KR102157789B1 - Method for preparing aluminosilicate particles, a reinforcing materials for rubber comprising the aluminosilicate particles, and rubber composition for tires comprising the reinforcing materials - Google Patents

Abstract

The present invention relates to a method for producing aluminosilicate particles having excellent dispersibility, a rubber reinforcing material including the aluminosilicate particles, and a rubber composition for a tire including the rubber reinforcing material. The rubber reinforcing material including aluminosilicate particles obtained by the manufacturing method of the present invention exhibits excellent dispersibility in the rubber composition and thus improved reinforcing effect, and thus can be suitably used for eco-friendly tires requiring high efficiency and high fuel efficiency.

Description

A method for producing aluminosilicate particles, a rubber reinforcing material including the aluminosilicate particles, and a rubber composition for tires including the same TECHNICAL FIELD TECHNICAL FIELD }

The present invention relates to a method for producing aluminosilicate particles having excellent dispersibility and rubber reinforcing effect, a rubber reinforcing material including the aluminosilicate particles, and a rubber composition for a tire including 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. It is known that even when alumina, clay, kaolin, etc. are applied as a white additive for rubber reinforcement, it can be used as an eco-friendly tire material by lowering rolling resistance. However, the white additive for rubber reinforcement decreases dispersibility due to the formation of strong aggregates, and thus, problems such as a decrease in mechanical strength may appear.

Kay Saalwachter, Microstructure and molecular dynamics of elastomers as studied by advanced low-resolution nuclear magnetic resonance methods, Rubber Chemistry and Technology, Vol. 85, No. 3, pp. 350-386 (2012).

The present invention is to provide a method for producing aluminosilicate particles having excellent dispersibility and a rubber reinforcing effect in a rubber composition.

The present invention is to provide a rubber reinforcing material capable of imparting excellent reinforcing effect and workability to a tire.

And, the present invention is to provide a rubber composition for a tire comprising the rubber reinforcement.

According to the present invention,

Preparing a raw material mixture including an inorganic source and a basic or alkaline aqueous solution containing a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 3.0 to 3.5 (Si/Al);

Curing the raw material mixture to obtain aluminosilicate particles;

Washing the aluminosilicate particles; And

Drying the washed aluminosilicate particles

A method for producing aluminosilicate particles comprising a is provided.

And, according to the present invention,

As a rubber reinforcing material including amorphous aluminosilicate particles having a composition of the following formula (1);

The aluminosilicate particles,

In the data graph obtained by X-ray diffraction (XRD), the full width at half maximum (FWHM) of the maximum peak in the range of 20° to 37° of 2θ is 3° to 8.5°, and 26° to It has a maximum peak intensity (I _max ) in the 2θ range of 31°,

With a Bruner-Emmett-Teller specific surface area (S _BET ) of 120 to 250 m ² /g by nitrogen adsorption/desorption analysis and an external specific surface area (S _EXT ) of 100 to 240 m ² /g,

Having an average primary particle diameter of 10 to 50 nm,

Rubber reinforcement is provided:

[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, Na, K, Rb, Cs, Be, and Fr, or an ion thereof;

x> 0, y> 0, n> 0, and m> 0;

1.0 ≤ y/x ≤ 2.0,

0.8 ≤ x/n ≤ 1.2.

And, according to the present invention, there is provided a rubber composition for a tire comprising the rubber reinforcing material and at least one diene elastomer.

Hereinafter, a method for producing aluminosilicate particles according to embodiments of the present invention, a rubber reinforcing material including the aluminosilicate particles, and a rubber composition for a tire including the rubber reinforcing material will be described.

Unless expressly stated in the specification, terminology is only intended to refer to specific embodiments and is not intended to limit the invention.

The singular forms used in the present specification also include plural forms unless the phrases clearly indicate the opposite.

The meaning of'comprising' as used herein specifies a specific characteristic, region, integer, step, action, element or component, and excludes the addition of another specific characteristic, region, integer, step, action, element, or component. It is not.

I. Aluminosilicate Particle manufacturing method

According to one embodiment of the invention,

Preparing a raw material mixture including an inorganic source and a basic or alkaline aqueous solution containing a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 3.0 to 3.5 (Si/Al);

Curing the raw material mixture to obtain aluminosilicate particles;

Washing the aluminosilicate particles; And

Drying the washed aluminosilicate particles

A method for producing aluminosilicate particles comprising a is provided.

As a result of continuous research of the present inventors, it was confirmed that the average primary particle diameter and abrasion resistance of the aluminosilicate particles may vary depending on the molar ratio of silicon atoms and aluminum atoms included in the raw material mixture when preparing aluminosilicate particles.

In particular, according to the present invention, when the molar ratio (Si/Al) of silicon atoms and aluminum atoms added to the raw material mixture satisfies the range of 3.0 to 3.5, the prepared aluminosilicate particles have an average of 10 to 50 nm. It was confirmed that it has a uniform particle distribution of the primary particle diameter and can exhibit excellent dispersibility in the rubber composition.

In addition, the aluminosilicate particles obtained by the above manufacturing method can exhibit an improved reinforcing effect (especially abrasion resistance) in the rubber composition, but do not impair the processability of the rubber composition. I can.

Hereinafter, each step that may be included in the method for producing the aluminosilicate particles will be described in more detail.

In order to prepare the aluminosilicate particles, a step of preparing a raw material mixture including a basic or alkaline aqueous solution and an inorganic source is performed.

The raw material mixture is a liquid composition in which the inorganic source is uniformly mixed in a basic or alkaline aqueous solution.

For example, the raw material mixture may be prepared by adding an inorganic source including a silicon source and an aluminum source to a basic or alkaline aqueous solution and stirring vigorously. As a non-limiting example, the raw material mixture may be prepared by adding an inorganic source having a predetermined molar ratio (Si/Al) to a basic or alkaline aqueous solution and stirring vigorously at 200 to 1000 rpm using an overhead stirrer. have.

Here, the basic or alkaline aqueous solution may be an aqueous solution containing a basic or alkaline compound known to be applicable to the synthesis of aluminosilicate. Examples of the basic or alkaline compound include sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide.

As the inorganic source, a compound known to be applicable to the synthesis of aluminosilicate may be applied without particular limitation.

Preferably, the inorganic source is fumed silica, rice husk, colloidal silica, celite, pearlite, rice husk ash, silica fume , Organosilane, clay, mineral, metakaolin, calcined clay, activated clay, fly ash, slag, pozzolan, glass powder, red mud, silicon salt, alumina, alumina It may be one or more compounds selected from the group consisting of nate, aluminum salt, and organoaluminoxane.

In particular, according to an embodiment of the invention, it is preferable to prepare a mixture of silicon atoms (Si) and aluminum atoms (Al) in a molar ratio of 3.0 to 3.5 (Si/Al) as the inorganic source. Specifically, the molar ratio (Si/Al) is 3.00 or more, or 3.05 or more, or 3.10 or more, or 3.15 or more, or 3.20 or more, or 3.25 or more; And or 3.50 or less, or 3.45 or less, or 3.40 or less, or 3.35 or less.

In order to be able to produce aluminosilicate particles having a desirable range of porosity and abrasion resistance as a rubber reinforcing material for tires, the inorganic source preferably has the molar ratio (Si/Al) of 3.0 or more. However, when silicon atoms (Si) are included in the inorganic source at an excessively high molar ratio, the molar ratio of Si/Al of the aluminosilicate particles as the final product tends to decrease, and the aluminosilicate particles tend to decrease compared to the cost of the silicon source. The content of silicon may be reduced. Therefore, it is preferable that the inorganic source has the molar ratio (Si/Al) of 3.5 or less.

Meanwhile, the step of obtaining aluminosilicate particles by curing the raw material mixture is performed.

The curing may be performed by placing the raw material mixture in an appropriate container and storing the container for a predetermined time in a constant temperature oven while the container is sealed or opened.

Specifically, the curing may be performed by storing the raw material mixture for 2 to 48 hours or 2 to 24 hours at a temperature of 20 to 90 °C.

By the curing, a solid product is formed from the raw material mixture, which is dissociated to obtain aluminosilicate particles.

Subsequently, a step of washing the aluminosilicate particles is performed.

The aluminosilicate particles synthesized under a basic or alkaline aqueous solution exhibit a high hydrogen ion concentration (pH) of greater than 8.0. In the washing step, the aluminosilicate particles are dispersed in water such as distilled water and deionized water, and then washed several times until the pH reaches a level of 7.0 to 8.0.

The washing may be performed simultaneously or continuously with dissociation of the solid product.

Specifically, the solid product formed from the raw material mixture by the curing is dissolved in water such as distilled water and deionized water, heated and stirred to dissociate, washed several times with water until the level of pH 7 to 8, and centrifuged. The separated and washed aluminosilicate particles can be obtained.

Then, the step of drying the washed aluminosilicate particles is performed.

The drying may be performed for 1 to 48 hours in an oven maintained at a temperature of 20 to 150 °C.

If necessary, conventional steps such as grinding and classifying the obtained aluminosilicate particles may be further performed.

The aluminosilicate particles obtained by the above-described manufacturing method may be an amorphous compound having a composition of the following formula (1):

[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, Na, K, Rb, Cs, Be, and Fr, or an ion thereof;

x> 0, y> 0, n> 0, and m> 0;

1.0 ≤ y/x ≤ 2.0,

0.8 ≤ x/n ≤ 1.2.

II. Rubber reinforcement

According to another embodiment of the invention,

As a rubber reinforcing material including amorphous aluminosilicate particles having a composition of the following formula (1);

The aluminosilicate particles,

In the data graph obtained by X-ray diffraction (XRD), the full width at half maximum (FWHM) of the maximum peak in the range of 20° to 37° of 2θ is 3° to 8.5°, and 26° to It has a maximum peak intensity (I _max ) in the 2θ range of 31°,

With a Bruner-Emmett-Teller specific surface area (S _BET ) of 120 to 250 m ² /g by nitrogen adsorption/desorption analysis and an external specific surface area (S _EXT ) of 100 to 240 m ² /g,

Having an average primary particle diameter of 10 to 50 nm,

Rubber reinforcement is provided:

[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, Na, K, Rb, Cs, Be, and Fr, or an ion thereof;

x> 0, y> 0, n> 0, and m> 0;

1.0 ≤ y/x ≤ 2.0,

0.8 ≤ x/n ≤ 1.2.

According to the present invention, the aluminosilicate particles prepared by the above-described method and satisfying the above properties can exhibit an improved reinforcing effect according to excellent dispersibility in the rubber composition, but do not impair the processability of the rubber composition. It can be preferably used as a rubber reinforcing material imparted to the composition.

The aluminosilicate particles satisfying all of the above characteristics can be obtained by the above-described method for producing the aluminosilicate particles.

Existing aluminosilicates were not easy to disperse due to strong agglomeration between particles during dispersion in the rubber composition even when a coupling agent for improving dispersibility was used. On the other hand, the aluminosilicate particles satisfying the above-described characteristics can secure dispersibility equivalent to that of silica even at a low manufacturing cost, and improve the rubber reinforcing effect and lower the rolling resistance.

The aluminosilicate particles obtained by the above production method are amorphous.

In particular, the aluminosilicate particles have a full width at half maximum (FWHM) of 3° in the range of 20° to 37° of 2θ in the data graph obtained by X-ray diffraction (XRD). By satisfying the range of 8.5° to, it can exhibit excellent physical properties as a reinforcing material.

Preferably, the half width (FWHM) of the maximum peak is 3° or more, or 3.5° or more, or 4.0° or more, or 4.5° or more, or 5.0° or more, 5.5° or more, or 6.0° or more. Further, preferably, the half width (FWHM) of the maximum peak is 8.5° or less, or 8.0° or less, or 7.5° or less, or 7.0° or less.

The half width (FWHM) of the maximum peak is a numerical value of the peak width at a position of 1/2 of the maximum peak intensity in the range of 20° to 37° of 2θ obtained from X-ray diffraction of the aluminosilicate particles.

The unit of the half width (FWHM) of the maximum peak may be expressed in degrees (°), which is a unit of 2θ, and the value of the half width may be smaller as a compound having high crystallinity.

In addition, the aluminosilicate particles may exhibit maximum peak intensity (I _max ) in a 2θ range of 26° to 31° in a data graph obtained by X-ray diffraction (XRD).

Preferably, the maximum peak intensity (I _max ) is 26° or more, or 27° or more, or 28° or more of 2θ. Further, preferably, the maximum peak intensity (I _max ) is 31° or less of 2θ, or 30.5° or less, or 30° or less.

For reference, amorphous silica is seen the I _max in the 2θ range of 20 ° to 25 °, amorphous alumina is generally visible to I _max in the 2θ range of 30 ° to 40 °.

On the other hand, the aluminosilicate particles have a composition of Formula 1:

[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, Na, K, Rb, Cs, Be, and Fr, or an ion thereof;

x> 0, y> 0, n> 0, and m> 0;

1.0 ≤ y/x ≤ 2.0,

0.8 ≤ x/n ≤ 1.2.

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≦2.0 and 0.8≦x/n≦1.2.

Specifically, in Formula 1, y/x is 1.00 or more, or 1.15 or more, or 1.3 or more, or 1.45 or more, or 1.50 or more, or 1.55 or more, or 1.60 or more; 2.00 or less, or 1.95 or less, or 1.90 or less, or 1.85 or less may be advantageous for the expression of all the characteristics described above.

Further, specifically, in Formula 1, x/n is 0.80 or more or 0.81 or more; 1.20 or less, or 1.15 or less, or 1.10 or less, or 1.05 or less, or 1.00 or less, or 0.95 or less, or 0.90 or less, or 0.85 or less, or less than 0.85 may be advantageous for the expression of all the characteristics described above.

The aluminosilicate particles have an average primary particle diameter of 10 to 50 nm.

Specifically, the aluminosilicate particles are 10 nm or more, or 15 nm or more, or 20 nm or more; It may have an average primary particle diameter of 50 nm or less, or 45 nm or less, or 40 nm or less, or 35 nm or less.

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.

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 and an external surface of 100 to 240 m ² /g by nitrogen adsorption/desorption analysis. It has an external specific surface area (S _EXT ).

Specifically, the S _BET is 120 m ² /g or more, or 125 m ² /g or more, or 130 m ² /g or more, or 135 m ² /g or more, or 140 m ² /g or more, or 145 m ² /g or more, or 150 m ² /g or more; It is 250 m ² /g or less, or 240 m ² /g or less, or 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.

Specifically, the S _EXT is 100 m ² /g or more, or 105 m ² /g or more, or 110 m ² /g or more, or 115 m ² /g or more, or 120 m ² /g or more, or 125 m ² /g or more, or 130 m ² /g or more; 240 m ² /g or less, or 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, or 190 m ² /g or less, or 180 m ^{It is 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.

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 for the expression of the above-described characteristics. Specifically, the S _EXT /S _BET is 0.80 or more, or 0.81 or more, or 0.82 or more, or 0.83 or more, or 0.84 or more, or 0.85 or more; It is 1.00 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 have a volume of micropores (V _micro ) having a pore size of less than 2 nm calculated by the t-plot method from the S _BET is less than 0.05 cm ³ /g It is small and enables the expression of excellent mechanical properties as a rubber reinforcement. Specifically, the V _micro is less than 0.050 cm ³ /g, or less than 0.025 cm ³ /g, or less than 0.020 cm ³ /g, or less than 0.015 cm ³ /g, or less than 0.010 cm ³ /g, or 0.008 cm ³ /g or less.

III. Tire rubber composition

On the other hand, according to another embodiment of the invention, there is provided a rubber composition for a tire comprising the above-described rubber reinforcement.

The rubber reinforcing material includes the aluminosilicate particles described above.

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.

In addition, the aluminosilicate particles exhibit excellent mechanical properties (e.g., excellent durability, abrasion resistance, compressive strength, etc.) compared to reinforcing materials that do not satisfy the above-described physical properties as the formation of micropores inside the particles is suppressed. I can.

The tire rubber composition may include a conventional diene elastomer without particular limitation.

For example, the diene elastomer is a 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 compounds selected from the group consisting of.

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.

The rubber reinforcing material including aluminosilicate particles obtained by the manufacturing method of the present invention exhibits excellent dispersibility in the rubber composition and thus improved rubber reinforcing effect, and thus can be suitably used for eco-friendly tires requiring high efficiency and high fuel efficiency.

1 is a scanning electron microscopy (SEM) image of the aluminosilicate particles of Example 1. FIG.
2 is an SEM image of the aluminosilicate particles of Example 2.
3 is an SEM image of the aluminosilicate particles of Comparative Example 1.
4 is a SEM image of the aluminosilicate particles of Comparative Example 2.
5 is a SEM image of the aluminosilicate particles of Comparative Example 3.

Hereinafter, preferred embodiments are presented to aid the understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Example One

68 g of KOH (Daejung chemicals & metals) and 100 g of sodium silicate powder (Junsei chemical) were completely dissolved in 245 ml of distilled water. After 45 g of metakaolin was added to the solution, a raw material mixture was prepared by mixing at 800 rpm for 40 minutes using an overhead stirrer. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the inorganic source contained in the raw material mixture contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 3.0 (Si/Al). .

The raw material mixture was cured in a constant temperature oven at 70° C. for 4 hours.

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

The washed solid product was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the aluminosilicate particles contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 1.66 (Si/Al).

Example 2

68 g of KOH (Daejung chemicals & metals) and 125 g of sodium silicate powder (Junsei chemical) were completely dissolved in 245 ml of distilled water. After 45 g of metakaolin was added to the solution, a raw material mixture was prepared by mixing at 800 rpm for 40 minutes using an overhead stirrer. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the inorganic source contained in the raw material mixture contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 3.5 (Si/Al). .

The raw material mixture was cured in a constant temperature oven at 70° C. for 4 hours.

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

The washed solid product was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the aluminosilicate particles contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 1.82 (Si/Al).

Comparative example One

68 g of KOH (Daejung chemicals & metals) and 75 g of sodium silicate powder (Junsei chemical) were completely dissolved in 245 ml of distilled water. After 45 g of metakaolin was added to the solution, a raw material mixture was prepared by mixing at 800 rpm for 40 minutes using an overhead stirrer. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the inorganic source contained in the raw material mixture contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 2.5 (Si/Al). .

The raw material mixture was cured in a constant temperature oven at 70° C. for 4 hours.

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

The washed solid product was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the aluminosilicate particles contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 1.57 (Si/Al).

Comparative example 2

68 g of KOH (Daejung chemicals & metals) and 150 g of sodium silicate powder (Junsei chemical) were completely dissolved in 245 ml of distilled water. After 45 g of metakaolin was added to the solution, a raw material mixture was prepared by mixing at 800 rpm for 40 minutes using an overhead stirrer. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the inorganic source contained in the raw material mixture contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 4.0 (Si/Al). .

The raw material mixture was cured in a constant temperature oven at 70° C. for 4 hours.

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

The washed solid product was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the aluminosilicate particles contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 1.77 (Si/Al).

Comparative example 3

68 g of KOH (Daejung chemicals & metals) and 50 g of sodium silicate powder (Junsei chemical) were completely dissolved in 245 ml of distilled water. After 45 g of metakaolin was added to the solution, a raw material mixture was prepared by mixing at 800 rpm for 40 minutes using an overhead stirrer. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the inorganic source contained in the raw material mixture contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 2.0 (Si/Al). .

The raw material mixture was cured in a constant temperature oven at 70° C. for 4 hours.

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

The washed solid product was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles. As a result of atomic ratio analysis using X-ray fluorescence (XRF), it was confirmed that the aluminosilicate particles contained a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 1.42 (Si/Al).

Manufacturing example One

730.96 g of diene elastomer mixture (SSBR 3626, LG Chem) in a Banbury mixer, 372.12 g of aluminosilicate according to Example 1 above as rubber reinforcement, 59.54 g of silane coupling agent (X50-S, Evonik Industries), and 53.16 A rubber composition was prepared by adding g of other additives (antioxidant, dispersion accelerator, vulcanization aid, etc.).

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 (CMB sheet preparation). After aging the CMB sheet at room temperature for 24 hours, it was put into a Banbury mixer with 24.84 g of a vulcanizing agent and a vulcanization accelerator to perform FMB (final master batch), and then extruded into a sheet of 2 to 3 mm (FMB Sheet manufacturing). The FMB sheet was crosslinked at 160°C to obtain a rubber molded article.

Manufacturing example 2

A rubber composition and a rubber molded product were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Example 2 were added instead of Example 1 as a rubber reinforcing material.

Manufacturing example 3

A rubber composition and a rubber molded product were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Comparative Example 1 were added instead of Example 1 as a rubber reinforcing material.

Manufacturing example 4

A rubber composition and a rubber molded article were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Comparative Example 2 were added instead of Example 1 as a rubber reinforcing material.

Manufacturing example 5

A rubber composition and a rubber molded article were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Comparative Example 3 were added instead of Example 1 as a rubber reinforcing material.

Test example One

The composition of the particles according to the Examples and Comparative Examples was confirmed using X-ray fluorescence (XRF, Rigaku zsx primus II, wavelength dispersive type). The XRF measurement was performed using a Rh target, and the particle powder was mounted on a holder having a diameter of 30 mm.

Composition (Chemical Formula 1) M y/x x/n Example 1 K 1.66 0.81 Example 2 K 1.82 0.80 Comparative Example 1 K 1.57 0.85 Comparative Example 2 K 1.77 0.67 Comparative Example 3 K 1.42 0.88

Test example 2

(1) Scanning electron microscopy (SEM) was used to measure the average primary particle diameter of the particles according to the Examples and Comparative Examples. Taken SEM images are shown in FIGS. 1 to 5.

When measuring the average primary particle diameter, the particle diameter refers to the Feret diameter and was calculated as an average value obtained by measuring the diameter of the particles in various directions. Specifically, after obtaining an SEM image in which more than 100 particles are observed, a random straight line is plotted, and the primary particle diameter of the particles can be calculated through the length of the straight line, the number of particles included in the straight line, and the magnification. By setting it as 20 or more, the average primary particle diameter was calculated|required.

(2) Nitrogen adsorption/desorption of the particles according to the Examples and Comparative Examples using a specific surface area analyzer (BEL Japan Inc., BELSORP_MAX) Brunner-Emit-Teller specific surface area (S _BET ) and fines of less than 2 nm The external specific surface area (S _EXT ) excluding pores 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.

Average primary particle diameter
(nm) S _BET
(m ² /g) S _EXT
(m ² /g) S _EXT /S _BET V _micro
(cm ³ /g) Example 1 <25 151.20 130.65 0.864 0.0080 Example 2 <25 168.61 145.30 0.862 0.0090 Comparative Example 1 <30 112.66 97.82 0.868 0.0058 Comparative Example 2 <25 151.59 130.21 0.859 0.0083 Comparative Example 3 <50 57.85 57.28 0.990 0.0029

Test example 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-ray diffraction analysis was performed on the particles of Examples and Comparative Examples.

The measured 2θ ranges from 10° to 90°, 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.

In the data graph obtained by X-ray diffraction, the full width at half maximum (FWHM) of about 29° peak, which is the maximum peak in the range of 20° to 37° of 2θ, was calculated.

FWHM (°) I _max (°) Crystal form Example 1 6.590 29.2 Amorphous Example 2 6.612 29.0 Amorphous Comparative Example 1 6.667 29.5 Amorphous Comparative Example 2 7.131 28.8 Amorphous Comparative Example 3 6.708 28.9 Amorphous

Test example 4

For the rubber moldings according to Preparation Examples 1 to 3, abrasion resistance index (A.R.I.) was evaluated by measuring relative volume loss according to the standard of DIN ISO 4649 using an abrasion tester (Bareiss GmbH). The wear resistance was normalized based on the value of Example 1 and shown in Table 4 as an index value.

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: neutral rubber).

Rubber moldings Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Rubber reinforcement Example 1 Example 2 Comparative Example 1 A.R.I. (index) 100 106.5 98.9

Referring to Table 4, it is confirmed that the rubber moldings of Preparation Examples 1 and 2 exhibit excellent wear resistance compared to the rubber moldings of Preparation Example 3.

Claims (9)

Preparing a raw material mixture including an inorganic source and a basic or alkaline aqueous solution containing a silicon atom (Si) and an aluminum atom (Al) in a molar ratio of 3.0 to 3.5 (Si/Al);
Curing the raw material mixture to obtain aluminosilicate particles;
Washing the aluminosilicate particles; And
Drying the washed aluminosilicate particles
Including,
The aluminosilicate particles are amorphous compounds having a composition of the following formula (1), a method for producing aluminosilicate particles:
[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, Na, K, Rb, Cs, Be, and Fr, or an ion thereof;
x> 0, y> 0, n> 0, and m>0;
1.60 ≤ y/x ≤ 1.85,
0.8 ≤ x/n ≤ 0.85.
The method of claim 1,
The inorganic source is fumed silica, rice husk, colloidal silica, celite, pearlite, rice husk ash, silica fume, organosilane, Clay, minerals, metakaolin, calcined clay, activated clay, fly ash, slag, pozzolan, glass powder, red mud, silicon salt, alumina, aluminate, aluminum salt , And a method for producing aluminosilicate particles comprising at least one compound selected from the group consisting of organoaluminoxane.
The method of claim 1,
The curing is carried out under a temperature of 20 to 90 °C, a method for producing aluminosilicate particles.
delete As a rubber reinforcing material including amorphous aluminosilicate particles having a composition of the following formula (1);
The aluminosilicate particles,
In the data graph obtained by X-ray diffraction (XRD), the full width at half maximum (FWHM) of the maximum peak in the range of 20° to 37° of 2θ is 6.0° to 7.0°, and 28° to It has a maximum peak intensity (I _max ) in the 2θ range of 30°,
With a Brunner-Emmett-Teller specific surface area (S _BET ) of 150 to 200 m ² /g by nitrogen adsorption/desorption analysis and an external specific surface area (S _EXT ) of 130 to 150 m ² /g,
Having an average primary particle diameter of 10 to 50 nm,
Rubber reinforcement:
[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, Na, K, Rb, Cs, Be, and Fr, or an ion thereof;
x> 0, y> 0, n> 0, and m>0;
1.60 ≤ y/x ≤ 1.85,
0.80 ≤ x/n ≤ 0.85.
The method of claim 5,
The aluminosilicate particles meet 0.8 ≤ S _EXT /S _BET ≤ 1.0,
Rubber reinforcement.
The method of claim 5,
The aluminosilicate particles have a volume of micropores (V _micro ) having a pore size of less than 2 nm calculated by the t-plot method from the S _BET is less than 0.05 cm ³ /g,
Rubber reinforcement.
A rubber composition for a tire comprising the rubber reinforcement according to claim 5 and at least one diene elastomer.
The method of claim 8,
The diene elastomer is a group consisting of natural rubber, polybutadiene, polyisoprene, butadiene/styrene copolymer, butadiene/isoprene copolymer, butadiene/acrylonitrile copolymer, isoprene/styrene copolymer, and butadiene/styrene/isoprene copolymer. At least one compound selected from, a rubber composition for a tire.

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