KR102157788B1 - Manufacturing method of aluminosilicate particles and manufacturing method of rubber composition for tires comprising the same - Google Patents

Abstract

The present invention provides a method for preparing amorphous aluminosilicate particles having a composition represented by the following Chemical Formula 1, comprising: controlling a particle size distribution of metakaolin; And a curing step of curing the metakaolin, silicon compound and alkali with controlled particle size distribution to prepare aluminosilicate particles, wherein the metakaolin with controlled particle size distribution has a cumulative volume in particle size distribution of 50% and 90 When the particle sizes of% are respectively d50 and d90, the present invention relates to a method for producing aluminosilicate particles having a d50 of 0.05 to 1.50 µm and a d90 of 0.30 to 4.50 µm, and a method for producing a rubber composition comprising the same.
[Formula 1]
M _{x / n} [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)
In Formula 1, M is an element selected from the group consisting of Li, K, Ca, Zn, Mg, Na, Rb, Cs, Be, and Fr, or an ion thereof, x> 0, y> 0, n> 0, and m ≥ 0, 1.0 ≤ y/x ≤ 5.0, and 0.5 ≤ x/n ≤ 1.2.

Description

A method for producing aluminosilicate particles and a method for producing a rubber composition for tires comprising the same TECHNICAL FIELD [MANUFACTURING METHOD OF ALUMINOSILICATE PARTICLES AND MANUFACTURING METHOD OF RUBBER COMPOSITION FOR TIRES COMPRISING THE SAME}

The present invention relates to a method for producing aluminosilicate particles and a method for producing a rubber composition for a tire comprising the same.

As concerns over global warming and environmental issues spread, the concept of eco-friendly energy to reduce carbon emissions by increasing energy efficiency is being emphasized in many ways. This eco-friendly concept is being visualized in the tire industry as a result of the development of highly efficient eco-friendly tires and the search for a method of recycling waste tires.

Eco-friendly tires (or green tires) refer to tires that lower the rolling resistance of rubber to give high efficiency and high fuel efficiency characteristics, and consequently reduce carbon emissions. In order to manufacture such eco-friendly tires, modified rubber materials and white additives for rubber reinforcement (eg, precipitated silica) are mainly used.

In general, silica materials have problems such as low dispersibility in the rubber composition and loss of wear resistance. In order to compensate for this, it is known that an eco-friendly tire material having good wear resistance can be made by using a highly dispersible precipitated silica under a specific condition together with a silane coupling agent.

On the other hand, there is also a high interest in additives that can favorably have opposite properties (mechanical strength such as rolling resistance and abrasion resistance) like highly dispersible precipitated silica. In particular, interest in aluminosilicate is high, and in the application of Invention 10-2016-0116739, aluminosilicate is synthesized using kaolin, a natural mineral raw material, and the synthesized aluminosilicate is applied to rubber. The content is described.

However, kaolin contains a number of impurities such as Fe ₂ O ₃ and TiO _{2 in} addition to SiO ₂ and Al ₂ O ₃ due to the nature of natural minerals, and has a wide particle size distribution. In the case of the process of synthesizing aluminosilicate using kaolin, the impurities do not participate in the reaction, and the activation of the synthesis reaction is low due to a wide particle size distribution.

The present invention introduces a raw material processing process to synthesize aluminosilicate having a high specific surface area, thereby producing aluminosilicate particles capable of improving abrasion resistance, viscoelasticity, and mechanical properties of the rubber containing the aluminosilicate particles. It is to provide a way.

In addition, the present invention is to provide a rubber composition for a tire including the aluminosilicate particles.

According to an embodiment of the present invention, a method for preparing amorphous aluminosilicate particles having a composition of the following Formula 1, comprising: controlling a particle size distribution of metakaolin; And a curing step of curing the metakaolin, silicon compound and alkali with controlled particle size distribution to prepare aluminosilicate particles, wherein the metakaolin with controlled particle size distribution has a cumulative volume in particle size distribution of 50% and 90 When the particle size of% is d50 and d90, respectively, a method for producing aluminosilicate particles having a d50 of 0.05 to 1.50 μm and a d90 of 0.30 to 4.50 μm may be provided.

[Formula 1]

M _x/n [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)

In Formula 1,

The M is an element selected from the group consisting of Li, K, Ca, Zn, Mg, Na, Rb, Cs, Be, and Fr, or an ion thereof,

x> 0, y> 0, n> 0, and m ≥ 0,

1.0 ≤ y/x ≤ 5.0,

0.5 ≤ x/n ≤ 1.2.

In addition, according to another embodiment of the present invention, a rubber reinforcing material including aluminosilicate particles prepared by the above manufacturing method and a diene elastomer are stirred to prepare a rubber composition for a tire. I can.

Hereinafter, a method for producing aluminosilicate particles and a method for producing a rubber composition for a tire including the same according to a specific embodiment of the present invention will be described in more detail.

Prior to that, the terminology is only intended to refer to specific embodiments and is not intended to limit the invention unless expressly stated throughout this specification.

In addition, the singular forms used herein also include plural forms unless the phrases clearly represent the opposite meaning.

In addition, the meaning of'comprising' used in the specification specifies a specific characteristic, area, integer, step, action, element or component, and excludes the addition of other specific characteristics, areas, integers, steps, actions, elements, or components. It is not to order.

I. Method for producing aluminosilicate particles

According to an embodiment of the present invention, as a method of preparing amorphous aluminosilicate particles having a composition of the following formula (1),

Controlling the particle size distribution of metakaolin; And

And a curing step of curing the metakaolin, a silicon compound, and an alkali whose particle size distribution is controlled to prepare aluminosilicate particles,

The particle size distribution-controlled metakaolin is an aluminum having a d50 of 0.05 to 1.50 µm and a d90 of 0.30 to 4.50 µm when the particle sizes at which the cumulative volume in the particle size distribution is 50% and 90% are respectively d50 and d90. A method for producing nosilicate particles is provided.

[Formula 1]

M _x/n [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)

In Formula 1,

The M is an element selected from the group consisting of Li, K, Ca, Zn, Mg, Na, Rb, Cs, Be, and Fr, or an ion thereof,

x> 0, y> 0, n> 0, and m ≥ 0,

1.0 ≤ y/x ≤ 5.0,

0.5 ≤ x/n ≤ 1.2.

As a result of continuous research by the present inventors, it was confirmed through an experiment that the aluminosilicate particles prepared by the above-described method have a high specific surface area, and that the rubber composition including such aluminosilicate particles improves abrasion resistance, viscoelasticity and mechanical properties. And completed the invention.

Kaolin contains a number of impurities such as Fe ₂ O ₃ and TiO _{2 in} addition to SiO ₂ and Al ₂ O ₃ due to the nature of natural minerals, and has a wide particle size distribution. In the case of the process of synthesizing aluminosilicate using kaolin, the impurities do not participate in the reaction, and the activation of the synthesis reaction is low due to a wide particle size distribution.

On the other hand, the present invention controls the particle size of metakaolin particles to d50 = 0.05 to 1.50 µm and d90 = 0.30 to 4.50 µm by introducing a processing process of a raw material, and then using this to prepare aluminosilicate, the final product It was confirmed that the particle size of the aluminosilicate particles can be reduced and the specific surface area can be increased.

Specifically, since a number of impurities such as Fe ₂ O ₃ and TiO ₂ are not easily crushed and do not participate in the synthesis process, the raw material can be easily purified through a processing process that controls the raw material to the above-described particle size range. I can. In addition, the aluminosilicate synthesized using the unrefined kaolin material contains about 1.3% by weight of TiO ₂ , which is an impurity, whereas the TiO ₂ content of the aluminosilicate prepared through the raw material purification process is 0.7% by weight. Therefore, only the parent material of SiO ₂ and Al ₂ O ₃ components that can participate in the reaction through the processing of the raw material is crushed, so that the content of impurities contained in the aluminosilicate decreases, and the synthesis of aluminosilicate is more effective. It takes place actively. Accordingly, the yield of nanoparticles is improved, and the effect of improving the specific surface area by reducing the particles can be achieved.

Furthermore, when the aluminosilicate particles having such a high specific surface area are included in the rubber composition for a tire, the bonding site with the rubber increases and the bonding force with the rubber becomes strong, so that the rubber composition for a tire has abrasion resistance, viscoelasticity, and mechanical properties. This excellent effect appears.

In the method for producing aluminosilicate particles according to an embodiment of the present invention, first, the particle size distribution of metakaolin is controlled.

Metakaolin having a controlled particle size distribution has a particle size of 50% and 90% cumulative volume in the particle size distribution as d50 and d90, respectively, d50 is 0.05 to 1.50 µm, and d90 is 0.30 to 4.50 µm. It is desirable. Specifically, d50 is 0.05 µm or more, or 0.10 µm or more, or 0.15 µm or more, or 0.2 µm or more, or 0.25 µm or more; It may be 1.50 μm or less, or 1.30 μm or less, or 1.10 μm or less, or 0.9 μm or less, or 0.7 μm or less, or 0.5 μm or less. On the other hand, d90 is 0.30 µm or more, 0.35 µm or more, or 0.40 µm or more, or 0.45 µm or more, or 0.50 µm or more; It may be 4.50 µm or less, or 4.20 µm or less, or 3.90 µm or less, or 3.70 µm or less, or 3.50 µm or less.

When the d50 of metakaolin whose particle size distribution is controlled is less than 0.05 µm or d90 is less than 0.30 µm, it takes a lot of time and energy to control the particle size of the raw material, and thus economic feasibility may be lowered, and d50 may exceed 1.50 µm or d90 When the amount exceeds 4.50 μm, the degree of activation of the aluminosilicate synthesis reaction may be lowered due to the broad particle size distribution of metakaolin, and thus the yield of nanoparticles decreases, and the effect of improving the specific surface area cannot be achieved.

The metakaolin can be pulverized to control the particle size of the metakaolin. The step of pulverizing metakaolin may be performed by a conventional pulverization method, for example, by adding metakaolin and ceramic (eg, zirconium oxide) balls together in a stirrer and stirring. When the pulverization is performed in this way, the rotational speed of the stirrer is 100 to 200 rpm, and it is preferable that the stirring is performed for 2 to 6 days. Specifically, the rotational speed is 100 rpm or more, or 110 rpm or more, or 120 rpm or more, or 130 rpm or more; It is 200 rpm or less, or 190 rpm or less, or 180 rpm or less, or 170 rpm or less. Meanwhile, the stirring time may be 2 to 6 days or 3 to 5 days.

After controlling the particle size of metakaolin, metakaolin, a silicon compound and an alkali whose particle size is controlled are added to a solvent and stirred to obtain a mixture. Alternatively, the aluminosilicate particles may be prepared by curing metakaolin, a silicon compound and an alkali whose particle size distribution is controlled without the stirring process.

Meanwhile, the Al-O-Si structure of a monomer unit satisfying a specific metal atom ratio may be formed by adding and stirring metakaolin, a silicon compound and an alkali controlled in particle size distribution to a solvent.

The silicon compound is not limited thereto, but for example, fumed silica, rice husk, colloidal silica, cellite, pearlite, rice husk husk ash), silica fume, organosilanes, clay, minerals, calcined clay, activated clay, fly ash, slag, pozzolan, incinerated utility waste, industrial by-products, glass powder ( glass powder) and red mud may be at least one selected from the group consisting of.

The aluminosilicate particles may be prepared by curing metakaolin, a silicon compound, and an alkali whose particle size distribution is controlled. By curing such a mixture under atmospheric pressure, Al-O-Si polymerization may occur.

The curing may be performed at a temperature of room temperature to 90°C, 30 to 80°C, 35 to 70°C, or 40 to 80°C. If the curing temperature is less than room temperature, curing may not be performed, and thus an aluminosilicate having the composition of the following formula (1) may not be prepared. If the curing temperature exceeds 90°C, a problem may occur in that the crystal structure is changed. For example, when the curing temperature exceeds 90° C., an amorphous structure may become a crystalline structure, or a structure may change from a faujasite to sodalite.

Meanwhile, the curing may be performed for 3 to 24 hours, 8 to 22 hours, 10 to 20 hours, or 12 to 18 hours. If the curing time is less than 3 hours, curing does not occur, and thus an aluminosilicate having the composition of the following formula (1) may not be prepared.If less than 24 hours, no more reaction due to curing occurs, resulting in excessive energy consumption, resulting in reduced economic efficiency. There is a problem.

After the aluminosilicate particles are prepared by the curing step, the particles may be washed and dried.

The aluminosilicate particles prepared by the method for preparing the aluminosilicate particles have the composition of the following formula (1).

[Formula 1]

M _x/n [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)

In Formula 1,

The M is an element selected from the group consisting of Li, K, Ca, Zn, Mg, Na, Rb, Cs, Be, and Fr, or an ion thereof,

x> 0, y> 0, n> 0, and m ≥ 0,

1.0 ≤ y/x ≤ 5.0,

0.5 ≤ x/n ≤ 1.2.

That is, the aluminosilicate particles contain an alkali metal or an ion thereof as a metal element (M) or an ion thereof, and particularly satisfy a composition of 1.0≦y/x≦5.0 and 0.5≦x/n≦1.2.

Specifically, in Formula 1, y/x is 1.0 or more, or 1.15 or more, or 1.3 or more, or 1.45 or more; 5.0 or less, or 4.5 or less, or 4.0 or less, or 3.5 or less, or 3.0 or less, or 2.5 or less, or 2.0 or less may be advantageous for the expression of various characteristics according to the present invention.

In addition, specifically, in Formula 1, x/n is 0.5 or more, or 0.55 or more, or 0.6 or more, or 0.65 or more, or 0.7 or more, or 0.75 or more, or 0.8 or more; 1.2 or less, or 1.15 or less may be advantageous for the expression of various characteristics according to the present invention.

In general, a rubber reinforcing material may exhibit an excellent reinforcing effect as the particle diameter decreases, but as the particle diameter decreases, aggregation between particles in the rubber composition easily occurs, resulting in poor dispersibility. When such agglomeration becomes severe, phase separation between the rubber reinforcement material and the rubber components may occur, and as a result, the workability of the tire decreases, and it may be difficult to obtain a target reinforcing effect.

However, the aluminosilicate particles may be amorphous particles having the above-described composition and may exist as primary particles that are not substantially aggregated in the rubber composition.

The primary particle size of the aluminosilicate particles may be 10 to 50 nm, which may be advantageous for the expression of various characteristics according to the present invention. Specifically, the number average particle diameter of all the aluminosilicate particles is 10 nm or more, or 15 nm or more, or 20 nm or more; It is 50 nm or less, or 40 nm or less, or 30 nm or less.

According to an embodiment of the present invention, the aluminosilicate particles have a Brunner-Emmett-Teller specific surface area (S _BET ) of 120 to 250 m ² /g by nitrogen adsorption/desorption analysis and 100 to 240 m ² /g _Having an external specific surface area (S _EXT ) of may be advantageous for the expression of all properties according to the present invention.

Specifically, the S _BET is 100 m ² /g or more, or 110 m ² /g or more, or 115 m ² /g or more, 120 m ² /g or more or 125 m ² /g or more; 250 m ² /g or less, or 190 m ² /g or less, or 180 m ² /g or less, or 170 m ² /g or less, or 160 m ² /g or less, or 150 m ² /g or less, or 130 m ² /g or less.

Specifically, the S _EXT is 100 m ² /g or more, or 110 m ² /g or more, or 120 m ² /g or more, or 130 m ² /g or more; It is 240 m ² /g or less, 230 m ² /g or less, or 220 m ² /g or less, or 210 m ² /g or less, or 200 m ² /g or less.

In addition, the ratio of the S _BET and S _EXT (S _EXT /S _BET ) of the aluminosilicate particles may be 0.8 to 1.0, which may be more advantageous in the expression of various characteristics according to the present invention. Specifically, the S _EXT /S _BET is 0.70 or more, or 0.73 or more, or 0.76 or more, or 0.79 or more, or 0.82 or more; It is 1.0 or less, or 0.99 or less, or 0.95 or less, or 0.90 or less.

On the other hand, it is preferable that the content of micropores is minimized in the inorganic material applied as a rubber reinforcing material. This is because the micropores can act as defects and degrade physical properties as a rubber reinforcing material.

According to an embodiment of the present invention, the aluminosilicate particles may be used as a rubber reinforcing material, and the aluminosilicate particles are pores of less than 2 nm calculated by the t-plot method from the S _BET . The volume of micropores having a size (V _micro ) is small, less than 0.05 cm ³ /g, enabling the expression of excellent mechanical properties as a rubber reinforcing material. Specifically, the V _micro is less than 0.05 cm ³ /g, or less than 0.025 cm ³ /g, or less than 0.02 cm ³ /g, or less than 0.015 cm ³ /g, or less than 0.01 cm ³ /g, or 0.007 cm ³ /g or less.

As described above, the aluminosilicate particles according to the present invention have a small particle size and a large specific surface area. For this reason, when aluminosilicate particles having a high specific surface area are included in the rubber composition for a tire, the bonding site with the rubber increases and the bonding force with the rubber becomes strong, so that the rubber composition for a tire has abrasion resistance, viscoelasticity, and mechanical properties. This excellent effect appears.

In addition, the aluminosilicate particles may exhibit superior mechanical properties compared to reinforcing materials that do not satisfy the above-described physical properties, as the formation of micropores inside the particles is suppressed.

Further, the aluminosilicate particles do not hinder the progress of the vulcanization process and the curing process of the rubber composition, so that the processability of the rubber composition and the productivity of the tire manufacturing process using the same can be secured.

II. Method for producing rubber composition for tire

According to another embodiment of the present invention, there is provided a method of manufacturing a rubber composition for a tire comprising aluminosilicate particles manufactured by the above manufacturing method.

The method for producing a rubber composition for a tire according to another embodiment includes the step of preparing a rubber composition by stirring a rubber reinforcing material including the aluminosilicate particles and a diene elastomer.

The aluminosilicate particles satisfying the above-described properties can exhibit an improved reinforcing effect according to excellent dispersibility in the rubber composition, but do not impede the processability of the rubber composition, so it is very preferable as a rubber reinforcing material imparted to the rubber composition for tires. Can be applied.

Furthermore, when the aluminosilicate particles having a high specific surface area are included in the rubber composition for a tire, the bonding site with the rubber increases and the bonding strength with the rubber increases, so that the rubber composition for a tire has abrasion resistance, viscoelasticity, and mechanical properties. This excellent effect can appear.

The tire rubber composition may include a conventional diene elastomer without particular limitation. For example, the diene elastomer is natural rubber, polybutadiene, polyisoprene, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, isoprene-styrene copolymer, and butadiene-styrene-isoprene copolymer. It may be one or more selected from the group consisting of polymers.

In addition, the rubber composition for a tire may include a coupling agent that provides a chemical and/or physical bond between the rubber reinforcement and the diene elastomer. Conventional components such as polysiloxane-based compounds may be included as the coupling agent without particular limitation.

In addition, plasticizers, pigments, antioxidants, ozone deterioration inhibitors, vulcanization accelerators, etc. commonly used in the tire field may be added to the rubber composition for tires.

According to the present invention, it is possible to reduce the particle size of the aluminosilicate particles and increase the specific surface area by introducing the processing process of the raw material, and improve the abrasion resistance, viscoelasticity, and mechanical properties of the rubber containing such aluminosilicate particles. A method for producing aluminosilicate particles having an effect and a rubber composition for a tire including the same may be provided.

1 to 3 are images of metakaolin of Example 1 and Comparative Examples 1 and 3 taken by SEM.
4 is a graph showing the results of particle size analysis of metakaolin of Example 1 and Comparative Examples 1 and 3 with PSA.
5 is a graph showing the results of particle size analysis of metakaolin of Examples 1 to 3 and Comparative Example 1 with PSA.
6 to 9 are images of the aluminosilicates of Example 1 and Comparative Examples 1 to 3 taken by SEM.
Figure 10 is a graph of the nitrogen adsorption/desorption Brunner-Emit-Teller specific surface area (S _BET ) and external specific surface area (S _EXT ) results for the aluminosilicate particles of Example 1 and Comparative Examples 1 to 3.
11 is a graph showing the results of XRD analysis on the aluminosilicate particles of Example 1 and Comparative Examples 1 and 3;

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Example 1

1) Preparation of aluminosilicate particles

100 g of metakaolin (Al ₂ Si ₂ O ₇ , Aldrich), 300 g of EtOH (Daejung chemicals & metals), and 2 kg of zirconium oxide balls (ZrO, 5 mm) were placed in a 1 L Nalgene bottle. The pulverized metakaolin was prepared by ball milling at 150 rpm for 3 days.

23 g of KOH (Daejung chemicals & metals) and 27 g of colloidal silica (Ludox HS 30 wt%; Sigma-Aldrich) were completely dissolved in 63 g of distilled water (DW). After 15 g of the pulverized metakaolin was added to the solution, the mixture was stirred at 800 rpm for 40 minutes using an overhead stirrer.

It was cured at about 70° C. for 4 hours.

The cured product was put in distilled water at 90° C., stirred for 12 hours, and washed until the pH reached 7 level by centrifugation.

After washing, the dried aluminosilicate has an amorphous structure (FWHM = 6.745°, 2θ @ I _max = 29.2° in the 2θ range of XRD 20° to 37°), and y/x=1.6, x/ It was found to have a composition of n=1.12.

The aluminosilicate formed of primary particles having a primary volume particle diameter of about 20 nm without secondary particle formation is S _BET = 175 m ² /g, S _EXT = 153 m ² /g, S _EXT /S _BET = 0.77 when analyzing specific surface area , V _micro = 0.008 cm ³ /g.

2) Tire rubber composition and specimen preparation

In a Banbury mixer 730.96 g of a diene elastomer mixture (SSBR 3626, LG Chem) and 372.12 g of the aluminosilicate, 59.54 g of silane coupling agent (X50-S, Evonik Industries), and 53.16 g of other additives (oxidation) as rubber reinforcement. Inhibitors, dispersion accelerators, vulcanization aids, etc.) were added. CMB (carbon master batch) was carried out at 150°C. The resulting mixture was extruded into a sheet having a thickness of 2 to 3 mm.

After aging the CMB sheet at room temperature for 24 hours, it was added to a Banbury mixer with 24.84 g of a vulcanizing agent and a vulcanization accelerator, followed by FMB (final master batch), and then extruded into a sheet of 2 to 3 mm. This was crosslinked at 160°C to obtain a rubber molded product.

Example 2

An aluminosilicate, a rubber composition, and a specimen were prepared in the same manner as in Example 1, except that metakaolin was stirred and pulverized for 1 day.

Example 3

An aluminosilicate, a rubber composition, and a specimen were prepared in the same manner as in Example 1, except that metakaolin was stirred and pulverized for 6 days.

Comparative Example 1

Aluminosilicate, rubber composition, and specimen were prepared in the same manner as in Example 1, except that metakaolin was not pulverized and used as a raw material.

Comparative Example 2

Evonik's silica (trade name Ultrasil ^® 7000GR) was prepared.

In addition, a rubber composition and a specimen were prepared in the same manner as in Example 1, except that the silica was used.

Comparative Example 3

An aluminosilicate, a rubber composition, and a specimen were prepared in the same manner as in Example 1, except that metakaolin having d50 = 3.29 µm and d90 = 28.54 µm was not pulverized and used as a raw material.

Test Example 1: Analysis of metakaolin

(1) The metakaolin of Example 1 and Comparative Examples 1 and 3 were photographed using a scanning electron microscopy (SEM), and are shown in FIGS. 1 to 3.

(2) Meanwhile, the particle size distribution of the metakaolin particles of Examples 1 to 3 and Comparative Examples 1 to 3 was analyzed using a particle size analyzer (PSA). The graphs of the analysis results of the particle size analyzer are shown in Figs. 4 and 5, and d50 and d90 are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 3 d50(㎛) 0.29 0.38 0.25 5.27 3.29 d90(㎛) 1.07 2.10 0.75 9.28 28.54

4 and Table 1, it was confirmed that the metakaolin of Example 1 had a narrower particle size distribution, and the values of d50 and d90 were significantly smaller than that of the metakaolin of Comparative Examples 1 and 3.

In addition, referring to FIG. 5 and Table 1, it was confirmed that the particle size distribution of metakaolin narrowed and the values of d50 and d90 decreased as the grinding time increased. Specifically, the metakaolin of Example 3 pulverized for 6 days-the metakaolin of Example 1 pulverized for 2 days-the metakaolin of Example 2 pulverized for 1 day-the sequence of the metakaolin of Comparative Example 1 without pulverization It was confirmed that the particle size distribution became wider and the values of d50 and d90 gradually increased.

Test Example 2: Analysis of aluminosilicate

(1) Using a scanning electron microscopy (SEM), the aluminosilicates of Example 1 and Comparative Examples 1 to 3 were photographed, and the images are shown in FIGS. 6 to 9.

(2) Nitrogen adsorption/desorption Brunner-Emit-Teller specific surface area (S _BET ) for the aluminosilicate particles of Example 1 and Comparative Examples 1 to 3 using a specific surface area analyzer (BEL Japan Inc., BELSORP_MAX) and The external specific surface area (S _EXT ) was measured. Then, the volume of micropores (V _micro ) having a pore size of less than 2 nm was calculated from the S _BET by t-plot method. 10 is a graph showing the results of nitrogen adsorption/desorption Brunner-Emit-Teller specific surface area (S _BET ) and external specific surface area (S _EXT ) for the aluminosilicate particles of Example 1 and Comparative Examples 1 to 3, and Table 2 below. The analysis result values are described in.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 V _micro (cm ³ /g) 0.0084 0.0052 0.0086 0.0043 S _BET (m ² /g) 175.45 104.80 171.50 120.91 S _EXT (m ² /g) 153.39 92.74 151.60 109.43

Referring to Table 2 and FIG. 10, it was confirmed that Example 1 using pulverized metakaolin had higher S _BET , S _EXT , and V _micro values than Comparative Examples 1 and 3 using unground metakaolin.

(3) Using an X-ray diffraction analyzer (Bruker AXS D4-Endeavor XRD), under an applied voltage of 40 kV and an applied current of 40 mA, X for the aluminosilicate particles of Example 1 and Comparative Examples 1 and 3 -Ray diffraction analysis was performed. The measured 2θ ranges from 15° to 45°, and scans are performed at an interval of 0.05°. At this time, a variable divergence slit 6 mm was used as the slit, and a large PMMA holder (diameter = 20 mm) was used to eliminate background noise caused by the PMMA holder. 11 is a graph showing the results of XRD analysis on the aluminosilicate particles of Example 1 and Comparative Examples 1 and 3;

Referring to FIG. 11, in Example 1, Comparative Examples 1 and 3, it was confirmed that amorphous aluminosilicate was synthesized.

Test Example 3: Analysis of rubber composition

(1) For the rubber moldings according to Example 1 and Comparative Examples 1 to 3, an abrasion resistance index (A. R. I.) was measured according to the standard of DIN ISO 4649 using an abrasion tester (Bareiss GmbH).

The wear resistance was calculated as {[(loss weight of the material) X (specific gravity of the material)]/[(loss weight of the reference material) X (specific gravity of the reference material)]} X 100 (reference material: neutralrubber). The results are shown in Table 3 below.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 A.R.I 103 92 100 91

Referring to Table 3, it was confirmed that Example 1 has better wear resistance than Comparative Examples 1 to 3.

(2) For the rubber moldings according to Example 1 and Comparative Examples 1 to 3, a dynamic loss factor (tanδ) was measured under 3% dynamic strain and 3% static strain using a viscoelasticity meter (DMTS 500N, Gabo, Germany). .

For reference, the dynamic loss coefficient at 0 ℃ (tanδ @60 ℃) is related to the tire wet grip characteristics, and the higher the value, the better the wet grip characteristics. And, the dynamic loss coefficient at 60°C (tanδ @60°C) is related to the rolling resistance characteristics of the tire, and the lower the value, the better the rolling resistance characteristics. The results are shown in Table 4.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 tanδ(0 ℃) 0.748 0.826 0.738 0.826 tanδ(60 ℃) 0.144 0.137 0.149 0.142 E ^* (60 ℃) 5.25 3.74 5.10 4.27

Referring to Table 4, it was confirmed that Example 1 had a lower tanδ (0 °C) value and higher tanδ (60 °C) than Comparative Examples 1 and 3, but had excellent properties of E* (60 °C). .

(3) The specimens of Example 1 and Comparative Examples 1 to 3 were measured for tensile strength (TS) at the time of cutting and tensile stress at 300% elongation (300% modulus) by the tensile test method of ASTM 412. . For this, Instron's Universal Test Machine 4204 tensile tester was used, and it was measured at room temperature at a tensile speed of 50 cm/min.

The larger the index of M300%, the greater the rigidity in high temperature conditions, and the greater the durability of the grip performance when driving at high speed for a long time during tire manufacturing. In addition, the higher the index of the tensile strength is, the higher the tensile breaking strength in the high temperature condition is, and it means that the wear resistance in the high temperature condition is excellent when the pneumatic tire is used for a long time and at high speed.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 M300% 116 115 116 112 T.S (Tensile Strength) 221 170 223 185 E.B (elongation at break) 490 420 430 460

Referring to Table 5, it was confirmed that Example 1 has excellent mechanical properties such as 300% modulus and tensile strength than Comparative Examples 1 and 3.

Claims (12)

Having the composition of the following formula (1), Brunner-Emmett-Teller specific surface area (S _BET ) of 125 to 250 m ² /g and external specific surface area (S _EXT ) of 110 to 240 m ² /g by nitrogen adsorption/desorption analysis As a method for producing amorphous aluminosilicate particles having a and satisfying 0.7 ≤ S _EXT /S _BET ≤ 1.0,
Controlling the particle size distribution of metakaolin; And
And a curing step of curing the metakaolin, a silicon compound, and an alkali whose particle size distribution is controlled to prepare aluminosilicate particles,
The particle size distribution-controlled metakaolin has a particle size at which the cumulative volume in the particle size distribution is 50% and 90%, respectively, d50 and d90, d50 is 0.05 to 1.50 μm, and d90 is 0.30 to 4.50 μm, Method for producing aluminosilicate particles:
[Formula 1]
M _x/n [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)
In Formula 1,
The M is an element selected from the group consisting of Li, K, Ca, Zn, Mg, Na, Rb, Cs, Be, and Fr, or an ion thereof,
x> 0, y> 0, n> 0, and m ≥ 0,
1.0 ≤ y/x ≤ 5.0,
0.5 ≤ x/n ≤ 1.2.
The method of claim 1, wherein the aluminosilicate particles are included in a rubber reinforcing material.
The method of claim 1, wherein the metakaolin is pulverized to control the particle size distribution of the metakaolin.
The method of claim 3, wherein the pulverization is performed by putting metakaolin and ceramic balls into a container and performing ball milling at a rotation speed of 100 to 200 rpm for 2 to 6 days, and the method for producing aluminosilicate particles .
The method of claim 1, wherein the silicon compound is fumed silica, rice husk, colloidal silica, cellite, pearlite, rice husk ash, Silica fume, organosilanes, clays, minerals, calcined clays, activated clays, fly ash, slag, pozzolan, incinerated utility waste, industrial by-products, glass powder and Red mud (red mud) is at least one selected from the group consisting of, aluminosilicate particles manufacturing method.
The method of claim 1, wherein the aluminosilicate particle production method comprises:
Controlling the particle size distribution of metakaolin;
Adding metakaolin, a silicon compound, and an alkali whose particle size distribution is controlled to a solvent and stirring to obtain a stirred material;
Curing the stirred material at a temperature of room temperature to 90° C. to prepare aluminosilicate particles; And
A method for producing aluminosilicate particles comprising washing and drying the aluminosilicate particles.
The method of claim 1, wherein the aluminosilicate particles have a primary particle size of 10 to 50 nm.
delete delete The method of claim 1, wherein the aluminosilicate particles have a volume of micropores (V _micro ) having a pore size of less than 2 nm calculated by a t-plot method from the S _BET of less than 0.05 cm ³ /g. Nosilicate particle production method.
A rubber composition for a tire comprising the step of preparing a rubber composition by stirring a rubber reinforcement material including aluminosilicate particles prepared by the manufacturing method of any one of claims 1 to 7 and 10, and a diene elastomer. Manufacturing method.
The method of claim 11, wherein the diene elastomer is natural rubber, polybutadiene, polyisoprene, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, isoprene-styrene copolymer, and butadiene-styrene- At least one selected from the group consisting of isoprene copolymers, a method for producing a rubber composition for a tire.

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