KR101716057B1 - The rubber composition having a self-cleaning function, a preparation method thereof and the tire prepared by using it - Google Patents
The rubber composition having a self-cleaning function, a preparation method thereof and the tire prepared by using it Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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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
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- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
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- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Abstract
Description
본 발명은 자기세정기능을 갖는 타이어용 고무 조성물에 관한 것으로, 보다 상세하게는 불소실리콘고무를 고무 조성물에 혼합함으로써 자기세정기능이 부여된 고무 조성물 및 이의 제조방법 및 이를 이용하여 제조된 타이어에 관한 것이다.The present invention relates to a rubber composition for a tire having a self-cleaning function, and more particularly to a rubber composition having a self-cleaning function by mixing fluorosilicone rubber with a rubber composition, a method for producing the rubber composition, and a tire will be.
종래의 타이어는 외부 환경에 의한 오염을 피할 수 없다. 하지만 최근 타이어들은 외관에 민감하여, 타이어의 세정을 위해 타이어 성능에 악영향을 줄 수 있는 불소계 코팅 광택제등을 사용하는데, 이는 주행 안전성에 문제를 유발한다.Conventional tires can not avoid contamination due to the external environment. However, recent tires are sensitive to the appearance and use a fluorine-based coating varnish or the like which can adversely affect tire performance for cleaning the tire, which causes problems in driving safety.
일반적으로 자기세정기능을 부여하기 위해서는 불소 화합물을 코팅 또는 혼합해야 한다. 종래 기술을 살펴보면 통상적으로 건축 외장재용으로 사용되고 있는 아크릴계 또는 우레탄계 도료에 사용해 자외선, 습기, 산성비 등에 의해 오염된 도막을 자연적으로 제거하는 자기세정효과를 얻으며, 건축물의 추가적인 보수 도장 등의 노동력과 보수비용을 줄일 수 있다. 하지만 단순히 건축용 도료 등 일부 특정한 소재나 내유성이 필요한 특정 커넥터용 오링(o-ring)의 고무조성물 등은 그 사용이 한정될 뿐 타이어 등에 적용된 사례는 없다. 이는 다양한 고무가 접착제로 결합되며, 탄소계 불소(C-F) 화합물과 상용성이 좋지 않은 오일 및 실리카가 다량 사용됨에 따라 타이어에서는 사용이 어려운 점이 있기 때문이다.Generally, in order to impart a self-cleaning function, a fluorine compound must be coated or mixed. As a result of the conventional techniques, the acrylic or urethane-based coatings, which are usually used for building exterior materials, have a magnetic cleaning effect that naturally removes the coating film contaminated with ultraviolet rays, moisture, acid rain, etc., . However, the use of o-ring rubber compositions for specific connectors such as architectural paints and certain specific materials requiring oil resistance is limited, and there is no case applied to tires. This is because various rubber is bonded by an adhesive and oil and silica having poor compatibility with a carbon-based fluorine (C-F) compound are used in large amounts, which is difficult to use in a tire.
한국등록특허공보 제10-1212639호Korean Patent Registration No. 10-1212639
한국등록특허공보 제10-1378916호Korean Patent Registration No. 10-1378916
본 발명은 상기한 바와 같은 종래기술의 문제점을 해소하기 위해 안출된 것으로서, 타이어에 자기세정기능을 부여함으로써 타이어 외관 성능을 향상시킬 수 있는 자기세정기능을 갖는 타이어용 고무 조성물을 제공하는 데에 있다. Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a rubber composition for a tire having a magnetic cleaning function capable of improving tire appearance performance by imparting a self- .
본 발명에 따른 자기세정기능을 갖는 타이어용 고무 조성물에 있어서, 원료고무 100중량부에 대하여 불소실리콘고무를 1~20중량부, 더욱 바람직하게는 5 ~ 15중량부를 포함하는 것을 특징으로 한다. 상기 불소실리콘 수지가 1중량부 미만인 경우, 자기세정 효과가 미비하여 바람직 하지 않고, 20중량부를 초과하는 경우, 단가가 상승하여 바람직하지 않다.The rubber composition for a tire having a self-cleaning function according to the present invention is characterized by comprising 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, of a fluorosilicone rubber based on 100 parts by weight of the raw rubber. When the amount of the fluorine silicone resin is less than 1 part by weight, the self-cleaning effect is insufficient, which is undesirable. When the amount is more than 20 parts by weight, the unit price is undesirably increased.
상기 불소실리콘고무는 하기 [화학식 1] 로 선택되는 것을 특징으로 한다.The fluorosilicone rubber is characterized by being selected by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, n은 500 ~ 2000이고, m은 3 ~ 10이고, 보다 바람직하게는 n은 1000 ~ 1500이고, m은 5 ~ 8인데, n이 500 미만일 경우, 분자량이 작아 타이어 사용 중 외부로 유출될 가능성이 있어 바람직하지 않고, 2000초과일 경우, 불소함량이 많아 타이어 고무의 접착공정에 문제를 일으킬 수 있어 바람직하지 않다. 또한, m이 3미만일 경우, 오일과 실리카와의 상용성이 떨어질 수 있어 바람직하지 않고, 10초과일 경우 단가가 상승할 수 있어 바람직하지 않다.In the formula 1, n is 500 to 2000, m is 3 to 10, more preferably 1000 to 1500, and m is 5 to 8. When n is less than 500, the molecular weight is small, And if it is more than 2000, the fluorine content is large, which may cause problems in the adhesion process of the tire rubber, which is not preferable. If m is less than 3, the compatibility between oil and silica may be deteriorated, and if m is more than 10, the unit cost may increase, which is not preferable.
본 발명에 따른 자기세정기능을 갖는 고무 조성물에 있어서, 일반적으로 물과 접촉한 경계면의 에너지가 크면, 서로 접촉하는 면적을 작게 하여 덜 적시게 되고, 경계면 에너지가 작으면, 접촉하는 면적이 넓어져 물이 표면을 적시는 것처럼 보인다. 물이 표면을 많이 적시면 물과 친하다는 뜻으로 친수성이라 하고, 그 반대는 소수성이라 하는데, 이런 성질을 흔히 물방울과 표면이 접촉하는 각도로 표시하는데, 소수성은 물방울과 물체의 표면의 접촉각을 통해 그 물체의 소수성을 확인 할 수 있으며, 통상적으로 타이어 표면은 소수성을 가져 물이 접촉하는 각도는 90 ~ 130o이다. 자기세정기능이 부여되기 위해서는 불소계 특유의 강한 소수성을 가져야 하는데, 본 발명에서는 불소실리콘고무를 효과적으로 원료고무 조성물에 혼합하고, 이를 이용하여 제조한 타이어 표면과 물방울의 접촉각이 150o이상~300o이하인 것이 바람직한데, 150o 미만인 경우, 자기세정 효과가 미비하여 바람직하지 않고, 300o초과인 경우, 높은 단가의 불소실리콘고무의 함량이 크게 상승하여 단가가 상승하는 문제가 있다. 따라서 본 발명은 접촉각이 150o이상 ~ 300 o이하 되는 강한 소수성 고무 조성물의 제조 방법을 제공하고, 이를 타이어에 적용 시, 자기세정기능이 부여된 타이어를 제조 가능하게 한다. In the rubber composition having the self-cleaning function according to the present invention, when the energy of the interface in contact with water is large, the contact area becomes smaller and less wettable. When the interface energy is smaller, Water appears to wet the surface. Water is often called hydrophilic, meaning it is friendly to water, and vice versa. This property is often referred to as the angle at which the droplet contacts the surface. Hydrophobicity is measured by the contact angle of water droplets and the surface of the object The hydrophobicity of the object can be confirmed. Normally, the surface of the tire is hydrophobic and the contact angle of the water is 90 to 130 ° . In order to impart a self-cleaning function, fluorosilicone rubber should be strongly hydrophobic. In the present invention, fluorosilicone rubber is effectively mixed with a raw material rubber composition, and the contact angle of water droplets with the tire surface prepared using the fluorosilicone rubber is 150 o to 300 o If it is less than 150 o , the self-cleaning effect is insufficient, which is undesirable. If it is more than 300 o , there is a problem that the content of the fluor silicone rubber at a high unit price is greatly increased and the unit price is increased. Accordingly, the present invention provides a method for producing a strong hydrophobic rubber composition having a contact angle of 150 o to 300 o , and when applied to a tire, a tire having a self-cleaning function can be manufactured.
본 발명에 따르면 타이어에 사용되는 오일 및 실리카와 상용성이 우수한 불소실리콘고무를 혼합함으로써, 타이어에 자기세정기능을 부여함으로써 타이어 외관 성능을 향상시킬 수 있다.According to the present invention, by mixing the oil used in a tire and the fluorosilicone rubber excellent in compatibility with silica, a self-cleaning function is imparted to the tire to improve the appearance of the tire.
이하 본 발명을 하기의 실시예 및 비교예에 의하여 보다 구체적으로 설명한다. 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않으며, 본 발명의 보호범위를 제한하는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. The following examples are only illustrative of the present invention and do not limit the scope of protection of the present invention.
<실시예 1>≪ Example 1 >
스티렌 부타디엔 고무 70중량부 및 부틸고무 30중량부가 혼합된 원료고무 100중량부에 대하여 상업적으로 구할 수 있는 불소실리콘고무 (FVMQ, HRS사, n=ca.1200, m=ca.7) 1중량부와 실리카 (Evonic사, Z115GR) 70중량부, Bis(triethoxysilylpropyl)tetrasulfide (Evonic사, Si69) 5중량부, 카본블랙 5중량부, 산화아연 3중량부, 스테아린산 2중량부, 왁스 2중량부, 노화방지제(Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, TMDQ) 1중량부를 원료고무와 함께 밴버리 믹서에서 배합하여 고무 배합물을 얻었다.1 part by weight of commercially available fluorine silicone rubber (FVMQ, HRS, n = ca.1200, m = ca.7) was added to 100 parts by weight of a raw rubber mixed with 70 parts by weight of styrene butadiene rubber and 30 parts by weight of butyl rubber 5 parts by weight of silica (Evonic, Z115GR), 5 parts by weight of bis (triethoxysilylpropyl) tetrasulfide (Evonic, Si69), 5 parts by weight of carbon black, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ) was blended with a raw rubber in a Banbury mixer to obtain a rubber blend.
상기의 고무배합물에 가류제로서 황 2중량부, 가류촉진제(N-cyclohexyl-2-benzothiazol sulfenamide, CZ) 2중량부를 첨가하고 160℃에서 30분 동안 가류시켜 고무시편을 제조하였다.2 parts by weight of sulfur and 2 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide (CZ) as vulcanizing agents were added to the rubber compound and vulcanized at 160 DEG C for 30 minutes to prepare rubber specimens.
<실시예 2>≪ Example 2 >
불소실리콘고무 (FVMQ, HRS사, n=ca.1200, m=ca.7) 5중량부 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 조성 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Example 1, except that 5 parts by weight of a fluorine silicone rubber (FVMQ, HRS, n = ca.1200, m = ca.7) was used.
<실시예3>≪ Example 3 >
불소실리콘고무 (FVMQ, HRS사, n=ca.1200, m=ca.7) 15중량부 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 조성 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Example 1, except that 15 parts by weight of a fluorine silicone rubber (FVMQ, HRS, n = ca.1200, m = ca.7) was used.
<실시예4><Example 4>
불소실리콘고무 (FVMQ, HRS사, n=ca.1200, m=ca.7) 20중량부 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 조성 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Example 1, except that 20 parts by weight of fluorine silicone rubber (FVMQ, HRS, n = ca.1200, m = ca.7) was used.
<비교예><Comparative Example>
불소실리콘고무 (FVMQ, HRS사, n=ca.1200, m=ca.7)를 사용하지 않는 것을 제외하고는, 상기 실시예 1과 동일한 조성 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Example 1 except that fluorine silicone rubber (FVMQ, HRS, n = ca.1200, m = ca.7) was not used.
<시험예><Test Example>
상기 실시예 1 내지 4 및 비교예에 따라 제조한 각각의 고무시편에 대해 물성을 ASTM 관련규정에 의해 측정하였고, 소수성 평가를 실시하여 그 결과를 하기 표 2에 나타내었다. The physical properties of each of the rubber specimens prepared according to Examples 1 to 4 and Comparative Examples were measured according to the ASTM regulations, and the results were shown in Table 2 below.
접촉각을 제외한 실시예의 측정값은 비교예의 고무시편의 값을 100으로 하였을 때, 환산한 물성 수치로서 모든 물성 수치는 높을수록 우수한 결과를 의미한다.Except for the contact angle, the measured value of the embodiment is the converted physical property value when the value of the rubber specimen of the comparative example is taken as 100. The higher the value of all physical properties, the better the result.
접촉각은 타이어 표면과 물방울이 형성하는 실제 각도를 측정한 값을 의미한다.The contact angle means a value obtained by measuring the actual angle formed by the surface of the tire and water droplets.
상기 표 2에서 나타난 바와 같이, 불소실리콘고무를 1중량부 이상 사용하였을 때, 접촉각이 상승하며, 20중량부 이상일 경우 제동특성 및 연비특성이 하락하고, 인장강도 및 신장률이 하락함을 알 수 있다.
As shown in Table 2, when the fluorosilicone rubber is used in an amount of 1 part by weight or more, the contact angle increases. When the fluorosilicone rubber is used in an amount of 20 parts by weight or more, the braking property and the fuel consumption property are lowered and the tensile strength and elongation are decreased .
Claims (4)
[화학식 1]
(식 중, n은 500 ~ 2000의 정수이며, m은 3 ~ 10의 정수이다.)인 것을 특징으로 하는 자기세정기능을 갖는 타이어용 고무 조성물.1 to 20 parts by weight of a fluorine-containing silicone rubber per 100 parts by weight of a raw material rubber, wherein the fluorine-containing silicone rubber is a rubber composition for a tire having a self-cleaning function by mixing a fluorine- :
[Chemical Formula 1]
(Wherein n is an integer of 500 to 2000 and m is an integer of 3 to 10).
타이어로 하였을 경우, 타이어 표면과 물방울의 접촉각이 150˚이상~300˚이하가 되는 자기세정기능을 갖는 타이어용 고무 조성물.The method according to claim 1,
Wherein the tire has a self-cleaning function in which the contact angle between the tire surface and water drops is not less than 150 DEG and not more than 300 DEG.
(1) 스티렌 부타디엔 고무 70중량부 및 부틸고무 30중량부가 혼합된 원료고무 100중량부에 대하여, 하기 화학식 1로 선택되는 불소실리콘고무 1~20중량부, 실리카 70중량부, Si69 5중량부, 카본블랙 5중량부, 산화아연 3중량부, 스테아린산 2중량부, 왁스 2중량부, 노화방지제 1중량부를 혼합하여 고무 배합물을 제조하는 단계; 및
[화학식 1]
(식 중, n은 500 ~ 2000의 정수이며, m은 3 ~ 10의 정수이다.)
(2) 상기 단계(1)의 결과물에 가류제인 황 2중량부, 가류촉진제 2중량부를 첨가한 후, 160℃에서 30분 동안 가류하는 단계.A method of manufacturing a rubber composition having a self-cleaning function, comprising the steps of:
(1) 1 to 20 parts by weight of a fluorine-containing silicone rubber selected from the following formula (1), 70 parts by weight of silica, 5 parts by weight of Si69, and 100 parts by weight of a raw rubber mixed with 70 parts by weight of styrene butadiene rubber and 30 parts by weight of butyl rubber, 5 parts by weight of carbon black, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of wax and 1 part by weight of an antioxidant to prepare a rubber blend; And
[Chemical Formula 1]
(Wherein n is an integer of 500 to 2000 and m is an integer of 3 to 10.)
(2) adding 2 parts by weight of sulfur as the vulcanizing agent and 2 parts by weight of the vulcanization accelerator to the result of the step (1), and then vulcanizing at 160 DEG C for 30 minutes.
A tire comprising a rubber composition for a tire having a self-cleaning function according to any one of claims 1 to 3.
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| KR20220101275A (en) | 2021-01-11 | 2022-07-19 | 한국타이어앤테크놀로지 주식회사 | Self-cleaning tire comprising surface modified sidewall by hydrophobic structure |
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