CN101792545B - Tread rubber glue stock of tyre with low rolling resistance and tyre adopting tread rubber - Google Patents
Tread rubber glue stock of tyre with low rolling resistance and tyre adopting tread rubber Download PDFInfo
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- CN101792545B CN101792545B CN2010101171979A CN201010117197A CN101792545B CN 101792545 B CN101792545 B CN 101792545B CN 2010101171979 A CN2010101171979 A CN 2010101171979A CN 201010117197 A CN201010117197 A CN 201010117197A CN 101792545 B CN101792545 B CN 101792545B
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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 filed of tyre manufacture, in particular to a tread rubber glue stock of a tyre with low rolling resistance and a tyre with low rolling resistance prepared from tread rubber. The tread rubber glue stock of the tyre with low rolling resistance is prepared by mixing the following components in parts by weight: 65-85 solution polymerized butadiene styrene rubber (SSBR), 15-35 butadiene rubber or natural rubber, 10-20 Nanopren material, 6-40 carbon black, 45-80 white carbon black, 3.0-6.0 silane coupling agent, 20-45 linaloe wood oil, 1.0-5.0 tackifying resin, 1.0-4.5 zinc oxide, 0.5-2.5 stearic acid, 1.5-3.5 sulfur and 2.0-5.0 accelerant, wherein the content of a styrene monomer in the solution polymerized butadiene styrene rubber is less than or equal to 35 percent and the content of ethylene is 35-65 percent. The tandelta of the tread rubber glue stock at 60DEG C is as low as possible, general between 0.11 and 0.14; and the tandelta at 0DEG C for ensuring the holding performance is as high as possible, which is higher than 0.35.
Description
Technical field
The present invention relates to tire and make field, the low rolling resistance tyre that relates in particular to a kind of tread rubber sizing material of low rolling resistance tyre and adopt this tread rubber manufacturing to obtain.
Background technology
In recent years, because automobile is universal day by day, cause CO2 emissions increasingly high.The increase of carbonic acid gas has caused global warming, and world petroleum resource is deficient day by day, and therefore automotive industry revolution that reduces oil consumption has directly caused the requirement that the automaker reduces tire drag.Hinder in the car progressive resistance, rolling resistance accounts for 18%～30%, and the rolling resistance energy consumption accounts for 14.4% of oil consumption, this means that rolling resistance reduces by 30%, but then fuel-economizing 4.5%～6%.It is reported that the rolling resistance that is only produced by tyre surface just accounts for 49% of tire drag, the oil consumption that is directly caused by tyre surface accounts for 7.1%.At present, many in the world major companies release low rolling resistance tyre one after another, and titled with the good name of " green tire ".Though all also the requirement of tire drag is not listed in the various standards of tire, each auto vendor (mainly being the U.S.) has all begun to classify the rolling resistance of tire as to first wife's tire quality a index request.
" 2006 the 26th volumes of tire industry " discloses the approach that reduces tire drag, and the document reduces the approach of tire drags from material selection and structure design two aspect introductions.All components all has certain influence to hysteresis loss in the sizing compound formula, and wherein polymer type has the greatest impact; Tread rubber adopts SSBR, trans 1; 42 TR 301, integrated rubber (isoprene 2 divinyl 2 styrol copolymers), high vinyl polybutadiene rubber, urethane or modification ESBR etc. can effectively reduce tire drag, keep good abrasion resistance and wet-sliding resistant performance simultaneously; Suitably select Synergist S-421 95s such as WHITE CARBON BLACK, silane coupling agent, staple fibre and reinforcement promotor can further reduce the hysteresis loss of sizing material.Use the plow-steel silk cord and make framework material, adopts suitable tire design theory, utilize means such as finite element technique optimization tire construction design also to help to reduce tire drag with high-performance fiber.
" 2000 the 20th volumes of tire industry " discloses the research of low rolling resistance tyre tread rubber, and the document adopts orthogonal test method, and each component of sizing material is optimized, and the tread rubber rolling resistance is reduced, and can keep good wet-sliding resistant performance again simultaneously.Test-results shows, can effectively reduce the rolling resistance of tread rubber with the alternative emulsion polymerized styrene butadiene rubber of solution polymerized butadiene styrene rubber with WHITE CARBON BLACK part alternative carbon black; Total consumption of filler and aromatic hydrocarbon oil consumption are the main factors that influences rolling resistance and wet-sliding resistant performance.
(application number is 01104025.4 to Chinese invention patent; The applying date: 2001-02-19) disclose high trans-1; The high-speed and energy-saving tire tread compound of 4-TR 301 and high vinyl polybutadiene and usefulness, this patent is taked high trans-1, and 4-TR 301 (TPI) and high vinyl polybutadiene rubber (HVBR) are also used; Cooperate the preparation of blend co-cure with other conventional rubber.For example; The natural gum of prescription employing 20-25 mass parts TPI and 20-25 mass parts HVBR replacement equivalent or butadiene-styrene rubber or cis-butadiene cement etc. are as the sizing material of tyre surface; Can reduce tire drag 15-20%, save fuel oil about 2.5%, and wet-sliding resistant performance does not reduce even also raising to some extent; It is functional to run at high speed, and is a kind of more satisfactory tread mix of preparation high-speed and energy-saving tire.
Summary of the invention
In order to realize falling effectively the low-rolling-resistance of tire, an object of the present invention is to provide a kind of tread rubber sizing material of low rolling resistance tyre, the existing low rolling resistance of this tread rubber sizing material has the high-performance tire tread mix of high wet-sliding resistant performance again.Another object of the present invention provides a kind of low rolling resistance tyre that adopts above-mentioned tread rubber sizing material.
In order to realize above-mentioned first purpose, the technical scheme below the present invention has adopted:
A kind of tread rubber sizing material of low rolling resistance tyre, this tread rubber sizing material makes by following component is mixing according to the mass fraction:
Solution polymerized butadiene styrene rubber 65～85 cis-1,4-polybutadiene rubbers or tree elastomer 15～35
Nanoprene material 10～20 carbon blacks 6～40
WHITE CARBON BLACK 45～80 silane coupling agents 3.0～6.0
High virtue oil 20～45 tackifying resins 1.0～5.0
Zinc oxide 1.0～4.5 Triple Pressed Stearic Acid 0.5～2.5
Sulphur 1.5～3.5 promotor 2.0～5.0;
Wherein, the content of styrene monomer in solution polymerized butadiene styrene rubber is smaller or equal to 35% in the solution polymerized butadiene styrene rubber, and the content of vinyl is 35%～65%, and total umber of described tree elastomer or cis-1,4-polybutadiene rubber and solution polymerized butadiene styrene rubber is 100 parts.
As preferably, this tread rubber sizing material makes by following component is mixing according to the mass fraction:
Solution polymerized butadiene styrene rubber 70～80 cis-1,4-polybutadiene rubbers or tree elastomer 20～30
Nanoprene material 10～20 carbon blacks 10～30
WHITE CARBON BLACK 50～70 silane coupling agents 3.0～6.0
High virtue oil 25～40 tackifying resins 2.0～4.0
Zinc oxide 1.5～3.5 Triple Pressed Stearic Acid 0.5～1.5
Sulphur 2.0～3.0 promotor 3.0～4.0.
Preferred as again, this tread rubber sizing material makes by following component is mixing according to the mass fraction:
Solution polymerized butadiene styrene rubber 75 cis-1,4-polybutadiene rubbers or tree elastomer 25
Nanoprene material 10～20 carbon blacks 10～30
WHITE CARBON BLACK 50～70 silane coupling agents 3.0～6.0
Oily 30 tackifying resins 3 of high virtue
Zinc oxide 2.5 Triple Pressed Stearic Acid 1.0
Sulphur 2.3 promotor 3.5.
As preferably, it is SSBR that above-mentioned solution polymerized butadiene styrene rubber adopts the trade mark
1#And SSBR
2#Solution polymerized butadiene styrene rubber in one or both mixing.Preferred as again, it is SSBR that above-mentioned solution polymerized butadiene styrene rubber adopts the trade mark
1#And SSBR
2#Solution polymerized butadiene styrene rubber two kinds of mixing, wherein SSBR
1#Usage quantity be 20～30 parts, SSBR
2#Usage quantity be 40～60 parts.
As preferably, above-mentioned WHITE CARBON BLACK is selected inferior MP1165 in sieve ground or the solid Sha U7000 of moral for use.
As preferably, it is the high reinforcement property carbon black of N234 or N375 that above-mentioned carbon black is selected the trade mark for use.
Tire technology development has in the last few years proved the remarkably influenced of crown district sizing material to tyre performance; The generation of tire drag about 50% derives from the hysteresis characteristic of crown district material; The little then tire of the tire tread material hysteresis loss of 60 ℃ of temperature measurings on the data test dynamic resistance low (performance is made an appointment) that billows; The hysteresis loss of 0 and 20 ℃ of temperature test of tread mix, then wet road surface of representative and main line face are being grabbed performance respectively, and be opposite with 60 ℃ of temperature effects.Hysteresis loss tire wet-sliding resistant performance good more (tyre performance is good more) more greatly then under 0 ℃ of temperature, more greatly then the dried performance of grabbing of tire is good more for hysteresis loss under 20 ℃ of temperature.Tread rubber design of the present invention is gone up the main solution polymerized butylbenzene glue that adopts also with a small amount of natural gum or cis-butadiene cement; The white carbon black of high dispersive; Carbon black; The adapted silane coupling agent; Vulcanization system will be according to the adjustment of white carbon black consumption, and the tread rubber hysteresis loss factor that obtains through specific calendering process reduces more than 20% than common carbon black tread rubber, the more important thing is that the most this patent adopts the Nanoprene novel material (patent No. EP1149868 GelContaining Rubber Compounds for Dynamically Loaded Tyre Parts) of a kind of German LANXESS company; Novel material is a kind of rubber gels, can on original basis, further reduce tread mix hysteresis loss 16%.The tan δ of the 60C of the tread mix of this patent should be low as far as possible, generally between 0.11～0.14, in order to guarantee to grab 0 ℃ of following tan δ of performance height of should trying one's best, is higher than 0.35.
In order to realize above-mentioned second purpose, the technical scheme below the present invention has adopted:
A kind of low rolling resistance tyre is characterized in that: the tread rubber of this tire adopts the tread rubber sizing material of above-mentioned any technical scheme.
As preferably, the base portion glue sizing material of above-mentioned low rolling resistance tyre makes by following component is mixing according to the mass fraction:
Tree elastomer 60～75 cis-1,4-polybutadiene rubbers 20～30
Fluid rubber 5～10 carbon blacks 45～60
Zinc oxide 2.0～4.0 Triple Pressed Stearic Acid 1.0～3.0
Tackifying resin 1.5～4.0 anti-recovery agent 0-1.5
Liquid reinforced resin 0.00-8.00 chemistry Synergist S-421 95 0.00-3.00
Sulphur 1.5～4.0 promotor 1.0～3.0;
The total amount of tree elastomer, cis-1,4-polybutadiene rubber, fluid rubber is 100 parts in the above-mentioned base portion glue sizing material.
On the formulating of recipe of base portion glue of the present invention; Adopt low-heat-generation property polymkeric substance such as All Pure Nature glue or and the BR of usefulness; Adopt higher carbon black consumption 45-60PHR in order to reach good conductivity and modulus; Carbon black can be selected for use like high abrasion carbon blacks such as N330, N339, N375, improves modulus simultaneously in order to guarantee use characteristics, is to use liquid PI rubber (improve technology but do not reduce modulus) or liquid reinforced resin (increase modulus and improve use characteristics simultaneously) without process oil; Fluid rubber can use 5-10PHR; The liquid reinforced resin can be selected the cashew nut oil liquid reinforced resin of producing like Cardolite company for use, and the double effects of tenderizer and strengthening agent is arranged, and as strengthening action methyl donor chemistry Synergist S-421 95 adapted such as HMT (vulkacit H) or HMMM (hexakis-methoxy methyl melamine) with it must be provided certainly.In order to improve the reversion resistance of base portion sizing material, use the PK900 of anti-recovery agent such as FLYSESIS or home-made WK901 can further improve performance in right amount in addition.
As preferably, the base portion glue sizing material of above-mentioned tire makes by following component is mixing according to the mass fraction:
Tree elastomer 60～75 cis-1,4-polybutadiene rubbers 20～30
Fluid rubber 5～10 carbon blacks 45～60
Zinc oxide 3.0 Triple Pressed Stearic Acid 1.5
Tackifying resin 2.5 anti-recovery agent 0-1.5
Liquid reinforced resin 4.00-6.00 chemistry Synergist S-421 95 0.00-3.00
Sulphur 2.5 promotor 2.0.
Base portion glue major function is the transitional function between tyre surface and the high-modulus string of a hat sizing material, occupies certain tire tread material volume simultaneously, so low hysteresis loss also has obvious contribution to the rolling resistance of tire.To guarantee performances such as base portion glue physical mechanical simultaneously: as be higher than the conductivity (solution electrostatic problem) that the stress at definite elongation (higher modulus reduce roll distortion) of tread rubber is become reconciled.Through the employing natural gum or also with BR and HAF carbon black such as N375; Reduce the process oil consumption; Improve the conductivity of mixing extrusion processing characteristics and base portion rubber (through stretching out surface of tyre) simultaneously in order to increase modulus; Use liquid PI rubber (improve technology but do not reduce modulus) or liquid reinforced resin (increase modulus and improve use characteristics simultaneously), the base portion glue hysteresis loss that obtains like this is suitable with general base portion glue.But modulus obviously increases and conductivity improves.The base portion colloidality that this patent relates to can for; 100% stretches 3.0～5.0MPA surely, and 300% stress at definite elongation should not be lower than 15-19MPA, guarantees that the tread slab base stress at definite elongation is higher than the corresponding stress at definite elongation value of tread mix, plays the transitional function between tyre surface and the high-modulus string of a hat sizing material.Base portion glue is as previously mentioned when guaranteeing the rerum natura mechanical property; The tan δ of 60C is low more good more; Be preferably lower than 0.11; Base portion glue sizing material hysteresis loss is lower than tire tread material like this, so as above-mentioned increase base portion colloid long-pending reduce simultaneously the tread rubber volume then tire drag further descend, this is that material is given birth to thermogenetic because tire drag is; And the heat of giving birth to of material is directly proportional with material unit cubic deformation amount, material volume amount, material hysteresis factors, so tire drag can be similar to and use following formulate;
RR?∝∑i(U*V*tanδ)
U: (each distortion of materials amount/volume)
V: (volume of each material)
Tan: loss (representing) after each material energy with material hysteresis factors tan δ
According to formula; Increase during design as far as possible base portion glue material modulus (stress at definite elongation high) then tire constant when stressed base portion glue deflection less than; Both U was less in the formula; Increase the volume V that the long-pending ratio of base portion colloid is equivalent to increase the littler material of tan δ in addition, the minimizing of string of a hat material also is equivalent to reduce material volume V, so can obtain the lower tire of rolling resistance.
The present invention is through above technical scheme; In car radial-ply tyre production technical field; Realize that tire drag guarantees simultaneously that tire is wet and grabbing or handling and wear hardness is the target of always pursuing; This patent is based on abrasion with guarantee significantly to have reduced the rolling resistance of tire under the prerequisite of wet-sliding resistant performance of tire.Main technical points is:
One) designed remarkable reduction sizing material the hysteresis loss tread rubber and the base portion glue of (representing with hysteresis factors tan δ) again, simultaneously new 0 ℃ of tread rubber is higher.Tyre industry is verified, and 60 ℃ of low more tire drags of following sizing material tan δ are low more, and 0 ℃ high more then tire wet-sliding resistant performance of tread rubber is good more.
Two) crown district sizing material working design change; In adopting tread rubber and base portion glue machine, adjust the ratio of tyre surface and base portion glue during compound extrusion; Significantly increase the base portion glue ratio that lower 60 ℃ of following tan δ are arranged than tyre surface; Making that the crown material is actual is divided into two-layerly up and down, and the big and lower base portion glue of tan δ of volume reduces whole tire drag and plays an important role, and base portion glue thickness is greatly between 2.0-2.5mm; Being no more than finished tire decorative pattern bottom, sulfuration back parallel lines with thickness is that to also have the surplus of tread rubber 0.5mm be good in the ditch bottom simultaneously on the boundary; Functions such as outer field like this tread mix form abrasion performance and road surface gripping power, internal layer base portion glue play the bonding transitional function of tyre surface and the string of a hat, belt, reduce and give birth to the rolling vibrations that the thermal absorption tyre surface transmits.
Three) band structure construction adjustment; Generation and material volume amount according to rolling resistance have relation; Under the prerequisite that does not reduce performance; The two-layer nylon string of a hat of common view picture structure changes the one deck and the two-layer wide string of a hat of the 30mm of limit portion millimeter (being one deck half hitch structure) into, and the function that has guaranteed the nylon band has like this reduced material volume simultaneously and further reduced tire drag.
Embodiment
Comparative Examples
Mixing the making of component of the mass fraction below general tread mix adopts:
Embodiment 1
The tread rubber sizing material of low rolling resistance tyre, this tread rubber sizing material is according to the mass fraction by following component
Mixing making:
Solution polymerized butadiene styrene rubber SSBR1#25 solution polymerized butadiene styrene rubber SSBR2#50
Cis-1,4-polybutadiene rubber or tree elastomer 25 Nanoprene materials 15
Carbon black 32 WHITE CARBON BLACKs 53
Silane coupling agent 4.5 high virtue oil 38
Zinc oxide 2.5 tackifying resins 4.3
Triple Pressed Stearic Acid 1.2 sulphur 2.0
Promotor 3.4.
SSBR1# styrene comprise polymkeric substance 39% (total polymer) in this example, 38% of ethene fiduciary point butadiene gross weight, Tg-22 ℃; SSBR2# styrene comprise polymkeric substance 33% (total polymer), 34% of ethene fiduciary point butadiene gross weight, Tg-34 ℃.
Above-mentioned tread rubber sizing material compounding process such as traditional tread rubber sizing material.Product test data after mixing and Comparative Examples following: (differing temps tan δ adopts Japan to go up island VR-7120DMA test in the example.)
Can find out from the comparison of above table, improve that 60 ℃ of following tan δ work decline indication tire drags can obviously descend simultaneously so 0 ℃ of following tan δ is higher than general tyre surface tire wet-sliding resistant performance.
Embodiment 2
The tread rubber sizing material of low rolling resistance tyre, this tread rubber sizing material makes by following component is mixing according to the mass fraction:
Solution polymerized butadiene styrene rubber SSBR1#15 solution polymerized butadiene styrene rubber SSBR2#60
Cis-1,4-polybutadiene rubber BR9000 25 Nanoprene materials 12
Carbon black N23425 WHITE CARBON BLACK 1165MP 65
Silane coupling agent 5.2 high virtue oil 25
Zinc oxide 3.2 tackifying resins 4.0
Triple Pressed Stearic Acid 2.0 sulphur 3.0
Promotor 3.5.
Above-mentioned tread rubber sizing material compounding process such as traditional tread rubber sizing material.
Embodiment 3
The tread rubber sizing material of low rolling resistance tyre, this tread rubber sizing material makes by following component is mixing according to the mass fraction:
Solution polymerized butadiene styrene rubber SSBR1#25 solution polymerized butadiene styrene rubber SSBR2# 50
Cis-1,4-polybutadiene rubber BR9000 25 Nanoprene materials 15
Carbon black N234 31 WHITE CARBON BLACK 1165MP 52
Silane coupling agent 3.2 high virtue oil 32
Zinc oxide 2.2 tackifying resins 3.0
Triple Pressed Stearic Acid 1.0 sulphur 2.0
Promotor 2.5.
Above-mentioned tread rubber sizing material compounding process such as general tread rubber sizing material.
Embodiment 4
The base portion glue sizing material of low rolling resistance tyre makes by following component is mixing according to the mass fraction:
Tree elastomer 70 cis-1,4-polybutadiene rubbers 25
Fluid rubber 5 carbon blacks 50
Zinc oxide 3.0 Triple Pressed Stearic Acid 1.5
Tackifying resin 2.5 anti-recovery agents 1.0
Liquid reinforced resin 5.00 chemical Synergist S-421 95s 2.00
Sulphur 2.5 promotor 2.0.
Above-mentioned base portion glue sizing material compounding process such as general base portion glue sizing material.The above-mentioned base portion glue sizing material test data that makes is following:
Embodiment 5
Low rolling resistance tyre, its tread rubber adopts embodiment 1 described tread rubber sizing material, and base portion glue adopts embodiment 4 described base portion glue sizing materials, and tire is produced by general moulding and vulcanization process, the structure change details and the rolling resistance test result of tire:
Claims (7)
1. the tread rubber sizing material of a low rolling resistance tyre is characterized in that this tread rubber sizing material makes by following component is mixing according to the mass fraction:
Wherein, the content of styrene monomer in solution polymerized butadiene styrene rubber is smaller or equal to 35% in the solution polymerized butadiene styrene rubber, and the content of vinyl is 35%～65%, and total umber of described tree elastomer or cis-1,4-polybutadiene rubber and solution polymerized butadiene styrene rubber is 100 parts.
2. the tread rubber sizing material of a kind of low rolling resistance tyre according to claim 1 is characterized in that this tread rubber sizing material makes by following component is mixing according to the mass fraction:
3. the tread rubber sizing material of a kind of low rolling resistance tyre according to claim 1 is characterized in that this tread rubber sizing material makes by following component is mixing according to the mass fraction:
4. according to the tread rubber sizing material of claim 1 or 2 or 3 described a kind of low rolling resistance tyres, it is characterized in that: it is the high reinforcement property carbon black of N234 or N375 that carbon black is selected the trade mark for use.
5. low rolling resistance tyre is characterized in that: the tread rubber of this tire adopts like claim 1 or 2 or 3 described tread rubber sizing materials.
6. a kind of low rolling resistance tyre according to claim 5 is characterized in that: the base portion glue sizing material of this tire makes by following component is mixing according to the mass fraction:
The total amount of tree elastomer, cis-1,4-polybutadiene rubber, fluid rubber is 100 parts in the above-mentioned base portion glue sizing material; Above-mentioned fluid rubber adopts liquid polyisoprene rubber.
7. a kind of low rolling resistance tyre according to claim 6 is characterized in that: the base portion glue sizing material of this tire makes by following component is mixing according to the mass fraction:
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| CN2010101171979A CN101792545B (en) | 2010-03-04 | 2010-03-04 | Tread rubber glue stock of tyre with low rolling resistance and tyre adopting tread rubber |
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| CN2010101171979A CN101792545B (en) | 2010-03-04 | 2010-03-04 | Tread rubber glue stock of tyre with low rolling resistance and tyre adopting tread rubber |
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| CN101792545B true CN101792545B (en) | 2012-04-11 |
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| CA2424815C (en) * | 1999-11-12 | 2009-12-29 | Bridgestone Corporation | Modified polymers prepared with lanthanide-based catalysts |
| CN101220177B (en) * | 2008-01-25 | 2010-06-09 | 北京化工大学 | Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material |
| CN101628992B (en) * | 2009-07-31 | 2011-03-23 | 杭州中策橡胶有限公司 | Tire side rubber material utilizing regenerated rubber as well as blending method and application thereof |
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