KR20130017456A - Highly shielding composition for tire innerliner - Google Patents

Highly shielding composition for tire innerliner Download PDF

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Publication number
KR20130017456A
KR20130017456A KR1020110079874A KR20110079874A KR20130017456A KR 20130017456 A KR20130017456 A KR 20130017456A KR 1020110079874 A KR1020110079874 A KR 1020110079874A KR 20110079874 A KR20110079874 A KR 20110079874A KR 20130017456 A KR20130017456 A KR 20130017456A
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KR
South Korea
Prior art keywords
rubber
composition
tire
weight
resin
Prior art date
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KR1020110079874A
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Korean (ko)
Inventor
강유신
주용태
조현철
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현대자동차주식회사
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Priority to KR1020110079874A priority Critical patent/KR20130017456A/en
Publication of KR20130017456A publication Critical patent/KR20130017456A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A high shielding composition for a tire inner-liner is provided to manufacture excellent tire inner-liner with excellent shielding property, to reduce the thickness of the tire inner-liner, and to reduce the weight of a tire. CONSTITUTION: A high shielding composition for a tire inner-liner is obtained by mixing 5-60 weight% of plastic resin, 30-90 weight% of rubber resin, and 3-60 weight% of additive. The plastic resin is a single rubber or a mixture rubber of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinylchloride, polyamide, polyphenylene sulfide, polyketone, ethylene vinyl alcohol and/or polytetrafluoroethylene. [Reference numerals] (AA) Measuring raw materials; (BB) Manufacturing CMB; (CC) Roll mixing milling rubber and plastic<introducing additives such as carbon black, oil, stearic acid, zinc oxide, and etc>(temperature of the plastic melting point or more); (DD) Manufacturing FMB; (EE) Introducing a vulcanizing and curing agent and a promoter

Description

Highly Shielding Composition for Tire Innerliner

The present invention relates to a high shielding tire composition having excellent air permeation performance made by mixing plastic and rubber.

Recently, due to the light weight of automobiles, low specific gravity and high performance characteristics of rubber materials used in tire manufacturing are required, and the development of materials with low specific gravity or excellent physical properties compared to existing materials while maintaining the mechanical properties of rubber materials for existing tires Research is ongoing.

In particular, research is being actively conducted on the polymer composite composition having improved air permeability applied to the inner liner part that maintains the function of maintaining the tire pressure inside.

Until now, the material used for tire inner liner is butyl rubber, which is known to have excellent air permeability. Among these, halogenated butyl rubber is used, which has better air permeability, and is easily bonded with other rubbers. Commonly used halogenated rubbers include chlorobutyl and bromobutyl. The halogenated butyl rubber is applied in blend with natural rubber, and a specific tire manufacturer sometimes applies butyl rubber to the inner liner. However, conventional halogenated butyl rubber has a problem in that air permeability is not excellent. In addition, when a tire finished product is made of conventional halogenated butyl rubber, there is a problem in that the thickness of the inner liner becomes thick, making it difficult to reduce the weight of the entire weight.

The present invention provides a high shielding resin composition for a tire kneaded by mixing 5 to 60% by weight of a plastic resin, 30 to 90% by weight of a rubber resin and 3-60% of an additive.

Other objects and advantages of the present invention will become apparent from the following detailed description, claims and drawings.

According to one aspect of the present invention, the present invention provides a high shielding resin composition for a tire kneaded by mixing 5 to 60% by weight of a plastic resin, 30 to 90% by weight of a rubber resin and 3-60% of an additive.

The features and advantages of the present invention are summarized as follows.

(i) A tire inner liner having excellent shielding property can be manufactured by mixing rubber and plastic.

(ii) When manufacturing a tire inner liner comprising the composition of the present invention, it is possible to thin the material, thereby reducing the weight of the entire tire.

1 is a schematic diagram showing an approximate procedure for preparing a composition of the present invention.

According to one aspect of the present invention, the present invention provides a high shielding resin composition for a tire kneaded by mixing 5 to 60% by weight of a plastic resin, 30 to 90% by weight of a rubber resin and 3-60% of an additive.

According to a preferred embodiment of the present invention, the plastic resin is PE (Polyethylene), PP (Polypropylene), PS (Poly Styrene), PET (Polyethylene terephthalate), PEN (Polyethylene naphthalate), PC (Poly Carbonate), PVC (Poly Polyvinylchloride (PA), polyamide (PA), polyphenylene sulfide (PPS), polyketone (PK), ethylene vinyl alcohol (EVOH) or polyethylene (Polytetrafluoroethylene) alone or in combination of two or more.

According to a preferred embodiment of the present invention, the rubber resin is normal butyl, chlorobutyl, bromo butyl, NBR (acrylonitrile-butadiene rubber), EPDM (ethylene propylene diene rubber), ACM (acrylic rubber), AEM (ethylene Acrylic rubber), SBR (styrene-butadiene rubber), BR (butadiene rubber), CR (chloroprene rubber), CSM (chlorosulfonated polyethylene rubber), ECO (epichlorohydrin rubber), natural rubber, fluorine rubber or Silicone rubber is a single or mixed rubber of two or more.

According to a preferred embodiment of the invention, the additive is carbon black, stearic acid, zinc oxide, magnesium oxide or process oil alone or in admixture of two or more.

According to a preferred embodiment of the invention, the kneading is kneading at a temperature above the melting point of the plastic resin.

According to a preferred embodiment of the present invention, an additive, a vulcanizing agent, or an accelerator is added to the high shielding resin composition for tires alone or after two or more additional vulcanization treatments.

According to a preferred embodiment of the present invention, there is provided a tire innerliner comprising the composition prepared by the above method.

Hereinafter, the present invention will be described in more detail.

The present invention is a technology for blending plastic resin and rubber to blend a material with excellent shielding performance. The plastic material used in the blending is PE (Polyethylene), PP (Polypropylene), PS (Poly Styrene), PET (Polyethylene terephthalate), PEN (Polyethylene naphthalate), PC (Poly Carbonate), PVC (Poly Vinylchloride), PA (Polyamide), PPS (Polyphenylene Sulfide), PK (Polyketone), EVOH (Ethylene Vinyl Alcohol), PTFE (Polytetrafluoroethylene), etc. The material is butyl rubber (normal butyl, chlorobutyl, bromo butyl), NBR (acrylonitrile-butadiene rubber), EPDM (ethylene propylene diene rubber), ACM (acrylic rubber), AEM (ethylene-acrylic rubber), SBR ( Styrene-butadiene rubber), BR (butadiene rubber), CR (chloroprene rubber), CSM (chlorosulfonated polyethylene rubber), ECO (epichlorohydrin rubber), natural rubber, fluorine rubber, silicone rubber and the like.

The above materials are not limited to only introduction to the main materials used in the polymer composite composition used in the present invention. Plastics and rubber used in the present invention include all materials of various materials corresponding to the category of plastics and rubber. The tire production process consists of a refining process that mixes chemicals with rubber as a raw material, a rolling / extrusion process that manufactures the compounded rubber into semi-finished products, and a molding that assembles the semi-finished products manufactured by a cutting process that cuts semi-finished products to a certain size. It can be divided into a vulcanization process that gives elasticity by applying heat and pressure to the green case made by the process and molding process.

In the first tire forming process, the tires, such as body plies, beads, and treads, which are completed through semi-finished processes, are sequentially attached to the molding machine drum to form a cylindrical rubber composite. The cylindrical object made at this time is called a green case. In the forming process, the green case is made by assembling the inner liner and body ply on the drum band, attaching beads, and inflating a rubber balloon called 'Bladder' to turn up both ends of the semi-finished product. . After that, they attach sidewalls, assemble belts, cap plies, and treads to take out the green case shaped like a tire.

The tire is vulcanized by the secondary process. The vulcanization process, the final process of the manufacturing process, is the process of making a complete tire from a green case made of semi-finished products. Insert the green tire into the mold and apply constant pressure and heat to complete the tread pattern according to the type of tire. At this time, the subdivided pressure, time, and temperature should be adjusted according to the type of tire. During vulcanization in the mold, not only the pressure is very high but also the temperature of the parts can be different, which can cause the rubber to pull out. In order to prevent this, a hole is drilled in the mold. As a result, a tire having a vulcanized process has a rubber protrusion called a vent. These rubber bumps are cleaned and trimmed. Among them, the inner liner of the tire is wound on the innermost side of the tire, and the inner liner of the tire is pressed into the bladder in the forming process to have the shape and thickness of the inner liner. Halogenated butyl rubber, the most widely used inner liner material to date, is cut and processed to a thickness of about 1 to 2 mm.

The high shielding formulation developed by the present invention has an excellent air permeability of about 3 to 7 times compared to the conventional halogenated butyl rubber, and can reduce the thickness of the existing inner liner.

That is, the tire can be thinned up to about 0.1 to 0.3 mm on the basis of the finished tire, thereby reducing the weight of the tire as a whole. Since the specific gravity is also smaller than that of the existing inner liner, the weight reduction effect is maximized. Generally, 500g ~ 800g weight can be reduced per tire.

Another advantage of the present invention is a high shielding material using a conventional plastic resin, but a separate additional process is required to form a tire, the material developed by the present invention can be applied without changing the existing tire process.

In order to apply the above-mentioned high shielding resin, a special molding process is required unlike the general tire process. Before assembling the inner liner and body ply on the drum band, a dedicated extruder for each tire size is prepared, and a semi-finished donut type inner liner is used.

This method could overcome the weakness of moldability due to its thin thickness and plastic characteristics, but it needed to invest in exclusive extrusion equipment, and it was not suitable for mass production method using existing cutting process. There is this. In addition, since the plastic resin is not smoothly bonded to other rubbers, a separate adhesive material is required.

However, the material of the present invention can be applied without any special changes in the existing process, it is also good adhesion with other rubber. Therefore, the product can be produced while maintaining the production efficiency of the existing tire.

The blending process of the present invention is as follows.

At a temperature above the melting point of the plastic resin, the rubber and plastic resin are mixed in a specific ratio. Carbon Black, Stearic Acid, Zinc Oxide (ZnO) and Process Oil are added to make Carbon Master Batch. The important point here is that they must be kneaded at temperatures above the melting point of the plastic resin. Otherwise, the plastic resin will not melt, resulting in poor dispersibility with the rubber. If the dispersion is not perfect, not only the mechanical properties of the formulation are lowered, but also the shielding performance is deteriorated.

In addition, it should be noted that since the melting point of the plastic resin is generally high, when kneading at a corresponding temperature for a long time, the mechanical chain of the material is degraded because the polymer chain is cut by heat. Therefore, it is important to fully understand the properties of rubber and plastics and knead them for the shortest time possible.

After CMB manufacture, sulfur and vulcanization accelerator are added to the final kneaded rubber to make FMB (Final Master Batch) material.

The mixing ratio of rubber and plastic can be determined by the physical properties and production process required for the tire. The required physical properties include hardness, tensile strength and elongation, and shielding performance. The properties required in the production process include uncured rubber behavior, vulcanization rate and viscosity.

The tire is a component that is composed of materials with different characteristics, and it can be molded only when the unvulcanized behavior characteristics with other materials are similar, and the durability of the tire must be satisfied after the product is molded. The composition and content of the formulation can be adjusted to meet these requirements, the composition of the plastic is 5 to 60 wt% in the total formulation, the composition of the rubber can be up to 90 to 30% by weight of the total formulation. The composition of other carbon blacks and various additives can be up to 3 to 60% by weight of the total formulation.

If the composition ratio of the plastic in the compounding composition is higher than 60% by weight, not only tire molding is difficult because the total hardness is too high, but cracking may occur due to stretching fatigue during driving. On the other hand, if the composition ratio of the plastic is less than 5% by weight, the shielding property is lowered, and mechanical properties such as tensile strength and elongation are lowered, so that the composition ratio of the compounding within a certain amount can be adjusted. On the contrary, when the composition of the rubber is 30% by weight or less, the hardness is excessively high, and the mechanical properties are deteriorated, while when the composition ratio is higher than 90% by weight, the desired shielding performance cannot be obtained.

The composition of other fillers and additives should likewise be adjusted to take into account the mechanical properties, shielding and formability of the material.

Hereinafter, the effects of the present invention will be described in detail through examples and comparative examples according to the present invention.

Examples 1 to 8

Air permeability coefficients were measured through high-shielding materials containing rubber and plastic resins in specific proportions. Table 1 shows the composition ratios and air permeability coefficients of Examples 1 to 8.

Comparative Example 1

The halogenated butyl rubber used for the existing tires was used as the inner liner material. Table 2 below shows the air permeability coefficient of the comparative example.

division For inner liner  Material Composition ratio
(Rubber: plastic) Air permeability
(Cm 3 * cm / Cm2 * sec * cmHg ) Example  One Polar rubber + polar plastic
( NBR  + EVOH ) 70:30 2.71 Example  2 80:20 3.23 Example  3  Nonpolar Rubber + Polar Plastic
(Butyl rubber + EVOH ) 70:30 1.86 Example  4 80:20 1.57 Example  5 Polar rubber + polar plastic
( NBR  + PA ) 70:30 2.57 Example  6 80:20 3.54 Example  7 Nonpolar Rubber + Polar Plastic
( EPDM  + PA ) 70:30 2.77 Example  8 80:20 3.82

division For inner liner  Material Air permeability
(Cm 3 * cm / Cm2 * sec * cmHg ) Comparative Example 1 Butyl rubber
(Chlorobutyl) 11.40

Table 3 below shows the composition ratios of carbon black, process oil, zinc oxide, sulfur, Relative parts by weight of accelerator, stearic acid are indicated.

Kinds Creation costs (unit phr ) 70:30 80:20 Rubber 100 100 plastic 43 25 Carbon black 25 35 Process oil (paraffinic) 5 5 Zinc Oxide (ZnO) 2 2 Sulfur (S) 1.5 1.5 Accelerator (Cz) 1.5 1.5 Stearic acid One One

Air permeation performance under high pressure was performed using the specimen prepared as in Example and Comparative Example. The pressure condition is about 3 atmospheres, and the smaller the air permeability coefficient, the better the shielding performance. Comparative example is butyl rubber, which is a tire inner liner material, which is composed of polar rubber and polar plastic, and has 3 ~ 4 times better shielding performance than butyl rubber. ~ 7 times better shielding performance.

Therefore, if the current air leakage performance of the tire is maintained at the same, when applying the material developed by the present invention it can be formed thin to 1/3 to 1/7 of the thickness of the existing inner liner.

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that such a specific technology is only a preferred embodiment, and the scope of the present invention is not limited thereto. Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (7)

A high shielding resin composition for tires kneaded by mixing 5 to 60% by weight of plastic resin, 30 to 90% by weight of rubber resin and 3-60% of additives.
The method of claim 1, wherein the plastic resin is polyethylene (PE), polypropylene (PP), poly styrene (PS), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly carbonate (PC), poly vinyl chloride (PVC), PA (Polyamide), PPS (Polyphenylene Sulfide), PK (Polyketone), EVOH (Ethylene Vinyl Alcohol) or PTFE (Polytetrafluoroethylene) composition, characterized in that the composition of two or more.
The method of claim 1, wherein the rubber resin is normal butyl, chlorobutyl, bromo butyl, NBR (acrylonitrile-butadiene rubber), EPDM (ethylene propylene diene rubber), ACM (acrylic rubber), AEM (ethylene-acrylic rubber) SBR (styrene-butadiene rubber), BR (butadiene rubber), CR (chloroprene rubber), CSM (chlorosulfonated polyethylene rubber), ECO (epichlorohydrin rubber), natural rubber, fluororubber or silicone rubber alone Or a mixture of two or more rubbers.
The composition of claim 1, wherein the additive is carbon black, stearic acid, zinc oxide, or a mixture of two or more process oils.
The composition of claim 1, wherein the kneading is kneaded at a temperature above the melting point of the plastic resin.
The composition according to claim 1, wherein the vulcanization treatment is performed after the additive, the vulcanizing agent, or the accelerator alone or two or more are additionally added to the high-shielding resin composition for tires.
A tire innerliner comprising the composition produced by the method of claim 1.


KR1020110079874A 2011-08-10 2011-08-10 Highly shielding composition for tire innerliner KR20130017456A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101471415B1 (en) * 2013-05-31 2014-12-10 한국타이어 주식회사 Rubber composition for tire innerliner and tire manufactured by using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101471415B1 (en) * 2013-05-31 2014-12-10 한국타이어 주식회사 Rubber composition for tire innerliner and tire manufactured by using the same

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