JP6334314B2 - Rubber composition for tire and pneumatic tire - Google Patents

Description

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

In recent years, due to soaring fuel costs and the introduction of environmental regulations, tires with excellent fuel efficiency have been demanded, and there has been a demand for fuel efficiency reductions such as treads that greatly contribute to fuel efficiency. Since natural rubber is frequently used for tire members, it is necessary to reduce the fuel consumption of natural rubber in order to reduce the fuel consumption of the entire tire.

For example, Patent Document 1 discloses a method of adding a surfactant to natural rubber latex and performing a cleaning process as fuel efficiency reduction by modifying natural rubber. However, although the protein and gel content can be reduced to some extent by this method, it is not a sufficient level and further reduction of tan δ is desired. Also, tire rubbers are required to have performance such as heat aging resistance, but the method of Patent Document 1 is insufficient in heat resistance, and an improvement in both low fuel consumption and heat aging resistance is desired. Yes.

In addition, natural rubber has a high Mooney viscosity compared to other synthetic rubbers and has poor processability, and is usually used after mastication with a masticant added to reduce Mooney viscosity. The nature is bad. Furthermore, the molecular chain of natural rubber is cleaved by mastication, so that there is a problem that the characteristics (good fuel efficiency, wear resistance, rubber strength, etc.) of the high molecular weight polymer inherent to natural rubber are lost.

On the other hand, in recent years, the tire wear resistance has been improved and the period of use in the market has been prolonged, so the rubber strength, adhesive strength, rim slip resistance due to long-term damage and deterioration of the tire, It is required to improve various performances such as blowout resistance. Grip performance in terms of safety and durability constantly (especially wet grip performance for summer tires, especially low temperature grip performance for all-season tires, especially dry grip performance for competition tires), steering stability and wear resistance, etc. There is still a need for improved performance.

As described above, in a rubber composition for a tire, low fuel consumption, workability, heat aging resistance, and wear resistance, wet grip performance, low temperature grip performance, dry grip performance, steering stability, rubber strength, adhesive strength, Further improvements in various performances such as rim displacement and blowout resistance are desired.

Japanese Patent No. 3294901

The present invention solves the above-mentioned problems, and has low fuel consumption, workability, heat aging resistance, and wear resistance, wet grip performance, low temperature grip performance, dry grip performance, steering stability, rubber strength, adhesive strength, rim resistance It aims at providing the rubber composition for tires which improved various performances, such as shift nature and blowout resistance in good balance, and the pneumatic tire produced using the rubber composition.

The present invention relates to a modified natural rubber having a high purity and a pH adjusted to 2 to 7, carbon black and / or white filler, and a styrene butadiene rubber having a weight average molecular weight (Mw) of 800,000 or more. And a rubber composition for tires.

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.

The amount of bound styrene of the styrene butadiene rubber is preferably 20% by mass or more.

It is preferable that the oil whose polycyclic aromatic content calculated | required by IP346 method is 3 mass% or more is substantially not included.

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 tire rubber composition.

According to the present invention, high-purity modified natural rubber having a pH adjusted to 2 to 7, carbon black and / or white filler, and styrene having a weight average molecular weight (Mw) of 800,000 or more. Since it is a rubber composition for tires containing butadiene rubber, it has low fuel consumption, processability, heat aging resistance, and abrasion resistance, wet grip performance, low temperature grip performance, dry grip performance, steering stability, rubber strength, adhesion Various performances such as strength, rim slip resistance and blowout resistance can be improved in a well-balanced manner.

The tire rubber composition of the present invention has a high-purity modified natural rubber whose pH is adjusted to 2 to 7, carbon black and / or white filler, and a weight average molecular weight (Mw) of 800, 000 or more styrene butadiene rubbers.

The modified natural rubber is highly purified and has a pH adjusted to 2-7.
Non-rubber components such as proteins and phospholipids are removed to improve the purity, and the modified natural rubber controls the pH of the rubber to an appropriate value. Therefore, processability, low fuel consumption, wear resistance, wet grip Performance, low-temperature grip performance, dry grip performance, steering stability, rubber strength, adhesive strength, rim displacement resistance, and blowout resistance 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. As a result, the rubber physical properties are prevented from being deteriorated in the kneading step, and the dispersibility of the filler is improved. Furthermore, in the present invention, in addition to the modified natural rubber, by blending a styrene butadiene rubber having an Mw of 800,000 or more, the performance balance of the various performances is synergistically improved, and the performance balance is remarkably improved. can do.

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, resulting in energy. It is presumed that loss can be reduced, durability can be 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, a decrease in heat aging resistance is prevented, and the various performances 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 preferably has a Mooney viscosity ML (1 + 4) of 130 ° C. and a heat aging index represented by the following formula of 75 to 120%.

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 the various performances 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 is (Production method 1) Step 1-1 of saponifying natural rubber latex; A production method comprising a step 1-2 for washing the saponified 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; It can be prepared by a production method including a step 2-2 for washing rubber latex and a step 2-3 for treating with an 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.

As pH of the aqueous solution of the said basic compound, 9-13 are preferable and 10-12 are more preferable from the point of processing efficiency.

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 this washing treatment, it is possible to sufficiently remove non-rubber components such as proteins trapped in the rubber at the time of aggregation, and at the same time sufficiently remove not only the surface of the aggregated rubber but also the basic compounds present inside. . In particular, by removing the basic compound remaining in the entire rubber in the washing step, it becomes possible to sufficiently treat the entire rubber with an acidic compound described later, and not only the surface of the rubber but also the internal pH is 2 Can be adjusted to ~ 7.

As the washing method, a non-rubber component contained in the whole rubber, means capable of sufficiently removing the basic compound can be suitably used, for example, a method of diluting the rubber with water and washing, followed by centrifugation, There is a method in which the rubber is floated by standing, and the rubber component is taken out by discharging only the aqueous phase. The number of washings can be any number of times that can reduce the amount of non-rubber components such as proteins and basic compounds to a desired amount. However, washing is performed by adding 1000 mL of water to 300 g of dry rubber and stirring and dehydrating. If it is the method of repeating a cycle, 3 times (3 cycles) or more are preferable, 5 times (5 cycles) or more are more preferable, and 7 times (7 cycles) or more are still 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. The various performances are improved by sufficiently removing phospholipids and proteins by the washing treatment.

(Step 1-3)
In Step 1-3, the washed rubber obtained in Step 1-2 is treated with an acidic compound. As described above, by performing the treatment, the pH of the entire rubber is adjusted to 2 to 7, and a modified natural rubber having excellent various performances can be provided. In addition, although there exists a tendency for heat aging resistance to fall resulting from the process of a basic compound, such a problem is prevented by further processing with an acidic compound, and favorable heat aging resistance is obtained.

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, a method of immersing the agglomerated rubber in an aqueous solution of the acidic compound, an aqueous solution of the acidic compound in the agglomerated rubber 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 carried out by the same method as in Step 1-2, whereby non-rubber components such as proteins and basic compounds 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. In many cases, in order to adjust the final pH of the entire rubber to 2 to 7, the deproteinization treatment of the natural rubber latex in the step 2-1 is preferably performed at pH 8 to 11, and pH 8.5 to 11 Is more preferable. 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 is obtained by drying after the washing treatment. In addition, drying is not specifically limited, The above-mentioned method etc. are employable.

In the tire rubber composition of the present invention, the content of the modified natural rubber in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. Especially preferably, it is 30 mass% or more. Moreover, this content becomes like this. Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less.

In the present invention, a styrene butadiene rubber (hereinafter also referred to as high molecular weight SBR) having a weight average molecular weight (Mw) of 800,000 or more is used as the rubber component together with the modified natural rubber. By using the high molecular weight SBR and the modified natural rubber in combination, the performance balance of the various performances can be remarkably improved.

The high molecular weight SBR can be prepared by using a known method such as an anionic polymerization method, a solution polymerization method, an emulsion polymerization method, etc., for example, a monolithium initiator such as n-butyllithium or sec-butyllithium, tetra Polymerization using a polyfunctional polymerization initiator such as methylene-1,4-dilithium, dilithiobenzene, dilithiomethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, A polymer can be obtained by performing a coupling reaction with tin such as 6-bis (trimethoxysilyl) hexane, dinutyldichlorosilane, tin tetrachloride, tetraethoxysilane, or a silicon compound. Moreover, you may add polyfunctional monomers, such as divinylbenzene and diisopropenylbenzene. Commercial products can also be used.

The high molecular weight SBR has a weight average molecular weight (Mw) of 800,000 or more, preferably 900,000 or more, more preferably 1,000,000 or more. If it is less than 800,000, the effects of the present invention may not be sufficiently exhibited. The upper limit of Mw is not particularly limited as long as processability such as polymer dispersion does not deteriorate, but it is preferably 3,000,000 or less. The weight average molecular weight (Mw) of SBR can be determined by the method shown in the examples.

The amount of bound styrene of the high molecular weight SBR is preferably 20% by mass or more, more preferably 25% by mass or more. If it is less than 20% by mass, the effects of the present invention may not be sufficiently obtained. The amount of bound styrene is preferably 60% by mass or less, more preferably 50% by mass or less. When it exceeds 60% by mass, there is a possibility that excellent fuel efficiency performance cannot be obtained. The cis content is not particularly limited.
In the present specification, the styrene content of SBR is calculated by H ¹ -NMR measurement.

The vinyl content of the high molecular weight SBR is preferably 10% by mass or more, more preferably 15% by mass or more. If it is less than 10% by mass, the effects of the present invention may not be sufficiently obtained. The vinyl content is preferably 65% by mass or less, more preferably 60% by mass or less. When it exceeds 65 mass%, there is a possibility that excellent fuel efficiency performance cannot be obtained.
In the present specification, the vinyl content of the SBR, shows that the vinyl content of the butadiene portion and is calculated by H ¹ -NMR measurement.

In 100 parts by mass of the rubber component, the content (solid content) of the high molecular weight SBR is preferably 3 to 90% by mass, more preferably 5 to 85% by mass, and still more preferably 10 to 80% by mass. When it is less than 3% by mass, grip performance and rubber strength tend to be inferior, and when it exceeds 90% by mass, fuel economy and processability tend to decrease.

The randomness of the high molecular weight SBR styrene unit and butadiene unit is not particularly limited, and a random SBR or an inclined structure SBR can be used depending on the application.

The molecular weight distribution, monomodality, and multimodality of the high molecular weight SBR are not particularly limited, and can be appropriately selected depending on the application.

The high molecular weight SBR may be modified with a polar group having an affinity for the filler. The polar group to be introduced is not particularly limited, and examples thereof include alkoxysilyl groups, amino groups, hydroxyl groups, glycidyl groups, amide groups, carboxyl groups, ether groups, thiol groups, cyano groups, metal atoms such as tin and titanium, An alkoxysilyl group and an amino group are preferred.

The position of the polar group is not particularly limited, and may be a terminal, a main chain, or a graft structure branched from the main chain. One polymer chain may have a plurality of modifying groups.

The high molecular weight SBR is preferably extended with oil from the viewpoint of improving processability.

The oil used for the extension is not particularly limited, but from the viewpoint of the environment, it is preferable to use an oil (low PCA oil) having a polycyclic aromatic content determined by the IP346 method of less than 3% by mass. Examples of such low PCA oils include mild extraction solvate (MES), treated distillate aromatic extract (TDAE), heavy naphthenic oil, vegetable oil and the like. The content of the extending oil is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the polymer SBR.

When low PCA oil is used, it is known that the wear resistance is reduced as compared with conventional aroma oil, but the physical properties are lowered by using it together with the modified natural rubber in the present invention. It can be considered environmentally.

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

SBR other than the above high molecular weight SBR is not particularly limited, and examples thereof include solution polymerization SBR (S-SBR), emulsion polymerization SBR (E-SBR), and modified SBR thereof, and those prepared by a known method are used. Alternatively, a commercially available product may be used. Examples of commercially available products include Nipol NS116R manufactured by Nippon Zeon Co., Ltd.

The amount of bound styrene of SBR other than the high molecular weight SBR is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. If it is less than 5% by mass, sufficient grip performance and rubber strength may not be obtained. The amount of bound styrene is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less. If it exceeds 60% by mass, there is a possibility that excellent fuel efficiency cannot be obtained. In the present specification, the styrene content of SBR is calculated by H ¹ -NMR measurement.

The vinyl content of SBR other than the high molecular weight SBR is preferably 10% by mass or more, more preferably 15% by mass or more. If it is less than 10% by mass, sufficient grip performance and rubber strength may not be obtained. The vinyl content is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 30% by mass or less. If it exceeds 65% by mass, excellent fuel efficiency may not be obtained. In the present specification, the vinyl content of the SBR indicated that the vinyl content of the butadiene portion and is calculated by H ¹ -NMR measurement.

From the viewpoint of low fuel consumption, rubber strength, and wet grip performance, it is preferable to blend SBR other than the high molecular weight SBR. When SBR other than the high molecular weight SBR is blended, the content of SBR other than the high molecular weight SBR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more. The content is preferably 50% by mass or less, more preferably 30% by mass or less. The effect of this invention can fully be exhibited as it exists in the said range.

BR is not particularly limited, and those commonly used in the tire industry can be used. For example, high-cis 1,4-polybutadiene rubber (high-cis BR), butadiene rubber containing 1,2-syndiotactic polybutadiene crystals (SPB-containing BR) ), Modified butadiene rubber (modified BR), BR synthesized using a rare earth catalyst (rare earth BR), and the like.

For the reason of sufficiently ensuring low temperature characteristics and durability, 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.

From the viewpoint of low temperature characteristics, it is preferable to blend BR. When blending BR, the content of BR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 15% by mass or more. Moreover, this content becomes like this. Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 30 mass% or less. The effect of this invention can fully be exhibited as it exists in the said range.

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

Carbon black is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF, and SAF. These carbon blacks may be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 10 m ² / g or more, more preferably 20 m ² / g or more, and further preferably 23 m ² / g or more. The N ₂ SA is preferably 300 m ² / g or less, more preferably 250 m ² / g or less, and still more preferably 200 m ² / g or less. When it is less than 10 m ² / g, there is a tendency that a sufficient reinforcing effect cannot be obtained, and when it exceeds 300 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, and further preferably 5 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, the effects of the present invention are sufficiently 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 Silica is preferable from the viewpoints of reinforcement and fuel efficiency.

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.

The nitrogen adsorption specific surface area (N ₂ SA) of the silica is preferably 40 m ² / g or more, more preferably 50 m ² / g or more, and still more preferably 80 m ² / g or more. If it is less than 40 m < ² > / g, there exists a tendency for the reinforcement property after a vulcanization to fall. The _N 2 SA of the silica is preferably 500 meters ² / g or less, more preferably ^{300m 2 / g, 200m 2 /} g or less is more preferable. When it exceeds 500 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.

When the white filler or silica is blended, the content of the white filler or silica is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass with respect to 100 parts by mass of the rubber component. That's it. If it is less than 5 parts by mass, the low heat build-up may be insufficient. The content is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 130 parts by mass or less. When it exceeds 200 parts by mass, it becomes difficult to disperse the rubber into the filler, and the processability of the rubber tends to deteriorate.

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 8 parts by mass or more, and still more preferably 10 parts by mass with respect to 100 parts by mass of the rubber component. That's it. The content is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less. Within the above range, the effects of the present invention can be sufficiently obtained.

The rubber composition of the present invention preferably contains a silane coupling agent together with silica when silica is blended. Examples of the silane coupling agent include sulfides such as bis (3-triethoxysilylpropyl) disulfide, mercaptos such as 3-mercaptopropyltrimethoxysilane and 3-octanoylthiopropyltriethoxysilane, and vinyltriethoxysilane. Such as vinyl, amino such as 3-aminopropyltriethoxysilane, glycidoxy of γ-glycidoxypropyltriethoxysilane, nitro such as 3-nitropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, etc. And chloro-based. Of these, sulfide type and mercapto type are preferable, and 3-octanoylthiopropyltriethoxysilane is particularly preferable. Examples of commercially available products include Si69, Si75, Si363 manufactured by Degussa, NXT, NXT-LV, NXTULV, NXT-Z manufactured by Momentive, etc. These silane coupling agents may be used alone. Two or more kinds may be used in combination. The content of the silane coupling agent is preferably 0.5 to 20 parts by mass, more preferably 1.5 to 15 parts by mass with respect to 100 parts by mass of silica. The effect of this invention can fully be exhibited as it exists in the said range.

The rubber composition of the present invention may contain substantially no oil (aromatic oil) having a polycyclic aromatic content determined by the IP346 method of 3% by mass or more as a plasticizer from the viewpoint of environmental considerations. preferable. That is, the plasticizer preferably contains oil (low PCA oil) having a polycyclic aromatic content of less than 3% by mass determined by the IP346 method, a liquid polymer such as liquid SBR, a liquid resin, and the like. In the present invention, the extending oil contained in the high molecular weight SBR also corresponds to the plasticizer.

The content of the plasticizer is preferably 3 parts by mass or more and more preferably 5 parts by mass or more with respect to 100 parts by mass of the rubber component. The content is preferably 100 parts by mass or less, and more preferably 90 parts by mass or less. The effect of this invention can fully be exhibited as it exists in the said range. In the present invention, the extending oil contained in the high molecular weight SBR is also included in the above content.

In addition to the above materials, the rubber composition of the present invention includes stearic acid, various anti-aging agents, plasticizers other than oil (such as wax), vulcanizing agents (such as sulfur and organic peroxides), resins, and crosslinks. Various materials generally used in the tire industry such as a vulcanizing agent and a vulcanization accelerator (sulfenamide-based, guanidine-based vulcanization accelerator, 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 for tires of the present invention can be used for each member of a tire. Examples of the member include treads such as cap treads, base treads, and under treads, sidewalls, wings, bright toppings, clinch apex, bead apex, side wall reinforcing layers, inner liners, chafers, breaker toppings, and the like. Especially, the occupation ratio of the member which comprises a tire is high, and it can be suitable for the cap tread with the big effect of this invention.

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

The pneumatic tire of the present invention can be suitably used for passenger cars, truck / bus (heavy duty vehicle) summer tires, studless tires, all-season tires, competition tires, and the like.

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
Cyclohexane: Kanto Chemical Co., Ltd. 1,3-Butadiene: Tokyo Chemical Industry Co., Ltd. Styrene: Wako Pure Chemical Industries, Ltd. Tetrahydrofuran: Kanto Chemical Co., Ltd. Tetramethylene-1,4-dilithium: Aldrich 1,6-bis (trimethoxysilyl) hexane manufactured by: Glasto di-tert-butyl-p-cresol: Ouchi Shinsei Chemical Co., Ltd. TDAE: H & R Viva Tec 400
Liquid SBR: RICON100 (Mw: 5000) manufactured by Sartomer
SBR1: SBR synthesized according to Preparation Example 1 below
SBR2: SBR synthesized according to Preparation Example 2 below
SBR3: SBR synthesized according to Preparation Example 3 below
SBR4: SBR synthesized according to Preparation Example 4 below
SBR5: SBR synthesized according to Preparation Example 5 below
SBR6: Nipol NS116R (bound styrene content: 21% by mass) manufactured by Nippon Zeon Co., Ltd.
BR: BR150B (High cis BR, cis content: 97% by mass, ML _{1 + 4} (100 ° C.): 40, 5% toluene solution viscosity (25 ° C.): 48 cps, Mw / Mn: 3.3 manufactured by Ube Industries, Ltd. )
Carbon Black 1: Dia Black I (ISAF, N ₂ SA: 114 m ² / g) manufactured by Mitsubishi Chemical Corporation
Carbon Black 2: Dia Black H (N330, N ₂ SA: 79 m ² / g) manufactured by Mitsubishi Chemical Corporation
Carbon black 3: N220 (N ₂ SA: 118 m ² / g) manufactured by Cabot Japan
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent: NXT silane (3-octanoylthiopropyltriethoxysilane) manufactured by Momentive Performance Materials
Wax: Ozoace 0355 manufactured by Nippon Seiwa 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)
Resin 1: PR12686 (cashew oil-modified phenol resin) manufactured by Sumitomo Bakelite Co., Ltd.
Resin 2: YS resin TO-125 manufactured by Yashara Chemical Co., Ltd. (aromatic modified terpene resin, softening point 125 ° C.)
HMT: Noxeller H (hexamethylenetetramine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
KA9188: KA9188 (1,6-bis (dibenzylthiocarbamoyldithio) hexane manufactured by LANXESS)
Sulfur: Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd .: Noxeller NS (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry 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) thus obtained was about 0.5 to 5 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.

(Production Example 2)
A solid rubber (high-purity natural rubber B) was obtained in the same procedure except that 2% by mass of formic acid was added until pH 1 in Production Example 1.

(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 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 C).

(Comparative Production Example 2)
The same procedure was followed, except that it was treated with an aqueous sodium carbonate solution in Production Example 1 and washed with water seven times, and then the sheet was formed by squeezing water with a water squeezing roll without acid treatment with 2% by mass formic acid. A solid rubber (high purity natural rubber D) was obtained.

(Production Example 3)
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 rubber particles of 0.5 to 5 mm. 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 dried at 90 ° C. for 4 hours to obtain a solid rubber (high-purity natural rubber E).

(Production Example 4)
A solid rubber (high-purity natural rubber F) was obtained in the same procedure except that 2% by mass formic acid was added until pH 1 in Production Example 3.

(Comparative Production Example 3)
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 G).

(Comparative Production Example 4)
The rubber solidified in Comparative Production Example 3 was taken out, immersed in an aqueous 0.5% by mass sodium carbonate solution for 1 hour, then formed into a sheet while being washed with water with a creper, and then dried at 90 ° C. for 4 hours. A solid rubber (high-purity natural rubber H) was obtained by the procedure described above.

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 to 5 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 to 90 ° C. for 2 minutes. The temperature was raised, and then irradiation with microwaves (300 W) was performed for 13 minutes (15 minutes in total) while adjusting the temperature to be maintained 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.

<Preparation of various molecular weight SBR>
(Preparation Example 1)
An autoclave with a stirrer is charged with 8 L of cyclohexane, 1.5 kg of 1,3-butadiene, and 0.6 kg of styrene. After adding 100 g of tetrahydrofuran, 12 mmol of tetramethylene-1,4-dilithium is added, and the initial polymerization temperature is 50 ° C. for 48 hours. Polymerization was performed. The maximum temperature during the polymerization reaction was 76 ° C. After the completion of the polymerization, coupling with 12 mmol of 1,6-bis (trimethoxysilyl) hexane gave a polymer, and then 0.5 parts by mass of di-tert-butyl-p-cresol with respect to 100 parts by mass of the polymer, Extending oil (TDAE) was added to 50.0 parts by mass with respect to 100 parts by mass of the polymer, and dried to obtain SBR1. The obtained SBR1 had a weight average molecular weight (Mw) of 1,550,000, a bound styrene content of 32% by mass, and a vinyl content of 36% by mass.

(Preparation Example 2)
SBR2 was obtained in the same manner as in Preparation Example 1, except that the initial polymerization temperature was 40 ° C. and the reaction time was changed to 36 hours. The Mw of the obtained SBR2 was 700,000, the bound styrene content was 34% by mass, and the vinyl content was 35% by mass.

(Preparation Example 3)
SBR3 was obtained in the same manner as in Preparation Example 1 except that 0.6 kg of butadiene and 12 mmol of 1,6-bis (trimethoxysilyl) hexane were not used and no oil extension was performed. The Mw of the obtained SBR3 was 190,000, the amount of bound styrene was 18% by mass, and the vinyl content was 56% by mass.

(Preparation Example 4)
SBR4 was obtained in the same manner as in Preparation Example 1, except that liquid SBR was used instead of extension oil (TDAE). The obtained SBR4 had a weight average molecular weight (Mw) of 1,550,000, a bound styrene content of 32% by mass, and a vinyl content of 37% by mass.

(Preparation Example 5)
SBR5 was obtained in the same manner as in Preparation Example 2, except that liquid SBR was used instead of extension oil (TDAE). The Mw of the obtained SBR5 was 700,000, the bound styrene content was 34% by mass, and the vinyl content was 35% by mass.

The weight average molecular weight, the amount of bound styrene, and the vinyl content of the various SBRs were measured using the following methods.
(Weight average molecular weight)
The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) method under the following conditions (1) to (8).
(1) Apparatus: HLC-8220 manufactured by Tosoh Corporation
(2) Separation column: Tosoh HM-H (two in series)
(3) Measurement temperature: 40 ° C
(4) Carrier: Tetrahydrofuran (5) Flow rate: 0.6 mL / min (6) Injection volume: 5 μL
(7) Detector: differential refraction (8) Molecular weight standard: Standard polystyrene (bound styrene content, vinyl content)
It measured using the NMR apparatus of AV400 made from BRUKER, and data analysis software TOP SPIN2.1.

<Preparation of unvulcanized rubber composition and test tire>
According to the formulation shown in Tables 2 to 7, 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 was molded into a 2.1 mm sheet and vulcanized at 150 ° C. for 30 minutes to obtain a 2 mm vulcanized rubber composition.
The obtained unvulcanized rubber composition and vulcanized rubber composition were evaluated for the following performance. The results are shown in each table. The reference comparative examples in each table were Comparative Examples 1-3, 2-3, 3-3, 4-3, 5-3, and 6-3. Rubber composition for cap tread, rubber composition for bead apex, rubber composition for chafer, and rubber composition for tread are molded into the shape of cap tread, bead apex, chafer or tread, and tire molding machine It is pasted together with other tire members to form an unvulcanized tire, vulcanized for 10 minutes at 170 ° C., and a test tire (size: 195 / 65R15, passenger car summer tire (cap tread, bead apex, chain) Fur) and all-season tires (cap treads) and competition tires (treads).

<Processability index>
About the obtained unvulcanized rubber composition, it measured at 130 degreeC according to the measuring method of the Mooney viscosity based on JISK6300: 2001-1. The Mooney viscosity (ML1 + 4) of the reference comparative example was set to 100, and the index was expressed by the following formula. The larger the index, the lower the Mooney viscosity and the better the workability.
(Processability index) = (ML _{1 + 4} of reference comparative example) / (ML _{1 + 4 of} each formulation) × 100

<Low fuel consumption (rolling resistance index)>
About the cap tread rubber composition for summer tires, and the cap tread rubber composition for all-season tires, a rolling resistance tester was used, and each test tire was rim (15 × 6 JJ), internal pressure (230 kPa), load (3. 43 kN), rolling resistance when running at a speed (80 km / h) was measured, and displayed as an index when the reference comparative example was 100. The larger the index, the better (low fuel consumption).

<Low fuel consumption (rolling resistance index)>
For the rubber composition for pre-tapping, the rubber composition for bead apex, and the rubber composition for chafer, the vulcanized rubber composition is subjected to a temperature of 70 using a viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho Co., Ltd.). The tan δ of each formulation was measured under the conditions of ° C., initial strain of 10%, and dynamic strain of 1%, and the tan δ of the reference comparative example was taken as 100 and indicated by the following formula. The larger the index, the better the rolling resistance.
(Rolling resistance index) = (tan δ of reference comparative example) / (tan δ of each formulation) × 100

<Wet grip performance index>
Each test tire was mounted on all wheels of a vehicle (domestic FF2000cc), and a braking distance from an initial speed of 100 km / h was determined on a wet asphalt road surface. The result is expressed as an index. The larger the number, the better the wet skid performance (wet grip performance). The index was calculated by the following formula.
Wet skid performance = (braking distance of reference comparative example) / (braking distance of each blending example) × 100

<Low temperature grip performance index>
Using the test all-season tire, the actual vehicle performance was evaluated on ice under the following conditions. The test tire was mounted on a domestic 2000cc FR vehicle. The test place was the Hokkaido Asahikawa test course (on ice) of Sumitomo Rubber Industries, Ltd., and the on-ice temperature was -1 to -6 ° C.
On-ice grip performance index (braking performance (on-ice braking stop distance)): The stop distance on ice required to stop the stepping on the lock brake at a speed of 30 km / h was measured. The standard comparative example was set to 100, and the index was expressed by the following formula. The larger the index, the better the braking performance on ice.
(Grip performance index on ice and snow) = (Stop distance of reference comparative example) / (Stop distance of each formulation) × 100

<Dry grip performance index>
Regarding the tread rubber composition for racing tires, each test tire is mounted on a 2000 cc domestic FR vehicle, 10 laps are run on a dry asphalt road test course, and control stability during steering is maintained. Was evaluated by a test driver, and a reference comparative example was taken as an index. The larger the index, the better the grip performance on the dry road surface.

<Abrasion resistance index>
For the rubber composition for cap treads, each test tire is mounted on a domestic FF vehicle, the groove depth of the tire tread portion after a running distance of 8000 km is measured, and the running distance when the tire groove depth is reduced by 1 mm is calculated. Then, it was indexed by the following formula. The higher the index, the better the wear resistance.
Abrasion resistance index = (travel distance when the tire groove of each compound is reduced by 1 mm) / (travel distance when the tire groove of the reference comparative example is reduced by 1 mm) × 100

<Abrasion resistance index>
For the tread rubber composition for competition tires, each test tire is mounted on a 2000 cc domestic FR vehicle, the vehicle is run on a dry asphalt road test course, and the remaining groove of the tire tread rubber is measured. (15 mm when new), evaluated as wear resistance. The greater the amount of remaining grooves, the better the wear resistance. The index was displayed with the remaining groove amount of the reference comparative example as 100. It shows that it is excellent in abrasion resistance, so that an index | exponent is large.

<Rubber strength index>
In accordance with JIS K 6251 “Determination of tensile properties of vulcanized rubber and thermoplastic rubber”, a tensile test was conducted using a No. 3 dumbbell, and the elongation at break (EB) of the vulcanized rubber composition and the tensile at break The strength (TB) was measured. In addition, EB × TB of the reference comparative example was set to 100, and EB × TB of each formulation was indicated by an index according to the following calculation formula. It shows that it is excellent in breaking strength, so that an index | exponent is large.
(Breaking strength index) = (EB × TB of each formulation) / (EB × TB of reference comparative example) × 100

<Adhesive strength index>
Eight cords were arranged at equal intervals of 10 mm, and 0.7 mm thick topping rubber (unvulcanized rubber composition) was pressure-bonded from both sides. After the obtained rubber crimping cord was stored under the condition of 60% humidity, two rubber crimping cords were bonded together at an angle of 90 degrees, and reinforcing rubber was crimped on both sides thereof. The shape of the obtained pressure-bonded product was rectangular according to the shape of the vulcanization mold. After the pressure-bonded material was vulcanized at 165 ° C. for 20 minutes with the mold, a tear was placed between the two rubber-bonded cords bonded together in the resulting vulcanized material, and an Instron tensile tester was used. At a rate of 50 mm / min, the film was pulled in the direction of 180 degrees, and the peel force (kN / 25 mm) between the rubber crimping cords was evaluated. The results are shown as an index with the peel strength of the reference comparative example as 100. The larger the value, the better the adhesion between the cord and the topping rubber, and the better the durability.

<Maneuvering stability index>
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 the handling stability of the reference comparative example as 100. The larger the value, the better the steering stability.

<Blowout resistance index>
Using the obtained vulcanized rubber composition, a flexometer (manufactured by Leo Lab Co., Ltd.) was subjected to repeated compression deformation, and the time until blow-out by self-heating of the rubber was measured. . The test conditions were 20% repeated compression strain, 10 Hz frequency, and indexed with the blowout time of the reference comparative example as 100. The larger the index, the better the blowout time and the better the blowout resistance.

<Rim slip resistance (wear resistance) index>
The test tire was run for 400 hours at a speed of 20 km / h under the condition of 230% of the maximum load of JIS standard (maximum internal pressure condition), and then the wear depth of the rim flange contact part was measured and compared with the standard. The rim deviation resistance index of the example was set to 100, and the wear depth (rim deviation resistance) of each formulation was indicated by an index according to the following formula. In addition, it shows that it is so hard to slip | deviate a rim and it is excellent in abrasion resistance, so that an index | exponent is large.
(Rim slip resistance index) = (Abrasion depth of reference comparative example) / (Abrasion depth of each compound) × 100

From Tables 1 and 2, in the example of the cap tread rubber composition for a summer tire in which high-purity natural rubber having a pH of 2 to 7 and high molecular weight SBR are used in combination, low fuel consumption, processability, heat aging resistance, It was revealed that the wearability and wet grip performance were well-balanced and improved significantly.

From Tables 1 and 3, in the cap tread rubber composition for all-season tires, in an example in which a high-purity natural rubber having a pH of 2 to 7 and a high molecular weight SBR are used in combination, fuel economy, processability, heat aging resistance, It was revealed that the wear resistance, low-temperature grip performance and wet grip performance are well-balanced and significantly improved.

From Tables 1 and 4, in the rubber composition for bright wrapping, in the examples in which high-purity natural rubber having a pH of 2 to 7 and high molecular weight SBR are used in combination, low fuel consumption, processability, heat aging resistance, adhesive strength and It was revealed that the rubber strength was well balanced and improved significantly.

From Tables 1 and 5, in the rubber composition for bead apex, in Examples using high purity natural rubber having a pH of 2 to 7 and high molecular weight SBR in combination, low fuel consumption, processability, heat aging resistance, rubber strength In addition, it was revealed that the steering stability is well balanced and markedly improved.

From Tables 1 and 6, in the tread rubber composition for racing tires, in the examples in which high-purity natural rubber having a pH of 2 to 7 and high molecular weight SBR are used in combination, processability, heat aging resistance, wear resistance, dryness It was revealed that the grip performance and blowout resistance were well balanced and improved significantly.

From Tables 1 and 7, in the example of the rubber composition for chafers in which high-purity natural rubber having a pH of 2 to 7 and high molecular weight SBR are used in combination, low fuel consumption, processability, heat aging resistance, rubber strength and It was revealed that the resistance to rim displacement was well-balanced and improved significantly.

From the above results, it was found that a tire rubber composition using a high-purity natural rubber having a pH of 2 to 7 and a high molecular weight SBR can synergistically improve the various performances such as fuel efficiency.

Claims (9)

Modified natural rubber having a phosphorus content of 200 ppm or less and / or a nitrogen content of 0.15 mass% or less and a pH adjusted to 2 to 7, carbon black and / or white filler, and weight average molecular weight (Mw) is a rubber composition for tires including a styrene butadiene rubber having 800,000 or more ,
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. A rubber composition for a tire having a determined value . 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. 1 Symbol mounting rubber composition for a tire section.

The rubber composition for a tire according to claim 1 or 2 , wherein the white filler is silica. The tire rubber composition according to any one of claims 1 to 3 , wherein the amount of bound styrene in 100% by mass of the styrene-butadiene rubber is 20% by mass or more. It is a manufacturing method of the rubber composition for tires in any one of Claims 1-4,
A method for producing a rubber composition for a tire, comprising removing a non-rubber component of natural rubber and then treating with an acidic compound to obtain the modified natural rubber. It is a manufacturing method of the rubber composition for tires in any one of Claims 1-4,
A method for producing a rubber composition for a tire, comprising a step of washing a saponified natural rubber latex and further treating with a acidic compound to obtain the modified natural rubber. It is a manufacturing method of the rubber composition for tires in any one of Claims 1-4,
A method for producing a rubber composition for a tire, comprising a step of washing a deproteinized natural rubber latex and further treating with an acidic compound to obtain the modified natural rubber. The method for producing a rubber composition for a tire according to any one of claims 5 to 7, wherein the modified natural rubber is produced without going through a kneading step. The pneumatic tire produced using the rubber composition for tires in any one of Claims 1-4 .