KR20220001669A - Rubber composite for tires equipped with antibacterial properties and tires by them - Google Patents

Abstract

The present invention discloses a rubber composition for a tire having antibacterial properties. The rubber composition for a tire having antibacterial properties according to the present invention comprises raw rubber and 0.0001 to 25 parts by weight of silver (Ag) particles and titanium dioxide (TiO_2) particle powder based on 100 parts by weight of raw rubber. Accordingly, the rubber composition for a tire having antibacterial properties according to the present invention has a strong antibacterial action against various viruses, bacteria and fungi comprising well-known viruses, mutant coronaviruses, infectious gastroenteritis viruses, Escherichia coli, influenza, and the like and thus exhibits the effect of maintaining initial physical properties of rubber for a long time.

Description

Rubber composite for tires equipped with antibacterial properties and tires by them

The present invention relates to a rubber composition for a tire having antibacterial properties and a tire therefrom, and more particularly, to various viruses, bacteria and molds including well-known viruses, mutant coronaviruses, infectious gastroenteritis viruses, E. coli, influenza, etc. The present invention relates to a rubber composition for a tire having a strong antibacterial action and antibacterial properties capable of maintaining the initial physical properties of rubber for a long period of time, and a tire by the same.

Microorganisms and viruses are harmful to humans and spread widely by being contaminated with air, water, seawater and soil, as well as industrial products, food, and clothing.

Therefore, research to prevent human diseases and damage to animals and plants by microorganisms and viruses has been conducted for a long time.

Recently, when the corona virus is infected with humans, it mainly causes respiratory symptoms such as a cold, and sometimes acts as a fatal pathogen, causing diseases.

On the other hand, since automobile tires are actively exported and imported between countries and their residues remain in the soil and aquatic ecosystems and can be related to the proliferation of microorganisms and viruses, they are processed with antibacterial or deodorization and can inhibit the growth of microorganisms or viruses over a long period of time. is needed.

Prior Documents Japanese Patent Registration Publication No. 4107900

Therefore, the technical problem to be solved by the present invention is a strong antibacterial action against various viruses, bacteria and fungi, including well-known viruses, mutant coronaviruses, infectious gastroenteritis viruses, Escherichia coli, influenza, etc., and thereby maintaining the initial physical properties of rubber for a long period of time An object of the present invention is to provide a rubber composition for a tire having antibacterial properties and a tire by the same.

In order to solve the above technical problem, the present invention comprises 0.0001 parts by weight to 25 parts by weight of the raw rubber, silver (Ag) particles, and titanium dioxide (TiO _{2 ) particle powder with respect to 100 parts by weight of the raw rubber.} To provide a rubber composition for a tire having antibacterial properties.

According to another embodiment of the present invention, the silver particles and titanium dioxide particles may have an average particle diameter of 1 nm to 100 nm.

According to another embodiment of the present invention, the silver particles and titanium dioxide particle colloid may be mixed with paraffin wax.

According to another embodiment of the present invention, it may be a microfine fiber fabric such as lyocell, aramid, polyurethane or polypropylene in which the silver particles and the titanium dioxide particle colloid form a plurality of pores as a solid support.

Meanwhile, in order to solve the above technical problem, the present invention provides a tire manufactured from the rubber composition for a tire having the above-described antibacterial properties.

The rubber composition for a tire having antibacterial properties according to the present invention and a tire therefrom have strong antibacterial action against various viruses, bacteria and fungi including well-known viruses, mutant coronaviruses, infectious gastroenteritis viruses, Escherichia coli, influenza, and the like, and thereby It exhibits the effect of maintaining the initial physical properties of rubber for a long period of time.

Hereinafter, preferred embodiments in which those of ordinary skill in the art to which the present invention pertains can easily practice the present invention will be described in detail.

However, when it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention in describing the operating principle of the preferred embodiment of the present invention in detail, the detailed description thereof will be omitted.

This is to more clearly convey the essence of the present invention by omitting unnecessary description.

In addition, since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated and described in the detailed description, which is not intended to limit the present invention to specific embodiments, and the present invention is not intended to It should be understood to include all modifications, equivalents and substitutes included in the spirit and scope.

The rubber composition for a tire having antibacterial properties according to the present invention comprises 0.0001 to 25 parts by weight _{of raw rubber, silver (Ag) particles, and titanium dioxide (TiO 2 ) particle powder based on 100 parts by weight of raw rubber.}

If the silver particles and titanium dioxide nanoparticle powder are less than 0.0001 parts by weight, it may be difficult to express antibacterial performance. Conversely, if it exceeds 25 parts by weight, the particles are agglomerated by a self-association reaction, and thus precipitation due to an increase in particle size, etc. It can be difficult to maintain homogeneity.

The silver particles and titanium dioxide particles used here have an average particle diameter of 1 nm to 100 nm, which improves dispersibility, minimizes the effect on rubber properties, and increases antibacterial properties. If less than 1 nm, mutually uniform bonding This may be difficult, and conversely, if it exceeds 100 nm, the bonding stability of the colloidal silver titanium dioxide particles may be reduced.

The silver and titanium dioxide particles are in the form of a mutually uniform mixture, and TiO ₂ as a photocatalyst can obtain sufficient energy by causing a photoexcitation reaction in the sunlight or visible light region, and is chemically stable and has excellent photoactivity. In addition, since holes (H+) generated during the photocatalytic reaction react with hydroxyl groups (OH ^- ), hydroxyl radicals have a high oxidation/reduction potential, so they can oxidize various pathogens and bacteria and have excellent sterilization power.

As the mixture of Ag and TiO ₂ , the excitation energy of _{Ag is lower than that of TiO 2} , so it acts as a medium for electron migration and enhances the surface electron excitation and separation performance of _{TiO 2 , and the resulting light induction} Holes oxidize surface hydroxyl groups, which facilitates the release of hydroxyl radicals and expands antibacterial properties.

The raw rubber may be used without limitation as long as it is a rubber that can be used for tires, and in particular, natural rubber or synthetic rubber or a mixture thereof may be used.

The silver particles and titanium dioxide particles may be provided in a colloidal form using water or alcohol as a solvent.

In addition, a mixture of the silver particles and titanium dioxide particle colloid with carbon black particle powder (Bead) or silica particle powder (Bead) may be mixed with the raw rubber.

In addition, the silver particles and titanium dioxide particle colloid can be mixed with the raw rubber as a gel blended with 0.0001 to 100 parts by weight of paraffin wax. If it is less than 0.0001, it is difficult to uniformly disperse the particles. If the concentration that can be impregnated in the Wax is saturated, the remaining amount of colloidal silver particles and titanium dioxide particles that are not impregnated may be separated or precipitated.

On the other hand, microfiber fabrics such as lyocell, aramid, polyurethane, or polypropylene that form a large number of pores as a solid support (average length 0.1 ~ 6 mm, BET 5 ~ 60, fine fibers, polymer and matrix) The silver particles and titanium dioxide particle colloid are impregnated with a mixture of a binder and paraffin oil, compressed, can

Here, emulsified asphalt can be used as the binder, and the emulsified asphalt is emulsified by mixing the emulsifier with the fine asphalt (average particle diameter of 1 to 5 μm) that is in a semi-solid state at room temperature at high speed, and the viscosity at 100° C. is 100MU or less. Asphalt is preferred.

In addition, the silver particles and the colloidal titanium dioxide particles may be added as 0.0001 to 100 parts by weight of a solid support, and if less than 0.0001 parts by weight, uniform dispersion may be difficult and antibacterial performance may be absent. Conversely, if it exceeds 100 parts by weight, impregnation , it may be difficult to prepare a masterbatch because binding is almost impossible.

On the other hand, a method for treating the silver particles and titanium dioxide particles will be described.

When silver particles or titanium dioxide particles are blended or impregnated with the liquid solvent such as water or alcohol or the solid support, it is preferable to determine the weight part to be added to the tire rubber composition according to the content weight part of silver and titanium dioxide. With respect to 100 parts by weight of the raw rubber, it is important to include 0.0001 parts by weight to 25 parts by weight of _{silver (Ag) particles and titanium dioxide (TiO 2 ) particle powder.} Because the amount to be changed is changed.

First, carbon black containing silver particles and titanium dioxide particles has a DBP of 70 to 140, N2SA 30 to 300 m 2 / g, and an aggregate size of 30 to 300 μm, generally particles smaller than 30 μm. It is difficult to disperse rubber and has a high moony viscosity, which leads to a decrease in fairness.

In addition, in the case of the silica, silver particles and titanium dioxide particles can be uniformly dispersed when N2SA is 30 to 300 m 2 / g. Conversely, when it exceeds 300 m 2 /g, silica cohesive force increases and dispersibility decreases, thereby reducing rotational resistance and abrasion performance.

Such silica can be used in an amount of 0.0001 to 100 parts by weight based on 100 parts by weight of the raw rubber. If it is less than 0.0001, the content of silver particles and titanium dioxide particles may not be the same when mixing and mixing, so it is difficult to express antibacterial performance, and vice versa. When it exceeds parts by weight, the dispersion of the particles may not be uniform upon mixing, so that the antibacterial properties may decrease.

Accordingly, it is possible to optimize the blending amount in relation to the content of colloidal silver/titanium dioxide and the specific surface area of carbon black and wax, which is the amount that can be impregnated with the antibacterial component according to the specific surface area of the carbon black or the average molecular weight of the wax This is different, the larger the specific surface area, the higher the impregnation rate, and the smaller the average molecular weight of the wax, the higher the impregnation rate.

On the other hand, an aramid fiber of particles compressed with 0.0001 to 100 parts by weight of silver particles and titanium dioxide particle powder in a mixture of microfine fiber fabrics such as lyocell, aramid, polyurethane, and polypropylene having a large number of pores, binder, and paraffin oil. The manufacturing method using the is as follows.

First, the emulsified asphalt is prepared as an emulsified asphalt having a viscosity of 100 MU or less at 100° C. by mixing an emulsifier at high speed with the fine particles (average particle diameter of 1 to 5 μm) of asphalt in a semi-solid state at room temperature.

Then, 10 to 30 wt% of the emulsified asphalt prepared above (the balance (microfine fibers, antibacterial mixture, process oil, carbon Black) 70 ~ 90 wt%) to 150 or more and 250 ℃ or less, and mix at 10 RPM or more.

Here, when it is less than 150 ° C, a large amount of ester groups of the emulsified asphalt are generated as well as no reaction with silver particles and titanium dioxide particles. fiber) occurs rapidly, making subsequent processing impossible, and when mixing at less than 10 RPM, the uniformity of the filler may not be constant.

Next, when the mixing viscosity is increased by 1.5 times or more compared to the start of mixing, the temperature is 150 ° C. or higher, and this starting point is that the moisture in the emulsified asphalt evaporates (Setting) to form a group of asphalt particles with high viscosity (Breaking). can see.

Afterwards, radicals of unsaturated asphalt are generated, and the asphalt and coal ash start to react with silver particles and titanium dioxide particles.

In order to increase dispersibility during mixing and maintain a constant temperature, 1 to 20 wt% of process oil (Process Oil, TDAE or RAE) (for the remainder including microfiber, antibacterial mixture, emulsified asphalt, carbon black, etc.) is added 10 After maintaining at RPM for 180 minutes, mix Aramid short fiber and maintain at 20 RPM at 200℃ for 5 to 10 minutes.

After that, carbon black (average diameter of agglomeration, 120 ~ 170um) 5 ~ 10 wt% (the balance (microfine fiber, antibacterial mixture, emulsified asphalt, emulsified asphalt, process oil) 90 ~ 95 wt%) is added to increase the viscosity, and then 3.0 times compared to the starting point of mixing It is dumped when the abnormal increase occurs.

If the time left to stand is prolonged, the viscosity tends to decrease, and when this abnormal reaction proceeds, radicals are generated in the mixture and the molecular structure of the reactant bonded thereto is deformed (Destruction), resulting in silver particles and titanium dioxide particles , the effectiveness of the aramid microfiber may be reduced.

After completion of the reaction, uniformly milled in a mold of 1 cm, dried at room temperature (25° C.) for 24 hours, and compressed at a pressure of 100 bar or more to prepare a width: 0.5 to 1.2 mm, length/thickness: 0.4 to 0.7 mm.

Here, when the mold thickness is compressed to 0.6 mm or less, the pellet hardness becomes 30 or more, and the compressed shape of the mixture of silver particles, titanium dioxide particles, and aramid microfine fibers is maintained, so that it can be put into the tire rubber process without unreasonableness. can

After 24 hours have elapsed, it is possible to prepare a mixture of silver particles, titanium dioxide particles, and aramid microfibers with increased resistance to deformation by reacting the remaining unsaturated asphalt through UV curing.

Examples and Comparative Examples

After preparing a tire rubber composition by mixing each component according to the composition shown in Table 1 below, preparing a specimen with each rubber composition and vulcanizing, mechanical properties, dynamic viscoelasticity, abrasion resistance, etc. were measured according to ASTM standards, The antibacterial activity was measured according to JIS Z 2801: 2010, film adhesion method, and the results are shown in Table 2 below.

Item Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 raw rubber
(SSBR/BR) 80/20 80/20 80/20 80/20 80/20 80/20 80/20 Silica (reinforcing material) 74 74 74 74 73.5 74 Silane 7 7 7 7 7 7 7 carbon black 10 10 10 10 9.5 10 10 Manufacturing 1 5 Manufacturing 2 75 One Manufacturing 3 One Manufacturing 4 One Manufacturing 5 One stearic acid 2 2 2 2 2 2 2 Terpene resin 5 5 5 5 5 5 5 Wax 2 2 2 1.5 2 2 2 antioxidant 2.5 2.5 2.5 2.5 2.5 2.5 2.5 brimstone 1.5 1.5 1.5 1.5 1.5 1.5 1.5 vulcanization accelerator 3.5 3.5 3.5 3.5 3.5 3.5 3.5

Item Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Mooney viscosity MV@125℃ 71 67 74 72 68 68 68 T05 21 17 22 21 20 20 19 MV@100℃ 91 102 89 95 94 94 97 tensile properties Hardness 70 75 72 71 71 71 71 M-300% 149 162 154 147 150 150 154 T.S. 174 164 185 180 176 176 182 E.B. 338 303 326 345 333 333 343 DMA Tg -6.6 -4.0 -7.0 -7.2 -7.0 -7.0 -6.8 Tand@0℃ 0.634 0.766 0.637 0.638 0.6259 0.6259 0.6273 Tand@70℃ 0.118 0.132 0.117 0.114 0.114 0.114 0.115 E"@22℃ 5.2 8.3 5.5 5.6 5.1 5.1 5.0 Wear Loss(g) 0.113 0.129 0.110 0.113 0.114 0.114 0.112 Index 100 86 103 100 99 99 101 strain 1 Initial number of bacteria 1.5*10^4 1.5*10^4 1.5*10^4 1.5*10^4 1.5*10^4 1.5*10^4 1.5*10^4 after 24 hours 2.5*10^4 <0.63 <0.63 <0.63 <0.63 <0.63 <0.63 antibacterial activity - 4.5 4.5 4.5 4.5 4.5 4.5 strain 2 Initial number of bacteria 1.7*10^4 1.7*10^4 1.7*10^4 1.7*10^4 1.7*10^4 1.7*10^4 1.7*10^4 after 24 hours 1.1*10^6 <0.63 <0.63 <0.63 <0.63 <0.63 <0.63 antibacterial activity - 6.2 6.2 6.2 6.2 6.2 6.2

* Number of bacteria/cm ² , antibacterial activity log (applied log because the activity value is large)

* Used strain

-Strain 1: Staphylococcus aureus ATCC 6538P

-Strain 2: Escherichia coli ATCC 8739

* Antibacterial effect: effective when the antibacterial activity is 2.0 log or more

Referring to Table 2, the tire rubber of Examples 2 to 5 has similar Mooney viscosity, workability, and abrasion performance as compared to Comparative Example 1, and when a silver particle and titanium dioxide particle mixture is applied, the antibacterial activity is 2.0 log or more. It can be seen that there is an antibacterial activity.

In Comparative Example 2, it can be seen that when silver particles and titanium dioxide particles are added in a weight ratio of 25 or more compared to raw rubber, antibacterial activity is effective, but rubber properties are remarkably reduced.

Claims (5)

A rubber composition for a tire having antibacterial properties, comprising 0.0001 to 25 parts by weight of raw rubber, silver (Ag) particles, and titanium dioxide (TiO _{2 ) particle powder based on 100 parts by weight of raw rubber.}
The method of claim 1,
The rubber composition for a tire having antibacterial properties, wherein the silver particles and titanium dioxide particles have an average particle diameter of 1 nm to 100 nm.
3. The method of claim 2,
A rubber composition for a tire having antibacterial properties, characterized in that the silver particles and the colloidal titanium dioxide particles are blended with paraffin wax.
3. The method of claim 2,
A rubber composition for a tire having antibacterial properties, characterized in that it is a microfine fiber fabric such as lyocell, aramid, polyurethane or polypropylene, in which the silver particles and titanium dioxide particle colloids are formed with a plurality of pores as a solid support.
A tire manufactured from the rubber composition for a tire having the antibacterial property according to any one of claims 1 to 4.