JP6487785B2 - Hydrous silicic acid for rubber reinforcement filling - Google Patents

Description

  The present invention relates to hydrous silicic acid for rubber reinforcement filling. In particular, the present invention is useful as a filler for reinforcing rubber with improved wear resistance when blended with diene rubber among natural rubber and synthetic rubber, and is required to have wear resistance. Provided is a hydrous silicic acid useful for reinforcing industrial products.

  Hydrous silicic acid is known as white carbon and has been used as a rubber reinforcing filler for a long time along with carbon black. Hydrous silicic acid is excellent in the heat aging resistance, tear resistance, flex crack resistance, adhesion and the like of the vulcanized rubber. On the other hand, the viscosity of the compound is high and the processability is inferior at the time of high filling compounding, and the tensile strength and wear resistance are inferior to those of carbon black among the general rubber characteristics. In order to eliminate these drawbacks, a silane coupling agent and other organic compounds are used in combination. However, hydrous silicic acid that can provide satisfactory rubber properties has not yet been obtained, and further modification of hydrous silicic acid is strongly desired along with research on rubber compounding formulations.

  For example, Patent Documents 1 and 2 disclose hydrous silicic acid capable of improving the wear resistance of organic rubber.

JP 2000-302912 A Japanese Patent Laid-Open No. 11-236208

  However, in the market related to the rubber composition, for example, the tire market, there is a demand for a rubber composition having improved wear resistance as compared with the related art in relation to environmental problems and energy problems. There is a need for hydrous silicic acid for rubber reinforcement filling that can provide a rubber composition. An object of the present invention is to provide a water-containing silicic acid for filling and reinforcing a rubber capable of providing a rubber composition having an improved wear resistance as compared with the prior art.

  The present inventors have intensively studied from the viewpoint of controlling the pore structure of hydrous silicic acid so that rubber molecules can easily penetrate into the pores of hydrous silicic acid. In addition, intensive studies were conducted from the viewpoint of strengthening the chemical bond between the surface of the hydrous silicic acid and the rubber molecules. The present invention was completed by finding that hydrous silicic acid having a predetermined pore structure of hydrous silicic acid can provide a rubber composition having unprecedented excellent wear resistance.

That is, the present inventors have a hydrous silicic acid having a CTAB specific surface area of 160 m ² / g or more, the peak of the pore distribution by the nitrogen adsorption / desorption method is in the range of the pore radius of 10 to 24 nm, and the pore distribution X1 is 55% or less of the pore radius at the peak of the pore distribution, and x2 is the above when the pore radius x of the pore distribution showing the half value of the peak is x1 and x2 (x2> x1) Providing a pore distribution characterized by being 190% or more of the pore radius at the peak of the pore distribution increases the reinforcement to the rubber and improves the wear resistance of the rubber filled with hydrous silicate. As a result, the present invention has been completed.

  The hydrous silicic acid for filling and reinforcing rubber of the present invention can improve the wear resistance of rubber when blended with diene rubber among natural rubber and synthetic rubber. It can be usefully used as a reinforcing filler for rubber industrial products such as belts.

The pore distribution measurement result by the nitrogen adsorption-and-desorption method of the hydrous silicic acid of Example 1 and Comparative Example 1.

<Hydrosilicate for rubber reinforcement filling>
The hydrous silicic acid for rubber reinforcement filling of the present invention is
(A) The CTAB specific surface area is 160 m ² / g or more,
(B) The value of x (pore radius) when the nitrogen pore peak is in the range of 10 to 24 nm in the desorption distribution by the nitrogen adsorption / desorption method, and (C) is half the value of the peak of the pore distribution. Where x1 and x2 (x2> x1), x1 is 55% or less of the peak radius, and x2 is 190% or more of the peak radius.

(A) The hydrous silicic acid of the present invention has a CTAB specific surface area of 160 m ² / g or more. The CTAB specific surface area is measured according to ASTM D3765 (CARBON BLACK-CTAB SURFACE AREA), and the CTAB molecule adsorption cross section is calculated as 35 ² . The CTAB specific surface area is preferably in the range of 200 m ² / g or more. If the CTAB specific surface area is less than 160 m ² / g, the compatibility between the rubber molecules and silica is weakened, and only low reinforcement can be provided for the rubber. The higher the CTAB specific surface area, the more reinforcing the rubber. However, hydrous silicic acid having a CTAB specific surface area of over 380 m ² / g is difficult to produce, so the practical upper limit of the CTAB specific surface area is 380. m ² / g.

(B) The hydrous silicic acid of the present invention has a pore distribution peak by a nitrogen adsorption / desorption method in a pore radius range of 10 to 24 nm. The pore distribution is the pore distribution obtained in the desorption distribution by the nitrogen adsorption / desorption method, and the measurement method is described in the examples. The peak of the pore distribution is in the range of the pore radius of 10 to 24 nm. The peak of the pore distribution is more preferably in the range of the pore radius of 12 to 20 nm. If the pore radius at which the pore distribution shows a peak is too small, rubber molecules do not enter the pores, making it difficult to obtain the desired reinforcing effect. Further, if the pore radius at which the pore distribution has a peak is too large, rubber molecules cannot be captured in the pores, and in this case, it is difficult to obtain a desired reinforcing effect.

(C) In the hydrous silicic acid of the present invention, when the pore radius x of the pore distribution showing the half value of the pore distribution peak is x1 and x2 (x2> x1), x1 is at the peak of the pore distribution. It is 55% or less of the pore radius, and x2 is 190% or more of the pore radius at the peak of the pore distribution. Preferably, x1 is a range of 50% or less of the pore radius at the peak, and x2 is a range of 200% or more of the pore radius at the peak. When the value of x1 is too large or when the value of x2 is too small, it is difficult for rubber molecules to penetrate into the pores, making it difficult to obtain a desired reinforcing effect.

  The hydrous silicic acid of the present invention satisfying the above (A) has high compatibility with rubber, and the hydrous silicic acid of the present invention satisfying (B) and (C) is a pore distribution by a nitrogen adsorption / desorption method. Is relatively broad, so rubber molecules can easily penetrate into the pores.As a result, an unprecedented high reinforcing effect can be obtained, and the rubber composition containing the hydrous silicic acid of the present invention has high wear resistance. It is inferred to show.

  The hydrous silicic acid of the present invention that satisfies (A), (B) and (C) of the present invention is a hydrous silicic acid prepared by an excessive sulfuric acid method. In order to prepare hydrous silicic acid of the present invention, the sulfuric acid excess method causes the aggregation of primary particles of silicic acid quickly and satisfies the present invention (A), (B) and (C). The initial sodium silicate concentration in the neutralization reaction is set higher than in the usual method. Thus, the present invention has a broad pore distribution by forming a dense aggregate than the hydrous silicic acid provided in the prior art, and forming a developed pore structure, thereby generating a large number of pores of various radii. Can be produced. Furthermore, in order to prepare the hydrous silicic acid of the present invention satisfying (A), (B) and (C) of the present invention by increasing the opportunities for new nucleation, the amount of sulfuric acid dropped during the neutralization reaction Is dripped in an excess amount from the usual method. As a result, it is possible to produce a large amount of silica having a non-uniform particle size than the hydrous silicic acid provided in the prior art, and to produce the hydrous silicic acid of the present invention having a broad pore distribution.

It is known that the wet manufacturing method of hydrous silicic acid is generally performed by reacting an aqueous alkali metal silicate solution with a mineral acid. The method for producing hydrous silicic acid according to the present invention is also basically based on this method. However, the hydrous silicic acid of the present invention having a broad pore distribution is obtained by the sulfuric acid excess method as described above. The excessive sulfuric acid method is a method for producing hydrous silicic acid including the following step (a), and can further include steps (a) to (e).
(A) An alkali silicate aqueous solution and sulfuric acid are added to an alkali silicate aqueous solution heated to 80 to 85 ° C. having a SiO ₂ concentration of 15 to 25 g / l and a pH of 11 to 12 at a temperature of 80 to 85 ° C. The neutralization reaction is performed while controlling the addition amount (ratio) of the alkali silicate aqueous solution and sulfuric acid so that the pH of the solution is in the range of 10 to 11, until the SiO ₂ concentration is in the range of 60 to 70 g / l. Performing the addition to form silicic acid in the aqueous solution;
(A) Stopping the addition of the alkali silicate aqueous solution, continuing the addition of sulfuric acid, and adding until the pH of the reaction solution is 5 or less to obtain a precipitate;
(C) a step of filtering and washing the obtained precipitate to obtain a cake; and (d) a step of drying and pulverizing the obtained cake to obtain a silicate powder.

In the step (a), an alkali silicate aqueous solution having a SiO ₂ concentration of 15 to 25 g / l and a pH of 11 to 12 is charged in a reaction tank in advance, and this is heated to 80 to 85 ° C., and then an alkali silicate aqueous solution and sulfuric acid are added. By adding, the neutralization reaction of alkali silicate is advanced. The temperature at the time of addition of the alkali silicate aqueous solution and sulfuric acid is set to a range of 80 to 85 ° C. This neutralization reaction is carried out until the pH of the reaction solution is maintained in the range of 10 to 11, preferably 10.2 to 10.8, and the SiO ₂ concentration is in the range of 60 to 70 g / l. To form silicic acid. The SiO ₂ concentration and pH and temperature of the alkali silicate aqueous solution charged in the reaction vessel in advance into the reaction vessel, the temperature and pH when adding the alkali silicate aqueous solution and sulfuric acid, and the SiO ₂ concentration at the end of the neutralization reaction By setting the content in the above range, the hydrous silicic acid of the present invention having desired physical properties can be obtained. Although the alkali silicate aqueous solution used for the said reaction is not specifically limited, For example, sodium silicate aqueous solution can be used. In the step (a), the SiO ₂ concentration of the alkali silicate aqueous solution previously charged in the reaction vessel is set to 15 to 25 g / l, and the pH of the reaction solution in the neutralization reaction is maintained in the range of 10 to 11, A hydrous silicic acid satisfying the inventions (A) to (C) can be obtained.

  In the step (a), the addition of the aqueous alkali silicate solution is stopped, and the sulfuric acid addition is continued until the pH of the reaction solution is 5 or less, preferably 3 or less to obtain a precipitate. In the middle of the neutralization reaction, the reaction solution becomes white turbid and a gelation phenomenon occurs in which the viscosity rapidly increases. When the solid concentration of the reaction solution reaches a predetermined value, the reaction is stopped by adding sulfuric acid so that the pH is 5 or less.

  In the step (c), the obtained precipitate is filtered and washed with water to obtain a cake, and then in the step (d), the obtained cake is dried and ground to obtain a silicic acid powder. In the steps (c) and (d), the precipitated silicic acid of the present invention is obtained by filtering, washing and drying the resulting precipitate, and optionally pulverizing or granulating it. Specifically, the obtained precipitate is filtered with a filter press or the like, and washed with water until the pH becomes 5.5 to 7.5 and the electric conductivity is 200 μs / cm or less, for example, to obtain a hydrous silicate cake. The obtained wet cake is dried and then pulverized or granulated as necessary to obtain the hydrous silicic acid of the present invention.

<Preferred embodiment 1>
In addition to the hydrous silicic acid satisfying (A), (B) and (C) as described above, the hydrous silicic acid of the present invention has the following mass ratio of Al ₂ O ₃ and SiO ₂ . From the viewpoint that the organic rubber molecules and the silicic acid surface can be chemically bonded via a silane coupling agent to increase the reinforcement and improve the wear resistance. preferable.
Mass ratio of Al ₂ O ₃ and SiO ₂ Al ₂ O ₃ / SiO ₂ is ASR1, and this hydrous silicic acid is dispersed in 10% dilute hydrochloric acid at a concentration of 10% by mass for 30 minutes and then separated to a pH of 6 or more. when and the Al ₂ O ₃ of hydrous silicic acid obtained by washing SiO ₂ weight ratio Al ₂ O ₃ / SiO ₂ amount ASR2 until a 0.200 ≦ ASR1-ASR2 ≦ 0.600.

  The existence of a catalyst is indispensable for the chemical bond between the organic rubber molecule and the surface of the hydrous silicate, and the existence of non-chemically bonded aluminum (hereinafter referred to as surface aluminum) is indispensable as the catalyst. It became clear from the examination results of the inventors. The surface aluminum content is preferably in the range of 0.200% or more and 0.600% or less, and particularly exhibits a sufficient effect in the blending of a rubber composition using a silane coupling agent. Surface aluminum is aluminum that can be easily removed by washing with 10% dilute hydrochloric acid, and its content is measured according to the following method.

The positively charged acid spots of Al ₂ O ₃ supported on the outside of hydrous silicic acid (aluminum is thought to be supported in the form of Al ₂ O ₃ ) act as a catalyst, It is considered that by promoting the reaction of the silane coupling agent, the bond between the hydrous silicic acid and the rubber is further strengthened, and the wear resistance is improved.
When 0.200 ≦ ASR1-ASR2 ≦ 0.600, the amount of Al ₂ O ₃ supported on the outside of the hydrous silicic acid is sufficient, and the wear resistance of the rubber composition containing the hydrous silicic acid is improved. In contrast, when ASR1-ASR2 <0.200, the amount of Al ₂ O ₃ supported on the outside of the hydrous silicic acid is not sufficient, and the improvement in wear resistance is 0.200 ≦ ASR1-ASR2. small. In the case of 0.600 <ASR1-ASR2, the amount of Al ₂ O ₃ supported on the outside of the hydrous silicic acid is excessive, so that the bonding point between the hydrous silicic acid and the silane coupling agent tends to decrease, and the rubber The dispersibility of the hydrous silicic acid in it tends to deteriorate and the wear resistance tends to deteriorate.

  The hydrous silicic acid of the present invention can be applied for reinforcing and filling various rubber compositions, and uses of the rubber composition include not only tires but also industrial parts such as belts.

  The rubber composition in which the hydrous silicic acid of the present invention can be used (blended) is not particularly limited, but as the rubber, a rubber composition containing natural rubber (NR) or diene synthetic rubber alone or blended with them. Can be a thing. Examples of the synthetic rubber include synthetic polyisoprene rubber (IR), polybutadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and butyl rubber (IIR). The hydrous silicic acid of the present invention has a remarkable effect of improving wear resistance, particularly in a rubber composition containing a diene synthetic rubber. Accordingly, the effect of improving the wear resistance in a rubber composition in which 50% by mass or more of the rubber component is a diene-based synthetic rubber is remarkable, and 70% by mass or more of the rubber component is preferably a diene-based synthetic rubber. The hydrous silicic acid of this invention can mix | blend 5-100 mass parts with respect to 100 mass parts of natural rubber and / or diene type synthetic rubber, for example. However, it is not intended to limit to this range.

The rubber composition may be one to which a silane coupling agent is added. Examples of the silane coupling agent include those used in rubber compositions, and examples include at least one of the following formulas (I) to (III).
(In the formula, X represents an alkyl group having 1 to 3 carbon atoms or a chlorine atom, n represents an integer of 1 to 3, m represents an integer of 1 to 3, p represents an integer of 1 to 9, and q represents an integer of 1 or more. May have a distribution)
(Wherein X is an alkyl group having 1 to 3 carbon atoms or chlorine atom, Y is a mercapto group, vinyl group, amino group, imide group, glycidoxy group, methacryloxy group or epoxy group, n is an integer of 1 to 3, m Represents an integer of 1 to 3, and p represents an integer of 1 to 9.)
(Wherein X is an alkyl group having 1 to 3 carbon atoms or chlorine atom, Z is a benzothiazolyl group, N, N-dimethylthiocarbamoyl group or methacrylate group, n is an integer of 1 to 3, and m is an integer of 1 to 3) , P represents an integer of 1 to 9, and q may be an integer of 1 or more and have a distribution.)

  Specifically, bis (3-triethoxysilylpropyl) polysulfide, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylcarbamoyl tetrasulfide, 3-trimethoxysilyl And propylbenzothiazolyl tetrasulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, and the like. The compounding quantity of a silane coupling agent is 1-20 mass% with respect to the mass of a hydrous silicic acid, Preferably it is 2-15 mass%. However, it is not intended to limit to this range.

  When the hydrous silicic acid of the present invention is used in a rubber composition, in addition to the above rubber and silane coupling agent, carbon black, softening agent (wax, oil), anti-aging agent, vulcanizing agent may be used as necessary. Compounding agents usually used in the rubber industry, such as vulcanization accelerators and vulcanization accelerators, can be appropriately blended. The rubber composition can be prepared by using a kneader such as a Banbury mixer with the rubber component, hydrous silicic acid, silane coupling agent, the carbon black to be blended as necessary, a rubber compounding agent, and the like.

  The rubber composition containing the hydrous silicic acid of the present invention can be suitably applied to rubber products such as tires, conveyor belts, hoses, etc., and the rubber products such as tires, conveyor belts, hoses and the like that are products are reinforcing. It is excellent in high wear resistance and the like. In addition, a pneumatic tire using the rubber composition containing the hydrous silicic acid of the present invention can be obtained by using the rubber composition in a tire tread portion, and the tire tread portion has a reinforcing property and high abrasion resistance. A pneumatic tire having excellent wear characteristics can be obtained.

  In order to describe the present invention in detail, examples and comparative examples will be described below, but the present invention is not limited to these examples. In addition, the measurement of each physical-property value of hydrous silicic acid was implemented by the method shown next based on JIS K-5101 (pigment test method).

● After dissolving measuring powder samples of Al ₂ O ₃ of hydrous silicic SanHara Konachu in an acid solution, ICP emission spectrometer (Model: SPS3100; manufactured by SII Nano Technology Inc.) Al ₂ O ₃ amount using the Quantitative analysis was performed.

● Measurement of SiO ₂ content in hydrous silicate raw powder Quantitative analysis of SiO ₂ content was performed by the silicic acid quantification method of Quasi-drug raw material standard 2006. 10% dilute hydrochloric acid was prepared based on the Quasi-drug Raw Material Standard 2006. Of the measurement samples, ASR2 was prepared by stirring 10 g of amorphous hydrous silicic acid in 100 ml of 10% dilute hydrochloric acid for 30 minutes, vacuum filtration using Nutsche and 5A filter paper, and washing with water until the pH reached 6 or more. The hydrous silicic acid that was filtered off later was used after sufficiently drying at 105 ° C. for 2 hours or more. The pH was measured with a commercially available glass electrode pH meter (model: D-14, manufactured by Horiba, Ltd.).

-CTAB method specific surface area It measured based on ASTM D3765 (CARBON BLACK-CTAB SURFACE AREA). However, the adsorption cross section of CTAB molecules was calculated as 35 ² .

● BET specific surface area (N2 method specific surface area)
Measurement was carried out by a one-point method using a fully automatic specific surface area measuring device (model: Macsorb ^(R) HM model-1201; manufactured by Mountec Co., Ltd.).

● Pore distribution by nitrogen adsorption / desorption method Measured by the Barret-Joyner-Halenda method using a high-accuracy gas / vapor adsorption amount measuring device (model: Belsorp max; manufactured by Nippon Bell Co., Ltd.).

● Pore distribution by mercury intrusion method Mercury pores were measured using a mercury porosimeter (model: PASCAL 440; manufactured by ThermoQuest).

Formulation preparation method In a Banbury mixer with a capacity of 1.7 liters, 80 parts of JSR SL552 (solution-polymerized styrene butadiene rubber) and 20 parts of IR2200 (polyisoprene rubber) were masticated for 30 seconds, and then stearic acid was added. 2 parts, 45 parts of hydrous silicic acid, and silane KBE846 (bis (triethoxysilylpropyl) tetrasulfide) in the range of 1.8 to 10.8 parts (details are given in Tables 1 to 3), The kneading time was taken out after 5 minutes. The compound temperature at the time of removal is adjusted to 140 to 150 ° C. by ram pressure and rotation speed, the compound is cooled at room temperature, and the anti-aging agent NOCRACK 810NA (N-phenyl-N′-isopropyl-p-phenylenediamine) 1 part, Zinc flower 3 parts, Vulcanization accelerator Noxeller D (1,3-diphenylguanidine) 1.5 parts, Noxeller CZ-G (N-cyclohexyl-2-benzothiazolylsulfenamide) 1.2 parts and 1.5 parts of sulfur (200 mesh) are added and kneaded for about 1 minute (the temperature at the time of taking out is 100 ° C. or less), then sheeted with an 8-inch roll and unvulcanized. And vulcanizate properties were measured.

● Mooney viscosity Measured with Mooney viscometer VR-1132 type (manufactured by Ueshima Seisakusho) at 125 ° C with L-type rotor
● Clasting Time The optimum vulcanization time (T90) was measured with a JSR type Clastometer IIF type.
Vulcanizate characteristics (TB, M300, EB, Hs)
Measurements were performed according to the JIS test method.

● Abrasion test Measured with an Akron-type abrasion tester. Tilt angle: 15 °, load; 6 pound test number; wear reduction at 1000 revolutions was measured. The measurement result was obtained by an index when Comparative Example 1 was set to 100. The higher the index, the better the wear resistance. When the index was 110 or more, the wear resistance was regarded as having been improved by 10% or more, and it was marked as ◯.

Example 1
A reaction was carried out to increase the initial sodium silicate concentration for the purpose of causing the aggregation of the primary particles of silicate early. Thus, by forming a denser aggregate than in Comparative Example 1 described later and forming a developed pore structure, a large number of pores with various radii are generated, and hydrous silicic acid having a broad pore distribution can be produced. . Specifically, in a 240 liter jacketed stainless steel vessel equipped with a stirrer, 80 liters of water and 14 liters of sodium silicate aqueous solution more than usual (SiO ₂ 150 g / l, SiO ₂ / Na ₂ O mass ratio 3 3) was added and heated to a temperature of 82 ° C. At this time, the SiO ₂ concentration was 22 g / l, and the pH was 11.5.

By carrying out a neutralization reaction by excessive sulfuric acid, silicic acid having a non-uniform particle size was formed, and a reaction was carried out in which hydrous silicic acid having a broad pore distribution was generated. Specifically, the same sodium silicate aqueous solution and sulfuric acid (18.4 mol / l) as above were added to this aqueous solution for 100 minutes while maintaining a temperature of 82 ± 1 ° C., with a SiO ₂ concentration of 65 g / l, pH. Was added to 10.9, and only the aqueous sodium silicate solution was stopped in 100 minutes. Sulfuric acid was added so that the amount of sulfuric acid added to the sodium silicate aqueous solution was excessive so that the pH in the above reaction solution (pH before starting the reaction was 11.5) was 10.9.

  After completion of the predetermined neutralization reaction, the same sulfuric acid was added until pH 3 was obtained to obtain a precipitate. Thereafter, the obtained reaction product was filtered and washed with water to obtain a cake. The obtained cake was emulsified, and this emulsion was dried to produce hydrous silicic acid and evaluated. The measurement results of the pore distribution by the nitrogen adsorption / desorption method are shown in FIG.

(Example 2)
Example 1 except that the obtained cake was emulsified, and sodium aluminate was added to the emulsion in an amount of 0.30% by mass of Al ₂ O ₃ / SiO ₂ with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced in the same manner as described above and evaluated.

(Example 3)
Example 1 except that the obtained cake was emulsified, and sodium aluminate was added to this emulsion in an amount of 0.50% in terms of Al ₂ O ₃ / SiO ₂ mass ratio with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced in the same manner as described above and evaluated.

Example 4
Example 1 except that the obtained cake was emulsified, and sodium aluminate was added to this emulsion in an amount of 0.70% by mass of Al ₂ O ₃ / SiO ₂ with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced in the same manner as described above and evaluated.

  As shown in Table 1, Examples 1, 2, 3, and 4 having a broad pore distribution (satisfying all the conditions of claim 1) have an effect of improving wear resistance as compared with Comparative Example 1 described later. It was. In particular, among these Examples 1, 2, 3, and 4, Examples 2 and 3 in which an appropriate amount of sodium aluminate was added to the emulsion and ASR1-ASR2 was in the range of 0.2 to 0.6 were: In particular, a high wear resistance improving effect was observed.

(Example 5)
Into a 240 liter jacketed stainless steel vessel equipped with a stirrer, 80 liters of water and 3.5 liters of an aqueous sodium silicate solution (SiO ₂ 150 g / l, SiO ₂ / Na ₂ O mass ratio 3.3) were added, Heated to a temperature of 72 ° C. At this time, the SiO ₂ concentration was 6.0 g / l, and the pH was 10.9. To this aqueous solution, an aqueous sodium silicate solution and sulfuric acid (18.4 mol / l) similar to the above are added so that the SiO ₂ concentration becomes 65 g / l in 100 minutes while maintaining a temperature of 72 ± 1 ° C. and a pH of 10.9. And only the aqueous sodium silicate solution was stopped after 100 minutes. By making the reaction temperature lower than in the case of Comparative Example 1, the growth rate of the silicic acid primary particles is suppressed, and the primary particles cause aggregation at the fine particle stage. Thus, a denser aggregate than in Comparative Example 1 was formed, and a developed pore structure was formed, whereby a large number of pores with various radii were generated, and hydrous silicic acid having a broad pore distribution was produced.

  After completion of the predetermined neutralization reaction, the same sulfuric acid was added until pH 3 was obtained to obtain a precipitate. Thereafter, the obtained reaction product was filtered and washed with water to obtain a cake. The obtained cake was emulsified, and this emulsion was dried to produce hydrous silicic acid and evaluated.

(Example 6)
Example 5 was carried out except that the obtained cake was emulsified, and sodium aluminate was additionally added to this emulsion in an amount of 0.30% by mass of Al ₂ O ₃ / SiO ₂ with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced in the same manner as described above and evaluated.

(Example 7)
Immediately after the simultaneous addition of the sodium silicate aqueous solution and sulfuric acid (18.4 mol / l) was completed, sodium aluminate was added in an amount of 0.40 at a mass ratio of Al ₂ O ₃ / SiO _{2 with} respect to the amount of silicic acid in the reaction solution. A hydrous silicic acid was produced and evaluated in the same manner as in Example 5 with the exception that an additional% was added.

(Example 8)
The obtained cake was emulsified, and sodium aluminate was added to the emulsified liquid as in Example 5 except that 0.50% of Al ₂ O ₃ / SiO ₂ mass ratio was added to the amount of silicic acid in the cake. Hydrous silicic acid was produced by the same method and evaluated.

Example 9
The obtained cake was emulsified, and sodium aluminate was added to the emulsified liquid as in Example 5 except that 0.70% of Al ₂ O ₃ / SiO ₂ mass ratio with respect to the amount of silicic acid in the cake was added. Hydrous silicic acid was produced by the same method and evaluated.

  As shown in Table 2, Examples 5, 6, 7, 8, and 9 having broad pore distribution (satisfying all the conditions of claim 1) have an effect of improving wear resistance compared to Comparative Example 1 described later. Admitted. In particular, among these Examples 5, 6, 7, 8, and 9, Examples in which an appropriate amount of sodium aluminate is added to the emulsion or reaction solution and ASR1-ASR2 is in the range of 0.2 to 0.6. Nos. 6, 7 and 8 were found to have a particularly high wear resistance improving effect.

(Comparative Example 1)
Into a 240 liter jacketed stainless steel vessel equipped with a stirrer, 85 liters of water and 6.0 liters of sodium silicate aqueous solution (SiO ₂ 150 g / l, SiO ₂ / Na ₂ O mass ratio 3.3) were added, Heated to a temperature of 90 ° C. At this time, the pH was 11.2 and the SiO ₂ concentration was 10.0 g / l. To this aqueous solution, the same sodium silicate aqueous solution and sulfuric acid (18.4 mol / l) as described above were added so that the SiO ₂ concentration became 60 g / l in 100 minutes while maintaining the temperature 90 ± 1 ° C. and pH 11.2. And only the aqueous sodium silicate solution was stopped after 100 minutes. Subsequently, similar sulfuric acid was added until pH 3 was obtained to obtain a precipitate. Thereafter, the obtained reaction product was filtered and washed with water to obtain a cake.

  The obtained cake was emulsified (the cake was dispersed in water by vigorous stirring to form a liquid), and this emulsion was dried to produce a hydrous silicic acid serving as a reference for rubber and evaluated. Fig. 1 shows the measurement results of the pore distribution by the nitrogen adsorption / desorption method.

  The hydrous silicic acid of Comparative Example 1 has been widely used as a standard reaction for hydrous silicic acid for rubber. The abrasion index of Examples 1 to 9 and Comparative Examples 2 to 4 was determined with the abrasion index of this hydrous silicate being 100.

(Comparative Example 2)
Comparative Example 1 except that the obtained cake was emulsified, and sodium aluminate was added to the emulsified liquid in an amount of 0.30% in terms of Al ₂ O ₃ / SiO ₂ mass ratio with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced by the same method and evaluated.

(Comparative Example 3)
Comparative Example 1 except that the obtained cake was emulsified, and sodium aluminate was added to the emulsified liquid in an amount of 0.50% in terms of Al ₂ O ₃ / SiO ₂ mass ratio with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced by the same method and evaluated.

(Comparative Example 4)
Comparative Example 1 except that the obtained cake was emulsified and sodium aluminate was added to the emulsion in an amount of 0.70% in terms of Al ₂ O ₃ / SiO ₂ mass ratio with respect to the amount of silicic acid in the cake. Hydrous silicic acid was produced by the same method and evaluated.

  The conditions of claim 1 are divided into (A), (B), and (C) as described above, and claim 3 shows the conditions (D) that are satisfied in Comparative Examples 1 to 4 in Table 3.

  As shown in Table 3, Comparative Examples 1 to 4 have lower wear resistance than Examples 1 to 9 having a broad pore distribution.

  The present invention is useful in fields related to hydrous silicic acid, particularly hydrous silicic acid suitable for reinforcing and filling rubber compositions.

Claims (7)

CTAB specific surface area is 160 m ² / g or more,
The pore radius x is x1 and x2 (x2> x1) where the peak of the pore distribution by the nitrogen adsorption / desorption method is in the range of the pore radius of 10 to 24 nm and shows the half value of the peak of the pore distribution. when, x1 is not less than 55% of the pore radius at the peak of the pore distribution, x2 is Ri der 190% or more of the pore radius at the peak of the pore distribution, Al ₂ O ₃ and SiO ₂ The mass ratio of Al ₂ O ₃ / SiO ₂ is ASR1, and this hydrous silicic acid is dispersed in 10% dilute hydrochloric acid at a concentration of 10% by mass for 30 minutes and then separated and washed with water until the pH reaches 6 or more. when the Al ₂ O ₃ and SiO ₂ weight ratio Al ₂ O ₃ / SiO ₂ weight precipitated silica and ASR2, rubber reinforcing filler for precipitated silica and 0.20 ≦ ASR1-ASR2 ≦ 0.60 der wherein Rukoto . The hydrous silicic acid for rubber reinforcement filling according to claim 1, which is a hydrous silicic acid prepared by an excessive sulfuric acid method. The hydrous silicic acid for rubber reinforcement filling according to claim 1 , which is for reinforcement filling of a diene rubber composition used in combination with a silane coupling agent. The hydrous silicic acid for filling and reinforcing rubber according to any one of claims 1 to 3 , wherein a peak in a pore distribution by a mercury method intrusion method has a radius in a range of 7 to 12 nm. (A) An alkali silicate aqueous solution and sulfuric acid are added to an alkali silicate aqueous solution heated to 80 to 85 ° C. having a SiO ₂ concentration of 15 to 25 g / l and a pH of 11 to 12 at a temperature of 80 to 85 ° C. The neutralization reaction is performed while controlling the addition amount of the alkali silicate aqueous solution and sulfuric acid so that the pH of the solution is in the range of 10 to 11, and the addition is performed until the SiO ₂ concentration is in the range of 60 to 70 g / l. Carrying out and forming silicic acid in the aqueous solution,
The CTAB specific surface area is 160 m ² / g or more,
The peak of pore distribution by nitrogen adsorption / desorption method is in the range of pore radius of 10 to 24 nm, and
When the pore radius x of the pore distribution showing the half value of the peak of the pore distribution is x1 and x2 (x2> x1), x1 is 55% or less of the pore radius in the peak of the pore distribution, x2 is not less than 190% of the pore radius at the peak of the pore distribution, 10 Al ₂ O ₃ mass ratio Al ₂ O ₃ / SiO ₂ of SiO ₂ and ASR1, the hydrated silicic acid 10% diluted hydrochloric acid separated after dispersing for 30 minutes at a concentration of mass%, the Al ₂ O ₃ mass ratio Al ₂ O ₃ / SiO ₂ of SiO ₂ of hydrous silicic acid obtained by washing with water until the pH reached 6 or more ASR2 When 0.20 ≦ ASR1-ASR2 ≦ 0.60,
A method for producing hydrous silicic acid. Furthermore, the manufacturing method of the hydrous silicic acid of Claim 5 including the following processes (I), (U), and (D).
(A) Stopping the addition of the alkali silicate aqueous solution, continuing the addition of sulfuric acid, and adding until the pH of the reaction solution is 5 or less to obtain a precipitate;
(C) a step of filtering and washing the obtained precipitate to obtain a cake; and (d) a step of drying and pulverizing the obtained cake to obtain a silicate powder. CTAB specific surface area of 160 m ² / g or more,
The peak of pore distribution by nitrogen adsorption / desorption method is in the range of pore radius of 10 to 24 nm, and
When the pore radius x of the pore distribution showing the half value of the peak of the pore distribution is x1 and x2 (x2> x1), x1 is 55% or less of the pore radius in the peak of the pore distribution, x2 is 190% or more of the pore radius at the peak of the pore distribution, Al ₂ O _Three And SiO ₂ Mass ratio of Al ₂ O _Three / SiO ₂ ASR1, and this hydrous silicic acid is dispersed in 10% dilute hydrochloric acid at a concentration of 10% by mass for 30 minutes, separated, and washed with water until the pH reaches 6 or higher. ₂ O _Three And SiO ₂ Mass ratio of Al ₂ O _Three / SiO ₂ Use of hydrous silicic acid for rubber reinforcement filling where ASR2 is 0.20 ≦ ASR1-ASR2 ≦ 0.60.