KR100533266B1 - Tire tread rubber composition - Google Patents
Tire tread rubber composition Download PDFInfo
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- KR100533266B1 KR100533266B1 KR10-2002-0028848A KR20020028848A KR100533266B1 KR 100533266 B1 KR100533266 B1 KR 100533266B1 KR 20020028848 A KR20020028848 A KR 20020028848A KR 100533266 B1 KR100533266 B1 KR 100533266B1
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- South Korea
- Prior art keywords
- weight
- parts
- rubber
- raw material
- thermoplastic resin
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
- 239000005060 rubber Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 47
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 21
- 229920002472 Starch Polymers 0.000 claims abstract description 19
- 235000019698 starch Nutrition 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 239000008107 starch Substances 0.000 abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 229920000945 Amylopectin Polymers 0.000 description 4
- 229920000856 Amylose Polymers 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000010692 aromatic oil Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/10—Ultra-violet radiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2307/00—Location of water treatment or water treatment device
- C02F2307/10—Location of water treatment or water treatment device as part of a potable water dispenser, e.g. for use in homes or offices
Abstract
본 발명은 통상의 원료고무 및 첨가제를 포함하는 타이어 트레드용 고무 조성물에 열팽창후의 입자경이 10∼100㎛인 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자를 상기 원료고무 100중량부에 대하여 1∼10중량부 되도록 더 포함하고, 또한 원료고무 100중량부에 대하여 전분 1∼20중량부를 더 포함하는 타이어 트레드용 고무 조성물에 관한 것으로서, 이는 빙상제동성능과 핸들링성능 및 내마모성능을 크게 향상시킬 수 있다. The present invention relates to thermoplastic resin particles containing a thermosetting liquid or a solid having a particle diameter of 10 to 100 µm after thermal expansion in a rubber tread rubber composition containing a conventional raw material rubber and an additive, based on 1 to 10 parts by weight of the raw material rubber. The present invention relates to a tire tread rubber composition further comprising a weight part, and further comprising 1 to 20 parts by weight of starch, based on 100 parts by weight of the raw material rubber, which can greatly improve ice sheet braking performance, handling performance, and wear resistance.
Description
본 발명은 빙상제동성을 유지하면서 핸들링 성능과 내마모성을 향상시킨 타이어 트레드용 고무조성물에 관한 것으로서, 더욱 상세하게는 기존에 사용하는 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자를 감량하여 첨가하고 전분을 더 첨가하여 기존의 빙상제동성을 유지하며 핸들링 성능과 내마모성을 향상시킨 타이어 트레드용 고무 조성물에 관한 것이다.The present invention relates to a rubber tread rubber composition that improves handling performance and abrasion resistance while maintaining ice-braking properties. More specifically, a thermoplastic resin particle mixed with a thermosetting liquid or a solid used in the past is reduced and added to starch. It further relates to a rubber composition for tire treads that maintains conventional ice sheet braking properties and improves handling performance and wear resistance.
타이어의 빙상제동성을 향상시키기 위한 종래의 방법으로는 트레드 표면에 스파이크(spike)를 부착시키는 방법이 사용되어 왔으나, 스파이크가 노면을 손상시켜 분진을 발생시키는 문제로 인해 최근 환경에 대한 관심이 높아지면서 그 사용이 규제되고 있다. As a conventional method for improving the ice sheet braking performance of a tire, a method of attaching a spike to the surface of the tread has been used. However, due to the problem that the spike damages the road surface and generates dust, recent interest in the environment is high. Its use is regulated.
따라서, 빙상제동성을 향상시키기 위하여 고무조성물의 배합제를 변경시키는 방법이 사용되고 있으나, 배합제 변경만으로 빙상제동성을 향상시키는 것은 한계가 있다. Therefore, the method of changing the compounding agent of the rubber composition is used to improve the ice sheet braking property, but there is a limit to improving the ice sheet braking property only by changing the compounding agent.
또한, 빙상제동성을 향상시키기 위하여 최근에는 고무표면에 미세한 요철을 형성시킴으로써 얼음 표면에 존재하는 미세한 수막을 제거하는 방법이 통상적으로 사용되고 있다. In addition, in order to improve ice braking property, in recent years, a method of removing the fine water film existing on the ice surface by forming fine irregularities on the rubber surface has been commonly used.
이중에서 고무표면에 미세한 기포를 형성시키는 방법(국내특허공개 제1999-80303호, 일본공개특허 2002-36816호 및 2001-287508호)은 빙상제동성을 크게 향상시킬 수는 있었으나, 타이어의 블록 강성이 떨어지기 때문에 일반 노면에서의 주행안정성이 저하되며, 주행시에 발생되는 칩컷(chip-cut)에 의한 마모에 크게 불리한 단점을 가지고 있다. 또한, 기포가 트레드 전부위에 생성되기 때문에 트레드 블록의 강성이 떨어져 핸들링 성능에 불리한 단점이 있다. Among them, the method of forming fine bubbles on the rubber surface (Korean Patent Laid-Open Publication No. 1999-80303, Japanese Patent Laid-Open Publication No. 2002-36816 and 2001-287508) can greatly improve ice sheet braking, but the tire block rigidity Because of this fall, the running stability on the general road surface is lowered, and has a disadvantage that is greatly disadvantageous to wear due to the chip-cut generated during driving. In addition, since bubbles are generated all over the tread, the rigidity of the tread block is reduced, which is disadvantageous in handling performance.
한편, 내마모성이 떨어지는 문제를 해결하기 위한 종래의 방법으로 통상적인 것은 트레드 고무조성물에 사용하는 보강제(카본블랙이나 실리카 등)의 함량을 증가시키는 방법, 가교제의 함량을 증가시키는 방법 등을 사용하고 있다. 이러한 방법을 사용하면 내마모성을 향상시킬 수는 있으나, 고무의 경도가 상승하여 유연성이 떨어지기 때문에 노면과의 접지면적이 줄어들게 되어 빙상제동성이 크게 저하되는 단점이 있다. On the other hand, the conventional method for solving the problem of poor wear resistance is a method of increasing the content of the reinforcing agent (carbon black, silica, etc.) used in the tread rubber composition, the method of increasing the content of the crosslinking agent, etc. . Although this method can improve abrasion resistance, since the hardness of the rubber is increased and the flexibility is reduced, the ground area with the road surface is reduced, resulting in a significant deterioration of ice sheet braking performance.
또한, 고경도 물질을 배합하여 고무 표면에 미세한 요철을 형성시키는 방법으로는 일본특허공개 소60-258235(세라믹 미세 분말), 평2-274740(단섬유), 평2-170840(금속) 등이 있으나, 고무의 경도가 상승하여 유연성이 떨어지기 때문에 노면과의 접지면적이 떨어지게 되어 빙상제동성이 오히려 저하되는 단점을 가지고 있다. In addition, Japanese Patent Application Publication No. 60-258235 (ceramic fine powder), flat 2-274740 (short fiber), flat 2-170840 (metal), etc. are used as a method of forming fine concavo-convex on the rubber surface by blending a high hardness material. However, since the hardness of the rubber rises, the flexibility decreases, so that the ground area with the road surface falls, and thus the ice sheet braking performance is deteriorated.
이에, 본 발명자들은 상기와 같은 문제점을 유발시키지 않고 타이어 트레드용 고무 조성물의 빙상제동성 및 내마모성을 향상시키기 위한 연구를 수행하던 중, 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자를 감량 첨가하고 친수성 입자인 전분을 첨가한 결과, 고무의 가류시에 가해지는 열에 의하여 열기화성 액체 또는 고체가 기화됨으로써 팽창된 열가소성 수지 입자가 고무표면에 미세한 요철을 형성시킴으로써 얼음 표면에 존재하는 미세한 수막을 제거하게 되어 우수한 빙상제동성을 가짐과 아울러 전분이 표면에 노출될 때 지면의 수분에 의해 용해되어 미세한 요철을 형성시켜 동일한 특성을 나타내며 동시에 트레드 블록 내부에 있는 경우는 보강제로 작용하여 일정 수준이상의 강성을 나타내어 핸들링 성능과 내마모성을 향상시킬 수 있음을 알게되어 본 발명을 완성하게 되었다. Accordingly, the present inventors are reducing the amount of thermoplastic resin mixed with a thermosetting liquid or solid and hydrophilic, while conducting research to improve ice-brake resistance and wear resistance of the rubber tread rubber composition without causing the above problems. As a result of the addition of starch, which is a particle, the thermosetting liquid or solid is vaporized by the heat applied when the rubber is vulcanized, and thus the expanded thermoplastic resin particles form fine irregularities on the rubber surface to remove the fine water film present on the ice surface. It has excellent ice braking ability and when starch is exposed to the surface, it is dissolved by water in the ground to form fine unevenness, and shows the same characteristics.In the case of inside the tread block, it acts as a reinforcing agent to show a certain level of rigidity. Can improve performance and wear resistance It was found that the present invention was completed.
따라서, 본 발명의 목적은 스노우 타이어 트레드용 고무조성물의 요구물성인 빙상제동성을 향상시킴과 아울러 종래의 방법에서 가장 문제가 되고 있는 핸들링 성능과 내마모성을 크게 향상시킨 타이어 트레드용 고무조성물을 제공하는 데 있다. Accordingly, an object of the present invention is to provide a rubber composition for tire treads that improves the ice-brake property, which is a required property of the rubber composition for snow tire treads, and greatly improves handling performance and abrasion resistance which are most problematic in the conventional methods. There is.
상기와 같은 목적을 달성하기 위한 본 발명의 타이어 트레드용 고무조성물은 원료고무 100중량부에 대하여 열팽창후의 입자경이 10∼100㎛인 열기화성 액체 또는 고체를 혼입한 열가소성 수지입자 1∼10중량부와 입자경이 2∼100㎛인 전분 1∼20중량부를 더 포함하는 것임을 그 특징으로 한다. The rubber composition for tire treads of the present invention for achieving the above object comprises 1 to 10 parts by weight of thermoplastic resin particles incorporating a thermosetting liquid or solid having a particle diameter of 10 to 100 μm after thermal expansion with respect to 100 parts by weight of raw rubber. It is characterized by further comprising 1 to 20 parts by weight of starch having a particle diameter of 2 to 100 µm.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
통상적으로 빙상에서는 입자크기 10㎛ 정도의 미세한 수막이 형성되어 타이어 구동 및 제동시 타이어와 노면과의 접촉을 방해함으로써 수막 위에서 미끄러지는 현상을 유발시키며, 이러한 현상으로 인하여 사고가 발생하게 된다. In general, on the ice sheet, a fine water film having a particle size of about 10 μm is formed to cause a phenomenon of slipping on the water film by interfering with the tire and the road surface during tire driving and braking, and an accident occurs.
본 발명에서는 이러한 문제를 해결하기 위해 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자와 수용성 전분입자를 사용한다. In order to solve this problem, the present invention uses thermoplastic resin particles and water-soluble starch particles incorporating a thermosetting liquid or solid.
본 발명에서 사용한 열기화성 액체 또는 고체를 혼입한 열가소성 수지입자는 도 1에 나타낸 바와 같이 구형의 구조를 형성하고 있는 것으로, 고무에 혼합된 후 가류시에 열을 가하게 되면 입자 내부에 혼입되어 있는 열기화성 액체 또는 고체가 기화되어 기체를 발생시켜 열가소성 수지 입자가 팽창하게 됨으로써 고무 내부에 기포를 형성하게 된다. 형성된 기포는 타이어 트레드가 마모되면서 표면에 미세한 요철을 형성시킴으로써 주행시 빙상의 수막을 제거하여 노면과의 접지면적을 높힘으로써 빙상제동성을 향상시키게 된다. The thermoplastic resin particles incorporating the thermophilizable liquid or solid used in the present invention have a spherical structure as shown in FIG. 1, and when mixed with rubber and applied with heat during vulcanization, the heat is mixed into the particles. The chemical liquid or solid is evaporated to generate gas to expand the thermoplastic resin particles, thereby forming bubbles in the rubber. The formed air bubbles improve the ice braking ability by removing the water film on the ice while driving and forming a fine unevenness on the surface as the tire tread is worn.
이러한 역할을 하는 열기화성 액체 또는 고체를 혼입한 열가소성 수지입자는 열팽창후의 입자경이 10∼100㎛, 바람직하게는 30∼70㎛인 것이 좋다. 만일, 발포후 입자경이 10㎛ 미만인 것이면 빙상제동성의 향상을 기대할 수 없고, 100㎛ 초과하는 것이면 내마모성이 급격히 떨어진다. The thermoplastic resin particles incorporating the thermosetting liquid or the solid having such a role preferably have a particle diameter of 10 to 100 µm, preferably 30 to 70 µm after thermal expansion. If the particle size after foaming is less than 10 mu m, the improvement of ice sheet braking resistance cannot be expected, and if it exceeds 100 mu m, the wear resistance is sharply inferior.
이와같은 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자는 기화온도 및 열팽창후의 입자크기에 따라 다양한 종류를 사용할 수 있으며, 본 발명 실시예에서는 스웨덴 Expancel사의 Expancel 092-DU80, Expancel 092-DU120 등을 사용하였다. 그러나, 본 발명의 효과를 갖는 것이라면 어떠한 열기화성 액체 또는 고체를 혼입한 열가소성 수지입자라도 좋다. The thermoplastic resin particles incorporating such a thermosetting liquid or solid may be used in various kinds according to the vaporization temperature and the particle size after thermal expansion. In the present invention, Expancel 092-DU80, Expancel 092-DU120, etc., of Expancel, Sweden is used. It was. However, any thermoplastic resin particles incorporating any thermosetting liquid or solid may be used as long as it has the effects of the present invention.
본 발명에서 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자는 원료고무 100중량부에 대하여 1∼10중량부, 바람직하게는 1∼5중량부로 사용하는 것이 바람직하다. 만일, 그 첨가량이 원료고무 100중량부에 대하여 1중량부 미만이면 빙상제동성의 향상을 기대할 수 없고, 10중량부 초과면 내마모성이 급격히 떨어진다. In the present invention, the thermoplastic resin particles incorporating the thermosetting liquid or the solid are preferably used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the raw material rubber. If the added amount is less than 1 part by weight based on 100 parts by weight of the raw material rubber, the improvement of ice sheet braking resistance cannot be expected.
그러나, 상기한 바와 같이 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자만을 단독으로 사용하는 경우 빙상제동성은 향상되지만 타이어 트레드 표면에 미세한 요철이 존재하며, 또한 트레드 내부에 기체를 포함한 열가소성 수지 입자가 존재하기 때문에 고무의 경도가 떨어지고, 핸들링 성능과 마모성이 크게 저하되는 단점을 유발시킨다. However, when only the thermoplastic resin particles incorporating the thermosetting liquid or solid as described above are used alone, ice-braking property is improved, but fine unevenness is present on the surface of the tire tread, and the thermoplastic resin particles containing gas are present in the tread. Because of its presence, the hardness of the rubber is lowered, which causes a disadvantage in that handling performance and wearability are greatly reduced.
따라서, 빙상제동성을 유지하면서 핸들링 성능과 내마모성을 향상시키기 위한 방법이 필요하다. 내마모성과 핸들링성을 향상시키기 위해서 종래에는 카본블랙이나 실리카와 같은 보강제의 배합량을 높임으로써 고무의 경도를 올리는 방법을 주로 사용하여 왔으나, 고무의 경도가 높아지면 고무의 유연성이 떠어지게 되어 빙상제동성이 저하되는 단점을 가지게 된다. Therefore, there is a need for a method for improving handling performance and wear resistance while maintaining ice braking. Conventionally, in order to improve wear resistance and handling property, a method of increasing the hardness of rubber by increasing the amount of reinforcing agent such as carbon black or silica has been mainly used. This has the disadvantage of deterioration.
따라서, 본 발명에서는 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자를 감량 혼입하고 동시에 전분입자를 사용하여 빙상제동성을 유지하면서 핸들링 성능과 내마모성이 저하되는 문제점을 해결하고자 한다. Therefore, the present invention is to solve the problem that the handling performance and wear resistance is reduced while reducing the mixing of the thermoplastic resin particles incorporating the thermosetting liquid or solid and at the same time maintaining the ice-braking resistance using starch particles.
전분 입자는 표면에 노출된 경우에만 지면의 수분에 용해되어 미세한 요철을 형성하여 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자와 같은 동일한 원리로 빙상제동성을 향상시키게 된다.Starch particles are dissolved in the water of the ground only when exposed to the surface to form fine concavities and convexities, thereby improving ice-breakability on the same principle as thermoplastic resin particles incorporating a thermosetting liquid or a solid.
이와같은 전분 입자는 입자경이 2∼100㎛, 바람직하게는 10∼50㎛인 것이 좋다. 입자경이 2㎛ 미만인 전분은 빙상제동성의 향상을 기대하기 어렵고, 만일 100㎛ 초과면 내마모성이 급격히 떨어진다. Such starch particles have a particle diameter of 2 to 100 µm, preferably 10 to 50 µm. Starch having a particle diameter of less than 2 μm is difficult to expect the improvement of ice-break braking property, and if it exceeds 100 μm, wear resistance is sharply inferior.
본 발명에서 사용한 전분 입자는 도 2에 나타낸 바와 같은 구조를 갖는 아밀로스와 아밀로펙틴으로 이루어진 것으로서, 구체적으로는 대상(주)의 제품인 아밀로스와 아밀로펙틴의 구성비가 25:75인 옥수수 전분이다. 그러나, 본 발명의 효과를 갖는 것이라면 어떠한 종류의 전분 입자라도 좋다. The starch particles used in the present invention are composed of amylose and amylopectin having a structure as shown in FIG. 2, and specifically, corn starch having a composition ratio of amylose and amylopectin, which is a product of the company, is 25:75. However, any kind of starch particle may be used as long as it has the effect of the present invention.
이같은 전분 입자를 원료고무 100중량부에 대하여 1∼20중량부, 바람직하게는 5∼15중량부로 사용하는 것이 바람직하다. 만일, 그 첨가량이 원료고무 100중량부에 대하여 2중량부 미만이면 빙상제동성의 향상을 기대할 수 없고, 20중량부 초과면 내마모성과 가공성이 급격히 떨어진다. Such starch particles are preferably used in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the raw material rubber. If the added amount is less than 2 parts by weight with respect to 100 parts by weight of the raw material rubber, it is not expected to improve the ice sheet braking resistance, and if it exceeds 20 parts by weight, wear resistance and workability are drastically inferior.
본 발명의 타이어 트레드용 고무조성물은 이와같은 열기화성 액체 또는 고체를 혼입한 열가소성 수지입자와 전분입자를 포함하면서, 통상적인 원료고무 및 배합제를 포함한다. 원료고무로는 천연고무, 부타디엔 고무, 스티렌-부타디엔 고무 등을 사용할 수 있다. 배합제로는 산화아연, 스테아린산, 카본블랙, 실리카, 실리카 커플링제, 아로마틱 오일, 레진, 가공조제, 유황부, 촉진제 등을 첨가할 수 있다. The rubber composition for tire treads of the present invention includes conventional raw material rubbers and compounding agents, including thermoplastic resin particles and starch particles incorporating such a thermosetting liquid or solid. As the raw material rubber, natural rubber, butadiene rubber, styrene-butadiene rubber and the like can be used. As the compounding agent, zinc oxide, stearic acid, carbon black, silica, silica coupling agent, aromatic oil, resin, processing aid, sulfur part, accelerator and the like can be added.
구체적으로는, 원료고무로는 천연고무 단독 또는 천연고무 60∼90중량부와 부타디엔 고무 10∼40중량부를 혼용하여 사용하거나 스티렌-부타디엔 고무 단독 또는 스티렌-부타디엔 고무 60∼90중량부와 부타디엔 고무 10∼40중량부를 혼용할 수 있고, 이들 원료고무 100중량부에 대하여 보강제로서 카본블랙 30∼100중량부 또는 실리카 30∼100중량부와 실리카 커플링제 1∼15중량부 또는 카본블랙 10∼80중량부와 실리카 10∼80중량부와 실리카 커플링제 1∼12중량부를 혼용하여 첨가할 수 있고, 이와 함께 산화아연 1∼5중량부, 스테아린산 1∼5중량부, 아로마틱 오일 10∼50중량부, 노화방지제 1∼5중량부, 왁스 1∼5중량부, 유황 1∼5중량부, N-t-부틸-2-벤조티아졸 설펜아미드 0.5∼4중량부를 첨가할 수 있다.Specifically, as the raw material rubber, natural rubber alone or 60 to 90 parts by weight of natural rubber and 10 to 40 parts by weight of butadiene rubber may be used in combination, or styrene-butadiene rubber alone or 60 to 90 parts by weight of styrene-butadiene rubber and butadiene rubber 10 It can mix -40 weight part, and 30-100 weight part of carbon black or 30-100 weight part of silicas, 1-15 weight part of silica coupling agents, or 10-80 weight part of carbon blacks as a reinforcement agent with respect to 100 weight part of these raw material rubbers And 10 to 80 parts by weight of silica and 1 to 12 parts by weight of a silica coupling agent can be mixed and added, together with 1 to 5 parts by weight of zinc oxide, 1 to 5 parts by weight of stearic acid, 10 to 50 parts by weight of aromatic oil, and anti-aging agent. 1 to 5 parts by weight, 1 to 5 parts by weight of wax, 1 to 5 parts by weight of sulfur, and 0.5 to 4 parts by weight of N- t-butyl-2-benzothiazole sulfenamide can be added.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
실시예 1∼4 및 비교예 1∼4Examples 1-4 and Comparative Examples 1-4
가류전 고무시트는 다음 표 1에 기재된 배합비율로 고무와 첨가제를 통상적인 혼합방법에 의해 혼합하였으며, 혼합된 고무를 160℃에서 20분 동안 가류하여 측정시편을 준비하였다. 이와같이 준비된 고무조성물의 물성결과를 다음 표 1에 나타내었다. The rubber sheet before vulcanization was mixed with the rubber and the additive by the conventional mixing method in the mixing ratio shown in Table 1 below, and the mixed rubber was vulcanized at 160 ° C. for 20 minutes to prepare a test specimen. The physical properties of the rubber composition thus prepared are shown in Table 1 below.
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 고무조성물로 만들어진 실시예 1 내지 4의 가류시편은 매우 우수한 핸들링 성능과 빙상제동성 및 내마모성을 가진다. 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자와 전분을 사용하지 않은 비교예 1의 경우는 빙상 제동성이 크게 떨어진다. 그리고, 열기화성 액체 또는 고체를 혼입한 비교예 2는 비교예 1에 비하여 빙상 제동성은 향상되지만 핸들링 성능과 내마모성이 크게 저하됨을 알 수 있다. 또한, 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자의 함량이 본 발명의 범위보다 많은 비교예 3의 경우는 빙상 제동성은 향상되지만 핸들링 성능과 가류시편의 경도가 크게 떨어지게 되어 내마모성이 크게 감소한다. As shown in Table 1, the vulcanization specimens of Examples 1 to 4 made of the rubber composition according to the present invention have very excellent handling performance, ice sheet braking resistance, and abrasion resistance. In the case of Comparative Example 1 in which the thermoplastic resin particles containing the thermosetting liquid or the solid and the starch are not used, the ice sheet braking property is greatly inferior. In addition, Comparative Example 2 incorporating a thermosetting liquid or a solid has improved ice-phase braking properties compared to Comparative Example 1, but it can be seen that handling performance and wear resistance are greatly reduced. In addition, in the case of Comparative Example 3 in which the content of the thermoplastic resin particles incorporating the thermosetting liquid or the solid is greater than the range of the present invention, the ice sheet braking performance is improved, but the handling performance and the hardness of the vulcanization specimen are greatly reduced, thereby greatly reducing the wear resistance. .
또한, 전분의 함량이 본 발명의 범위를 벗어나는 비교예 4의 경우는 빙상제동성은 약간 향상되지만 신장율이 크게 저하되고 핸들링 성능 및 내마모성이 크게 감소함을 알 수 있다. In addition, in the case of Comparative Example 4 in which the starch content is out of the range of the present invention, the ice sheet braking performance is slightly improved, but the elongation rate is greatly decreased, and the handling performance and the wear resistance are greatly reduced.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 열팽창후에 일정 직경의 입자크기를 갖는 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자의 일정 함량과 전분 일정 함량을 포함하는 고무조성물을 사용한 경우 빙상제동성능과 핸들링성능 및 내마모성능을 크게 향상시킬 수 있다. As described in detail above, in the case of using a rubber composition including a predetermined amount of a thermoplastic resin particle mixed with a thermosetting liquid or a solid having a particle size of a predetermined diameter after thermal expansion and a predetermined amount of starch according to the present invention, Handling performance and wear resistance can be greatly improved.
도 1은 열기화성 액체 또는 고체를 혼입한 열가소성 수지 입자의 열팽창 전후의 모식도이고, 1 is a schematic diagram before and after thermal expansion of a thermoplastic resin particle mixed with a thermosetting liquid or a solid,
도 2는 아밀로스 및 아밀로펙틴의 분자구조를 나타낸 모식도이다.Figure 2 is a schematic diagram showing the molecular structure of amylose and amylopectin.
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| US5374671A (en) * | 1993-02-16 | 1994-12-20 | The Goodyear Tire & Rubber Company | Hydrophilic polymer composite and product containing same |
| JPH10316801A (en) * | 1997-05-19 | 1998-12-02 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire using the same |
| KR20000029071A (en) * | 1998-10-15 | 2000-05-25 | 스위셔 케드린 엠 | Preparation of starch reinforced rubber and use thereof in tires |
| KR20010034392A (en) * | 1998-11-27 | 2001-04-25 | 하기와라 세이지 | Rubber composition for tire tread having improved running performance on ice and pneumatic tire using the same |
| JP2001089599A (en) * | 1999-08-06 | 2001-04-03 | Goodyear Tire & Rubber Co:The | Rubber containing reinforcing agent of starch, and tire having the same as component |
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| Publication number | Publication date |
|---|---|
| KR20030090956A (en) | 2003-12-01 |
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