CN115124773B - Tire with low rolling resistance, high wet grab and good controllability - Google Patents
Tire with low rolling resistance, high wet grab and good controllability Download PDFInfo
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- CN115124773B CN115124773B CN202210888979.5A CN202210888979A CN115124773B CN 115124773 B CN115124773 B CN 115124773B CN 202210888979 A CN202210888979 A CN 202210888979A CN 115124773 B CN115124773 B CN 115124773B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
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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
- B60C1/0016—Compositions of the tread
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention relates to the technical field of tire manufacturing, in particular to a tire with low rolling resistance, high wet grip and good controllability. The invention ensures the microcosmic compatibility with natural rubber or butadiene rubber and simultaneously ensures the rolling resistance and wet gripping performance by regulating and controlling the styrene content of the solution polymerized styrene-butadiene rubber; by adding a large amount of white carbon black into the tread and matching with two silane coupling agents, the white carbon black has better dispersibility and flocculation resistance in rubber. The addition of the two wet grip resins ensures that the resins respectively enter the solution polymerized styrene butadiene rubber and the natural rubber (or butadiene rubber), and further improves the wet grip on the premise of ensuring the rolling resistance. In the above means, although the rolling resistance and wet grip are improved, since the decrease in modulus leads to the weakening of the handling, the handling is improved by increasing the width of the center rib of the pattern, the ground contact area, and the like.
Description
Technical Field
The invention relates to the technical field of tire manufacturing, in particular to a tire with low rolling resistance, high wet grip and good controllability.
Background
The labeling method for tires sets forth requirements for wet grip and rolling resistance of the tire. On the other hand, as safety is improved, handling performance of tires is also receiving more and more attention. In a typical design, the less filler content used in the tread, the lower the rolling resistance of the tire. However, a reduction in the amount of filler results in a reduction in the modulus of the tread rubber, ultimately affecting the handling properties of the tire. At the same time, the wet grip and rolling resistance of the tire are two sets of contradictory properties. In the wet grip resistance, more white carbon black needs to be added into the tread, and the increase of the rolling resistance is brought about by more white carbon black. Therefore, in designing a tread rubber formula, attention is paid to wet grip, rolling resistance and handling of a tire, and the design is one of the research focuses of a tire formula designer in the future.
In the inventor's early patent CN106750668B, full solution polymerized styrene-butadiene rubber and other technologies are used in time, especially the technology of compound use of a silane coupling agent I and a silane coupling agent II is used, and a tire tread rubber material with ultra-low rolling resistance and ultra-high wet grip performance is invented. The technology of using the composite silane coupling agent can improve the dispersibility of the white carbon black in the rubber material and simultaneously improve the flocculation capability of the rubber material in the processing processes of vulcanization and the like, but the increase of the dispersion and the decrease of the flocculation of the white carbon black can bring the decrease of the modulus of the rubber material, so that the hardness of the tread rubber material is obviously decreased, and the control performance is extremely weakened.
Patent CN114409980A by the inventor proposes a rubber composition designed to have a micro-phase separation such that a temperature sweep curve of a hysteresis factor tan δ has two peaks, a temperature corresponding to a peak having a low temperature is denoted by T1, and a temperature corresponding to a peak having a high temperature is denoted by T2; the relation between T1 and T2 is required to satisfy the temperature T2-T1 being more than 10 ℃ and less than 20 ℃. In this case, the rolling resistance and wear of the tread are well balanced. More importantly, in this invention, we provide a solution to evaluate the tread rubber performance using the difference in the different peak values tan δ. However, the idea of guiding the design of rolling resistance and wet grip still has a large optimization space.
Finally, the inventors have found that it is difficult to achieve a good optimization space in terms of the balance of wet grip, rolling resistance and rolling resistance by means of formulation optimization alone, and therefore it is necessary to provide auxiliary support such as rib width, ground contact area and land-sea ratio of the tread pattern design of the tire. The width of the tread ribs is increased, and the control and ground gripping capability of the tire can be effectively improved. In addition, the balance of rolling resistance and wet grip can be greatly optimized by adjusting the actual ground contact area and sea-land ratio.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a tire with low rolling resistance, high wet grip and good handling performance, which can achieve better balance of handling, wet grip and rolling resistance by controlling the number and position of the peaks of the hysteresis factor tan δ, compatibility of the resin, and rib width, ground contact surface and sea-land ratio in the pattern design.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low rolling resistance, high wet grab, good controllability tire, the tread of the tire is vulcanized by tread rubber composition, the tread rubber composition in the result of the temperature scanning of dynamic analytical analyzer (DMA), loss factor tan delta needs to form two peaks, high temperature peak1 and low temperature peak2, the peak value difference of the two peaks is satisfied, delta T = peak1-peak2 is more than or equal to 5 ℃, the tread rubber composition is prepared by mixing the following raw materials according to 100 parts by weight of rubber component:
the rubber component consists of natural rubber or butadiene rubber and solution-polymerized styrene-butadiene rubber, wherein the weight portion of the natural rubber or butadiene rubber is between 10 and 50phr, and the portion of the solution-polymerized styrene-butadiene rubber is between 50 and 90 phr; meanwhile, the solution polymerized styrene-butadiene rubber needs to meet the requirements that the number average molecular weight Mn of the solution polymerized styrene-butadiene rubber meets the requirement that Mn is more than 30 ten thousand and less than 80 ten thousand, the weight average molecular weight Mw meets the requirement that Mw is more than 50 ten thousand and less than 100 ten thousand, and the molecular weight distribution Mw/Mn meets the requirement that Mw/Mn is more than 1.5 and less than 2.5; the styrene in the solution polymerized styrene-butadiene rubber accounts for the percentage S of the solution polymerized styrene-butadiene, and the S is more than 30 percent and less than 42 percent;
the specific surface area CTAB value of the high-dispersion white carbon black meets, CTAB is more than 150 and less than 200;
the silane coupling agent is composed of more than two silane coupling agents, wherein one silane coupling agent is Si747, the other silane coupling agent is Si75 and/or Si69, the amount of the Si747 is 8-20phr, and the amount of the Si75 and/or Si69 is 2-10 phr;
the width W of the central rib of the tread pattern of the tire needs to be more than 23cm, the actual sea-land ratio of the tread needs to be between 32 and 36 percent, and the actual contact surface is 240 to 260cm 2 In the meantime.
Preferably, the natural rubber or the butadiene rubber is between 30 and 45phr, and the solution polymerized styrene-butadiene rubber is between 60 and 70phr; the weight portion of the high-dispersion white carbon black is 90 to 120phr.
Preferably, the width W of the central rib of the tread pattern is 24-27cm, the actual sea-land ratio of the tread is 32-34%, and the actual contact surface is 240-250 cm 2 In the meantime.
Preferably, the silane coupling agent is Si747 and Si75, the amount of Si747 is 10-15phr, and the amount of Si75 is 2-6 phr.
Preferably, the α -methylstyrene resin is used in an amount of 15 to 25phr, and the hydrogenated dicyclopentadiene resin is used in an amount of 5 to 10phr.
Preferably, the α -methylstyrene resin has a molecular weight distribution satisfying 4 < Mw/Mn < 5, and the hydrogenated dicyclopentadiene (hydrogenated DCPD) resin has a molecular weight distribution satisfying 3 < Mw/Mn < 4.
Preferably, the delta T is between 6 ℃ and 15 ℃.
Preferably, the rubber composition further comprises other fillers, vulcanizing agents, vulcanization accelerators, different types of oils, activators, antioxidants and plasticizers conventionally used in tires and other rubber compositions.
Preferably, the rubber composition further comprises 20 to 40phr of softening oil, 1.0 to 3.0phr of zinc oxide, 1.0 to 3.0phr of stearic acid, 1.0 to 3.0phr of antioxidant 4020,1.0 to 3.0phr of microcrystalline wax, 1.0 to 4.0phr of sulfur, 0.5 to 3.5phr of accelerator CZ, and 0.2 to 1.0phr of accelerator DPG.
Preferably, the rubber composition is compounded by using a tandem one-shot internal mixer, controlling the rotor speed of the internal mixer to be 10-60rpm and the top plug pressure to be 55N/cm 2 The temperature of the cooling water of the internal mixer is 30-40 ℃, and the method comprises the following steps:
1. an upper auxiliary machine process:
(1) adding a rubber component, high-dispersion white carbon black, a silane coupling agent, alpha-methyl styrene resin, hydrogenated dicyclopentadiene resin and other processing aids, and pressing a top bolt for 55-65 seconds;
(2) lifting the top bolt and keeping for 4-6 seconds;
(3) pressing a top bolt to heat the rubber material to 140-150 ℃;
(4) lifting the top plug and adding zinc oxide;
(5) pressing a top bolt to mix the rubber material at the constant temperature of 140-150 ℃ for 55-65 seconds;
(6) discharging the rubber material to a lower auxiliary machine.
2. The following auxiliary machine process:
(1) heating the sizing material to 140-150 ℃;
(2) mixing at 140-150 deg.c for 200-300 sec;
(3) discharging rubber to an open mill, turning and cooling the rubber material to 90-100 ℃, adding a vulcanizing agent on the open mill, uniformly dispersing, and cooling the lower piece to room temperature.
By adopting the technical scheme, the invention ensures the microcosmic compatibility with natural rubber or butadiene rubber and simultaneously ensures the rolling resistance and wet grip performance by regulating and controlling the styrene content of the solution polymerized styrene-butadiene rubber; by adding a large amount of white carbon black into the tread and matching with two silane coupling agents, the white carbon black has better dispersibility and flocculation resistance in rubber. The addition of the two wet grip resins ensures that the resins respectively enter the solution polymerized styrene butadiene rubber and the natural rubber (or butadiene rubber), and further improves the wet grip on the premise of ensuring the rolling resistance. In the above means, although the rolling resistance and wet grip are improved, since the decrease in modulus leads to the weakening of the steering, the controllability is improved by increasing the width of the pattern center rib, the ground contact area, and the like.
Drawings
FIG. 1 is a schematic structural view of pattern A designed according to the present invention; the width of the central rib is 24cm, the sea-land ratio is 34%, and the grounding area is 240cm 2 。
FIG. 2 is a schematic structural view of pattern B designed according to the present invention; the width of the central rib is 25cm, the sea-land ratio is 32%, and the grounding area is 242cm 2 。
FIG. 3 is a schematic view of pattern C designed according to the present invention; the width of the central rib is 26cm, the sea-land ratio is 32%, and the grounding area is 248cm 2 。
FIG. 4 is a schematic structural view of pattern D designed according to the present invention; the width of the central rib is 20cm, the sea-land ratio is 31 percent, and the grounding area is 220cm 2 。
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be reviewed and fully described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention selects 11 tread rubbers, all the tread rubbers are 100 parts, and the main formula of the rubber composition is shown in table 1.
TABLE 1 formulation of the rubber compositions
*1: the solution-polymerized styrene-butadiene rubber is commercially known as E581, the mass of styrene accounts for 36% of the total weight of the polymer, the weight-average molecular weight Mw is 202 ten thousand, and Japanese Asahi formed product.
*2: the natural rubber has a Vietnam 3L grade and a weight-average molecular weight of 250W.
*3: the white carbon black has the trade name of 1165MP and is a product of Solvay company.
*4: alpha-methylstyrene resin, a product of Keteng corporation, USA.
*5: hydrogenated DCPD resin, tongtong chemical.
*6: the total softening oil is the sum of oil in the solution polymerized butylbenzene and additional added oil in the formula.
*7: other raw materials comprise 1.5 percent of ZnO, 2.0 percent of stearic acid, 0.0 percent of age inhibitor 402, 2.0 percent of microcrystalline wax, 2.0 percent of promoter CZ, 0.5 percent of promoter DPG and 1.7 percent of sulfur. The total amount is 11.7 parts.
The preparation process of the sizing material with the formula is as follows:
a series one-step internal mixer is used, the rotor speed of the internal mixer is controlled to be 10-60rpm, the upper ram pressure is controlled to be 55N/cm < 2 >, and the cooling water temperature of the internal mixer is controlled to be 30-40 ℃, and the method comprises the following steps:
1. an upper auxiliary machine process:
(1) adding a rubber component, high-dispersion white carbon black, a silane coupling agent, alpha-methyl styrene resin, hydrogenated dicyclopentadiene resin and other processing aids, and pressing a top bolt for keeping for 60 seconds;
(2) lifting the top bolt and keeping for 5 seconds;
(3) pressing a top bolt to heat the rubber material to 145 ℃;
(4) lifting the top plug and adding zinc oxide;
(5) pressing a top bolt to mix the rubber material at the constant temperature of 145 ℃ for 60 seconds;
(6) discharging the rubber material to a lower auxiliary machine.
2. The following auxiliary machine process:
(1) heating the sizing material to 145 ℃;
(2) mixing at 145 ℃ for 250 seconds;
(3) discharging rubber to an open mill, turning and cooling the rubber material to 90-100 ℃, adding a vulcanizing agent on the open mill, uniformly dispersing, and cooling the lower piece to room temperature.
And testing the performance of the tread rubber material.
Temperature sweep experiments for DMA were performed after all tread rubbers were cured. Frequency: 20Hz; static strain: 10% and dynamic strain 2%. Temperature scanning range: -50 to 80 ℃. The loss factor tan delta needs to form two peaks, peak1 (high temperature) and peak2 (low temperature), the peak difference of the two peaks is satisfied, and delta T = peak1-peak2
The hardness of the tread rubber is implemented according to the national standard general method.
Testing of tire rolling resistance, wet grip and handling.
Tires of 245/50R19 specification were manufactured using 11 selected tread rubbers in a test run with tread patterns as per Table 1. The rolling resistance of the tire is tested according to ISO2850, the wet grip test result is European Union 117 regulation, and the handling performance is subjectively evaluated by a driver. In the table, the rolling resistance, wet grip and handling results of example 1 are taken as 100, and the remaining 10 groups of tires are scored as percentages of example 1. The higher the score, the better the performance.
And (4) conclusion:
examples 1 to 3 are variables of the amount of rubber, where NR and SSBR both satisfy the range of the claims, and tread patterns a to C both satisfy the range of the requirements of center rib width, sea-land ratio, and ground contact area in the claims. Examples 4 to 5, in which the silane coupling agent variables were changed, si747 and Si75 were used in amounts satisfying the scope of the claims, and the tread pattern B was used. Examples 6 to 7 are variables of the grip resin, and the amounts of the α -methylstyrene resin and the hydrogenated DCPD resin both satisfy the scope of claims.
In contrast, the comparative examples, which did not achieve the object of the present invention, showed an unbalanced or overall decrease in rolling resistance, wet grip, or handling performance. The tread rubber composition of comparative example 1 was exactly the same as example 1, but a tread pattern D not in accordance with the claims was used. The amount of NR and SSBR in comparative example 2 is not satisfactory, resulting in an unsatisfactory Δ T and finally in a very poor wet grip and rolling resistance. The amounts of Si747 and Si75 in comparative example 3 do not meet the claims. The α -methylstyrene resin and the hydrogenated DCPD resin of comparative example 4 do not satisfy the requirements.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, including any reference to the above-mentioned embodiments. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A low rolling resistance, high wet grab, good controllability tire, the tread of the tire is vulcanized by tread rubber composition, the tread rubber composition in the dynamic analysis analyzer (DMA) temperature scanning results, loss factor tan delta needs to form two peaks, high temperature peak1 and low temperature peak2, the peak value difference of the two peaks needs to satisfy, 6 ℃ is more than or equal to delta T = peak1-peak2 is less than or equal to 15 ℃, the tread rubber composition is characterized by comprising the following components by 100 parts by weight of rubber component and is prepared by mixing the following raw materials:
100phr of rubber component
80-150phr of high-dispersion white carbon black
15 to 30phr of silane coupling agent
15 to 25phr of an alpha-methylstyrene resin
5-10phr of hydrogenated dicyclopentadiene resin;
the rubber component consists of natural rubber and solution-polymerized styrene-butadiene rubber, wherein the weight part of the natural rubber is between 30 and 45phr, and the weight part of the solution-polymerized styrene-butadiene rubber is between 55 and 70phr; meanwhile, the solution polymerized styrene butadiene rubber needs to meet the requirements that the number average molecular weight Mn is more than 30 ten thousand and less than 80 ten thousand, the weight average molecular weight Mw is more than 50 ten thousand and less than 100 ten thousand, the molecular weight distribution Mw/Mn is more than 1.5 and less than 2.5; the styrene in the solution polymerized styrene-butadiene rubber accounts for the percentage S of the solution polymerized styrene-butadiene, and the S is more than 30 percent and less than 42 percent;
the specific surface area CTAB value of the high-dispersion white carbon black meets, CTAB is more than 150 and less than 200;
the silane coupling agent is composed of more than two silane coupling agents, wherein one silane coupling agent is Si747, the other silane coupling agent is Si75, the amount of Si747 is 10-15phr, and the amount of Si75 is 2-6 phr;
the width W of the central rib of the tread pattern of the tire needs to be more than 23cm, the actual sea-land ratio of the tread needs to be between 32 and 36 percent, and the actual contact surface is 240 to 260cm 2 In between.
2. A tire having low rolling resistance, high wet grip and good handling properties as claimed in claim 1, wherein the natural rubber is present in an amount of 30 to 45phr, and the solution-polymerized styrene-butadiene rubber is present in an amount of 60 to 70phr; the weight portion of the high dispersion white carbon black is between 90 and 120phr.
3. A tire with low rolling resistance, high wet grip and good handling properties as claimed in claim 1, wherein the width W of the center rib of the tread pattern is 24-27cm, the actual sea-land ratio of the tread is 32-34%, and the actual ground contact area is 240-250 cm 2 In the meantime.
4. A tire having low rolling resistance, high wet grip and good handling properties as claimed in claim 1, wherein the α -methylstyrene resin has a molecular weight distribution of 4 < Mw/Mn < 5, and the hydrogenated dicyclopentadiene (hydrogenated DCPD) resin has a molecular weight distribution of 3 < Mw/Mn < 4.
5. A low rolling resistance, high wet grip, and good handling tire according to claim 1, wherein said rubber composition further comprises vulcanizing agents, vulcanization accelerators, oils, activators, antioxidants, and plasticizers conventionally used in tires and other rubber compositions.
6. A low rolling resistance, high wet grip, good handling tire according to claim 1 wherein the rubber composition further comprises 20 to 40phr of softening oil, 1.0 to 3.0phr of zinc oxide, 1.0 to 3.0phr of stearic acid, 1.0 to 3.0phr of anti-aging agent 4020,1.0 to 3.0phr of microcrystalline wax, 1.0 to 4.0phr of sulfur, 0.5 to 3.5phr of accelerator CZ,0.2 to 1.0phr of accelerator DPG.
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| CN202210888979.5A CN115124773B (en) | 2022-07-27 | 2022-07-27 | Tire with low rolling resistance, high wet grab and good controllability |
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| CN115651281A (en) * | 2022-11-07 | 2023-01-31 | 中策橡胶集团股份有限公司 | Tire tread rubber with high wet grip performance, preparation method and application thereof, and tire with high wet grip performance |
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| KR20120059118A (en) * | 2010-11-30 | 2012-06-08 | 한국타이어 주식회사 | Tread rubber composition and tire manufactured by using the same |
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