JP6006168B2 - Base tread rubber composition and heavy duty tire - Google Patents

Description

The present invention relates to a base tread rubber composition and a heavy duty tire manufactured using the rubber composition.

In the transportation industry, tires with excellent fuel efficiency are also desired for heavy-duty vehicles such as trucks and buses due to the increase in expenses due to soaring fuel costs and the increase in expenses due to the introduction of environmental regulations. Further study is indispensable due to the increasing demand for fuel efficiency. Since natural rubber is frequently used in the base tread of heavy duty tires, it is necessary to promote the reduction in 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. The tire rubber is also required to have performance such as heat aging resistance. However, the method of Patent Document 1 is insufficient in heat resistance, and improvement of both low fuel consumption and heat aging resistance is also desired.

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, which causes a problem that the characteristics (good wear resistance, low fuel consumption, rubber strength, etc.) of the high molecular weight polymer inherent to natural rubber are lost.

On the other hand, a method of reducing the content of carbon black or white filler is also known as a method of reducing fuel consumption of rubber blending. However, in this case as well, there are problems of wear resistance and rubber strength reduction. Thus, in the base tread of a heavy duty tire, etc., it is required to improve the fuel economy, heat aging resistance, wear resistance and rubber strength in a well-balanced manner.

Japanese Patent No. 3294901

The present invention solves the above-mentioned problems and provides a base tread rubber composition for a heavy duty tire having improved fuel economy, heat aging resistance, wear resistance and rubber strength in a well-balanced manner, and a heavy load produced using the rubber composition The object is to provide a tire.

The present invention relates to a base tread rubber composition for a heavy duty tire, which comprises a modified natural rubber having a high purity and 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 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 modified natural rubber is obtained by washing a saponified natural rubber latex until the phosphorus content in the rubber is 200 ppm or less, and further treating with an acidic compound, and the pH is preferably 2-7.

The modified natural rubber is obtained by washing the deproteinized natural rubber latex until the nitrogen content in the rubber is 0.15% by mass or less, and further treating with an acidic compound, and the pH is 2-7. Is preferred.

The content of the modified natural rubber in 100% by mass of the rubber component is 5% by mass or more, and the content of the carbon black and / or the white filler is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. It is preferable that

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

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

The base tread rubber composition of the heavy duty tire 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. Non-rubber components such as proteins and phospholipids are removed to improve the purity, and the modified natural rubber controls the rubber pH to an appropriate value, improving fuel economy, wear resistance, and rubber strength. The 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, wear resistance and rubber strength 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, 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, deterioration of heat aging resistance is prevented, and the performance balance of low fuel consumption, heat aging resistance, wear resistance and rubber strength 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 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 washing treatment, fuel economy, wear resistance, rubber strength 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, 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 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 is obtained by drying after 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 preferably 5% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, particularly preferably. 100% by mass. If it is less than 5% by mass, the effect of the modified natural rubber may not be sufficiently exhibited.

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.

The rubber composition of the present invention contains carbon black and / or a white filler. By blending these fillers with the modified natural rubber, a reinforcing effect can be obtained, and the effects of the present invention can be sufficiently obtained.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 m ² / g or more, more preferably 15 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, still more preferably 100 m ² / g or less, and particularly preferably 60 m ² / g or less. When it is less than 5 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.

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 Etc. can be used.

The content of carbon black is preferably 5 parts by mass or more, more preferably 10 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, wear resistance and rubber strength can be obtained.

When the white filler is included, the content thereof is preferably 5 parts by mass or more, more preferably 10 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, wear resistance and rubber strength can be obtained.

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, wear resistance and rubber strength can be obtained.

In addition to the above materials, the rubber composition of the present invention includes zinc oxide, stearic acid, various antioxidants, softeners (oil, wax, etc.), vulcanizing agents (sulfur, organic peroxides, etc.), additives Various materials generally used in the tire industry such as a sulfur 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 of the present invention can be used for a tire base 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.

The heavy duty tire of the present invention is produced by a normal 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 heavy duty tire of the present invention can be suitably used for trucks and buses.

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
Carbon black: Dia Black N550 (N ₂ SA: 42 m ² / g) manufactured by Mitsubishi Chemical Corporation
Zinc oxide: 2 types of zinc oxides manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Beads stearic acid anti-aging agent manufactured by NOF Corporation 6C: NOCRACK 6C (N-phenyl) manufactured by Ouchi Shinsei Chemical -N '-(1,3-dimethylbutyl) -p-phenylenediamine) (6PPD)
Insoluble sulfur: Seimi sulfur (oil content: 10%) manufactured by Nihon Kiboshi Kogyo Co., Ltd.
Vulcanization accelerator TBBS (NS): Noxeller NS 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 operation 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 obtain a solid rubber Obtained.

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

(Production Example 3)
A solid rubber was obtained in the same procedure except that 2% by mass of formic acid was added until pH 2 in Production Example 1.

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

(Production Example 5)
A solid rubber was obtained by the same procedure except that 2% by mass of formic acid was added until pH 5 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 diameter of the aggregate (aggregated rubber) thus obtained was about 3 to 15 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 3 times, and then dried at 90 ° C. for 4 hours to obtain a solid rubber.

(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 was obtained.

(Production Example 6)
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 then dried at 90 ° C. for 4 hours to obtain a solid rubber.

(Production Example 7)
A solid rubber was obtained in the same procedure except that 2% by mass formic acid was added until pH 1 in Production Example 6.

(Production Example 8)
A solid rubber was obtained in the same procedure except that 2% by mass formic acid was added to pH 2 in Production Example 6.

(Production Example 9)
In Production Example 6, after obtaining a rubber particle of 0.5 to 5 mm, it was immersed in 1000 ml of 2% by weight aqueous sodium carbonate solution for 30 minutes, this rubber was pulled up, and water was added at a ratio of 350 g to 100 g of dry rubber. The process was repeated for 5 minutes after stirring for 2 minutes and the water layer was discarded as much as possible. Thereafter, 50 g of water was added to 10 g of rubber, and 2% by mass formic acid was added until pH 3 was reached. A solid rubber was obtained by the procedure described above.

(Production Example 10)
A solid rubber was obtained in the same procedure except that 2% by mass formic acid was added until pH 5 in Production Example 6.

(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.

(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 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 weight average molecular weight of each solid rubber before and after aging was measured, and the heat aging resistance was evaluated by measuring the molecular weight retention rate according to the following formula. The aging treatment is performed by chopping each rubber into 2 to 5 mm squares and storing them in an oven at 80 ° C. for 72 hours. The weight average molecular weight is determined by using isoprene as a standard substance using a gel permeation chromatograph. It was measured. The larger the value, the better the heat aging resistance.
(Heat aging resistance) = Molecular weight after aging / Molecular weight before aging × 100 (%).

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 vulcanized rubber composition>
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 was press vulcanized at 150 ° C. for 12 minutes to obtain a vulcanized product. The obtained vulcanizates were evaluated as follows, and the results are shown in Table 2. The kneading was performed using 10 times the amount of rubber produced in the production examples and comparative production examples.

<Low fuel consumption: tan δ>
A test piece on a strip having a width of 1 mm or 2 mm and a length of 40 mm was punched out from the sheet-like vulcanized rubber composition and subjected to the test. Using a spectrometer manufactured by Ueshima Seisakusho, tan δ was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50 ° C. The value of tan δ was expressed as an index with Comparative Example 1 being 100. The smaller the value, the lower the rolling resistance and the lower the fuel consumption.

<Abrasion resistance>
Using a LAT tester (Laboratory Abrasion and Skid Tester), the volume loss amount of each vulcanized rubber composition was measured under the conditions of a load of 100 N, a speed of 20 km / h, and a slip angle of 6 °. The numerical values in Table 2 are relative values when the volume loss amount of Comparative Example 1 is 100. The larger the value, the better the wear resistance.

<Rubber strength>
In accordance with JIS K6251 “vulcanized rubber and thermoplastic rubber—how to obtain tensile properties”, a tensile test was conducted using No. 3 dumbbell-shaped test pieces made of each vulcanized rubber composition, and the breaking strength (TB) and The elongation at break (EB) was measured and the fracture energy (TB × EB / 2) was calculated. And the breaking energy of the comparative example 1 was set to 100, and the breaking energy of each combination was indicated by an index by the following calculation formula. The larger the value, the higher the mechanical strength and the better the cut resistance and separation resistance.
(Rubber strength index) = (Fracture energy of each formulation) / (Fracture energy of Comparative Example 1) × 100

From Table 2, it was found that in Examples using the solid rubbers of Production Examples 1 to 10, fuel economy, heat aging resistance, wear resistance, and rubber strength were remarkably improved.

Claims (7)

A base tread rubber composition for a heavy duty tire, comprising a modified natural rubber having a phosphorus content of 200 ppm or less and a pH of 2 to 7 , and carbon black and / or a white filler. A base tread rubber composition for a heavy duty tire comprising a modified natural rubber having a nitrogen content of 0.15% by mass or less and a pH of 2 to 7, and carbon black and / or a white filler. The content of the modified natural rubber in 100% by mass of the rubber component is 5% by mass or more,
Per 100 parts by mass of the rubber component, the carbon black and / or the white filler content is 5 to 150 parts by mass according to claim 1 or 2 heavy duty base tread rubber composition of the tire according. Removing the non-rubber component of the natural rubber and then treating with an acidic compound to obtain the modified natural rubber; and
The method for producing a base tread rubber composition for a heavy duty tire according to any one of claims 1 to 3, further comprising a step of kneading the obtained modified natural rubber with the carbon black and / or the white filler. . Washing the saponified natural rubber latex until the phosphorus content in the rubber is 200 ppm or less, and further treating with an acidic compound to obtain the modified natural rubber; and
The method for producing a base tread rubber composition for a heavy duty tire according to claim 1 or 3, comprising a step of kneading the resulting modified natural rubber with the carbon black and / or the white filler. Washing the deproteinized natural rubber latex until the nitrogen content in the rubber is 0.15% by mass or less, and further treating with an acidic compound to obtain the modified natural rubber; and
The method for producing a base tread rubber composition for a heavy duty tire according to claim 2 or 3, comprising a step of kneading the obtained modified natural rubber with the carbon black and / or the white filler. A heavy duty tire produced using the base tread rubber composition according to any one of claims 1 to 3 .