JP5650795B2 - Rubber composition for pneumatic tread and pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition for a base tread and a pneumatic tire produced using the rubber composition.

As a technique for reducing the fuel consumption of a tire, it has been proposed that the tread has a two-layer structure of a base tread and a cap tread to form a base tread having low heat generation properties. However, further improvement is required. On the other hand, with the improvement of automobile performance and the development of the road network, there is also a demand for improved handling stability for tires, particularly handling stability at high speeds.

In this regard, when a large amount of carbon black is added to the base tread, the rigidity of the tread portion increases and the handling stability increases. However, since rigidity (maneuvering stability) decreases, it is difficult to achieve both maneuvering stability and low fuel consumption.

On the other hand, natural rubber, which is frequently used for base treads, has a high Mooney viscosity and poor processability compared to other synthetic rubbers. Productivity is poor because it is used. Furthermore, the molecular chain of natural rubber is cleaved by mastication, which causes a problem that the characteristics (good fuel efficiency, rubber strength, etc.) of the high molecular weight polymer inherent to natural rubber are lost.

There are also reports of improving the processability of natural rubber by removing proteins in latex, a method of aging by adding proteolytic enzymes and surfactants, and immersing solid natural rubber swollen with solvent in alkali hydroxide A method, a method of adding a phosphate to remove magnesium phosphate, a method of adding a surfactant and performing a washing treatment, and the like are disclosed (see Patent Documents 1 to 5). However, protein removal is not sufficient and phospholipids are hardly removed, so there is room for improvement in fuel economy.

In addition, normal natural rubber does not deteriorate under aging conditions at 80 ° C. for about 18 hours, whereas modified natural rubber from which proteins and the like have been highly removed exhibits deterioration of the rubber under the same conditions. There is also a problem of poor aging. As described above, in the base tread, it is generally difficult to improve the fuel efficiency, the handling stability, and the heat aging resistance in a well-balanced manner, and improvement is required.

JP-A-8-12814 JP 2005-82622 A Japanese Patent Laid-Open No. 11-12306 JP 2004-250546 A Japanese Patent No. 3294901

The present invention provides a rubber composition for a base tread that solves the above-mentioned problems and has improved fuel economy, handling stability and heat aging resistance in a well-balanced manner, and a pneumatic tire produced using the rubber composition. Objective.

The present invention relates to a rubber composition for a base tread, which contains a modified natural rubber that is highly purified and has a pH adjusted to 2 to 7, and carbon black and / or a white filler.

The modified natural rubber is preferably obtained by removing the non-rubber component of the natural rubber and then treating with an acidic compound, and the pH is 2-7.

The modified natural rubber is obtained by washing saponified natural rubber latex and further treating with an acidic compound, and preferably has a pH of 2-7.

The modified natural rubber is preferably obtained by washing deproteinized natural rubber latex and further treating with an acidic compound, and having a pH of 2-7.

The phosphorus content of the modified natural rubber is preferably 200 ppm or less.

The nitrogen content of the modified natural rubber is preferably 0.15% by mass or less.

The pH is measured by cutting the modified natural rubber into 2 mm squares of each side and immersing in distilled water, extracting at 90 ° C. for 15 minutes while irradiating with microwaves, and measuring the immersion water using a pH meter. It is preferable that it is a value obtained.

The modified natural rubber has a Mooney viscosity ML (1 + 4) of 130 ° C. measured in accordance with JIS K 6300: 2001-1 and a heat aging index represented by the following formula of 75 to 120%. Is preferred.

The white filler is preferably silica.

It is preferable that butadiene rubber is included.

It is preferable to contain oil.

The modified natural rubber is preferably produced without going through a mastication step.

The present invention also relates to a pneumatic tire produced using the rubber composition for a base tread.

According to the present invention, since it is a rubber composition for base tread comprising a highly purified and modified natural rubber whose pH is adjusted to 2 to 7, and carbon black and / or white filler, low fuel consumption , Handling stability and heat aging resistance can be improved in a well-balanced manner.

The rubber composition for a base tread of the present invention includes a modified natural rubber that is highly purified and has a pH adjusted to 2 to 7, and carbon black and / or a white filler.

The modified natural rubber is highly purified and has a pH adjusted to 2-7.
Since it is a modified natural rubber that removes non-rubber components such as proteins and phospholipids to achieve high purity and control the pH of the rubber to an appropriate value, fuel efficiency and driving stability are improved. Also, the removal of non-rubber components and the rubber becoming basic or strongly acidic facilitates the deterioration of the rubber, but the adjustment of the pH of the rubber to a predetermined range suppresses the decrease in molecular weight during storage. Therefore, good heat aging resistance can be obtained. Therefore, the performance balance of low fuel consumption, heat aging resistance, and steering stability can be remarkably improved.

Here, high purification means removing impurities such as phospholipids and proteins other than natural polyisoprenoid components. Natural rubber has a structure in which the isoprenoid component is covered with the impurity component. By removing the component, the structure of the isoprenoid component changes and the interaction with the compounding agent changes. It is presumed that energy loss is reduced, durability is improved, and a better rubber composition can be obtained.

The modified natural rubber having a high purity and a pH adjusted to 2 to 7 may be a modified natural rubber having a high purity by reducing the amount of non-rubber components and having a rubber pH of 2 to 7. Specifically, (1) modified natural rubber obtained by removing non-rubber components of natural rubber and then treating with an acidic compound, and having a pH of 2 to 7, (2) Ken Natural rubber latex is washed and further treated with an acidic compound, modified natural rubber having a pH of 2 to 7, and (3) deproteinized natural rubber latex is washed and further treated with an acidic compound. And modified natural rubber having a pH of 2 to 7.

As described above, the modified natural rubber can be prepared by a method of washing a saponified natural rubber latex or a deproteinized natural rubber latex with distilled water or the like and further treating with an acidic compound. It is important to lower the pH value by shifting to the acidic side by treatment with an acidic compound. Usually, the pH of distilled water is not 7.00 and is about 5 to 6, but in this case, it is important to reduce the pH value to the acidic side from 5 to 6 by treatment with an acidic compound. Become. Specifically, it is preferable to lower the pH value by 0.2 to 2 by treatment with an acidic compound, rather than the pH value of water used for washing.

The modified natural rubber has a pH of 2-7, preferably 3-6, more preferably 4-6. By adjusting within the above range, the deterioration of heat aging resistance is prevented, and the performance balance of low fuel consumption, heat aging resistance and steering stability can be remarkably improved. The pH of the modified natural rubber is cut into a size of 2 mm square or less on each side, soaked in distilled water, extracted at 90 ° C. for 15 minutes while irradiating with microwaves, and the soaked water was measured using a pH meter Specifically, it is measured by the method described in the examples described later. Here, regarding extraction, even if it is extracted for 1 hour with an ultrasonic cleaner or the like, the water-soluble component cannot be completely extracted from the inside of the rubber, so the internal pH cannot be accurately determined. The present inventor has found that the substance of rubber can be known by extracting.

The modified natural rubber is purified by various methods such as (1) to (3). For example, the phosphorus content in the modified natural rubber is preferably 200 ppm or less, more preferably It is 150 ppm or less. If it exceeds 200 ppm, the Mooney viscosity may increase during storage and processability may deteriorate, or tan δ may increase and fuel economy may not be improved. The phosphorus content can be measured by a conventional method such as ICP emission analysis. Phosphorus is considered to be derived from phospholipids contained in natural rubber.

When the modified natural rubber contains an artificial anti-aging agent, the nitrogen content after being immersed in acetone at room temperature (25 ° C.) for 48 hours is preferably 0.15% by mass or less, More preferably, it is 0.1 mass% or less. If it exceeds 0.15% by mass, the Mooney viscosity may increase during storage, resulting in poor processability, and the effect of improving fuel economy may not be sufficiently obtained. Highly purified natural rubber may be deteriorated by long-term storage because the natural anti-aging component, which is said to be inherent to natural rubber, has been removed. Therefore, an artificial anti-aging agent may be added. The nitrogen content is a measured value after removing an artificial anti-aging agent in rubber by extraction with acetone. The nitrogen content can be measured by a conventional method such as Kjeldahl method or trace nitrogen meter. Nitrogen is derived from proteins and amino acids.

The modified natural rubber preferably has a Mooney viscosity ML (1 + 4) 130 ° C. measured in accordance with JIS K 6300: 2001-1 of 75 ° C. or less, more preferably 40 to 75, still more preferably 45 to 75. Particularly preferred is 50 to 70, most preferred 55 to 65. By being 75 or less, the kneading normally required before rubber kneading becomes unnecessary. Therefore, the modified natural rubber produced without the mastication step can be suitably used as a compounding material for the rubber composition. On the other hand, when it exceeds 75, it is necessary to masticate before use, and there is a tendency for exclusive use of equipment, loss of electricity and thermal energy, and the like.

The modified natural rubber is preferably a rubber having a heat aging index represented by the following formula of 75 to 120% with respect to the Mooney viscosity ML (1 + 4) 130 ° C.

The heat aging index represented by the above formula is more preferably 80 to 115%, still more preferably 85 to 110%. Various methods have been reported for evaluating the heat aging resistance of rubber. By using the method of evaluating the rate of change before and after heat treatment at 80 ° C. for 18 hours for Mooney viscosity ML (1 + 4) at 130 ° C., tire production is possible. It is possible to accurately evaluate heat aging resistance at times and when using tires. Here, if it is within the above range, excellent heat aging resistance can be obtained, and the performance balance of low fuel consumption, steering stability and heat aging resistance can be remarkably improved.

The modified natural rubber having a high purity such as (1) to (3) and having a pH adjusted to 2 to 7 includes (Production method 1) Step 1-1 of saponifying natural rubber latex, A production method comprising a step 1-2 for washing the natural rubber latex and a step 1-3 for treating with the acidic compound, (Production method 2) a step 2-1 for deproteinizing the natural rubber latex, and a deproteinized natural rubber It can be prepared by a production method including the step 2-2 for washing the latex and the step 2-3 for treating with the acidic compound.

[Production method 1]
(Step 1-1)
In step 1-1, natural rubber latex is saponified. Thereby, saponified natural rubber latex in which phospholipids and proteins in the rubber are decomposed and non-rubber components are reduced is prepared.

Natural rubber latex is collected as sap of natural rubber trees such as Hevea, and contains rubber, water, proteins, lipids, inorganic salts, etc., and the gel content in rubber is based on the complex presence of various impurities. It is considered a thing. In the present invention, as natural rubber latex, raw latex (field latex) produced by tapping Hevea tree, or concentrated latex concentrated by centrifugal separation or creaming (refined latex, high ammonia to which ammonia is added by a conventional method) Latex, zinc oxide, TMTD, and LATZ latex stabilized with ammonia can be used.

As a method for the saponification treatment, for example, the method described in JP 2010-138359 A and JP 2010-174169 A can be suitably performed, and specifically, the following method can be used.

The saponification treatment can be performed by adding an alkali and, if necessary, a surfactant to natural rubber latex and allowing to stand at a predetermined temperature for a certain period of time. Stirring may be performed as necessary.

The alkali used for the saponification treatment is preferably sodium hydroxide or potassium hydroxide, but is not limited thereto. The surfactant is not particularly limited, and examples include known anionic surfactants such as polyoxyethylene alkyl ether sulfate salts, nonionic surfactants, and amphoteric surfactants. Anionic surfactants such as polyoxyethylene alkyl ether sulfates are preferred because they can be saponified. In the saponification treatment, the addition amount of alkali and surfactant, the temperature and time of the saponification treatment may be appropriately set.

(Step 1-2)
In step 1-2, the saponified natural rubber latex obtained in step 1-1 is washed. By the washing, non-rubber components such as proteins are removed.

Step 1-2 includes, for example, aggregating the saponified natural rubber latex obtained in Step 1-1 to produce an agglomerated rubber, and then treating the obtained agglomerated rubber with a basic compound and further washing. Can be implemented. Specifically, after the agglomerated rubber is produced, the non-rubber component can be removed by diluting with water and transferring the water-soluble component to the aqueous layer and removing the water, and further by treating with a basic compound after agglomeration. Non-rubber components confined in the rubber during agglomeration can be redissolved. Thereby, non-rubber components such as protein strongly adhered to the agglomerated rubber can be removed.

Examples of the aggregating method include a method of adjusting the pH by adding an acid such as formic acid, acetic acid or sulfuric acid, and further adding a polymer flocculant as necessary. Thereby, not a large aggregate but a granular rubber having a diameter of about 20 mm is formed from a diameter of several mm to 1 mm or less, and proteins and the like are sufficiently removed by the basic compound treatment. The pH is preferably adjusted in the range of 3.0 to 5.0, more preferably 3.5 to 4.5.

Examples of polymer flocculants include cationic polymer flocculants such as methyl chloride quaternary salt polymer of dimethylaminoethyl (meth) acrylate, anionic polymer flocculants such as acrylate polymer, and acrylamide polymer. Nonionic polymer flocculants such as, and amphoteric polymer flocculants such as dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt-acrylate copolymer. The addition amount of the polymer flocculant can be selected as appropriate.

Next, the resulting agglomerated rubber is treated with a basic compound. Here, although it does not specifically limit as a basic compound, A basic inorganic compound is suitable from the point of removal performance, such as protein.

Examples of basic inorganic compounds include metal hydroxides such as alkali metal hydroxides and alkaline earth metal hydroxides; metal carbonates such as alkali metal carbonates and alkaline earth metal carbonates; alkali metal hydrogen carbonates and the like Metal phosphates such as alkali metal phosphates; metal acetates such as alkali metal acetates; metal hydrides such as alkali metal hydrides; ammonia and the like.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, and barium hydroxide. Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate. Examples of the alkaline earth metal carbonate include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. Examples of the alkali metal phosphate include sodium phosphate and sodium hydrogen phosphate. Examples of the alkali metal acetate include sodium acetate and potassium acetate. Examples of the alkali metal hydride include sodium hydride and potassium hydride.

Of these, metal hydroxides, metal carbonates, metal hydrogen carbonates, metal phosphates, and ammonia are preferable, alkali metal carbonates, alkali metal hydrogen carbonates, and ammonia are more preferable, and sodium carbonate and sodium hydrogen carbonate are more preferable. preferable. The said basic compound may be used independently and may use 2 or more types together.

The method for treating the agglomerated rubber with the basic compound is not particularly limited as long as the agglomerated rubber is brought into contact with the basic compound. For example, the method of immersing the agglomerated rubber in an aqueous solution of the basic compound, And a method of spraying an aqueous solution of the active compound. An aqueous solution of a basic compound can be prepared by diluting and dissolving each basic compound with water.

The content of the basic compound in 100% by mass of the aqueous solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more. If it is less than 0.1% by mass, the protein may not be sufficiently removed. The content is preferably 10% by mass or less, more preferably 5% by mass or less. If it exceeds 10% by mass, a large amount of basic compound is required, but the amount of proteolysis does not increase, and the efficiency tends to be poor.

Although the said processing temperature should just be selected suitably, Preferably it is 10-50 degreeC, More preferably, it is 15-35 degreeC. Moreover, processing time is 1 minute or more normally, Preferably it is 10 minutes or more, More preferably, it is 30 minutes or more. If it is less than 1 minute, the effects of the present invention may not be obtained satisfactorily. The upper limit is not limited, but is preferably 48 hours or less, more preferably 24 hours or less, and still more preferably 16 hours or less from the viewpoint of productivity.

After the basic compound treatment, a washing treatment is performed. By the washing treatment, non-rubber components such as proteins can be removed. Examples of the washing method include a method of diluting a rubber component with water and washing and then centrifuging, and a method of allowing the rubber component to float by standing and discharging only the aqueous phase and taking out the rubber component. The number of washings can be any number of times that can reduce non-rubber components such as proteins to a desired amount, but a method of repeating a washing cycle of adding 1000 mL of water to 300 g of dry rubber and stirring and then dehydrating Then, 3 times (3 cycles) or more is preferable, 5 times (5 cycles) or more is more preferable, and 7 times (7 cycles) or more is more preferable.

The washing treatment is preferably carried out until the phosphorus content in the rubber is 200 ppm or less and / or the nitrogen content is 0.15 mass% or less. By sufficiently removing phospholipids and proteins by the washing treatment, fuel economy, handling stability and processability are improved.

(Step 1-3)
In Step 1-3, the washed rubber obtained in Step 1-2 is treated with an acidic compound. Although heat aging resistance tends to decrease due to the treatment of a basic compound or the like, further treatment with an acidic compound prevents such problems and provides good heat aging resistance.

The acidic compound is not particularly limited, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, metaphosphoric acid, boric acid, boronic acid, sulfanilic acid, sulfamic acid; formic acid, acetic acid, glycolic acid, oxalic acid, propion Acid, malonic acid, succinic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, salicylic acid, methanesulfonic acid, Itaconic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenedisulfonic acid, trifluoromethanesulfonic acid, styrenesulfonic acid, trifluoroacetic acid, barbituric acid, acrylic acid, methacrylic acid, cinnamic acid, 4-hydroxybenzoic acid, aminobenzoic acid , Naphthalene disulfonic acid, hydroxybenze Examples include organic acids such as sulfonic acid, toluenesulfinic acid, benzenesulfinic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, gallic acid, phloroglicin, sulfosalicylic acid, ascorbic acid, erythorbic acid, and bisphenolic acid. It is done. Of these, acetic acid, sulfuric acid, formic acid and the like are preferable. The said acidic compound may be used independently and may use 2 or more types together.

The method of treating the agglomerated rubber with an acid is not particularly limited as long as the agglomerated rubber is brought into contact with the acidic compound. For example, the method of immersing the agglomerated rubber in an aqueous solution of the acidic compound, The method of spraying etc. are mentioned. An aqueous solution of an acidic compound can be prepared by diluting and dissolving each acidic compound with water.

The content of the acidic compound in 100% by mass of the aqueous solution is not particularly limited, but the lower limit is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and the upper limit is preferably 15% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. When the content is within the above range, good heat aging resistance can be obtained.

Although the said processing temperature should just be selected suitably, Preferably it is 10-50 degreeC, More preferably, it is 15-35 degreeC. The treatment time is usually preferably 3 seconds or more, more preferably 10 seconds or more, and further preferably 30 seconds or more. If it is less than 3 seconds, it cannot be sufficiently neutralized and the effects of the present invention may not be obtained satisfactorily. Although there is no restriction | limiting in an upper limit, From the point of productivity, Preferably it is 24 hours or less, More preferably, it is 10 hours or less, More preferably, it is 5 hours or less.

In the treatment such as immersion of the acidic compound in an aqueous solution, the pH is preferably adjusted to 6 or less.
By such neutralization, excellent heat aging resistance is obtained. The upper limit of the pH is more preferably 5 or less, still more preferably 4.5 or less. The lower limit is not particularly limited, and although it depends on the immersion time, it is preferably 1 or more, more preferably 2 or more, because if the acid is too strong, the rubber deteriorates or the wastewater treatment becomes troublesome. The immersion treatment can be performed by leaving the agglomerated rubber in an acidic compound aqueous solution.

After the treatment, the compound used for the treatment of the acidic compound may be removed, and then the agglomerated rubber after the treatment may be appropriately washed. Examples of the cleaning treatment include the same methods as described above. For example, the non-rubber component may be further reduced by repeating the cleaning and adjusted to a desired content. Further, the agglomerated rubber after the treatment with the acidic compound may be squeezed with a roll type squeezer or the like to form a sheet. By adding a step of squeezing the agglomerated rubber, the pH of the agglomerated rubber surface and inside can be made uniform, and a rubber having a desired performance can be obtained. If necessary, the modified natural rubber can be obtained by carrying out a washing and squeezing step, then cutting through a creper and drying. In addition, drying is not specifically limited, For example, it can implement using normal dryers, such as a trolley-type dryer used in order to dry TSR, a vacuum dryer, an air dryer, and a drum dryer.

[Production method 2]
(Step 2-1)
In step 2-1, the natural rubber latex is deproteinized. Thereby, a deproteinized natural rubber latex from which non-rubber components such as proteins are removed can be prepared. Examples of the natural rubber latex used in Step 2-1 include those described above.

As a method for deproteinization, a known method capable of removing a protein can be used without particular limitation, and examples thereof include a method of degrading a protein by adding a proteolytic enzyme to natural rubber latex.

The proteolytic enzyme used for the deproteinization treatment is not particularly limited, and any of those derived from bacteria, those derived from filamentous fungi, and those derived from yeast may be used. Specifically, protease, peptidase, cellulase, pectinase, lipase, esterase, amylase and the like can be used alone or in combination.

The amount of proteolytic enzyme added is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the solid content in the natural rubber latex. It is. If it is less than the lower limit, the protein degradation reaction may be insufficient.

In the deproteinization treatment, a surfactant may be added together with the proteolytic enzyme. Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants.

(Process 2-2)
In step 2-2, the deproteinized natural rubber latex obtained in step 2-1 is washed. By the washing, non-rubber components such as proteins are removed.

Step 2-2 can be performed, for example, by aggregating the deproteinized natural rubber latex obtained in Step 2-1 to produce an aggregated rubber, and then washing the obtained aggregated rubber. Thereby, non-rubber components such as protein strongly adhered to the agglomerated rubber can be removed.

The aggregation method can be carried out in the same manner as in Step 1-2. Furthermore, you may process with a basic compound as mentioned above as needed. After the production of the agglomerated rubber, a cleaning process is performed. The washing treatment can be performed by the same method as in Step 1-2, and thereby non-rubber components such as proteins can be removed. The cleaning treatment is preferably performed until the phosphorus content in the rubber is 200 ppm or less and / or the nitrogen content is 0.15 mass% or less for the same reason as described above.

(Step 2-3)
In step 2-3, the washed rubber obtained in step 2-2 is treated with an acidic compound. When the acid amount is small in acid aggregation as well as in the treatment with a basic compound, the heat aging resistance is reduced due to the fact that the finally obtained rubber becomes alkaline to neutral when extracted with water. Tend. In general, an enzyme having an optimum pH in the alkaline region is used as a proteolytic enzyme because it can be suitably deproteinized, and the enzyme reaction is performed under alkaline conditions in accordance with the optimum pH. There are many cases. Thereafter, it is coagulated under acidity at the time of agglomeration, but if the rubber is washed only with water, the pH will be higher than that of the extract by the extraction described later, and in this case, particularly the heat aging resistance is greatly reduced. On the other hand, such a problem can be prevented and good heat aging resistance can be obtained by treatment with an acidic compound after solidification, if necessary, after solidification.

Examples of the acidic compound include the same ones as in Step 1-3. The method of treating the agglomerated rubber with an acid is not particularly limited as long as the agglomerated rubber is brought into contact with the acidic compound. For example, the method of immersing the agglomerated rubber in an aqueous solution of the acidic compound, Examples include a method of spraying an aqueous solution. An aqueous solution of an acidic compound can be prepared by diluting and dissolving each acidic compound with water.

The content of the acidic compound in 100% by mass of the aqueous solution is not particularly limited, but the lower limit is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and the upper limit is preferably 15% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. When the content is within the above range, good heat aging resistance can be obtained.

What is necessary is just to select the said process temperature and process time suitably, and should just employ | adopt the temperature similar to the said process 1-3. In the treatment such as immersion of the acidic compound in an aqueous solution, the pH is preferably adjusted to the same value as in Step 1-3.

After the treatment, the compound used for the treatment of the acidic compound may be removed, and then the agglomerated rubber after the treatment may be appropriately washed. Examples of the cleaning treatment include the same methods as described above. For example, the non-rubber component may be further reduced by repeating the cleaning and adjusted to a desired content. The modified natural rubber in the present invention is obtained by drying after completion of the washing treatment. In addition, drying is not specifically limited, The above-mentioned method etc. are employable.

In the rubber composition of the present invention, the content of the modified natural rubber in 100% by mass of the rubber component is 5% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass. % Or more. If it is less than 5% by mass, excellent fuel efficiency may not be obtained. The content is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. If it exceeds 90% by mass, the handling stability may be reduced.

Rubber components that can be used other than modified natural rubber include natural rubber (non-modified) (NR), epoxidized natural rubber (ENR), isoprene rubber (IR), butadiene rubber (BR), and styrene butadiene rubber (SBR). Styrene isoprene butadiene rubber (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and the like.

Especially, it is preferable to mix | blend BR from the point that favorable low-fuel-consumption property and steering stability are acquired. A compounded rubber in which a white filler such as silica is blended with BR generally has low dispersibility of the filler and it is difficult to obtain a desired performance. However, in the present invention, the blended rubber is filled by blending the modified natural rubber. The interaction between the agent and the rubber component is enhanced. Therefore, the dispersibility of the filler is improved, fuel efficiency and handling stability are improved, and good processability is also obtained.

The BR is not particularly limited, and those that are common in the tire industry can be used.
The cis content of BR is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 97% by mass or more.

The Mooney viscosity (ML _{1 + 4} (100 ° C.)) of BR is preferably 10 or more, more preferably 30 or more. If it is less than 10, the dispersibility of the filler tends to decrease. The Mooney viscosity is preferably 120 or less, more preferably 80 or less. If it exceeds 120, there is a concern about the occurrence of rubber burn (discoloration) during extrusion processing.

The content of BR in 100% by mass of the rubber component is preferably 10% by mass or more, and more preferably 20% by mass or more from the viewpoint of exhibiting necessary low fuel consumption and steering stability. Further, the content is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less, from the viewpoint of workability.

The rubber composition of the present invention preferably contains carbon black and / or a white filler. Thereby, the reinforcement effect is acquired.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 50 m ² / g or more, more preferably 60 m ² / g or more. The N ₂ SA is preferably 200 m ² / g or less, more preferably 180 m ² / g or less, and still more preferably 150 m ² / g or less. When it is less than 50 m ² / g, there is a tendency that a sufficient reinforcing effect cannot be obtained, and when it exceeds 200 m ² / g, there is a tendency that fuel efficiency is lowered.
In addition, the nitrogen adsorption specific surface area of carbon black is calculated | required by A method of JISK6217.

The content of carbon black is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the rubber component. The content is preferably 150 parts by mass or less, more preferably 100 parts by mass or less. Within the above range, good fuel economy and steering stability can be obtained.

As white filler, those commonly used in the rubber industry, for example, mica such as silica, calcium carbonate, sericite, aluminum hydroxide, magnesium oxide, magnesium hydroxide, clay, talc, alumina, titanium oxide From the viewpoint of low fuel consumption, silica is preferable.

The silica is not particularly limited, and examples thereof include dry process silica (anhydrous silicic acid), wet process silica (hydrous silicic acid), and the like, but wet process silica is preferable because of its large number of silanol groups.

Nitrogen adsorption specific surface area of the silica _(N 2 SA) of preferably at least ^{40 m} 2 / g, more preferably at least ^{50m 2 / g, 100m 2 /} g or more is more preferable. If it is less than 40 m < ² > / g, there exists a tendency for the fracture strength after vulcanization to fall. The _N 2 SA of the silica is preferably 300 meters ² / g or less, more preferably 200m ² / g. When it exceeds 300 m ² / g, there is a tendency that low heat build-up and rubber processability are lowered. The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

The content of silica is preferably 10 parts by mass or more, more preferably 20 parts by mass or more with respect to 100 parts by mass of the rubber component. Moreover, this content becomes like this. Preferably it is 120 mass parts or less, More preferably, it is 100 mass parts or less. Within the above range, good fuel economy and steering stability can be obtained.

When the rubber composition of this invention contains a silica, it is preferable to further mix | blend a silane coupling agent. The silane coupling agent is not particularly limited, and sulfide systems such as bis (3-triethoxysilylpropyl) disulfide and bis (3-triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Mercapto type such as triethoxysilane, vinyl type such as vinyltriethoxysilane, amino type such as 3-aminopropyltriethoxysilane, glycidoxy type of γ-glycidoxypropyltriethoxysilane, 3-nitropropyltrimethoxysilane, etc. And chloro-based silane coupling agents such as 3-nitropropyltrimethoxysilane.

The content of the silane coupling agent is preferably 0.5 parts by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2.5 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 0.5 parts by mass, it may be difficult to disperse silica well. Moreover, this content becomes like this. Preferably it is 20 mass parts or less, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less. Even if it exceeds 20 parts by mass, the effect of improving the dispersion of silica cannot be obtained, and the cost tends to increase unnecessarily. In addition, the scorch time is shortened, and the workability during kneading and extrusion tends to decrease.

In the rubber composition of the present invention, the total content of carbon black and white filler is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass with respect to 100 parts by mass of the rubber component. That's it. The content is preferably 150 parts by mass or less, more preferably 100 parts by mass or less. Within the above range, good fuel economy and steering stability can be obtained.

The rubber composition preferably contains oil as a plasticizer. Thereby, the hardness can be adjusted to an appropriate low level and good workability can be obtained. The oil is not particularly limited, and conventionally known oils such as paraffinic process oil, aroma based process oil, process oil such as naphthenic process oil, vegetable oil and fat, and mixtures thereof can be used.

The oil content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the rubber component. Moreover, this content becomes like this. Preferably it is 15 mass parts or less, More preferably, it is 10 mass parts or less. Within the above range, good processability is imparted, and excellent fuel economy and steering stability are also obtained.

In addition to the above materials, the rubber composition of the present invention includes zinc oxide, stearic acid, various anti-aging agents, plasticizers other than oil (such as wax), vulcanizing agents (such as sulfur and organic peroxides), Various materials generally used in the tire industry such as vulcanization accelerators (sulfenamide-based, guanidine-based vulcanization accelerators, etc.) may be appropriately blended.

As a method for producing the rubber composition of the present invention, known methods can be used. For example, the above components are kneaded using a rubber kneader such as an open roll or a Banbury mixer, and then vulcanized. Can be manufactured.

The rubber composition of the present invention is used for a tire tread. The base tread is an inner layer portion of a tread having a multilayer structure, and is an inner surface layer in a tread having a two-layer structure [a surface layer (cap tread) and an inner surface layer (base tread)]. Specifically, the base tread is a member shown in FIG. 1 of Japanese Patent Laid-Open No. 2008-285628, FIG. 1 of Japanese Patent Laid-Open No. 2008-303360, or the like.

A pneumatic tire using the rubber composition of the present invention is produced by a usual method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded in accordance with the shape of the base tread at an unvulcanized stage, molded by a normal method on a tire molding machine, After bonding together with the tire member to form an unvulcanized tire, the tire can be manufactured by heating and pressing in a vulcanizer.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
The various chemicals used in the examples are described below.
Field Latex: Field Latex Emar E-27C (surfactant) obtained from Muhiba Latex Co., Ltd .: Emar E-27C (Polyoxyethylene lauryl ether sodium sulfate, 27% by mass of active ingredient) manufactured by Kao Corporation
NaOH: NaOH manufactured by Wako Pure Chemical Industries, Ltd.
Wingstay L (anti-aging agent): WINGSTAY L (compound obtained by butylating the condensate of ρ-cresol and dicyclopentadiene) manufactured by ELIOKEM
Emulvin W (surfactant): Emalvin W (aromatic polyglycol ether) manufactured by LANXESS
Tamol NN9104 (surfactant): Tamol NN9104 manufactured by BASF (Naphthalenesulfonic acid / formaldehyde sodium salt)
Van gel B (surfactant): Van gel B (magnesium aluminum silicate hydrate) manufactured by Vanderbilt
NR: TSR20
BR: BR150B manufactured by Ube Industries, Ltd. (cis content: 97% by mass, ML _{1 + 4} (100 ° C.): 40)
Carbon Black: Show Black N330 (N ₂ SA: 75 m ² / g) manufactured by Cabot Japan
Silica: Ultrazil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent: Si266 manufactured by Degussa
Oil: Diana Process AH-24 manufactured by Idemitsu Kosan Co., Ltd.
Zinc oxide: 2 types of zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Beads stearic acid anti-aging agent manufactured by NOF Corporation: NOCRACK 6C (N-phenyl-) manufactured by Ouchi Shinsei Chemical Co., Ltd. N ′-(1,3-dimethylbutyl) -p-phenylenediamine) (6PPD)
Sulfur: Seimi Sulfur (oil content: 10%) manufactured by Nippon Kiboshi Kogyo Co., Ltd.
Vulcanization accelerator TBBS: Noxeller NS manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator DPG: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

<Examples and Comparative Examples>
(Preparation of anti-aging agent dispersion)
462.5 g of water was mixed with 12.5 g of Emulvin W, 12.5 g of Tamol NN9104, 12.5 g of Van gel B, and 500 g of Wingstay L (total of 1000 g) for 16 hours by a ball mill to prepare an antioxidant dispersion.

(Production Example 1)
After adjusting the solid content concentration (DRC) of the field latex to 30% (w / v), 25 g of 10% Emar E-27C aqueous solution and 60 g of 25% NaOH aqueous solution were added to 1000 g of the latex and saponified for 24 hours at room temperature. Reaction was performed to obtain a saponified natural rubber latex. Next, 6 g of the anti-aging dispersion was added and stirred for 2 hours, and then further diluted with water to a rubber concentration of 15% (w / v). Next, formic acid was added with slow stirring to adjust the pH to 4.0, and then a cationic polymer flocculant was added and stirred for 2 minutes for aggregation. The diameter of the aggregate (aggregated rubber) obtained in this way was about 0.5 to 3 mm. The obtained agglomerates were taken out and immersed in 1000 ml of a 2% by weight aqueous sodium carbonate solution at room temperature for 4 hours, and then the rubber was taken out. To this, 2000 ml of water was added and stirred for 2 minutes to remove water as much as possible 7 times. Thereafter, 500 ml of water was added, 2% by mass formic acid was added until pH 4 was reached, and the mixture was allowed to stand for 15 minutes. Further, after removing the water as much as possible, repeating the work of adding water again and stirring for 2 minutes three times, squeezing the water with a water squeezing roll to form a sheet, and then drying at 90 ° C. for 4 hours to solid rubber ( A high-purity natural rubber A) was obtained.

(Comparative Production Example 1)
After adjusting the solid content concentration (DRC) of the field latex to 30% (w / v), 25 g of 10% Emar E-27C aqueous solution and 60 g of 25% NaOH aqueous solution were added to 1000 g of the latex and saponified for 24 hours at room temperature. Reaction was performed to obtain a saponified natural rubber latex. Next, 6 g of the anti-aging dispersion was added and stirred for 2 hours, and then further diluted with water to a rubber concentration of 15% (w / v). Next, formic acid was added with slow stirring to adjust the pH to 4.0, and then a cationic polymer flocculant was added and stirred for 2 minutes for aggregation. The diameter of the aggregate (aggregated rubber) thus obtained was about 3 to 12 mm. The obtained agglomerates were taken out and immersed in 1000 ml of a 2% by weight aqueous sodium carbonate solution at room temperature for 4 hours, and then the rubber was taken out. To this, 1000 ml of water was added and stirred for 2 minutes to remove water as much as possible. Thereafter, 500 ml of water was added, 2% by mass formic acid was added until pH 4 was reached, and the mixture was stirred for 15 minutes. Further, the operation of removing water as much as possible, adding water again and stirring for 2 minutes was repeated three times, and then dried at 90 ° C. for 4 hours to obtain a solid rubber (high purity natural rubber B).

(Production Example 2)
Commercially available high-ammonia latex (manufactured by Mujiba Latex of Malaysia, solid rubber content 62.0%) is diluted with 0.12% sodium naphthenate aqueous solution to make the solid rubber content 10%, and dihydrogen phosphate. Sodium was added to adjust the pH to 9.2. And with respect to 10g of rubber | gum, after adding proteolytic enzyme (Alcalase 2.0M) in the ratio of 0.87g and adjusting pH again to 9.2, it maintained at 37 degreeC for 24 hours.
Next, a 1% aqueous solution of a nonionic surfactant (trade name Emulgen 810 manufactured by Kao Corporation) was added to the latex that had been subjected to the enzyme treatment to adjust the rubber concentration to 8%, and 11,000 r. p. m. The solution was centrifuged at a rotation speed of 30 minutes. Next, the cream-like fraction produced by centrifugation was dispersed in a 1% aqueous solution of Emulgen 810 to adjust the rubber concentration to 8%. p. m. The solution was centrifuged at a rotation speed of 30 minutes. After repeating this operation twice, the obtained creamy fraction was dispersed in distilled water to prepare a deproteinized rubber latex having a solid rubber content of 60%.
To this latex, 2% by mass formic acid was added until the pH reached 4, and a cationic polymer flocculant was further added to obtain 0.5 to 3 mm rubber particles. The water was removed as much as possible, 50 g of water was added to 10 g of rubber, and 2% by mass formic acid was added until pH 3 was reached. After 30 minutes, the rubber was pulled up, formed into a sheet with a creper, and then dried at 90 ° C. for 4 hours to obtain a solid rubber (high purity natural rubber C).

(Comparative Production Example 2)
Commercially available high-ammonia latex (manufactured by Mujiba Latex of Malaysia, solid rubber content 62.0%) is diluted with 0.12% sodium naphthenate aqueous solution to make the solid rubber content 10%, and dihydrogen phosphate. Sodium was added to adjust the pH to 9.2. And with respect to 10g of rubber | gum, after adding proteolytic enzyme (Alcalase 2.0M) in the ratio of 0.87g and adjusting pH again to 9.2, it maintained at 37 degreeC for 24 hours.
Next, a 1% aqueous solution of a nonionic surfactant (trade name Emulgen 810 manufactured by Kao Corporation) was added to the latex that had been subjected to the enzyme treatment to adjust the rubber concentration to 8%, and 11,000 r. p. m. The solution was centrifuged at a rotation speed of 30 minutes. Next, the cream-like fraction produced by centrifugation was dispersed in a 1% aqueous solution of Emulgen 810 to adjust the rubber concentration to 8%. p. m. The solution was centrifuged at a rotation speed of 30 minutes. After repeating this operation once more, the resulting creamy fraction was dispersed in distilled water to prepare a deproteinized rubber latex having a solid rubber content of 60%.
50% by mass formic acid was added to the latex until the rubber solidified, and the solidified rubber was taken out. The rubber was formed into a sheet while being washed with water with a creper and then dried at 90 ° C. for 4 hours to obtain a solid rubber (high-purity natural rubber D).

The solid rubber obtained above was evaluated as follows, and the results are shown in Table 1.

<Measurement of pH of rubber>
5 g of the obtained rubber was cut into a total of 3 mm or less (about 1-2 × about 1-2 × about 1-2 (mm)) and placed in a 100 ml beaker, and 50 ml of distilled water at room temperature was added. The temperature was raised to 90 ° C. for 1 minute, and then irradiation with microwaves (300 W) was performed for 13 minutes (total 15 minutes) while maintaining the temperature at 90 ° C. Next, the immersion water was cooled with an ice bath to 25 ° C., and then the pH of the immersion water was measured using a pH meter.

<Measurement of nitrogen content>
(Acetone extraction (test piece preparation))
About 0.5 g of a sample obtained by chopping each solid rubber into 1 mm square was prepared. The sample was immersed in 50 g of acetone, and after 48 hours at room temperature (25 ° C.), the rubber was taken out and dried to obtain each test piece (extracted with anti-aging agent).
(Measurement)
The nitrogen content of the obtained test piece was measured by the following method.
The nitrogen content was determined by decomposing and gasifying each of the acetone-extracted test pieces obtained above using a trace nitrogen carbon measuring device “SUMIGRAPH NC95A (manufactured by Sumika Chemical Analysis Center)”. The nitrogen content was quantified by analyzing with a gas chromatograph “GC-8A (manufactured by Shimadzu Corporation)”.

<Measurement of phosphorus content>
The phosphorus content was determined using an ICP emission spectrometer (P-4010, manufactured by Hitachi, Ltd.).

<Measurement of gel content>
About 70 mg of a raw rubber sample cut to 1 mm × 1 mm was accurately weighed, 35 mL of toluene was added thereto, and the mixture was allowed to stand in a cool dark place for 1 week. Subsequently, centrifugation was performed to precipitate a gel component insoluble in toluene, the soluble component of the supernatant was removed, and only the gel component was solidified with methanol, and then dried and the mass was measured. The gel content (mass%) was determined by the following formula.
Gel content (mass%) = [mass mg after drying / mg of initial sample] × 100

<Heat aging resistance>
The Mooney viscosity ML (1 + 4) 130 ° C. of the solid rubber before and after being treated at 80 ° C. for 18 hours was measured according to JIS K 6300: 2001-1, and the heat aging index was calculated by the above formula.

According to Table 1, the modified natural rubber having a rubber pH in the range of 2 to 7 was excellent in heat aging resistance as compared with the rubber outside the range.

<Production of test tire>
According to the formulation shown in Table 2, chemicals other than sulfur and a vulcanization accelerator were kneaded using 1.7 L Banbury. Next, using a roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition is molded into the shape of a base tread and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, which is vulcanized at 170 ° C. for 11 minutes, and used for testing. A tire (size: 195 / 65R15) was produced.
The obtained test tire was evaluated as follows, and the results are shown in Table 2.

<Low fuel consumption (rolling resistance)>
Using a rolling resistance tester, the rolling resistance when a test tire is run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h) is measured and compared. It was displayed as an index when Example 1 was taken as 100. A larger index is better (low fuel consumption).

<Steering stability>
The test tires were mounted on all wheels of a vehicle (domestic FF2000cc) and the vehicle was run on the test course, and the driving stability was evaluated by sensory evaluation of the driver. At that time, relative evaluation was performed with 10 points being the perfect score and the steering stability of Comparative Example 1 being 6 points. The larger the value, the better the steering stability.

From Table 2, it was revealed that in the examples using the high-purity natural rubber A or C, the fuel economy, heat aging resistance and steering stability were remarkably improved.

Claims (12)

A rubber composition for a base tread comprising a highly purified natural rubber having a pH adjusted to 2 to 7 and carbon black and / or a white filler ,
The pH is obtained by immersing 5 g of rubber produced by cutting the modified natural rubber into a size of 2 mm square on each side in 50 ml of distilled water and extracting at 90 ° C. for 15 minutes while irradiating with microwaves, A rubber composition for base tread which is a value obtained by measuring immersion water using a pH meter . The rubber composition for a base tread according to claim 1, wherein the modified natural rubber is obtained by removing a non-rubber component of natural rubber and then treating with an acidic compound, and having a pH of 2 to 7. The rubber composition for a base tread according to claim 1, wherein the modified natural rubber is obtained by washing a saponified natural rubber latex and further treating with an acidic compound, and having a pH of 2-7. The rubber composition for base tread according to claim 1, wherein the modified natural rubber is obtained by washing a deproteinized natural rubber latex and further treating with an acidic compound, and having a pH of 2-7. The rubber composition for base tread according to any one of claims 1 to 4, wherein the phosphorus content of the modified natural rubber is 200 ppm or less. The rubber composition for base tread according to any one of claims 1 to 5, wherein the modified natural rubber has a nitrogen content of 0.15 mass% or less. The modified natural rubber has a heat aging index represented by the following formula of 75 to 120% with respect to Mooney viscosity ML (1 + 4) 130 ° C. measured according to JIS K 6300: 2001-1. Item 7. A rubber composition for base treads according to item 6 .

The rubber composition for base tread according to any one of claims 1 to 7 , wherein the white filler is silica. The rubber composition for base tread according to any one of claims 1 to 8 , comprising butadiene rubber. The rubber composition for base treads according to any one of claims 1 to 9 , comprising oil. The rubber composition for base tread according to any one of claims 1 to 10 , wherein the modified natural rubber is produced without going through a mastication step. A pneumatic tire produced using the rubber composition for a base tread according to any one of claims 1 to 11.