KR102123011B1 - Method for preparing aluminosilicate particles having excellent dispersion, 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 comprising the aluminosilicate particles, and a rubber composition for a tire comprising the rubber reinforcing material. The rubber reinforcing material including the aluminosilicate particles obtained by the production method of the present invention shows excellent dispersibility in the rubber composition and an improved reinforcing effect accordingly, and thus can be suitably used for eco-friendly tires requiring high efficiency and high fuel efficiency.

Description

Manufacturing method of aluminosilicate particles having excellent dispersibility, rubber reinforcement material including the aluminosilicate particles, and rubber composition for tires including the same METHOD FOR PREPARING ALUMINOSILICATE PARTICLES HAVING EXCELLENT DISPERSION, A REINFORCING MATERIALS FOR RUBBER COMPRISING THE ALUMINOSILICATE PARTICLES RUBBER COMPOSITION FOR TIRES COMPRISING THE REINFORCING MATERIALS}

The present invention relates to a method for producing aluminosilicate particles having excellent dispersibility, a rubber reinforcing material comprising the aluminosilicate particles, and a rubber composition for a tire including the same.

As concerns about global warming and environmental problems spread, the concept of eco-friendly, which increases energy efficiency and reduces carbon emissions, is being emphasized in many ways. This environmentally friendly concept is being visualized in the tire industry by developing highly efficient eco-friendly tires and seeking recycling methods for waste tires.

An eco-friendly tire (or green tire) refers to a tire that lowers the rolling resistance of rubber to impart high efficiency and high fuel efficiency, resulting in reduction of 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 a rubber composition and loss of abrasion resistance. In order to compensate for this, it is known that a highly dispersible precipitated silica of a specific condition can be used together with a silane coupling agent to make an eco-friendly tire material having good wear resistance.

On the other hand, there is also a high interest in additives that can have good properties (mechanical strength such as rolling resistance and abrasion resistance) that are opposite to each other, such as highly dispersed 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 reducing rolling resistance. However, the white additive for reinforcing the rubber has reduced dispersibility due to the formation of strong agglomerates, and thus may have problems such as deterioration of mechanical strength.

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 in a rubber composition.

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

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

According to the invention,

Forming a raw material mixture comprising a basic or alkaline aqueous solution, silicon sources and aluminum sources;

Curing the raw material mixture to obtain aluminosilicate particles;

Washing the aluminosilicate particles with water;

Surface-treating the washed aluminosilicate particles with alcohol; And

Drying the surface-treated aluminosilicate particles

It provides a method for producing aluminosilicate particles comprising a.

And, according to the present invention,

A rubber reinforcement comprising amorphous aluminosilicate particles comprising an alcohol molecule adsorbed to at least a portion of the surface and having the composition of Formula 1 below;

The aluminosilicate particles have an average particle diameter of 10 to 100 nm, a Brunner-Emmett-Teller specific surface area (S _BET ) of 80 to 250 m ² /g by nitrogen adsorption/desorption analysis, 60 to 200 m ² /g A rubber reinforcement is provided, having an external specific surface area (S _EXT ) of:

[Formula 1]

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

In Chemical Formula 1,

M is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, and Fr or their ions;

x> 0, y> 0, n> 0, and m ≥ 0;

1.0 ≤ y/x ≤ 5.0,

0.5 ≤ 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 of manufacturing aluminosilicate particles according to embodiments of the present invention, a rubber reinforcement material including the aluminosilicate particles, and a rubber composition for a tire including the rubber reinforcement material will be described.

Prior to that, the terminology is only for referring to a specific embodiment, and is not intended to limit the present invention, unless expressly stated herein.

And, singular forms used in the present specification include plural forms unless the phrases express the opposite meaning.

Also, as used herein, the meaning of'include' specifies a specific characteristic, region, integer, step, operation, element, or component, and adds another specific characteristic, region, integer, step, operation, element, or component. It is not excluded.

I. Aluminosilicate Method for producing particles

According to one embodiment of the invention,

Forming a raw material mixture comprising a basic or alkaline aqueous solution, a silicon source and an aluminum source;

Curing the raw material mixture to obtain aluminosilicate particles;

Washing the aluminosilicate particles with water;

Surface-treating the washed aluminosilicate particles with alcohol; And

Drying the surface-treated aluminosilicate particles

It provides a method for producing aluminosilicate particles comprising a.

As a result of continuous research by the present inventors, in the method for producing aluminosilicate particles, when the aluminosilicate particles washed with water after curing of the raw material mixture are surface treated with alcohol, compared to those without surface treatment with alcohol, the formed aluminum It was found that aggregation between nosilicate particles was minimized and exhibited improved dispersibility in the rubber composition.

In addition, the aluminosilicate particles obtained by the above production method can exhibit an improved reinforcing effect according to excellent dispersibility in the rubber composition, but do not impair the processability of the rubber composition, and are preferably used as a rubber reinforcing material imparted to the rubber composition for tires. Can be applied.

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

In order to prepare aluminosilicate particles, a step of forming a raw material mixture comprising a basic or alkaline aqueous solution, a silicon source and an aluminum source is performed.

The raw material mixture is a liquid composition in which the silicon source and the aluminum source are uniformly mixed on the basic or alkaline aqueous solution; For example, a silicon source and an aluminum source may be added to the basic or alkaline aqueous solution, and the mixture may be prepared by vigorous stirring.

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

As the silicon source and the aluminum source, compounds known to be usable for the production of aluminosilicate may be applied without particular limitation.

Preferably, the silicon source is fumed silica, rice husk, colloidal silica, cellite, pearlite, rice husk ash, silica fume , Organosilane, clay, mineral, metakaolin, calcined clay, active clay, fly ash, slag, pozzolan, glass powder, and red mud 1 It may be a species or more compounds.

In addition, the aluminum source is selected from the group consisting of alumina, aluminate, aluminum salt, organoaluminoxane, pearlite, clay, mineral, metakaolin, calcined clay, active clay, fly ash, slag, pozzolanic, glass powder, and red mud. It may be one or more compounds.

The ratio of the silicon source and the aluminum source included in the raw material mixture may be adjusted according to the composition of the aluminosilicate particles that are finally formed and the types of the sources.

Meanwhile, a step of curing the raw material mixture to obtain aluminosilicate particles is performed.

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

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

A solid product is formed from the raw material mixture by the curing, and can be dissociated to obtain aluminosilicate particles as a solid product.

Subsequently, the step of washing the aluminosilicate particles with water is performed.

The washing can be carried out simultaneously or continuously with dissociation of the solid product.

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

In particular, in the method of manufacturing aluminosilicate particles according to an embodiment of the present invention, a step of surface-treating the aluminosilicate particles washed with water is performed.

The surface treatment step may be performed by agitating for 0.5 to 30 minutes while dispersing by adding the aluminosilicate particles washed with water to alcohol.

By the surface treatment, a hydroxyl group of alcohol is adsorbed on at least a part of the surface to the aluminosilicate particles, and an alkyl group of alcohol is introduced to the surface of the aluminosilicate particles.

The alkyl group introduced on the surface of the aluminosilicate particles can minimize agglomeration between particles in the drying process of the aluminosilicate particles. In addition, the alkyl group introduced on the surface of the aluminosilicate particles allows the aluminosilicate particles to exhibit improved dispersibility in a dispersion medium such as a rubber composition.

Examples of the alcohol that can be used for the surface treatment include one or more compounds selected from the group consisting of methanol, ethanol, propanol, and butanol.

Then, the step of drying the surface-treated aluminosilicate particles at room temperature is performed. The drying may be performed for 1 to 48 hours under a temperature of 20 to 150 ℃.

The aluminosilicate particles may be obtained through the above-described steps, and conventional steps such as pulverizing the aluminosilicate particles obtained as necessary may be further performed.

The aluminosilicate particles obtained by the above-described manufacturing method may have the composition of Formula 1 below, and at least a part of the surface thereof is introduced with an alkyl group by adsorption of alcohol molecules:

[Formula 1]

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

In Chemical Formula 1,

M is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, and Fr or their ions;

x> 0, y> 0, n> 0, and m ≥ 0;

1.0 ≤ y/x ≤ 5.0,

0.5 ≤ x/n ≤ 1.2.

II. Rubber reinforcement

According to another embodiment of the invention,

A rubber reinforcing material comprising amorphous aluminosilicate particles comprising an alcohol molecule adsorbed on at least a portion of the surface and having the composition of Formula 1;

The aluminosilicate particles have an average particle diameter of 10 to 100 nm, a Brunner-Emmett-Teller specific surface area (S _BET ) of 80 to 250 m ² /g by nitrogen adsorption/desorption analysis, 60 to 200 m ² /g A rubber reinforcement is provided, having an external specific surface area (S _EXT ) of:

[Formula 1]

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

In Chemical Formula 1,

M is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, and Fr or their ions;

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, 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 impair the processability of the rubber composition, and are imparted to the rubber composition for tires It can be preferably applied as a rubber reinforcement.

As the aluminosilicate particles are prepared by the above-described method, the alkyl groups introduced by adsorption of alcohol molecules are introduced on at least a part of the surface, and the formation of micropores inside the particles is suppressed, thereby meeting the above-described properties. It can exhibit excellent dispersibility and mechanical properties (eg, excellent durability, abrasion resistance, compressive strength, etc.) compared to the reinforcing materials that are not able to do so.

Even if a conventional aluminosilicate is used as a coupling agent for improving dispersibility, it is not easy to disperse due to strong aggregation between particles when dispersing in the rubber composition. However, the aluminosilicate particles satisfying the above-mentioned properties can secure an excellent level of dispersibility similar to that of silica, while also improving the reinforcing effect and lowering the rolling resistance.

According to the present invention, the aluminosilicate particles contained in the rubber reinforcement are amorphous (amorphous).

In the amorphous aluminosilicate particles according to an embodiment of the present invention, the amorphous is half-width of the maximum peak in the range of 20° to 37° of 2θ in the data graph obtained by X-ray diffraction (XRD) ( Full width at half maximum, FWHM) may mean that 3 ° to 8.5 °.

Preferably, the maximum peak half width (FWHM) 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, and 6.0° or more. Also, preferably, the maximum peak half width (FWHM) 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 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 higher the crystallinity, the smaller the value of the half-width.

In addition, the amorphous aluminosilicate particles according to an embodiment of the present invention, the maximum peak intensity in the 2θ range of 26 ° to 31 ° in the data graph obtained by X-ray diffraction (XRD) (maximum peak intensity, I _max ).

Preferably, the maximum peak intensity (I _max ) is 26° or more of 2θ, or 27° or more, or 28° or more. 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 °.

And, the aluminosilicate particles have the composition of Formula 1 below:

[Formula 1]

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

In Chemical Formula 1,

M is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, and Fr or their ions;

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 include 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 development of various characteristics according to the present invention.

Further, 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; Being 1.2 or less, or 1.15 or less may be advantageous for the expression of various properties according to the present invention.

The average particle diameter of all the aluminosilicate particles may be 10 to 100 nm, which may be advantageous for the expression of various properties 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; 100 nm or less, or 80 nm or less, or 60 nm or less, or 50 nm or less.

In general, a rubber reinforcing material may exhibit an excellent reinforcing effect as the particle size is small, but the smaller the particle size, the more easily the agglomeration phenomenon between particles in the rubber composition appears, resulting in poor dispersibility. When this cohesive phenomenon becomes severe, phase separation may occur between the rubber reinforcing material and the rubber components, and as a result, the workability of the tire may be reduced, and the target reinforcing effect may be difficult to obtain.

The aluminosilicate particles may be present in the form of primary particles that are not substantially aggregated in the rubber composition, while being amorphous particles having the above-described composition.

According to an embodiment of the invention, the aluminosilicate particles have a Brunner-Emmett-Teller specific surface area (S _BET ) of 80 to 250 m ² /g by nitrogen adsorption/desorption analysis and an external of 60 to 200 m ² /g Having an external specific surface area (S _EXT ) may be advantageous for the development of various properties according to the present invention.

Specifically, the S _BET is 80 m ² /g or more, or 85 m ² /g or more, or 90 m ² /g or more, 95 m ² /g or more, or 100 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, or 110 m ² /g or less.

Specifically, the S _EXT is 60 m ² /g or more, or 70 m ² /g or more, or 80 m ² /g or more, or 85 m ² /g or more; 200 m ² /g or less, or 180 m ² /g or less, or 160 m ² /g or less, or 140 m ² /g or less, or 120 m ² /g or less, or 100 m ² /g or less.

And, the ratio of the S _BET and S _EXT (S _EXT /S _BET ) of the aluminosilicate particles is 0.8 to 1.0 may be more advantageous for the expression of various characteristics according to the present invention. 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; 1.0 or less, or 0.99 or less, or 0.95 or less, or 0.90 or less.

On the other hand, the content of the micropores (micropore) in the inorganic material applied as a rubber reinforcement is preferably minimized. This is because the micropores can act as a defect and degrade physical properties as a rubber reinforcing material.

According to an embodiment of the present invention, the aluminosilicate particles have a micropore volume (V _micro ) having a pore size of less than 2 nm calculated by the t-plot method from the S _BET of less than 0.05 cm ³ /g. As it is small, it enables the expression of excellent mechanical properties as a rubber reinforcing material. Specifically, the V _micro is less than 0.05 cm ³ /g, or 0.025 cm ³ /g or less, or 0.02 cm ³ /g or less, or 0.015 cm ³ /g or less, or 0.01 cm ³ /g or less, or 0.007 cm ³ /g or less.

In addition, the aluminosilicate particles have a volume average particle diameter (D _mean ) of 1 to 25 μm, a geometric standard deviation of 1 to 20 μm, and a 90% cumulative particle size of 1 to 100 μm, measured under distilled water. It may have a particle size distribution indicating (D ₉₀ ).

Specifically, the aluminosilicate particles are 1 μm or more, or 2.5 μm or more, or 5 μm or more, or 7.5 μm or more, measured under distilled water; And it may have a volume average particle diameter (D _mean ) of 25 μm or less, or 20 μm or less, or 15 μm or less.

And, the alumino silicate particles are 1 μm or more, or 2.5 μm or more, or 5 μm or more measured under distilled water; And it may have a geometric standard deviation of 20 μm or less, or 15 μm or less, or 10 μm or less.

And, the alumino silicate particles are 1 μm or more, or 5 μm or more, or 10 μm or more, measured under distilled water; And it may have a 90% cumulative particle diameter (D ₉₀ ) of 100 μm or less, or 50 μm or less, or 25 μm or less, or 20 μm or less.

As described above, the rubber reinforcing material according to the present invention includes amorphous aluminosilicate particles having an average particle diameter of 100 nm or less.

In particular, the aluminosilicate particles may exhibit excellent dispersibility in the rubber composition while satisfying the specific surface area properties described above.

And, as the aluminosilicate particles are introduced with an alkyl group by adsorption of alcohol molecules on at least a part of the surface, and the formation of micropores inside the particles is suppressed, excellent dispersion compared to reinforcing materials that do not satisfy the above-described properties. It can show performance and mechanical properties.

Furthermore, the aluminosilicate particles do not impede the progress of the vulcanization process and the curing process of the rubber composition, thereby ensuring the processability of the rubber composition and the productivity of the tire manufacturing process using the same.

The aluminosilicate particles satisfying the above-mentioned properties can be obtained by the above-described method for producing aluminosilicate particles.

III. Tire rubber composition

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

The rubber reinforcing material includes the aluminosilicate particles described above.

The aluminosilicate particles satisfying the above-described properties are very preferable as a rubber reinforcing material imparted to the rubber composition for tires, while exhibiting an improved reinforcing effect according to excellent dispersibility in the rubber composition, but not impairing the processability of the rubber composition. Can be applied.

And, as the formation of micropores inside the particles is suppressed, the aluminosilicate particles exhibit excellent mechanical properties (eg, excellent durability, abrasion resistance, compressive strength, etc.) compared to reinforcing materials that do not satisfy the aforementioned properties. Can be.

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

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

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

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

1 is a scanning electron microscopy (SEM) of the aluminosilicate particles of Example 1 [(a) 5,000 times magnification; (b) 1,000,000 times magnification].
Figure 2 is SEM ((a) 5,000 times magnification for the aluminosilicate particles of Comparative Example 1; (b) 1,000,000 times magnification].
Figure 3 is a SEM of the silica particles of Comparative Example 2 ((a) 5,000 times magnification; (b) 1,000,000 times magnification].
4 is a graph showing particle size distribution for particles of Examples and Comparative Examples [(a) Example 1; (b) Comparative Example 1; (c) Comparative Example 2].
5 is a transmission electron microscopy (TEM) image for the rubber moldings of Example 2, Comparative Example 3 and Comparative Example 4 [(a) Example 2; (b) Comparative Example 3; (c) Comparative Example 4].

Hereinafter, preferred embodiments are presented to help 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

23 g of KOH (Daejung chemicals & metals) and 27 g of colloidal silica (Ludox HS 30 wt%; Sigma-Aldrich) were completely dissolved in 22 ml of distilled water (DW). After adding 15 g of metakaolin (Al ₂ Si ₂ O ₇ , Aldrich) to the solution, it was mixed for 40 minutes at 600 rpm using an overhead stirrer.

This was cured at room temperature of about 70° C. for 4 hours.

The solid product formed by curing was placed in distilled water at 90° C. and stirred for 12 hours and centrifuged to wash to pH 7 levels.

The solid product washed with distilled water was dispersed in ethanol to perform a surface treatment by stirring for 1 minute.

The surface-treated solid product was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles.

Comparative example One

Aluminosilicate particles were obtained in the same manner as in Example 1, except that the step of surface-treating the solid product washed with distilled water with ethanol was omitted.

Specifically, 23 g of KOH (Daejung chemicals & metals) and 27 g of colloidal silica (Ludox HS 30 wt%; Sigma-Aldrich) were completely dissolved in 22 ml of distilled water (DW). After adding 15 g of metakaolin (Al ₂ Si ₂ O ₇ , Aldrich) to the solution, it was mixed for 40 minutes at 600 rpm using an overhead stirrer.

This was cured at room temperature of about 70° C. for 4 hours.

The solid product formed by curing was placed in distilled water at 90° C. and stirred for 12 hours and centrifuged to wash to pH 7 levels.

The solid product washed with distilled water was dried in an oven at 70° C. for 24 hours to finally obtain aluminosilicate particles.

Comparative example 2

Silica particles (product name 7000GR) of Evonic were prepared.

Example 2

In a sealed mixer, 737.24 g of diene elastomer mixture (SSBR 2550, LG Chemical), 375.32 g of aluminosilicate particles according to Example 1 as a reinforcing material, and 60.05 g of a silane coupling agent (polysiloxane system) were added.

This was mixed under 150° C. for 5 minutes, and then 78.66 g of other additives (antioxidants, antioxidants, emulsifiers, vulcanization accelerators, waxes, etc.) were added and mixed for 90 seconds.

The obtained mixture was extruded into a sheet form having a thickness of 2 to 3 mm, and this was vulcanized at 160° C. to obtain a rubber molding. At this time, the vulcanization time was adjusted with reference to the data measured by using the MDR (moving die rheometer) at 160 ℃ the mixture.

Example 3

140.76 g diene elastomer mixture (SSBR 2550, LG Chem) in a sealed mixer, 188.56 g aluminosilicate particles according to Example 1 as a reinforcing material and 188.56 g silica particles according to Comparative Example 2, and 60.34 g silane couple Ring agent (polysiloxane) was added.

This was mixed under 150° C. for 5 minutes, and then 79.03 g of other additives (antioxidants, antioxidants, emulsifiers, vulcanization accelerators, waxes, etc.) were added and mixed for 90 seconds.

The obtained mixture was extruded into a sheet form having a thickness of 2 to 3 mm, and this was vulcanized at 160° C. to obtain a rubber molding.

Example 4

742.17 g diene elastomer mixture (SSBR 2550, LG Chemical) in a sealed mixer, 113.35 g aluminosilicate particles according to Example 1 as reinforcing material and 264.48 g silica particles according to Comparative Example 2, and 60.45 g silane couple Ring agent (polysiloxane) was added.

This was mixed under 150° C. for 5 minutes, and then 79.31 g of other additives (antioxidants, antioxidants, emulsifiers, vulcanization accelerators, waxes, etc.) were added and mixed for 90 seconds.

The obtained mixture was extruded into a sheet form having a thickness of 2 to 3 mm, and this was vulcanized at 160° C. to obtain a rubber molding.

Example 5

743.24 g diene elastomer mixture (SSBR 2550, LG Chem) in a sealed mixer, 56.76 g aluminosilicate particles according to Example 1 as a reinforcing material and 321.62 g silica particles according to Comparative Example 2, and 60.54 g silane couple Ring agent (polysiloxane) was added.

This was mixed under 150° C. for 5 minutes, and then 79.31 g of other additives (antioxidants, antioxidants, emulsifiers, vulcanization accelerators, waxes, etc.) were added and mixed for 90 seconds.

The obtained mixture was extruded into a sheet form having a thickness of 2 to 3 mm, and this was vulcanized at 160° C. to obtain a rubber molding.

Comparative example 3

In a sealed mixer, 737.24 g of diene elastomer mixture (SSBR 2550, LG Chemical), 375.32 g of aluminosilicate particles according to Comparative Example 1 as a reinforcing material, and 60.05 g of a silane coupling agent (polysiloxane system) were added.

This was mixed under 150° C. for 5 minutes, and then 78.66 g of other additives (antioxidants, antioxidants, emulsifiers, vulcanization accelerators, waxes, etc.) were added and mixed for 90 seconds.

The obtained mixture was extruded into a sheet form having a thickness of 2 to 3 mm, and this was vulcanized at 160° C. to obtain a rubber molding.

Comparative example 4

In a sealed mixer, 744.31 g of diene elastomer mixture (SSBR 2550, LG Chemical), 378.92 g of silica particles according to Comparative Example 2 as a reinforcing material, and 60.63 g of a silane coupling agent (polysiloxane-based) were added.

This was mixed under 150° C. for 5 minutes, and then 79.43 g of other additives (antioxidants, antioxidants, emulsifiers, vulcanization accelerators, waxes, etc.) were added and mixed for 90 seconds.

The obtained mixture was extruded into a sheet form having a thickness of 2 to 3 mm, and this was vulcanized at 160° C. to obtain a rubber molding.

Test example One

The average particle diameter and composition of the particles according to Example 1 and Comparative Examples 1 and 2 were confirmed using Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The photographed SEM images are shown in FIGS. 1 (Example 1), 2 (Comparative Example 1), and 3 (Comparative Example 2).

As a result, it was confirmed that the aluminosilicate particles according to Example 1 and Comparative Example 1 had compositions of y/x=1.6 and x/n=1.12 in Formula 1, respectively.

And, the particles according to Example 1 and Comparative Examples 1 and 2 mostly formed primary particles having an average particle size of 20 to 30 nm. In particular, the aggregation between particles was found to have relatively few particles according to Example 1.

Test example 2

Nitrogen adsorption/desorption Brunner-Emit-Teller specific surface area (S _BET ) and external specific surface area (S _BET ) for particles according to Examples 1 and Comparative Examples 1 and 2 using a specific surface area analyzer (BEL Japan Inc., BELSORP_MAX) _EXT ) was measured. Then, the volume (V _micro ) of micropores having a pore size of less than 2 nm was calculated from the S _BET by a t-plot method.

Primary particle size
(nm) S _BET
(m ² /g) S _EXT
(m ² /g) S _EXT /S _BET V _micro
(cm ³ /g) Example 1 30 104 89 0.86 0.007 Comparative Example 1 30 101 86 0.85 0.007 Comparative Example 2 30 175 144 0.82 0.012

Test example 3

X-ray diffraction analysis of the aluminosilicate particles of Example 1 and Comparative Example 1 under an applied voltage of 40 kV and an applied current of 40 mA, using an X-ray diffraction analyzer (Bruker AXS D4-Endeavor XRD). Was carried out.

The measured range of 2θ is 10° to 90° and scanned at intervals of 0.05°. At this time, a variable divergence slit 6 mm was used as a 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.

As a result, it was confirmed that the aluminosilicate particles of Example 1 and Comparative Example 1 each had an amorphous structure (FWHM = 6.745°, 2θ@I _max = 29.2° in the 2θ range of XRD 20° to 37°).

Test example 4

0.1 g of particles according to Example 1 and Comparative Examples 1 and 2 were added to 10 ml of distilled water. Sonication was performed at 100% pulsed ultrasonication equipment at 90% power for 5 minutes. At this time, the energy by sonication acts as a physical energy similar to the mechanical force applied to the composition when compounding the rubber composition, and thus it is possible to indirectly check the size distribution of aggregates dispersed in the rubber composition.

The obtained dispersion was sonication for an additional 2 minutes using a particle size analyzer (HORIBA, model name LA960, laser diffraction type), and then the size distribution of aggregates, volume average particle diameter (D _mean ), geometric standard deviation (geometric) standard deviation; Std.Dev.), and cumulative particle diameters (D ₁₀ , D ₅₀ , D ₉₀ ) of the volume distribution were measured.

The obtained particle size distribution graph is shown in Fig. 4 ((a) Example 1; (b) Comparative Example 1; (c) Comparative Example 2].

Example 1 Comparative Example 1 Comparative Example 2 D _mean (㎛) 10.86227 37.9613 20.55859 Std.Dev. (㎛) 7.4664 42.5011 14.1228 D ₁₀ (㎛) 6.57343 10.2584 11.21784 D ₅₀ (㎛) 9.84665 12.9935 14.35930 D ₉₀ (㎛) 14.64356 86.1392 45.09504

Test example 5

The dispersion state of the reinforcing material for the rubber moldings according to Example 2 and Comparative Examples 3 and 4 was observed using Transmission electron microscopy (TEM). The photographed TEM image is shown in FIG. 5 ((a) Example 2; (b) Comparative Example 3; (c) Comparative Example 4].

Referring to FIG. 5, Example 2 to which the aluminosilicate particles of Example 1 was applied was significantly superior in dispersion state of the reinforcing material compared to Comparative Example 3.

And, it was confirmed that the aluminosilicate particles of Example 1 applied to Example 2 can exhibit dispersibility equal to or higher than the silica particles of Comparative Example 2 applied to Comparative Example 3.

Test example 6

(1) Dynamic loss coefficient (tan δ) under dynamic strain 3% and static strain 3% using a viscoelasticity meter (DMTS 500N, Gabo, Germany) for rubber moldings according to Examples 2 to 5 and Comparative Examples 3 to 4 Was measured. The measured values are normalized based on the values of Comparative Example 4 and are shown in Table 3.

For reference, the dynamic loss coefficient at 0°C (tan δ @0°C) is related to the tire's wet grip properties, and the higher the value, the better the wet grip properties. In addition, the dynamic loss coefficient at 60°C (tan δ @60°C) is related to the rolling resistance property of the tire, and the lower the value, the better the rolling resistance property.

(2) Abrasion resistance index (ARI) was measured according to the standard of DIN ISO 4649 by using abrasion tester (abrasion tester, Bareiss GmbH) for rubber moldings according to Examples 2 to 5 and Comparative Examples 3 to 4. . The measured values are normalized based on the values of Comparative Example 4 and are shown in Table 3.

The wear resistance was calculated as {[(loss weight of the relevant substance) X (specific gravity of the substance)]/[(loss weight of the reference substance) X (specific gravity of the reference substance)]} X 100 (reference substance: neutral rubber).

tanδ @0℃ index tanδ @60℃ index A.R.I. Example 2 112 125 88 Example 3 109 117 96 Example 4 106 111 98 Example 5 101 106 100 Comparative Example 3 101 115 71 Comparative Example 4 100 100 100

Referring to Table 3, the rubber molding according to Comparative Example 3 exhibited excellent rolling resistance characteristics compared to Comparative Example 4, but it was confirmed that the wear resistance was significantly reduced.

The rubber moldings according to Examples 2 to 5 were found to have improved wet grip and rolling resistance characteristics, while showing a similar degree of wear resistance compared to Comparative Example 4.

In particular, it was confirmed that the rubber molding of Example 5 has the same wear resistance as the rubber molding of Comparative Example 4 and can exhibit improved rolling resistance characteristics.

Claims (12)

Forming a raw material mixture comprising a basic or alkaline aqueous solution, a silicon source and an aluminum source;
Curing the raw material mixture to obtain aluminosilicate particles;
Washing the aluminosilicate particles with water;
Surface-treating the washed aluminosilicate particles with alcohol; And
Drying the surface-treated aluminosilicate particles
Including,
The aluminosilicate particle is an amorphous compound having a composition of Formula 1 below, a method for producing aluminosilicate particle:
[Formula 1]
M _x/n [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)
In Chemical Formula 1,
M is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, and Fr or their ions;
x> 0, y> 0, n> 0, and m ≥ 0;
1.0 ≤ y/x ≤ 5.0,
0.5 ≤ x/n ≤ 1.2.
According to claim 1,
The silicon source is fumed silica, fumed silica, rice husk, colloidal silica, cellite, pearlite, rice husk ash, silica fume, organosilane, Is one or more compounds selected from the group consisting of clay, minerals, metakaolin, calcined clay, active clay, fly ash, slag, pozzolan, glass powder, and red mud ;
The aluminum source is one selected from the group consisting of alumina, aluminate, aluminum salt, organoaluminoxane, pearlite, clay, mineral, metakaolin, calcined clay, active clay, fly ash, slag, pozzolan, glass powder, and red mud. The above compound, a method for producing aluminosilicate particles.
According to claim 1,
The curing is carried out under a temperature of 20 to 90 ℃, the method of producing aluminosilicate particles.
According to claim 1,
The surface treatment is performed by a process of adding and stirring the washed aluminosilicate particles to alcohol, the method of manufacturing aluminosilicate particles.
According to claim 1,
The alcohol is a method of preparing aluminosilicate particles, which is at least one compound selected from the group consisting of methanol, ethanol, propanol, and butanol.
delete A rubber reinforcing material comprising amorphous aluminosilicate particles comprising an alcohol molecule adsorbed on at least a portion of the surface and having the composition of Formula 1;
The aluminosilicate particles have an average particle diameter of 10 to 100 nm, a Brunner-Emmett-Teller specific surface area (S _BET ) of 80 to 250 m ² /g by nitrogen adsorption/desorption analysis, 60 to 200 m ² /g Rubber reinforcement with an external specific surface area (S _EXT ) of:
[Formula 1]
M _{x /n} [(AlO ₂ ) _x ,(SiO ₂ ) _y ]·m(H ₂ O)
In Chemical Formula 1,
M is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, and Fr or their ions;
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 7,
The aluminosilicate particles satisfy 0.8 ≤ S _EXT /S _BET ≤ 1.0, rubber reinforcement.
The method of claim 7,
The aluminosilicate particles, the volume of the micropores having a pore size of less than 2 nm calculated by the t-plot method from the S _BET (V _micro ) is less than 0.05 cm ³ /g, rubber reinforcement.
The method of claim 7,
The aluminosilicate particles have a volume average particle diameter (D _mean ) of 1 to 25 μm, a geometric standard deviation of 1 to 20 μm, and a 90% cumulative particle size of 1 to 100 μm (D) measured under distilled water. ₉₀ ), having a particle size distribution.
A rubber composition for a tire comprising the rubber reinforcement according to claim 7 and at least one diene elastomer.
The method of claim 11,
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 the rubber composition for tires.

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