KR100902392B1 - Bead Wire Coating Rubber Composition with Improved Adhesion - Google Patents

Abstract

The present invention relates to a bead wire coated rubber composition with improved adhesion, and more particularly in a bead wire coated rubber composition, limestone saturation factor (SLF) 93-95%, silica modulus (SM) 2.4- The present invention relates to a bead wire-coated rubber composition having improved adhesion by including an inorganic adhesive containing 2.5% and 1.4 to 1.7% of iron modulus (IM).

Description

Beadwire coating rubber composition with improved adhesion force

The present invention relates to a bead wire coated rubber composition with improved adhesion, and more particularly in a bead wire coated rubber composition, limestone saturation factor (SLF) 93-95%, silica modulus (SM) 2.4- The present invention relates to a bead wire-coated rubber composition having improved adhesion by including an inorganic adhesive containing 2.5% and 1.4 to 1.7% of iron modulus (IM).

In general, the exterior of a tire for a car is a bead part closely coupled to the outer circumference of the rim of a car wheel, a tread part that contacts the ground when the vehicle moves, a shoulder that connects the bead part and the tread part and serves as a side wall of the tire; It consists of sidewalls. In addition, the inside of the tire is provided with a belt layer inside the tread portion for the reinforcement of the tire, the bead portion is provided with a bead wire, which is a reinforcing steel wire, and at the same time has a structure in which carcass is embedded along the entire tire cross section.

Among the components constituting the tire, the bead portion serves to maintain the complete wheel shape on the wheel by the air pressure injected into the tire in contact with the rim of the wheel. The bead part embeds the bead wire inside the rubber layer constituting the bead part for strength reinforcement, and the bead wire has a structure in which bead wires coated with bead wire coated rubber are laminated.

The rubber coating the bead wire is adhered to the bead wire to prevent moisture penetration into the bead portion, to prevent the individual bead wires from rubbing against each other, and to maintain the stacked bead wire structure even when driving. To perform. As a result, the bead wire coating rubber serves to secure the stability of the tire by preventing damage and deformation of the bead portion. Therefore, the adhesion of the bead wire coated rubber composition coating the bead wire is a very important factor in performing the role of the bead portion in the tire.

Bead wire coating rubbers used in automobile tires, especially heavy duty tires such as trucks and buses, are required to have excellent rigidity and adhesion in order to prevent the cord layers of the bead wires from collapsing due to vibrations and heat generated while driving the vehicle.

In order to meet such a requirement, Korean Patent No. 10-0411015 uses a fatty acid zinc salt A73A and carbon black having a large surface area instead of the cobalt complex used in the bead wire coating composition for a radial tire having excellent adhesion to the bead wire. A method of providing a bead wire coated rubber composition is provided. However, when the fatty acid zinc salt is used in the bead wire coated rubber composition, the fatigue characteristics of the bead wire coated rubber composition are reduced due to the characteristics of the tire used under high load / high speed conditions for a long time, thereby reducing the durability of the tire bead part.

Therefore, it is necessary to develop a bead wire coated rubber rubber having stiffness and adhesive strength that can maintain the adhesion between the bead wires even in long-term use.

The present invention relates to a rubber composition coated on the bead wire of the bead portion, in particular bead wire coated rubber composition which can maintain the rigidity of the bead portion by improving the adhesion to the bead wire, a bead wire coated with a rubber made of the coating composition, To provide a tire comprising a bead wire coated with a rubber made of the coating composition.

In the bead wire coated rubber composition, limestone saturation (Lime Saturation Factor, LSF) 93-95%, silica modulus (SM) 2.4-2.5%, iron modulus (Iron Modulus, IM) 1.4-1.7% It is intended to provide a tire including a bead wire coated rubber composition comprising an inorganic adhesive comprising an improved adhesive strength, a bead wire coated with a rubber made of the coating composition, and a rubber coated bead wire made of the coating composition.

According to the present invention, the bead wire coated rubber composition, which can maintain the rigidity of the bead portion by improving the adhesion with the bead wire, the bead wire coated with the rubber made of the coating composition, the rubber coated bead wire made of the coating composition It is possible to provide a tire that includes.

The present invention shows an improved bead wire coating rubber composition.

The present invention is a bead wire coating rubber composition, Lime Saturation Factor (LSF) 93-95%, Silica Modulus (SM) 2.4-2.5%, Iron Modulus (Iron Modulus) IM) A bead wire coated rubber composition having improved adhesion, including 0.5 to 10 parts by weight of an inorganic adhesive having 1.4 to 1.7%.

As the raw material rubber in the bead wire coated rubber composition of the present invention, any one or more rubbers selected from the group of natural rubber and synthetic rubber may be used.

In the bead wire-coated rubber composition of the present invention, when the raw rubber is a mixed rubber in which natural rubber and synthetic rubber are mixed, natural rubber and synthetic rubber may be mixed in a weight ratio of 1: 9 to 9: 1. have.

Synthetic rubber that can be used as a component of the raw material rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, Silicone rubber, nitrile rubber, hydrogenated nitrile rubber, nitrile butadiene rubber (NBR), modified nitrile butadiene rubber, chlorinated polyethylene rubber, styrene ethylene butylene styrene (SEBS) rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) rubber , Hypalon rubber, chloroprene rubber, ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethyl styrene butyl rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy Isoprene rubber, ethylene propylene maleate, carboxylic acid nitrile butadiate It may be at least one selected from the group consisting of rubber and BIMS (brominated polyisobutyl isoprene-co-paramethyl styrene).

In the bead wire-coated rubber composition of the present invention, when the inorganic adhesive is used in an amount of less than 0.5 parts by weight based on 100 parts by weight of the raw material rubber, a rubber composition that satisfies the purpose of the present invention cannot be obtained. There is a fear that the physical properties of the rubber may be reduced without a clear improvement of the adhesion. Therefore, the inorganic adhesive in the bead wire coated rubber composition of the present invention is preferably used 0.5 parts by weight to 10 parts by weight based on 100 parts by weight of the raw material rubber.

In the inorganic adhesive, lime saturation factor (LSF) of 93-95%, silica modulus (SM) of 2.4-2.5%, iron modulus (Iron Modulus, IM) of 1.4-1.7% can be used. have.

In the inorganic adhesive, the cement has a limestone saturation factor (LSF) of 93 to 95%, silica modulus (SM) of 2.4 to 2.5% and iron modulus (IM) of 1.4 to 1.7%. ) Can be used.

Lime saturation degree, silicic acid rate and iron rate of the inorganic adhesive in the above can be represented by the following formula (1) to formula (3).

Lime Saturation Factor (LSF) = CaO / (2.8SiO ₂ + 1.18Al ₂ O ₃ + 0.65Fe ₂ O ₃ ) × 100 ...... (1)

Silica Modulus (SM) = SiO ₂ / (Al ₂ O ₃ + Fe ₂ O ₃ ) × 100 ...... Equation (2)

Iron Modulus (IM) = Al ₂ O ₃ / Fe ₂ O ₃ × 100 ...... Equation (3)

Among the properties of the inorganic adhesive, lime saturation (LSF) is the most important, and when the LSF is increased 3CaO.SiO ₂ (C ₃ S) to increase the compressive strength, the inorganic adhesive with a high compressive strength of the bead wire It can exhibit excellent rigidity when bonding.

In the inorganic adhesive used in the present invention, a specific surface area (Blain) of 3,200 to 3,300 cm 2 / g and 44 µm residues in addition to the above-mentioned lime saturation, silicic acid ratio and iron ratio can be used.

The bead wire coated rubber composition of the present invention is a carbon black, syndiotactic-1,2-polybutadiene (syndiotactic-1,2-) as a reinforcing filler (hereinafter, abbreviated as filler) to improve the reinforcement of the rubber composition. 30 to 100 parts by weight of the raw material rubber, any one or more selected from the group consisting of polybutadiene (SPB), silica, titanium oxide, clay, layered silicate, and tungsten 95 parts by weight can be used.

If the filler is used in an amount of less than 30 parts by weight based on 100 parts by weight of the raw material rubber, reinforcement improvement is insignificant, and when used in excess of 95 parts by weight, the physical property of the rubber composition may be reduced due to the use of an excess filler. Therefore, it is preferable to use the filler of 30 to 95 parts by weight of the steel cord adhesive rubber composition of the present invention based on 100 parts by weight of the raw material rubber.

Among the above fillers, syndiotactic-1,2-polybutadiene (SPB) may have a diameter of 0.01 to 0.1 µm and a specific surface area of 80 to 90 m ² / g.

Among the above fillers, syndiotactic-1,2-polybutadiene (SPB) may have a diameter of 1 to 10 µm and a specific surface area of 100 to 120 m ² / g.

Among the fillers described above, carbon black may have a particle diameter of 20 to 30 nm.

Among the above fillers, carbon black may be one having an iodine adsorption value of 70 to 90 mg / g.

Among the above fillers, carbon black may have a DBP adsorption value of 80 to 120 mg / 100 g.

Of the above fillers, carbon black may have a particle diameter of 20 to 30 nm, an iodine adsorption value of 70 to 90 mg / g, and a DBP adsorption value of 80 to 120 mg / 100 g.

Among the above fillers, silica may be one having a BET adsorption value of 160 to 180 (m ² / g).

Among the above fillers, silica may be one having a DBP adsorption value of 190 to 210 (ml / 100g).

Among the fillers, silica may be one having a micropore volume of 0.015 to 0.020 (cc / g).

Among the fillers, silica may be one having a BET adsorption value of 160 to 180 (m ² / g), a DBP adsorption value of 190 to 210 (ml / 100g), and a micropore volume of 0.015 to 0.020 (cc / g).

The present invention includes a rubber consisting of the bead wire coated rubber composition mentioned above.

The present invention includes a rubber coated bead wire made of the bead wire coated rubber composition mentioned above.

The present invention includes a tire containing a rubber coated bead wire made of the bead wire coated rubber composition mentioned above.

The tire including the rubber-coated bead wire made of the bead wire-coated rubber composition mentioned above represents any one or more selected from the group of passenger car tires, truck tires, bus tires, motorcycle tires and aircraft tires. .

In the bead wire-coated rubber composition of the present invention, the bead wire-coated rubber composition is applied under various conditions such as various components and contents. In order to achieve the object of the present invention, the bead wire-coated rubber composition is preferably used. Do.

The bead wire coated rubber composition of the present invention requires various additives such as active materials, anti-aging agents, process oils, vulcanizing agents, and vulcanization accelerators, which are used in the conventional bead wire coated rubber compositions, in addition to the above-mentioned raw rubbers, inorganic adhesives, and fillers. Depending on the choice can be used in a predetermined amount. However, these are general components used in the bead wire coating rubber composition and are not essential components of the present invention.

Hereinafter, the present invention will be described by the following examples, comparative examples and test examples. However, these are not limited to the scope of the present invention by these as an embodiment of the present invention.

<Example 1>

Styrene butadiene rubber (SBR) as a raw material rubber, 90 parts by weight of carbon black, 10 parts by weight of zinc oxide (ZnO), 5 parts by weight of cobalt stearate, pressure-sensitive adhesive (Dyphene-) based on 100 parts by weight of the raw material rubber 8318) 7 parts by weight, anti-aging agent (Kumanox-13, Kumho Petrochemical), 1 part by weight of process oil, 1 part by weight of inorganic adhesive are mixed in a Banbury mixer, mixed for 2.5 minutes at 165 ° C and released to release the rubber compound. Got it.

5 parts by weight of sulfur as a vulcanizing agent and 1.1 parts by weight of N-cyclohexyl-2-benzothiazolsulfen amide (CZ) as a vulcanizing accelerator were added to the rubber compound and 1.2 at 105 ° C. Rubber was prepared by blending for minutes.

In the carbon black, a particle diameter of 25 ± 1 nm, an iodine adsorption value of 85 ± 2 mg / g, and a DBP adsorption value of 100 ± 5 mg / 100 g were used.

In the inorganic adhesive, lime saturation factor (LSF) is 94 ± 1%, silica modulus (SM) is 2.45 ± 0.5%, iron modulus (Iron Modulus, IM) is 1.55 ± 1.5%, specific surface area ( Blain) 3,250 ± 50 cm 2 / g, 44㎛ residue used a cement of 10 ± 1%.

Table 1 below shows the components of the rubber specimens together.

<Example 2>

A rubber was manufactured in the same manner as in Example 1, except that 3 parts by weight of the inorganic adhesive was used.

<Example 3>

A rubber was manufactured in the same manner as in Example 1, except that 5 parts by weight of the inorganic adhesive was used.

Comparative Example

Except that the inorganic adhesive was not used, the rubber was prepared in the same ingredients and methods as in Example 1.

Table 1. Composition Components of Comparative Example and Example (Unit: Weight part)

Item Comparative example Example 1 Example 2 Example 3 Raw rubber (SBR) 100 100 100 100 Carbon black 90 90 90 90 Zinc oxide 10 10 10 10 Cobalt stearate 5 5 5 75 adhesive 7 7 7 7 Anti-aging One One One One Mineral adhesive - One 3 5 Process oil 6 6 6 6 Vulcanizing agent 5 5 5 5 Vulcanization accelerator 1.1 1.1 1.1 1.1

<Test Example 1>

Tensile properties such as hardness, 100% modulus, tensile strength, and elongation and physical properties such as T-Test for each rubber manufactured according to Comparative Examples and Examples were measured by ASTM-related regulations, and the results are shown below. Table 2 shows.

Table 2. Rubber Properties of Comparative Examples and Examples

Item Comparative example Example 1 Example 2 Example 3 Shore A 85 87 89 92 100% modulus (kg / cm ² ) 132 145 150 162 Tensile Strength (kg / cm ² ) 216 224 228 243 Elongation (%) 178 182 185 188 T-test (kgf) 98 102 110 118

<Test Example 2>

Each rubber prepared according to the Comparative Example and Example was coated on a bead wire, the rubber coated bead wire was applied to the bead portion of the tire of the 12R22.5 standard, and the bead portion durability of the tire was evaluated. In addition, after dispersing the 150,000km actual vehicle bead was confirmed and the results are shown in Table 3 below.

Table 3.

Item Comparative example Example 1 Example 2 Example 3 Durability (120 "BAB) Travel Time 282 hr 312 hr 322 hr 328 hr Bead Cohesion After Actual Vehicle Good (lower) Good (medium) Good (upper) Good (the top)

The rubber composition made of the rubber composition prepared by adding the inorganic adhesive of the present invention, as in the results of Test Examples 1 and 2, has a tensile property equal to or higher than that of the comparative rubber which does not use the inorganic adhesive, and further comprises the rubber composition. It can be seen that the bead portion having the bead wire coated with rubber is made durable and bead aggregated.

As described above, those skilled in the art have been described with reference to the preferred embodiments of the present invention, various modifications and changes of the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. It will be appreciated that it can be changed.

Claims (5)

In the bead wire coating rubber composition, Minerals with Lime Saturation Factor (LSF) of 93 to 95%, Silica Modulus (SM) of 2.4 to 2.5% and Iron Modulus (IM) of 1.4 to 1.7% based on 100 parts by weight of raw material rubber Bead wire coated rubber composition with improved adhesion, characterized in that it comprises 0.5 to 10 parts by weight of the adhesive. The bead wire coated rubber composition according to claim 1, wherein the inorganic adhesive has a specific surface area of 3,200 to 3,300 cm 2 / g and 44 µm residues of 10 ± 1%. The method of claim 1, wherein the filler is carbon black, syndiotactic-1,2-polybutadiene (SPB), silica, titanium oxide, clay Bead-coated rubber composition further comprises 30 to 95 parts by weight of any one or more selected from the group of clay, layered silicate and tungsten, based on 100 parts by weight of the raw material rubber. A rubber coated bead wire consisting of the rubber composition of claim 1. A tire comprising a rubber-coated bead wire made of the rubber composition of claim 1.