WO2019164154A1

WO2019164154A1 - Rubber reinforcer comprising aluminosilicate particles, and tire rubber composition comprising same

Info

Publication number: WO2019164154A1
Application number: PCT/KR2019/001383
Authority: WO
Inventors: 최권일; 성은규; 이하나; 김우석; 오명환
Original assignee: 주식회사 엘지화학
Priority date: 2018-02-21
Filing date: 2019-01-31
Publication date: 2019-08-29

Abstract

The present invention relates to a rubber reinforcer comprising aluminosilicate particles, and a tire rubber composition comprising same. Aluminosilicate particles contained in the rubber reinforcer, according to the present invention, do not cause deterioration of the processability of a rubber composition while enabling an improved reinforcement effect according to excellent dispersibility in the rubber composition to be exhibited, and thus can be preferably applied as a rubber reinforcer provided to a tire rubber composition.

Description

[Name of invention]

Rubber reinforcement material containing aluminosilicate particles and rubber composition for tires containing the same [Technical Field]

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0020651 dated February 21, 2018 and Korean Patent Application No. 10-2019-0011316 dated January 29, 2019. All content disclosed in the literature is included as part of this specification. The present invention relates to a rubber reinforcement material comprising aluminosilicate particles and a rubber composition for a tire comprising the same. [Technique to become background of invention]

As global warming and environmental concerns spread, environmentally friendly concepts that reduce energy emissions by increasing energy efficiency are being emphasized in many ways. This eco-friendly concept is being visualized by developing high-efficiency eco-friendly tires in the tire industry and seeking ways to recycle used tires.

Eco-friendly tires (or green tires) are tires that lower the rolUng resistance of rubber and give them high efficiency and high fuel efficiency, resulting in lower carbon emissions. In order to manufacture such environmentally friendly tires, modified rubber materials and white additives for reinforcing rubber (for example, precipitated silica) are mainly used.

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

On the other hand, like highly dispersible precipitated silica, There is also a high interest in additives that can have good mechanical strengths such as wear resistance). As a white additive for rubber reinforcement, even when alumina, clay, kaolin, and the like are applied, it is known that the rolling resistance can be used as an environment-friendly tire material. However, such a white additive for rubber reinforcement is reduced in dispersibility due to the formation of a strong aggregate, and thus may cause problems such as mechanical strength degradation.

Prior Art Documents

[Non-patent literature]

(Non-Patent Document 1) 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).

[Content of invention]

【Problem to solve】

The present invention is to provide a rubber reinforcing material that can give excellent reinforcement effect and workability to the tire.

The present invention is to provide a rubber composition for a tire including the rubber reinforcing material.

[Measures of problem]

According to the invention,

As a rubber reinforcing material including amorphous aluminosilicate particles having a composition of Formula 1;

The aluminosilicate particles are

In the data graph obtained by X-ray diffraction (XRD), the full width at half maximum (FWHM) of 20 to 23 ^° to 37 ^° range is 5 ^° to 7 ^° , ^at least 23 ^° Having a maximum peak intensity (Imax) in the 26 range of less than 26 ^° ,

Rubber reinforcements are provided: 2019/164154 1 »（： 1 ^ 1 {2019/001383

[Formula 1]

[（1 必公）-（5 0 square）] · 1 ¾ ()）

In Chemical Formula 1,

An element selected from the group consisting of ions thereof,

ego,

3 /> <<1.2,

3.0 </ 乂 <20.0. In addition, according to the present invention, there is provided a rubber composition for a tire comprising the rubber reinforcing material. Hereinafter, a rubber reinforcing material and a rubber composition for a tire including the same according to embodiments of the present invention will be described.

Unless expressly stated herein, the terminology is merely for reference to particular embodiments and is not intended to limit the invention.

As used herein, the singular forms “a,” “an,” and “the” include plural forms unless the context clearly indicates the opposite.

As used herein, the term "comprising ¹ " embodies a particular characteristic, region, integer, step, operation, element, or component, and excludes the addition of other specific characteristics, region, integer, step, operation, element, or component. It is not.

1. Rubber reinforcement

According to one embodiment of the invention,

Amorphous having the composition of Formula 1 _. As a rubber reinforcement comprising aluminosilicate particles;

The aluminosilicate particles are

In the data graph obtained by X-ray diffraction (10), the half width of the maximum peak in the range of 20 to 23 ^° to 37 ^° (11 仕 I 1 1 1 1113x111111111, \\ 1, / [) is from 5 ^° to 7 ^°, and in the range of 20 to less than 23 ^{^°} 26 ^°

peak intensity, I _max ),

Rubber reinforcements are provided:

[Formula 1]

[(MaAlxOix) · (Si _y 0 _2y )] m (H ₂ 0)

In Chemical Formula 1,

Is an element selected from the group consisting of Li, Na, K, Rb, Cs, Be, Fr, Ca, Zn, and Mg or ions thereof,

a ³ 0, x 0 0, y ñ 0, and m ³ 0,

a / x <1.2

3.0 <y / x <20.0. As a result of continuous research by the present inventors, the aluminosilicate particles satisfying the above-described properties can exhibit improved reinforcing effect according to excellent dispersibility in the rubber composition, but do not impair the processability of the rubber composition, thereby imparting to the rubber composition for tires. It can be preferably applied as a rubber reinforcing material.

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

Existing aluminosilicate was not easy to disperse due to the strong aggregation between particles during dispersion in the rubber composition even when using a coupling agent for improving the dispersibility. However, the aluminosilicate particles satisfying the above-described characteristics can ensure a good dispersibility similar to that of silica, while also improving the reinforcing effect and lowering the cloud resistance. According to the present invention, the aluminosilicate particles included in the rubber reinforcement are amorphous. In particular, the amorphous aluminosilicate particles according to an embodiment of the present invention, In the data graph obtained by X-ray diffraction (XRD), the full peak at at maximum maximum (FWHM) in the range of 23 ^° to 37 ^° of 20 is satisfied by 5 ^° to 7 ^° . It can exhibit excellent physical properties as rubber reinforcement.

Preferably, the full width at half maximum (FWHM) of the maximum peak is at least 5.0 °, ^at least 5.5 ^° , or ^at least 6.0 ^° . Also preferably, the half width (FWHM) of the maximum peak is 7.0 ^° or less or 6.5 ^° or less.

More preferably, the full width at half maximum (FWHM) of the maximum peak may be 5 ° to T, or 5.5 ^° to T, or 5.5 ° to 6.5 ^° , or 6.0 ^° to 6.5 ^° . The half width of the maximum peak (FWHM) is a numerical value of the peak width at the half position of the maximum peak intensity in the range of 23 ^° to 37 ^° of 20 obtained by X-ray diffraction of the aluminosilicate particles.

The unit of the full width at half maximum (FWHM) of the maximum peak may be expressed in degrees ( ^° ), which is 20 units, and the higher the crystallinity, the smaller the half width. At the same time, of an amorphous aluminosilicate according to one embodiment of the invention the particles X- ray diffraction (XRD) data in the 20 range of less than 26 ^° more than 23 ^° graph maximum peak intensity (maximum peak intensity, obtained by Imax ), It can exhibit more improved physical properties as rubber reinforcement.

Preferably, the maximum peak intensity Imax is ^at least 23.0 ^° , or ^at least 23.5 ^° , or ^at least 24.0 ^° , or ^at least 24.5 ^° of 2e. Also preferably, the maximum peak intensity (Imax) is less than 26.0 ° of 20, or 25.9 ^° aha, or

25.8 ^° or less.

More preferably, the maximum peak intensity (23) may be ^at least 23 ^° and less than 26 ^° , or from 23.5 ^° to 25.9 °, or from 24.0 ^° to 25.9 ^° , or from 24.5 ^° to 25.8 ^° .

For reference, amorphous silica generally exhibits I _max in a range of 20 ^° to 25 ^° and amorphous alumina typically exhibits I _max in a range of 30 ^° to 40 ^° . Meanwhile, the aluminosilicate particles have a composition of Formula 1 below: 2019/164154 1 »（： 1 ^ 1 {2019/001383

[Formula 1]

[(M0 · 5 0)]-!

In Chemical Formula 1,

The IV! Is Ni, Na _/ X,] ¾, 氏 6 _{6 /}此, Ca _/ ¾ \, and the element selected from the group consisting of or ions thereof,

ego,

& / \ <1.2

3.0 <) ø <20.0.

The aluminosilicate particles comprise alkali metals or their ions as metal elements () or ions thereof, in particular 3.0 <

It satisfies the composition of <20.0 and X <1.2. Specifically, in Formula 1, 八 is greater than 3.0, or 3.1 or more, or 3.2 or more, or 3.3 or more, or 3.5 or more, or 4.0 or more; Less than 20.0, or less than or equal to 15.0, or less than or equal to 10.0, or less than or equal to 5.0, or less than or equal to 4.5, or less than or equal to 4.4, or less than or equal to 4.3, or less than or equal to 4.2, may be advantageous for the development of various properties according to the present invention.

Preferably, in Chemical Formula 1, it may be greater than 3.0 and less than 20.0, or 3.1 to 10.0, or 3.2 to 5.0, or 3.3 to 4.5, or 3.5 to 4.2, or 4.0 to 4.2. In addition, specifically, in Formula 1, X is less than 1.2, or 1.0 or less, or 0.9 or less, or 0.8 or less, or 0.7 or less; At least 0.01, or at least 0.02, or at least 0.03, or at least 0.04, or at least 0.05, or at least 0.1, or at least 0.2, or at least 0.3, or at least 0.5 may be advantageous for the development of various properties according to the present invention.

Preferably, in Chemical Formula 1, _X may be 0.01 to 1.0, or 0.01 to 0.9, or 0.05 to 0.9, or 0.1 to 0.8, or 0.3 to 0.8, or 0.5 to 0.7. 2019/164154 1 »（： 1 ^ 1 {2019/001383

According to an embodiment of the invention, the aluminosilicate particles have a Bruner-Emet-Tella specific surface area burr of 110 to 260 111 ² / silver and 90 to 220 1 high ² / of external specific surface area by nitrogen adsorption / desorption analysis 8 6 <: 냔 ovule ■, ¾） have.

Specifically, ¾ is at least 110 1 ₁₁₂ / is or at least 115 111 ² / is; 260 or less, or 250 hemp ² / or less, or 245 ^ 1 ² / or less. Preferably, ¾ may be 110 to 260 kPa, or 115 to 260 111 ² / _& or 115 to 250 1 and ² / _& or 115 to 245 is ² .

And 5 _£ ) _{0 '} is greater than or _equal to 90 江 ^ / or 95 1 and ² / is greater; 220 1 high ² / or less, or 210 111 ² / _§ or less, or 200 1 ^ / or less, or 195 111 ² / or less. Preferably, the table! · May be 90 to 220 111 ² /, or 90 to 210 · I 己^< , or 90 to 200111 ² / _& or 90 to 195 1 / _& or 95 to 195 1 / silver. In addition, the ratio of ¾ ^ · and ¾ of the aluminosilicate particles (¾ / ¾ burr is 0.65 to 0.95 may be more advantageous for the expression of various properties according to the present invention.

Specifically, ¾ / ¾ ^ is at least 0, or at least 0.70, or at least 0.75; 0.95 or less, or 0.93 or less, or 0.92 or less, or 0.91 or less.

Preferably, 5 £> 0 '/ 58' may be 0.65 to 0.95, or 0.70 to 0.93, or 0.75 to 0.92, or 0.75 to 0.91. In the inorganic material applied as a rubber reinforcement material, the content of micropores (fish moss) is preferably minimized. This is because the micropores can cause defects ((acting as urinary diastolic) and lowering the physical properties of the rubber reinforcing material.

According to an embodiment of the present invention, the aluminosilicate particles, the micropores having a pore size of less than 2 calculated

Small to below, it enables the development of excellent mechanical properties as a rubber reinforcement.

Specifically, the

0.05 / less than or 0.025

Or less, or 0.020 (: 111 ³ / less; 0.001 0 to ³ / or more, or 0.002 011 ³ / or more, or 0.003 2019/164154 1 »（： 1 ^ 1 {2019/001383

(: !!! ³ or more, or 0.004 1 _\ ³ / or more, or 0.005 «11 ³ / or more, or 0.006 011 ³ / or more.

Preferably, ▽ _{1 0} may be 0.001 to 0.025 11 ³ / & or 0.003 to 0.020 0 / _& or 0.005 to 0.020 0 ₁₁ ³ / or 0.006 to 0.020 «11 ³ / on: In an embodiment of the invention According to the above, the aluminosilicate particles have an average primary particle diameter of 10 to 50 11.

Specifically, the aluminosilicate particles are 10 11111 or more, or 15 1 ^ 1 or more, or 20 1 ^ 11 or more; 50 11 111 or less, or 45 11 111 or less, or 40

It may have an average primary particle diameter of less than or equal to 35 _.

In general, the rubber reinforcing material may exhibit an excellent reinforcing effect as the particle size is smaller, but the smaller the particle size, the less easily dispersibility due to the aggregation phenomenon between the particles in the rubber composition. If the mirror aggregation becomes severe, phase separation between the rubber reinforcement and the rubber components may occur, and as a result, the workability of the tire may be degraded and the target reinforcement effect may be difficult to obtain. On the other hand, the secondary particles of the aluminosilicate particles _{6 (} ： _{0) 1 (} 1 _¾ 1 句 year ie, the aggregate is a volume average particle diameter of 1 to 25 _ measured under distilled water using a particle size analyzer, 1 to 20 _ It can have a secondary particle size distribution that represents the geometric standard deviation of (approximately _{0111 1} μs acid dispersion) and 90% cumulative particle diameter (1½) of 1 to 50. Specifically, secondary particles of the aluminosilicate particles Is at least 1, or at least 2.5 lM, or at least 5 _, at least 7.5 _, or at least 10.0 _; and at least 25.0 1, or at most 22.5 _, or at most 20.0 _, or at most 19.5. It can have a particle diameter (1 ⁾ .

Preferably, the secondary particles of the aluminosilicate particles are 1 to 25, or 5 to 22.5, or 7.5 to 7.5 measured under distilled water.

It has a volume average particle diameter (0 _¥ ) of 10 to 19.5 / hand. 2019/164154 1 »（： 1 ^ 1 {2019/001383

And, the secondary particles of the aluminosilicate particles are 1.0 or more, or 2.5 measured in distilled water

Or above 5.0 or above, or above 7.0 / year; And a geometric standard of 20 II or less, or 15 or less, or 10 m or less.

have.

Preferably, the secondary particles of the aluminosilicate particles are 1 to 1 measured under distilled water

Have a geometric standard deviation of 15 or 7 to 10_. And, the secondary particles of the aluminosilicate particles are 1 _ or more, or 5 _ or more, or 10 m or more, or 15 / / III or more, or 20 _ or more, or 25 쌘！ measured under distilled water; And 50 _ or less, or 40]! 90% cumulative particle diameter of 35 or less.

It has a 90% cumulative particle diameter (1¾ ₀ ) of 25 to 35. On the other hand, aluminosilicate particles that meet the above-described characteristics can be prepared by a method comprising the following steps:

[1] adding a silicon source, an aluminum source, and water to a basic or alkaline solution (eg, sodium hydroxide solution) and stirring to form a -0-¾ structure of monomer units satisfying a specific metal atomic ratio;

[II] curing the aluminosilicate monomer at a low temperature (eg, room temperature to 90 ° C.) for 3 to 24 hours under normal pressure to cause a Show 1-0-¾ polymerization reaction;

[III] washing and drying the polymerized aluminosilicate particles; And

[IV] crushing the dried aluminosilicate particles to control the particle size distribution.

By adjusting the reactants and the type, the molar ratio of the reactants, the reaction conditions and the like applied to the formation of the monomer unit in the above production method to meet the above-mentioned characteristics 2019/164154 1 »（： 1 ^ 1 {2019/001383

Aluminosilicate particles can be obtained. Preferably, the aluminosilicate particles satisfying the above-mentioned characteristics are ( ₃ ) 70

Obtaining a reaction solution having a pH of 6 to 10 containing an aluminosilicate salt by neutralization of an alkaline silicon source and an acidic aluminum source under the following temperature; Washing the non-aluminosilicate salts to obtain aluminosilicate particles; And (0) drying the aluminosilicate particles. In particular, in the production method, the neutralization reaction is 70

It is carried out at a temperature exceeding 95 or less, wherein the reaction solution formed by the neutralization reaction has a hydrogen ion concentration of pH 6 to M Table 10, thereby exhibiting excellent dispersibility in the rubber composition while improving workability and productivity in the rubber molding process. Aluminosilicate particles may be provided that allow for the expression of.

The aluminosilicate particles provided by the production method can be preferably applied as a rubber reinforcing material added to the rubber composition for a tire.

In this preparation method, the silicon source is an alkaline solution of greater than 11 7 containing a water soluble silicone salt.

As the water-soluble silicone salt, a silicone compound capable of exhibiting an alkalinity of greater than 1 3/4 may be used without particular limitation. Preferably, the water-soluble silicone salt may be at least one compound selected from the group consisting of sod silicate (^ ¾¾0 ₃ ) and potassium silicate (¾¾0 ₃ ). In the production method, the aluminum source is an acidic solution of less than 1 line containing a water-soluble aluminum salt.

As the water-soluble aluminum salt in an aqueous solution

Aluminum compounds that can exhibit an acidity of less than 7 can be used without particular limitation. Preferably, the water-soluble aluminum salt is aluminum chloride 1 (part ₃ ), aluminum nitrate ((1 ¾) ₃ ), aluminum monoacetate (0) ₂ ¾¾0¾), aluminum diacetate ^ 0cin ([¾ [ 0 ₂ ） 2）, aluminum triacetate (Cho (（¾ (： 0 ₂ ) ₃ ), aluminum sulfate (New 2 (50 ₄切) and aluminum potassium sulfate (C. 50 ₄ ) 2) The above compound may be sufficient. More preferably, 2019/164154 1 »（： 1 ^ 1 {2019/001383

The use of aluminum nitrate, aluminum potassium sulphate or mixtures thereof as the water soluble aluminum salt may be advantageous in that the aggregation of the particles can be minimized during the recovery of the aluminosilicate particles. The neutralization reaction is performed by mixing the alkaline silicon source and the acidic aluminum source, whereby a reaction solution containing an aluminosilicate salt as a solid is obtained.

In particular, the neutralization reaction is

It is preferable to carry out under the following temperature.

Specifically, the neutralization reaction is

Greater than or equal to 75

Or 80 or more; And 95

Or below 90

Or at or below 85 X :. More preferably, the neutralization reaction is 75

To 90 ° to 10 °.

When the temperature of the neutralization reaction is too low, inorganic components including the silicon source and the aluminum source are aggregated during the neutralization reaction, so that the reaction does not proceed uniformly. Therefore, it becomes difficult to control the particle size of the aluminosilicate particles finally obtained after the neutralization reaction, and the particles are tightly aggregated to form huge secondary particles, and as a result, particles having a target rubber reinforcing effect cannot be obtained. Therefore, the neutralization reaction is 70

It is preferably carried out under temperatures above.

However, when the execution temperature of the neutralization reaction is too high, there is a fear that the reaction efficiency is lowered due to the boiling phenomenon of the solvent. Therefore, the neutralization reaction is preferably carried out under the following temperature.

In the neutralization reaction, the mixing ratio of the silicon source and the aluminum source is different from each other. And a reaction solution which is a product of the neutralization reaction.

It may be determined in consideration of the range.

In particular, according to an embodiment of the invention, the reaction solution is a product of the neutralization reaction

It is preferable to have a hydrogen ion concentration.

The hydrogen ion concentration of the reaction solution

If it is less than 6, it becomes difficult to control the particle size of the aluminosilicate particles and the size of the particles 2019/164154 1 »（： 1 ^ 1 {2019/001383

Overall, it may not be possible to achieve the targeted rubber reinforcement effect.

Furthermore, of the reaction solution

The aluminosilicate particles finally obtained represent

Affect In addition, the pH represented by the aluminosilicate particles has an influence on scorch time (8 (: Lee: 0: 11 acid 11½)) in the process of blending the particles with the rubber composition.

The scorch time refers to the time taken to start the thermosetting of the rubber composition in the rubber molding process. In general, since the rubber composition flows out of the mold after the thermosetting of the rubber composition starts and molding such as a press becomes difficult, proper scorch time is required to secure workability and productivity.

By the way, the aluminosilicate particles represent

If it is too low or too high, it is difficult to secure proper scorch time during the rubber molding process, and the workability and productivity of the rubber molding may be deteriorated, such as the addition of a separate heat curing retardant or additional measures to prevent the scorch.

For example, the aluminosilicate particles represent

When low, the scorch time slows down when rubber is mixed,

If it is too high, the scorch time can be dramatically faster.

Specifically, the pH of the particles greatly affects the reactivity of the components mixed together in the rubber compounding process, and in particular, promotes or alleviates the rate at which the amine-based functional groups react. That is, of the particles

In this case, the reactivity of the amine group is decreased, and when the pH of the particles is high, the reactivity of the amine group is promoted. If the reactivity is too accelerated in the rubber compounding process, there is a problem in forming the product, and if the reactivity is too low, productivity may be reduced.

Therefore, in order to ensure an appropriate scorch time in the rubber molding process in which the aluminosilicate particles are applied as a rubber reinforcing material, the neutralization reaction is carried out using a reaction solution containing an aluminosilicate salt.

It is preferably carried out to have a hydrogen ion concentration.

In the washing step, the aluminosilicate salt as a solid is recovered from the reaction solution obtained through the neutralization reaction, dispersed in water such as distilled water and deionized water, and washed several times to obtain aluminosilicate particles. 2019/164154 1 »（： 1 ^ 1 {2019/001383

Then, the step of drying the washed aluminosilicate particles is performed. The drying may be performed for 1 to 48 hours at a temperature of 20 to 150 ^° (：).

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

II. Rubber composition for tire

According to another embodiment of the invention, there is provided a rubber composition for a tire comprising the above-described aluminosilicate particles as a rubber reinforcing material.

To the method described above _. Aluminosilicate particles prepared by the above and satisfying the above properties can exhibit improved reinforcement effect according to good dispersibility in the rubber composition while also allowing for improved workability and productivity.

In addition, the aluminosilicate particles have excellent mechanical properties (for example, excellent durability, abrasion resistance, compressive strength, etc.) compared to rubber reinforcement materials that do not satisfy the above-described properties as the formation of micropores inside the particles is suppressed. Can be represented.

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

For example, the diene elastomer may be a natural rubber, polybutadiene, polyisoprene, butadiene / styrene copolymer, butadiene / isoprene copolymer, butadiene / acrylonitrile copolymer, isoptene / styrene copolymer, and butadiene / styreneten / isoprene copolymer It may be one or more compounds 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 aluminosilicate particles and the diene elastomer. The coupling agent may include conventional components such as polysiloxane compounds without particular limitation.

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

【Effects of the Invention】

The aluminosilicate particles included in the rubber reinforcing material according to the present invention 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 thus are provided as rubber reinforcing materials to the rubber composition for tires. It can be preferably applied.

【Brief Description of Drawings】

1 is aluminosilicate particles according to the Examples and Comparative Examples

It is a graph showing the result of X-ray diffraction analysis.

[Specific contents for carrying out invention]

Hereinafter, preferred embodiments will be presented to assist in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto. Example 1

After mixing 0.005 M sodium silicate (Na ₂ Si0 ₃ ) aqueous solution and 0.005 M aluminum nitrate (A1 (N0 ₃ ) ₃ ) aqueous solution at 80 ^° C. to pH 6.2, use an overhead stirrer The neutralization reaction was performed by mixing at rpm for 10 minutes. The neutralization reaction gave a reaction solution containing aluminosilicate salt (pH 6.2).

The aluminosilicate salt was added to distilled water at room temperature, stirred for 12 hours, and washed by centrifugation.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Example 2

0.005 M aqueous solution of 0.005 M sodium silicate (Na ₂ Si0 ₃ ) ^at 80 ^° C An aqueous solution of aluminum potassium sulfate (A1K (S0 ₄ ) ₂ ) was mixed to pH 6.2, followed by mixing for 10 minutes at 500 rpm using an overhead stirrer to carry out a neutralization reaction. The neutralization reaction gave a reaction solution (pH 6.2) containing the aluminosilicate salt.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Example 3

After mixing the aqueous solution of 0.005 M sodium silicate (Na ₂ Si0 ₃ ) and the aqueous solution of 0.005 M aluminum nitrate (A1 (N0 ₃ ) ₃ ) ^at 75 ^° C to pH 6.2, using an overhead stirrer The neutralization reaction was performed by mixing at 500 rpm for 10 minutes. The reaction solution (pH 6. ² ) containing the aluminosilicate salt was obtained by the said neutralization reaction.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Example 4

After mixing the aqueous solution of 0.005 M sodium silicate (Na ₂ SiC¾) and the aqueous solution of 0.005 M aluminum nitrate (A1 (N0 ₃ ) ₃ ) ^at 85 ^° C to pH 6.2, 500 rpm using an overhead stirrer The neutralization reaction was performed by mixing for 10 minutes at. By the neutralization reaction, a reaction solution containing aluminosilicate salt (pH 6.2) was obtained.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Example 5

After mixing 0.005 M sodium silicate (Na ₂ Si0 ₃ ) and 0.005 M aluminum nitrate (A1 (N0 ₃ ) ₃ ) aqueous solution to pH 6.2 at 90 ° C., using an overhead stirrer The neutralization reaction was performed by mixing at rpm for 10 minutes. By the neutralization reaction, a reaction solution containing aluminosilicate salt (pH 6.2) was obtained.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Comparative Example 1

23 silver KOH (Daejung chemicals & metals) and 27 silver colloidal silica (Ludox HS 30 wt%; Sigma-Aldrich 62 m ^ in distilled water to dissolve completely. The mixture was mixed at 800 rpm for 40 minutes using an overhead stirrer.

This was cured for 4 hours at a temperature of 70 ^° C.

The solid product formed by curing was put in 90 distilled water, stirred for 12 hours, and washed until reaching a pH of 7 by centrifugation.

The washed solid product was dispersed in distilled water to form a colloidal solution and then centrifuged for 5 minutes at 1500 rpm to settle the unreacted source. This yielded a supernatant in which the aluminosilicate particles were dispersed and discarded the unreacted source that had settled.

The supernatant in which the aluminosilicate particles were dispersed was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles.

Comparative Example 1 is a method of synthesizing aluminosilicate using metakaolin in an aqueous solution of a strong base (pH 14), which is not only complicated in the synthesis process but also requires high cost in forming a strong base atmosphere. do. Comparative Example 2

After mixing the aqueous solution of 0.005 M sodium silicate (Na ₂ Si0 ₃ ) and the aqueous solution of 0.005 M aluminum nitrate (A1 (N0 ₃ ) ₃ ) ^at 30 ^° C. to pH 6.2, using an overhead stirrer The neutralization reaction was performed by mixing at rpm for 10 minutes. The neutralization reaction gave a reaction solution (pH 6.2) containing the aluminosilicate salt.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Comparative Example 3

After mixing the aqueous solution of 0.005 M sodium silicate (Na ₂ Si0 ₃ ) and the aqueous solution of 0.005 M aluminum nitrate (A1 (N0 ₃ ) ₃ ) ^at 70 ^° C. to pH 6.2, using an overhead stirrer The neutralization reaction was performed by mixing at rpm for 10 minutes. By the neutralization reaction, a reaction solution containing aluminosilicate salt (pH 6.2) was obtained.

The washed aluminosilicate salt was dried in an oven at 70 ^° C. for 24 hours to finally obtain aluminosilicate particles. Comparative Example 4

Silica particles (ULTRA® L ^® 7000 GR) sold by Evonik industries were prepared. Preparation Example 1

In a closed mixer, 137 g of diene elastomer mixture (SSBR 2550, LG Chemical), 70 g of aluminosilicate particles according to Example 1 and 11.2 silver silane as reinforcement A coupling agent (polysiloxane system) was added. This was mixed ^at 150 ^° C. for 5 minutes and then mixed for 90 seconds with the addition of sulfur and vulcanization accelerators.

The resulting mixture was extruded in the form of a sheet of thickness 2-3, which was vulcanized at 160 ^° C. to obtain a rubber molding. At this time, the vulcanization time was adjusted with reference to the data immediately obtained by using the moving die rheometer (MDR) at 160 ^° C. Preparation Example 2

A rubber composition and a 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 the aluminosilicate particles of Example 1 as the reinforcing material. Preparation Example 3

A rubber composition and a molded product were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Example 3 were added instead of the aluminosilicate particles of Example 1 as a reinforcing material. Preparation Example 4

A rubber composition and a molded product were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Example 4 were added instead of the aluminosilicate particles of Example 1 as a reinforcing material. Preparation Example 5

A rubber composition and a molded product were obtained in the same manner as in Preparation Example 1, except that the aluminosilicate particles according to Example 5 were added instead of the aluminosilicate particles of Example 1 as a reinforcing material. Preparation Example 6

Same as Preparation Example 1, except that the aluminosilicate particles according to Comparative Example 1 were added instead of the aluminosilicate particles of Example 1 as the reinforcing material. 2019/164154 1 ^» （： 1 ^ 1 {2019/001383

The rubber composition and the molded product were obtained by the method. Preparation Example 7

A rubber composition and a molded product 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 the aluminosilicate particles of Example 1 as the reinforcing material. Preparation Example 8

A rubber composition and a molded product 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 the aluminosilicate particles of Example 1 as the reinforcing material. Preparation Example 9

A rubber composition and a molded product were obtained in the same manner as in Preparation Example 1, except that silica particles according to Comparative Example 4 were added instead of the aluminosilicate particles of Example 1 as the reinforcing material. Test Example 1

X-ray fluorescence (XRF, Rigaku zsx primus II, wavelength dispersive type) was used to confirm the composition of the particles according to the examples and comparative examples. The XRF measurement was performed using the Rh target, and was measured by mounting the particle powder in a holder of 30_ diameter.

Table 11

Referring to Table 1, it was confirmed that the aluminosilicate particles of Comparative Example 1 had the above eight values that did not satisfy the preferred range. Test Example 2

Using an X-ray diffractometer (Bmker AXS D4-Endeavor XRD), an X-ray diffraction analysis was carried out on the particles of the above examples and comparative examples under an applied voltage of 40 kV and an applied current of 40 iso.

The range of 20 measured was 10 ^degrees- 90 ^degrees, and it scanned at the interval of 0.05 ^degrees . In this case, a variable divergence slit 6 mm _/ slit was used, and a large PMMA holder (diameter = 20 mm) was used to eliminate background noise caused by the PMMA holder.

The data up to the peak of about ^ 9 ^° half-value width of a peak of 20 in the 20 ^° to 37 ^° range on the graph (full width at half maximum, FWHM ) obtained by the X- ray diffraction was calculated.

Table 2

Test Example 3

(1) Scanning electron microscopy (SEM) was used to measure the average primary particle diameter of the particles according to the examples and comparative examples.

In the measurement of the average primary particle diameter, the particle diameter means the Feret diameter and was calculated as an average value obtained by measuring the diameters of particles in various directions. Specifically, after obtaining an SEM image in which 100 or more particles are observed, after plotting a random straight line, the primary particle diameter of the particle can be calculated by the length of the straight line, the number of particles included in the straight line, and the magnification. The average primary particle diameter was calculated | required as 20 or more.

(2) Nitrogen adsorption / desorption Brunner-Emit-Teller specific surface area (S _BET ) and 2 for particles according to the examples and comparative examples using a specific surface area analyzer (BEL Japan Inc., BELSORP-max). External specific surface area (S _EXT ) excluding micropores less than ran was measured. From the S _BET , the volume (Vmicr _O ) of micropores having a pore size of less than 2 nm was calculated by a t-plot method.

In the measurement of this characteristic, the particles of interest were pretreated by heating for 4 hours under 250 ^° G, the temperature of the air oven mounted to the analyzer was maintained at 40 ^° C. Table 3

Referring to Table 3, it is confirmed that in the above examples, aluminosilicate particles having an average primary particle size of 20_ and excellent specific surface area characteristics can be obtained without formation of aggregates. Test Example 4

A solution containing 1% by weight of particles was prepared by adding particles of 0.1 silver according to the Examples and Comparative Examples to 10 ml of distilled water. The solution was sonicated at 100% pulsed ultrasonication equipment at 90% power for 5 minutes. At this time, the energy due to sonication acts as a physical energy similar to the mechanical force applied to the composition when the rubber composition is blended, thereby indirectly confirming the size distribution of aggregates (aggregates) present in the rubber composition.

The obtained dispersion was sonicated for 2 minutes using a particle size analyzer (HORIBA, model name LA-960, laser diffraction type), and then the size distribution of the aggregates of the particles and the volume average particle diameter (D _mean , m) , Geometric standard deviation (Std. Dev., Im), and cumulative particle diameters (Dio, D50, D90, _) of the volume distribution were instantaneated.

Table 4

Referring to Table 4, it is confirmed that the secondary particles of the aluminosilicate particles according to the embodiments exhibit a particle size distribution in a suitable range as a rubber reinforcing material. Test Example 5

The viscoelasticity meter (DMTS 500N, Gabo, Germany) was used to measure the dynamic loss factor (tan 5) for rubber moldings according to the examples under dynamic strain 3% and static strain 3%. The measured values were normalized based on the values of the rubber moldings of Preparation Example 9 and shown together.

For reference, the dynamic loss factor (tan 5 @ 0 at TC is associated with the wet grip characteristics of the tire, and the higher the absolute value is, the better the wet grip characteristic is, and the dynamic loss at 60 ^° C. The coefficient (tan 8 @ 60 ^° C) is associated with the rolling resistance properties of the tire, and the lower the absolute value, the better the rolling resistance properties.

Table 5

Referring to Table 5, the rubber molding according to Preparation Examples 1 to 5 has excellent rolling resistance characteristics and wet grip in comparison with the rubber molding of Preparation Examples 6 and 9. It was confirmed to exhibit characteristics.

In Production Example 7 and Production Example 8, molding of the rubber molded article (sheet) was impossible, and thus physical properties thereof could not be measured. Test Example 6

For the rubber moldings of the above production examples, the abrasion resistance index was determined by using the abrasion tester (Bareiss GmbH) to immediately determine the mass loss and specific gravity of the material to be tested and the reference material according to the standard of DIN ISO 4649. Was calculated and the wear resistance was evaluated.

The wear resistance index was calculated as ｛[(loss weight of reference material) X (specific gravity of reference material)] / [(loss weight of test material) X (specific gravity of test material)] 물질 父 100 (reference material : neutral rubber）.

Table 6

Referring to Table 6, the rubber molded article according to Preparation Examples 1 to 5

In comparison with the rubber molding of 6, it was confirmed that it shows remarkably excellent wear resistance.

Referring to Tables 5 and 6 above, the rubber molding of Preparation Example 6 exhibited excellent rolling resistance and wet grip characteristics compared to the rubber molding of Preparation Example 9, but was found to have a significantly low wear resistance.

Claims

[Claim 1] As a rubber reinforcing material comprising amorphous aluminosilicate particles having a composition of the following formula (1); The aluminosilicate particles have a full width at half maximum (FWHM) of 5 ° to 7 in the range of 23 ° to 37 ° of 20 in a data graph obtained by X-ray diffraction (XRD). Rubber reinforcement having a maximum peak intensity (I max) in the range of 20 to 23 ° and less than 26 °:

[Formula 1]

[(MaAlxOsx) · (Si _y 0 ₂ y)]-m (H ₂ 0)

In Chemical Formula 1,

a ³ 0, x 0 0, y ñ 0, and m ³ 0,

a / x <1.

2,

3.0 <y / x <20.0.

[Claim 2]

The method of claim 1,

The aluminosilicate particles,

Having a Brunner-Emmett-Teller specific surface area (S _BET ) of 110 to 260 m ² / g and an external specific surface area (S _E x _T ) of 90 to 220 m ² / g by nitrogen adsorption / desorption analysis,

The volume of the micropores (Vmi _Cro ) having a pore size of less than 2 nm calculated by the t-plot method from the S _BET is less than 0.05 cmVg,

Rubber stiffeners. [Claim 3]

The method of claim 1,

The aluminosilicate particles, 1 to 25 _ volume-average particle size (Dmean) of measured under distilled water, 1 to 20 the geometric standard deviation of _ (geometric standard deviation), and 1 to 50 _ 90% cumulative particle diameter of the (D ₉₀ With a secondary particle size distribution,

Rubber reinforcement.

[Claim 4]

A rubber composition for tires comprising the rubber reinforcement according to claim 1.

[Claim 5]

The method of claim 4, wherein

A rubber composition for a tire comprising the rubber reinforcing material and at least one diene elastomer.

[Claim 6]

The method of claim 5,

The diene elastomers include natural rubber, polybutadiene, polyisoprene, butadiene / styrene copolymers, butadiene / isoprene copolymers, butadiene / acrylonitrile copolymers, isoptene / styrene copolymers, and butadiene / styreneten / isoprene copolymers. At least one compound selected from the group consisting of, Rubber composition for the tire.