 5,000-200,000 or 5,000-300,000 is known (see the above Patent Article 2), it is not clear that such a SBR is made possible to establish the storage modulus and the loss factor as defined in the invention different from the copolymer (B) defined by the predetermined molecular structure according to the invention. The known liquid SBR (see Patent Article 2) is formed by the emulsion polymerization in which a broad molecular weight distribution is generally formed different from the copolymer (B) defined by the predetermined molecular structure according to the invention. When the rubber composition compounded with this SBR (see Patent Article 2) is used to form a tire, the loss factor is disadvantageously acted to deteriorate the low fuel consumption. In the invention, the problem on the low fuel consumption can be solved by the predetermined molecular structure of the copolymer (B) and the like.
Also, there is known a high molecular weight SBR matrix having a tapered structure of a styrene composition distribution through an increment process (see Patent Article 2). However, such a matrix has a broad tan δ temperature dispersion, so that when such a matrix is used in the rubber composition (see Patent Article 2), the loss factor is poor. In the invention, the problem on the loss factor can be solved by using the copolymer (B) defined by the predetermined molecular structure in a given amount, or the like.
(3) Filler
The rubber composition may further contain various fillers. As the filler is used at least one of C/B, silica, calcium carbonate, titanium oxide and the like, and at least one of C/B and silica is preferable.
The filler may be included in an amount of 30-90 parts by mass based on 100 parts by mass of the rubber component (A). When the amount is less than 30 parts by mass, the fracture properties, wear resistance and the like of the vulcanizate are not sufficient, while when it exceeds 90 parts by mass, the operability and the like are not favorable. An example of C/B used as the filler includes classes of FEF, HAF, ISAF, SAF and the like. Among them, ISAF-HAF class or SAF-HAF class is particularly preferable. In case of using C/B with silica, the compounding ratio may be arbitrarily changed in accordance with the compounding purpose.
(4) Softening agent
The rubber composition may further contain various softening agents. As the softening agent can be used at least one of process oils such as paraffinic oil, naphthenic oil, aromatic oil and the like. The aromatic oil is preferable in applications emphasizing the fracture properties and wear resistance, and the naphthenic oil or paraffininc oil is preferable in applications emphasizing the low heat buildup and low temperature properties.
Preferably, the total amount of the copolymer (B) and the softening agent is 5-80 parts by mass based on 100 parts by mass of the rubber component (A). When it exceeds 80 parts by mass, there is a tendency of deteriorating the fracture properties of the vulcanizate.
(5) Other additives
In addition to the above rubber component (A), copolymer (B) and the filler, the rubber composition may be compounded with other additives usually used in the rubber industry such as silane coupling agent, curing agent, vulcanization accelerator, accelerator activator, antioxidant, antiozonant, age resistor, process oil, zinc oxide, stearic acid and the like, if necessary.
As the curing agent are mentioned sulfur and the like. The amount of the curing agent used is 0.1-10 parts by mass, preferably 0.5-5 parts by mass as a sulfur content based on 100 parts by mass of the rubber component (A). When the amount is less than 0.1 part by mass, the fracture properties and wear resistance of the cured rubber lower, while when it exceeds 10 parts by mass, the rubbery elasticity tends to be lost.
(6) Pneumatic tire
The above rubber composition can be used in a pneumatic tire, particularly in a tire tread portion, preferably in at least ground contact part of the tread portion.
Although the liquid SBR having mainly a molecular weight of 10,000 is applied at the present day (see Patent Article 1), it is not clear that such a SBR is made possible to establish the storage modulus and the loss factor as defined in the invention different from the copolymer (B) defined by the predetermined molecular structure according to the invention. The rubber composition according to the invention enlarges the application range of the conventional technique by using the liquid copolymer (B) having the predetermined molecular structure and a relatively high molecular weight (5,000-200,000 or 5,000-300,000). That is, according to the invention, the predetermined copolymer (B) can be applied to the tire tread compounding, whereby the high storage modulus (high G′) and the low loss factor (low tan δ) can be established without damaging the operability as the rubber composition.
In order to distinguish the rubber composition over the compounding of the liquid SBR (2,000-50,000) (C/B 100 parts by mass, softening agent 100 parts by mass)(see Patent Article 1), not only the predetermined copolymer (B) is used as mentioned above, but also the tire tread compounding (30-90 parts by mass of C/B of ISAF and HAF class or SAF-HAF class (silica may be included) can be added) is used, and it is possible to add 5-80 parts by mass of softening agent + predetermined copolymer (B).
As the technique relating to the improvement of G′ is already known the PEGM compounding (Patent Article 3), but the invention can apply this technique. As a technique capable of simultaneously improving the storage modulus and loss factor without damaging the operability, the predetermined copolymer (B) can be compounded.
The invention is explained in detail with reference to the following examples.
A rubber composition is prepared according to a compounding of a tread portion shown in Table 1 by using a copolymer (B) shown in Table 2, and then vulcanized according to the production conditions of a pneumatic tire. In this example, the copolymer (B) is SBR having a weight average molecular weight of 25,000 and comprises 25 mass % of styrene and has a vinyl bond content in butadiene portion of 65 mass % as shown in Tables 1 and 2. Such a SBR is included in an amount of 30 parts by mass based on 100 parts by mass of a rubber component (SBR 1500: made by JSR Corporation). Moreover, 65 pasrt by mass of C/B of ISAF class as a filler is used.
A rubber composition is prepared and cured in the same manner as in Example 1 except that the weight average molecular weight of the copolymer (B) in Example 1 is changed into 40,000 (Example 2), 80,000 (Example 3) and 120,000 (Example 4), respectively.
For example, the liquid copolymer having a weight average molecular weight of 80,000 can be produced as follows.
Into a pressure glass vessel of 800 mL dried and purged with nitrogen are charged a cyclohexane solution of butadiene (16%) and a cyclohexane solution of styrene (21%) so as to be 40 g of butadiene monomer and 10 g of styrene monomer, and 0.66 millimol of 2,2-ditetrahydrofuryl propane is charged thereinto, and 1.32 millimol of n-butyllithium (BuLi) is added thereto, and thereafter the polymerization is carried out in a warm bath at 50° C. for 1.5 hours. The polymerization conversion is approximately 100%.
Then, 0.5 mL of a solution of 5 wt% of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol is further added to the polymerization system to stop the reaction. Thereafter, the reaction mass is dried according to the usual manner to obtain a polymer.
A rubber composition is prepared and cured in the same manner as in Example 1 except that an aromatic oil being a usual softening agent is used instead of the copolymer (B) in Example 1 as shown in Table 2.
A rubber composition is prepared and cured in the same manner as in Example 1 except that the weight average molecular weight of the copolymer in Example 1 is changed into 4,000 (Comparative Example 2) and 320,000 (Comparative Example 3), respectively.
(Evaluation)
With respect to the rubber compositions of Examples 1-4 and Comparative Examples 1-3 are evaluated the processability, storage modulus and loss factor. The results are also shown in Table 2.
The processability is evaluated by an index on the basis that Comparative Example 1 is 100 by measuring a Mooney viscosity (ML1+4/130° C.) of the rubber composition at 130° C. according to JIS K6300-1994. The smaller the index value, the better the processability.
The storage modulus and loss factor are evaluated by an index on the basis that Comparative Example 1 is 100 by measuring G′ value and tan δ by means of a low heat-buildup viscoelasticity measuring apparatus (made by Rheometrix Corp.) under conditions that a temperature is 50° C. and a strain is 5% and a frequency is 15 Hz.
*1 SBR 1500 (made by JSR Corporation)
*2 ISAF, Seast 3H, made by Tokai Carbon Co., Ltd.
*3 Nocrac 6C
*4 Nocceler D
*5 Nocceler NS
As shown in Table 2, the rubber compositions of Examples 1-4 can sufficiently satisfy all of the processability, storage modulus and loss factor though the processability of Example 4 is slightly poor as compared with that of Comparative Example 1 but is substantially comparable therewith. On the other hand, the insufficient performances are clearly observed in the rubber compositions of Comparative Examples 1-3.
Examples 5-7
A good compatible rubber composition is prepared in a tread compounding.
A copolymer (B), SBR [the same as in Example 3, weight average molecular weight: 80,000 (styrene content (St)/vinyl bond content (Vi)=25 mass %/65 mass %)] is included in an amount of 15 parts by mass based on 100 parts by mass of SBR as a rubber component (A) [Example 5: the same #1500 as in Examples 1-4, made by JSR Corporation, (emulsion-polymerized SBR, weight average molecular weight: 450,000) (St/Vi=23.5 mass %/18 mass %), and Example 6: #0202 made by JSR Corporation, (emulsion-polymerized SBR, weight average molecular weight: 450,000)(St/Vi=45.0 mass %/18 mass %)].
Also, as a rubber component (A) of Example 7 is used SBR* (St/Vi=25/60) prepared as follows, and the copolymer (B) is included in the same manner as in Example 5.
Into a pressure glass vessel of 800 mL dried and purged with nitrogen are charged a cyclohexane solution of butadiene (16%) and a cyclohexane solution of styrene (21%) so as to so as to be 40 g of butadiene monomer and 10 g of styrene monomer, and 0.12 millimol of 2,2-ditetrahydrofuryl propane is charged thereinto, and 0.24 millimol of n-butyllithium (BuLi) is added thereto, and thereafter the polymerization is carried out in a warm bath at 50° C. for 1.5 hours. The polymerization conversion is approximately 100%.
Then, 0.5 mL of a solution of 5 wt% of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol is further added to the polymerization system to stop the reaction. Thereafter, the reaction mass is dried according to the usual manner to obtain a polymer.
A master batch is prepared by compounding the above composition with 27 parts by mass of C/B [made by Tokai Carbon Co., Ltd. HAF class, trade name Seast KH (N339)], 27 parts by mass of silica (made by Nippon Silica Kogyo Co., Ltd. trade name: Nipsil AQ), 2.5 parts by mass of a coupling agent (made by Degussa, a mixture of trade name: Si69, bis(3-triethoxysilylpropyl) tetrasulfide (average number of S: 3.8) or trade name: Si75, bis(3-triethoxysilylpropyl) polysulfide having an average number of S of 2.4 in one molecule), 2 parts by mass of stearic acid and 1 part by mass of an antioxidant 6C (N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine), and further 3 parts by mass of zinc oxide, 0.8 part by mass of a vulcanization accelerator DPG (diphenyl guanidine), 1 part by mass of a vulcanization accelerator NS (N-t-butyl-2-benzothiazyl sulfenamide) and 1.5 parts by mass of sulfur are compounded to prepare a rubber composition. The rubber composition is cured at 160° for 15 minutes, and then the properties of the cured rubber are measured.
A rubber composition is prepared and cured in the same manner as in Example 5 except that the copolymer (B) of Example 5 is replaced with an aromatic oil.
A rubber composition is prepared and cured in the same manner as in Example 6 except that the copolymer (B) of Example 6 is replaced with an aromatic oil.
A rubber composition is prepared and cured in the same manner as in Example 7 except that the copolymer (B) of Example 7 is replaced with an aromatic oil. The properties are measured.
(Evaluation)
With respect to the rubber compositions of Examples 5-7 and Comparative Examples 4-6, the properties of the cured rubber are measured in the same manner as in Example 1. The results are shown in Table 3.
As to the properties, the fracture strength (TB) is measured instead of the processability in Examples 1-4, and the storage modulus (G′) and loss factor (tan δ) are evaluated in the same manner as in Example 1. They are evaluated by an index on the basis that Comparative Example 4, in which the larger the index value of the storage modulus, the better the steering stability and the smaller the index value of the loss factor, the better the low fuel consumption.
The fracture strength (TB) is measured according to JIS K6301-1995. It is evaluated by an index on the basis that Comparative Example 4 is 100. The larger the index value, the better the fracture strength.
As shown in Table 3, the rubber compositions of Examples 5-7 can sufficiently satisfy all of TB, G′ and tan δand indicate the stable TB. On the other hand, the expectable improvement of the properties is not observed in the rubber compositions of Comparative Examples 4-6.
Moreover, when 15 parts by mass of SBR as the copolymer (B) (weight average molecular weight: 80,000 (styrene content (St)/vinyl bond content (Vi)=65 mass %/65 mass %)) is included per 100 parts by mass of the copolymer (C): emulsion-polymerized SBR [#1500 made by JSR Corporation (weight average molecular weight of emulsion-polymerized SBR: 450,000) (St/Vi=23.5 mass %/18 mass %)], the difference in aromatic vinyl compound content is 41.5 mass % and the storage modulus is improved at a ratio of 115/100 and the loss factor is lowered at a ratio of 105/100 and the fracture strength is lowered at a ratio of 90/100 as compared with the composition containing aromatic oil instead of the copolymer (B) (an index of the property is 100), but it is considered that there is a place for adding another proper means such as improvement of compatibility or the like.
The rubber composition according to the invention can be produced by using usual starting materials such as styrene, butadiene and the like, and develops excellent predetermined performances by shaping into a tread portion or the like of a tire without damaging the operability such as milling or the like and has a versatility.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-074191 | Mar 2004 | JP | national |
| 2005-030510 | Feb 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP05/04448 | 3/14/2005 | WO | 9/13/2006 |
