KR101384402B1 - Method of manufacturing tire with reformed silica and tire thereof - Google Patents

Method of manufacturing tire with reformed silica and tire thereof Download PDF

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KR101384402B1
KR101384402B1 KR1020120042564A KR20120042564A KR101384402B1 KR 101384402 B1 KR101384402 B1 KR 101384402B1 KR 1020120042564 A KR1020120042564 A KR 1020120042564A KR 20120042564 A KR20120042564 A KR 20120042564A KR 101384402 B1 KR101384402 B1 KR 101384402B1
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tire
modified
silica
carbon black
nanosilica
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KR1020120042564A
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KR20130119624A (en
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정동신
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금호타이어 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00Producing pneumatic or solid tyres or parts thereof
    • B29D30/06Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/08Building tyres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00Characterised by the use of unspecified rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

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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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

본 발명은 표면개질된 실리카를 함유하는 타이어의 제조방법 및 그에 의한 타이어를 개시한다.
본 발명에 따르는 표면개질된 실리카를 함유하는 타이어의 제조방법 및 그에 의한 타이어는 카본블랙을 산처리하여 그 표면의 하이드록시 작용기의 밀도를 조절된 카본블랙을 수득하는 S1단계, 상기 조절된 카본블랙과 하이드록시 작용기의 평균밀도가 7 내지 9 OH그룹/㎚2이고 입자의 평균크기가 150 내지 250㎚인 나노실리카를 용매에 첨가하여 분산시키며 계면활성제를 적하시켜 표면개질된 나노실리카를 제조하는 S2단계, 상기 표면개질된 나노실리카를 여과하고 건조시키는 S3단계 및 상기 표면개질된 나노실리카를 타이어 원료고무와 첨가제를 혼합하여 타이어를 제조하는 S4단계를 포함하는 것을 특징으로 하는데, 이에 의할 때 실리카의 표면을 개질하여 그 사용량이나 제조공정상 불이익을 제거하고, 이를 함유하는 타이어의 내마모성, 마찰력, 저회전저항 특성(LRR)을 향상시킬 수 있다.
The present invention discloses a method for producing a tire containing surface modified silica and a tire thereby.
The method for producing a tire containing a surface-modified silica according to the present invention and the tire thereby yields a carbon black acid treated to obtain a carbon black having a controlled density of hydroxy functional groups on the surface thereof, the controlled carbon black S2 to prepare a surface-modified nanosilica by adding and dispersing a nanosilica having a mean density of 7 to 9 OH group / nm 2 and a particle size of 150 to 250 nm to a solvent, and adding a surfactant. Step, S3 step of filtering and drying the surface-modified nanosilica and S4 step of producing a tire by mixing the surface-modified nanosilica tire raw material rubber and additives, whereby silica The surface of the tire is modified to eliminate the amount of use and disadvantages in the manufacturing process, and the abrasion resistance, frictional force, It is possible to improve the rotational resistance (LRR).

Description

표면개질된 실리카를 함유하는 타이어의 제조방법 및 이에 의한 타이어{Method of manufacturing tire with reformed silica and tire thereof}Method of manufacturing tire with reformed silica and tire according to the present invention

본 발명은 표면개질된 실리카를 함유하는 타이어의 제조방법 및 이에 의한 타이어에 관한 것으로, 더욱 상세하게는 실리카의 표면을 개질하여 그 사용량이나 제조공정상 불이익을 제거하고, 이를 함유하는 타이어의 내마모성, 마찰력, 저회전저항 특성(LRR)을 향상시키는 표면개질된 실리카를 함유하는 타이어의 제조방법 및 이에 의한 타이어에 관한 것이다.
The present invention relates to a method for manufacturing a tire containing a surface-modified silica and to a tire according to the present invention. More particularly, the surface of the silica is modified to eliminate the disadvantages in terms of the amount of use and manufacturing process, and the wear resistance and frictional force of the tire containing the same. The present invention relates to a method for manufacturing a tire containing surface modified silica that improves low rolling resistance characteristics (LRR) and a tire thereby.

종래, 타이어의 경우 주행시 노면에서의 제동성을 향상시키기 위하여 타이어의 트레드부가 노면과 접촉하는 트레드의 접촉면과 노면 사이의 마찰력, 내마모성을 증대시킬 필요가 있었다.Conventionally, in the case of tires, in order to improve braking performance on the road surface, it is necessary to increase frictional force and abrasion resistance between the tread portion of the tire and the road surface in contact with the road surface.

이러한 증대를 위하여 실리카, 카본블랙과 같은 보강제를 사용하는데, 카본블랙의 경우는 하이드로포빅(hydrophobic)하고, 기타 첨가제는 하이드로필릭(hydrophilic) 특성도 가질 수 있어, 분산성이 저하될 수 있고, 따라서 마찰력이나 내마모성에 불리한 문제가 있었다.For this increase, reinforcing agents such as silica and carbon black are used. In the case of carbon black, hydrophobic and other additives may have hydrophilic properties, and thus dispersibility may be lowered. There were disadvantageous problems in friction and wear resistance.

또한, 실리카를 보강제로 첨가한 경우는 인장 성질이 우수하고 발열이 적어, 이를 함유하는 타이어는 연비가 높고, 안정성이 우수하며 수명이 긴 장점이 있으나, 실리카의 표면에는 하이드록실기가 발달되어 있어 소수성인 고무와 잘 섞이지 않고 고무 분자와 마찰이 심하여 점도가 높다. In addition, when silica is added as a reinforcing agent, it has excellent tensile properties and less heat generation, and the tire containing it has the advantages of high fuel efficiency, excellent stability and long life, but the hydroxyl group is developed on the surface of the silica. It does not mix well with hydrophobic rubber and has high viscosity due to high friction with rubber molecules.

아울러, 상기 실리카 표면에 발달된 하이드록시 작용기간 결합하여 실리카 알갱이가 서로 뭉쳐 덩어리지므로(clustering) 고무 내 분산성이 불량한 문제점이 있었고, 그 첨가량이 많아 질수록 점도가 커져 사출 압력이 높아지는 등 가공성이 불량해서 카본블랙처럼 많은 양을 첨가하기도 어려운 점이 있었다.
In addition, since the silica particles are clustered together due to the hydroxy working period developed on the surface of the silica, the dispersibility in the rubber was poor, and as the amount of the additive was increased, the viscosity increased and the injection pressure was increased. It was so poor that it was difficult to add as much as carbon black.

따라서, 본 발명이 해결하고자 하는 첫번째 기술적 과제는 실리카의 표면을 개질하여 그 사용량이나 제조공정상 불이익을 제거하고, 이를 함유하는 타이어의 내마모성, 마찰력, 저회전저항 특성(LRR)을 향상시키는 표면개질된 실리카를 함유하는 타이어의 제조방법을 제공하는 것이다.Therefore, the first technical problem to be solved by the present invention is to modify the surface of the silica to remove the amount of use or manufacturing process disadvantages, surface modification to improve the wear resistance, frictional force, low rolling resistance characteristics (LRR) of the tire containing it It is to provide a method for producing a tire containing silica.

또한, 본 발명이 해결하고자 하는 두번째 기술적 과제는 실리카의 표면을 개질하여 그 사용량이나 제조공정상 불이익을 제거하고, 이를 함유하는 타이어의 내마모성, 마찰력, 저회전저항 특성(LRR)을 향상시키는 표면개질된 실리카를 함유하는 타이어를 제공하는 것이다.
In addition, the second technical problem to be solved by the present invention is to modify the surface of the silica to remove its use or manufacturing process disadvantages, and to improve the wear resistance, frictional force, low rolling resistance characteristics (LRR) of the tire containing it It is to provide a tire containing silica.

본 발명은 상술한 첫번째 기술적 과제를 해결하기 위하여, 카본블랙을 산처리하여 그 표면의 하이드록시 작용기의 밀도를 조절된 카본블랙을 수득하는 S1단계, 상기 조절된 카본블랙과 하이드록시 작용기의 평균밀도가 7 내지 9 OH그룹/㎚2이고 입자의 평균크기가 150 내지 250㎚인 나노실리카를 용매에 첨가하여 분산시키며 계면활성제를 적하시켜 표면개질된 나노실리카를 제조하는 S2단계, 상기 표면개질된 나노실리카를 여과하고 건조시키는 S3단계 및 상기 표면개질된 나노실리카를 타이어 원료고무와 첨가제를 혼합하여 타이어를 제조하는 S4단계를 포함하는 것을 특징으로 하는 표면개질된 실리카를 함유하는 타이어의 제조방법을 제공한다.The present invention, in order to solve the first technical problem described above, step S1 to obtain a carbon black adjusted to the density of the hydroxy functional groups on the surface by acid treatment of carbon black, the average density of the adjusted carbon black and hydroxy functional groups Step S2 of preparing a surface-modified nanosilica by adding and dispersing nanosilica having a 7 to 9 OH group / nm 2 and an average particle size of 150 to 250 nm in a solvent, and adding a surfactant to the surface-modified nanoparticle It provides a method for producing a tire containing a surface-modified silica, characterized in that it comprises a step S3 of filtering and drying the silica and the surface-modified nanosilica by mixing tire raw rubber and additives to produce a tire. do.

본 발명의 일실시예에 의하면, 상기 조절된 카본블랙의 하이드록시 작용기의 평균밀도가 4 내지 5 OH그룹/㎚2일 수 있다. According to one embodiment of the invention, the average density of the hydroxy functional groups of the adjusted carbon black may be 4 to 5 OH groups / nm 2 .

본 발명의 다른 실시예에 의하면, 상기 S1단계 또는 S2단계에는 30 내지 70℃ 온도로 유지하는 S21단계가 더 포함될 수 있다.According to another embodiment of the present invention, the step S1 or step S2 may further include a step S21 to maintain at a temperature of 30 to 70 ℃.

한편, 본 발명은 상술한 두번째 기술적 과제를 해결하기 위하여, 상술한 제조방법에 의하여 제조되는 것을 특징으로 하는 표면개질된 실리카를 함유하는 타이어를 제공한다.
On the other hand, the present invention provides a tire containing a surface-modified silica, characterized in that produced by the above-described manufacturing method, in order to solve the second technical problem described above.

본 발명에 따르는 표면개질된 실리카를 함유하는 타이어의 제조방법 및 그 타이어는 실리카의 표면을 개질하여 그 사용량이나 제조공정상 불이익을 제거하고, 이를 함유하는 타이어의 내마모성, 마찰력, 저회전저항 특성(LRR)을 향상시킬 수 있다.
The method for producing a tire containing the surface-modified silica and the tire according to the present invention is to modify the surface of the silica to remove the amount of use and disadvantages in the manufacturing process, wear resistance, frictional force, low rolling resistance characteristics of the tire containing the same (LRR ) Can be improved.

도 1은 본 발명에 따르는 표면개질된 실리카를 함유하는 타이어의 제조방법을 보여주는 순서도이다.1 is a flow chart showing a method of making a tire containing a surface modified silica according to the present invention.

본 발명의 상기와 같은 목적, 특징 및 다른 장점들은 첨부도면을 참조하여 본 발명의 바람직한 실시예를 상세히 설명함으로써 더욱 명백해질 것이다. 이하 첨부된 도면을 참조하여 본 발명의 실시예에 따른 표면개질된 실리카를 함유하는 타이어의 제조방법 및 이에 의한 타이어를 상세하게 설명하기로 한다.These and other objects, features and other advantages of the present invention will become more apparent by describing in detail preferred embodiments of the present invention with reference to the accompanying drawings. Hereinafter, a method of manufacturing a tire containing a surface-modified silica and a tire thereby will be described in detail with reference to the accompanying drawings.

먼저, 본 발명에 따르는 표면개질된 실리카를 함유하는 타이어의 제조방법 및 그 타이어는 카본블랙을 산처리하여 그 표면의 하이드록시 작용기의 밀도를 조절된 카본블랙을 수득하는 S1단계와, 상기 조절된 카본블랙과 하이드록시 작용기의 평균밀도가 7 내지 9 OH그룹/㎚2이고 입자의 평균크기가 150 내지 250㎚인 나노실리카를 용매에 첨가하여 분산시키며 계면활성제를 적하시켜 표면개질된 나노실리카를 제조하는 S2단계와, 상기 표면개질된 나노실리카를 여과하고 건조시키는 S3단계 및 상기 표면개질된 나노실리카를 타이어 원료고무와 첨가제를 혼합하여 타이어를 제조하는 S4단계를 포함하는 것을 특징으로 하는데, 이를 첨부된 도 1를 참조하여 살펴본다.First, the method for producing a tire containing the surface-modified silica according to the present invention, and the tire is an S1 step of acid-treated carbon black to obtain a carbon black of which the density of hydroxy functional groups on its surface is adjusted, and the adjusted The surface-modified nanosilica was prepared by adding and dispersing nanosilica having an average density of carbon black and hydroxy functional groups of 7 to 9 OH group / nm 2 and an average particle size of 150 to 250 nm in a solvent and dropping a surfactant. Step S2, and S3 step of filtering and drying the surface-modified nanosilica and S4 step of producing a tire by mixing the surface-modified nanosilica with a tire raw material rubber and an additive, which is attached It will be described with reference to FIG.

도 1은 본 발명에 따르는 표면개질된 실리카를 함유하는 타이어의 제조방법을 보여주는 순서도이다.1 is a flow chart showing a method of making a tire containing a surface modified silica according to the present invention.

상기 S1단계는 카본블랙을 산처리하여 그 표면의 하이드록시 작용기의 밀도를 조절된 카본블랙을 수득하는 공정으로서, 상기 카본블랙은 N2 표면적이 130 내지 150이고, DBP가 100 내지 150이며, 톨루엔 착색도가 50% 이상인 것을 사용할 수 있는데, 이는 균일한 입자구조의 카본블랙으로 실리카와 결합능을 극대화하기 위함이다.The step S1 is a step of obtaining carbon black having an acid treatment of carbon black and adjusting the density of hydroxy functional groups on the surface thereof, wherein the carbon black has an N 2 surface area of 130 to 150, a DBP of 100 to 150, and a degree of toluene coloring. Is 50% or more can be used, which is to maximize the binding capacity with silica as carbon black of uniform particle structure.

또한, 상기 카본블랙은 산처리하는데, 이러한 산처리는 상기 카본블랙의 표면에는 계면활성제와 반응하는 하이드록실기(-OH) 밀도가 낮아서 이를 증가시키기 위한 것으로 에탄올 용매 분위기에서 염산(HCL)을 첨가하여 수행하게 된다.In addition, the carbon black is an acid treatment, and the acid treatment is to increase the density of the hydroxyl group (-OH) reacting with the surfactant on the surface of the carbon black to increase it, adding hydrochloric acid (HCL) in an ethanol solvent atmosphere. Will be performed.

상기 산처리는 카본블랙의 하이드록실기의 밀도를 평균 4 내지 5 OH(하이드록실기)그룹/㎚2인 까지 수행되는데 이는 1㎚2인 필러(filler) 표면당 OH가지 수를 의미한다. 만일 상기 밀도가 4 미만이면, 카본블랙과 실리카 결합에 결합수에 문제가 생길 수 있고, 반대로 5를 초과하면, 오히려 결합(bonding)이 원활하지 않을 수 있다.The acid treatment is performed to average the density of hydroxyl groups of carbon black to 4 to 5 OH (hydroxyl group) groups / nm 2 , which means the number of OH branches per 1 nm 2 filler surface. If the density is less than 4, there may be a problem in the number of bonds to the carbon black and silica bond, and if it exceeds 5, the bonding may not be smooth.

또한, 상기 산처리는 반응성을 고려하여 30 내지 70℃ 온도로 유지하며 수행될 필요도 있는데, 만일 30℃ 미만이면, 산처리능이 감소되어 카본블랙 표면에 적절한 수의 OH 그룹 생성에 문제가 발생할 수 있고, 70℃를 초과하면 카본블랙 구조에 악영향을 미칠 수 있어 바람직하지 않다.In addition, the acid treatment may need to be carried out at 30 to 70 ° C. in consideration of reactivity, and if it is less than 30 ° C., the acid treatment may be reduced, causing problems in the formation of an appropriate number of OH groups on the carbon black surface. If the temperature exceeds 70 ° C, the carbon black structure may be adversely affected, which is not preferable.

상술한 산처리에 의하여, 카본블랙의 조절된 하이드록실기가 후의 실리카의 표면을 개질하는 과정에서 물(H2O)이 생성/제거되며 결합력을 제공할 수 있게 된다. 예컨대, 계면활성제로 TESPT를 사용하는 경우에 그의 일단 -CH2CH2OH 기가 반응에 참여하며 물을 생성/제거한다.By the above-described acid treatment, water (H 2 O) is generated / removed in the process of modifying the surface of the silica after the controlled hydroxyl group of the carbon black, thereby providing a bonding force. For example, when TESPT is used as a surfactant, its once -CH 2 CH 2 OH group participates in the reaction and generates / removes water.

다음으로, S2단계를 보면, 상기 조절된 카본블랙과 하이드록시 작용기의 평균밀도가 7 내지 9 OH그룹/㎚2이고 입자의 평균크기가 150 내지 250㎚인 나노실리카를 용매에 첨가하여 분산시키며 계면활성제를 적하시켜 표면개질된 나노실리카를 제조하는 공정인데, 상기 나노실리카의 평균입도가 150 내지 250㎚인데, 만일, 150㎚미만이면, 구조가 너무 작아 고무와 혼용성이 떨어질 수 있고, 반대로 250㎚를 초과하면 적절한 보강성능이 발현되지 아니할 수 있다.Next, in the step S2, the average density of the adjusted carbon black and hydroxy functional groups is 7 to 9 OH group / nm 2 and the average size of the particles of 150 to 250 nm added to the dispersion in the solvent to disperse the interface In the process of preparing a surface-modified nanosilica by dropping the active agent, the average particle size of the nanosilica is 150 to 250nm, if less than 150nm, the structure is too small may be incompatible with rubber, on the contrary 250 If the thickness exceeds nm, the proper reinforcing performance may not be expressed.

또한, 상기 나노실리카의 하이드록시 작용기의 평균밀도가 7 내지 9 OH그룹/㎚2인데, 이 범위를 벗어나며, 카본블랙과 결합시 문제가 생기거나 결합위치(bondin-site)가 오히려 증가하여 TESPT의 반응부위가 실리카에만 존재할 우려가 있다.In addition, the average density of the hydroxy functional group of the nanosilica is 7 to 9 OH group / nm 2 , out of this range, causing problems when bonding with carbon black or rather the bond site (bondin-site) rather increases the There is a fear that the reaction site exists only in the silica.

아울러 상기 용매는 반응생성물인 물(H2O)이나 알콜을 수용할 수 있는 한 특별하게 한정하여 사용할 것은 아니나, 에탄올을 사용할 수 있다. In addition, the solvent is not particularly limited as long as it can accommodate the reaction product of water (H 2 O) or alcohol, ethanol can be used.

한편, 상기 계면활성제는 특별하게 한정하여 사용할 것은 아니며, 특히 TESPT(Bis-(3-(triethoxysilyl)-propyl)-tetrasulfide)를 사용할 수 있다. On the other hand, the surfactant is not particularly limited to use, in particular TESPT (Bis- (3- (triethoxysilyl) -propyl) -tetrasulfide) can be used.

여기서도 앞서 설명한 바와 같이, 실리카의 하이드록실기가 물(H2O) 생성/제거되는 반응에 참여하는데, 예컨대, 계면활성제로 TESPT를 사용하는 경우에 그 다른단 -CH2CH2OH 기가 반응에 참여하며 물을 생성/제거한다.As described above, the hydroxyl group of the silica participates in the reaction of generating / removing water (H 2 O), for example, when TESPT is used as a surfactant, the other -CH 2 CH 2 OH group is added to the reaction. Participate in generating and removing water.

다음으로, S3단계를 보면, 상기 표면개질된 나노실리카를 여과하고 건조시키는 공정으로서, 상기 표면개질된 나노실리카를 얻을 수 있는 범위 내에서 여과시키고, 통상의 오븐에서 열풍이나 복사로 건조시킬 수 있다.Next, in the step S3, as the process of filtering and drying the surface-modified nanosilica, the surface-modified nanosilica can be filtered within a range that can be obtained, and dried by hot air or radiation in a conventional oven. .

이러한 건조를 통하여 전공정에서 결합된 카본블랙과 실리카에서 에탄올이 제거되며 표면개질된 나노실리카를 얻을 수 있게 된다.Through this drying, ethanol is removed from the carbon black and silica bonded in the previous process, and thus surface modified nano silica can be obtained.

다음으로, S4단계를 보면, 상기 표면개질된 나노실리카를 타이어 원료고무와 첨가제를 혼합하여 타이어를 제조하는 공정으로서, 상기 표면개질된 나노실리카를 천연고무나 합성고무로 이루어진 원료고무에 배합하고, 여기에 특별하게 제조되는 타이어의 필요한 스펙에 따라 아연화, 스테아린산, 아로마계 오일, 유황, 가류촉진제와 같은 첨가제를 가하여 통상의 타이어 제조공정에 따라 본 발명에 따르는 표면개질된 실리카를 함유하는 타이어를 제조할 수 있다.Next, in the step S4, as a process for producing a tire by mixing the tire-modified rubber and additives of the surface-modified nanosilica, the surface-modified nanosilica is blended into a raw material rubber made of natural rubber or synthetic rubber, According to the required specifications of the tire to be specially manufactured, additives such as zincized, stearic acid, aromatic oils, sulfur and vulcanization accelerators are added to produce tires containing the surface-modified silica according to the present invention according to the conventional tire manufacturing process. can do.

이상에서 또한 다음에 본 발명의 바람직한 실시예에 대하여 설명하나 본 발명은 이와 같은 특정의 실시예에만 한정되지 아니한다. 즉, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 첨부된 특허청구범위의 사상 및 범주를 일탈함이 없이 본 발명에 대한 다수의 변경 및 수정이 가능하며, 그러한 모든 적절한 변경 및 수정의 균등물들도 본 발명의 범위에 속하는 것으로 간주되어야 할 것이다.In addition to the above, preferred embodiments of the present invention will be described below, but the present invention is not limited to these specific embodiments. It will be apparent to those skilled in the art that numerous modifications and variations can be made in the present invention without departing from the spirit or scope of the appended claims. And equivalents should also be considered to be within the scope of the present invention.

제조예. 표면개질된 나노실리카의 제조Production example. Preparation of Surface Modified Nanosilica

피흡착가스 질소(N2)로 비표면적(specific surface area)이 130~150이고, DBP흡유량이 100~150이며, 톨루엔 착색도 50% 이상인 카본블랙을 95wt%에탄올 용매에 첨가하고 35wt% 염산을 가하며 교반하여 60℃에서 6 시간 산처리하여 하이드록시 작용기의 평균밀도가 4.5 OH그룹/㎚2인 조절된 카본블랙을 수득하였다. 다음으로, 상기 조절된 카본블랙 75g과 입자크기가 150 내지 250 ㎚이고, 하이드록실기의 밀도가 7 내지 9 OH그룹/㎚2 인 실리카 75g을 용매 95wt%에탄올에 첨가하고 교반하면서 TESPT를 천천히 적하하여 분산용액을 준비하였다. 다음으로, 상기 분산용액을 여과하고 110℃가 유지된 오븐에서 건조하여 표면개질된 나노실리카를 제조하였다. Nitrogen (N 2 ) to be adsorbed, carbon black having a specific surface area of 130 to 150, a DBP absorption of 100 to 150, and a toluene coloring degree of 50% or more was added to 95 wt% ethanol solvent and 35 wt% hydrochloric acid was added. The mixture was stirred and acid treated at 60 DEG C for 6 hours to obtain adjusted carbon black having an average density of 4.5 OH groups / nm 2 of hydroxy functional groups. Next, 75 g of the adjusted carbon black and 75 g of silica having a particle size of 150 to 250 nm and a hydroxyl group of 7 to 9 OH group / nm 2 were added to 95 wt% ethanol solvent and slowly dropwise added TESPT while stirring. To prepare a dispersion solution. Next, the dispersion solution was filtered and dried in an oven maintained at 110 ℃ to prepare a surface-modified nanosilica.

실시예 1Example 1

원료고무로서 Styene butadiene rubber 137.5 중량부에 대하여, 상기 제조예에서 얻은 표면개질된 실리카 40 중량부, 아연화 3중량부, 스테아린산 2중량부, 아로마계 오일 10중량부, 유황 0.65 중량부, 가류촉진제 0.7 중량부를 사용하여 타이어 고무를 제조하였다.As raw material rubber, based on 137.5 parts by weight of styene butadiene rubber, 40 parts by weight of surface-modified silica obtained in the above preparation, 3 parts by weight of zinc, 2 parts by weight of stearic acid, 10 parts by weight of aromatic oil, 0.65 parts by weight of sulfur, and a vulcanization accelerator 0.7 Tire parts were prepared using parts by weight.

실시예 2Example 2

원료고무로서 Styene butadiene rubber 137.5 중량부에 대하여, 상기 제조예에서 얻은 표면개질된 실리카 60 중량부, 아연화 3중량부, 스테아린산 2중량부, 아로마계 오일 10중량부, 유황 0.65 중량부, 가류촉진제 0.7 중량부를 사용하여 타이어 고무를 제조하였다.As raw material rubber, based on 137.5 parts by weight of Styene butadiene rubber, 60 parts by weight of surface-modified silica obtained in the above preparation, 3 parts by weight of zinc, 2 parts by weight of stearic acid, 10 parts by weight of aromatic oil, 0.65 parts by weight of sulfur, and a vulcanization accelerator 0.7 Tire parts were prepared using parts by weight.

비교예Comparative Example

원료고무로서 Styene butadiene rubber 137.5 중량부에 대하여, 카본블랙 30 중량부, 실리카 20중량부, 아연화 3중량부, 스테아린산 2중량부, 아로마계 오일 10중량부, 유황 0.65 중량부, 가류촉진제 0.7 중량부를 사용하여 타이어 고무를 제조하였다.As a raw material rubber, 30 parts by weight of carbon black, 20 parts by weight of silica, 3 parts by weight of zinc, 3 parts by weight of stearic acid, 10 parts by weight of aroma oil, 0.65 parts by weight of sulfur, and 0.7 parts by weight of vulcanization accelerator based on 137.5 parts by weight of styene butadiene rubber. To produce tire rubber.

항목Item 비교예Comparative Example 실시예1Example 1 실시예2Example 2 SBRSBR 137.5137.5 137.5137.5 137.5137.5 카본블랙Carbon black 5.65.6 00 00 실리카Silica 7070 00 00 카본블랙 실리카 결합제Carbon Black Silica Binder 00 75.675.6 75.675.6 아연화Zincification 33 33 33 스테아린산Stearic acid 22 22 22 SI-69SI-69 5.65.6 00 00 유황brimstone 1.51.5 1.51.5 1.51.5 가류촉진제Vulcanization accelerator 1.51.5 1.51.5 1.51.5

실험예Experimental Example

상기 표 1은 실시예 1, 2 및 비교예에서 사용된 성분들의 함량을 나타낸 표이고, 하기 표 2는 실시예 1, 2 및 비교예에서 제조된 타이어 고무에 대하여 GABO(70℃), DIN마모, PICO 마모 및 FPS 마모에 대하여 ASTM에 근거하여 실험하고 그 결과를 나타낸 표이다.
Table 1 is a table showing the contents of the components used in Examples 1, 2 and Comparative Examples, Table 2 is GABO (70 ℃), DIN wear for the tire rubber prepared in Examples 1, 2 and Comparative Examples , PICO wear and FPS wear are tested based on ASTM and show the results.

구분division 비교예Comparative Example 실시예1Example 1 실시예2Example 2 GABO(70℃)GABO (70 ℃) 0.150.15 0.1330.133 0.1210.121 DIN마모DIN wear 100100 103103 105105 PICO 마모PICO wear 100100 101101 103103 FPS 마모FPS wear 100100 102102 104104

* 마모 결과는 비교예를 100으로 보았을때의 비교 상대값으로 나타내었다. * The abrasion result was shown by the comparative value when seeing the comparative example 100.

비교예에 대하여 실시예의 GABO(70'C) 값이 낮아 상대적으로 회전저항 값이 낮음을 알 수 있고, 세가지 마모 지수로 보아 비교예보다 실시예의 마모가 우수함을 알 수 있다. For the comparative example, the GABO (70'C) value of the embodiment is low, and thus the rotational resistance value is relatively low, and three wear indexes show that the wear of the embodiment is superior to the comparative example.

Claims (4)

삭제delete 카본블랙을 산처리하여 그 표면의 하이드록시 작용기의 밀도를 조절된 카본블랙을 수득하는 S1단계;
상기 조절된 카본블랙과 하이드록시 작용기의 평균밀도가 7 내지 9 OH그룹/㎚2이고 입자의 평균크기가 150 내지 250㎚인 나노실리카를 용매에 첨가하여 분산시키며 계면활성제를 적하시켜 표면개질된 나노실리카를 제조하는 S2단계;
상기 표면개질된 나노실리카를 여과하고 건조시키는 S3단계; 및
상기 표면개질된 나노실리카를 타이어 원료고무와 아연화, 스테아린산, 아로마계 오일, 유황 또는 가류촉진제를 혼합하여 타이어를 제조하는 S4단계;를 포함하는 것을 특징으로 하되,
상기 조절된 카본블랙의 하이드록시 작용기의 평균밀도가 4 내지 5 OH그룹/㎚2인 것을 특징으로 하는 표면개질된 실리카를 함유하는 타이어의 제조방법.
Acid treatment of the carbon black to obtain a carbon black having a controlled density of hydroxy functional groups on its surface;
The modified carbon black and the hydroxy functional group have a mean density of 7 to 9 OH group / nm 2 and nano silica having an average size of particles of 150 to 250 nm is added and dispersed in a solvent, and a surfactant is added to the surface modified nano. S2 step of preparing silica;
S3 step of filtering and drying the surface-modified nanosilica; And
S4 step of producing a tire by mixing the surface-modified nano-silica and tire raw rubber and zinc, stearic acid, aroma oil, sulfur or vulcanization accelerator; characterized in that it comprises a,
A method for producing a tire containing surface-modified silica, characterized in that the average density of hydroxy functional groups of the adjusted carbon black is 4 to 5 OH groups / nm 2 .
제 2 항에 있어서,
상기 S1단계 또는 S2단계에는 30 내지 70℃ 온도로 유지하는 S12단계를 더 포함하는 것을 특징으로 하는 표면개질된 실리카를 함유하는 타이어의 제조방법.
3. The method of claim 2,
The step S1 or S2 step of producing a tire containing a surface-modified silica, characterized in that it further comprises a step S12 maintained at a temperature of 30 to 70 ℃.
제 2 항 또는 제 3 항 중 어느 한 항의 제조방법에 의하여 제조되는 것을 특징으로 하는 표면개질된 실리카를 함유하는 타이어.A tire containing a surface-modified silica, characterized in that it is produced by the method of any one of claims 2 and 3.
KR1020120042564A 2012-04-24 2012-04-24 Method of manufacturing tire with reformed silica and tire thereof KR101384402B1 (en)

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JP2009185115A (en) 2008-02-04 2009-08-20 Bridgestone Corp Method for producing surface-treated silica-attached carbon black, surface-treated silica-attached carbon black and rubber composition using the same
KR20110118312A (en) * 2010-04-23 2011-10-31 금호타이어 주식회사 Tread rubber composition for tire

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JP2009185115A (en) 2008-02-04 2009-08-20 Bridgestone Corp Method for producing surface-treated silica-attached carbon black, surface-treated silica-attached carbon black and rubber composition using the same
KR20110118312A (en) * 2010-04-23 2011-10-31 금호타이어 주식회사 Tread rubber composition for tire

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