CN106366377A - Tread rubber composition for rain tires and production method for same - Google Patents
Tread rubber composition for rain tires and production method for same Download PDFInfo
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- CN106366377A CN106366377A CN201610726420.7A CN201610726420A CN106366377A CN 106366377 A CN106366377 A CN 106366377A CN 201610726420 A CN201610726420 A CN 201610726420A CN 106366377 A CN106366377 A CN 106366377A
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- weight portion
- rubber composition
- butadiene
- tread rubber
- rubber
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a tread rubber composition which is suitable for railway in all seasons and has better performance aiming to rainy day. The tread rubber composition includes styrene butadiene rubber, butadiene rubber and various fillers and has excellent anti-wet-skid performance.
Description
Technical field
The present invention relates to tire manufacturing techniques field is and in particular to a kind of tread rubber composition being exclusively used in rainy day tire
And its manufacture method.
Background technology
Tire is the parts that automobile is uniquely contacted with road surface, and the mobility of automobile all needs to pass power by tire
It is delivered to ground to realize, so the performance of tire directly affects the performance of automobile.At present, the wheel that each giant tyre company manufactures
Tire species gets more and more, and has multiduty, has single-use, such as four seasons tire, all-terrain baby tire, summer tire, winter tire, ice ground
Tire, snowfield tire, dry tire, the polytype such as rain tire, the tire of different purposes, not only tyre tread form, the difference such as structure design,
The tyre surface glue material that the material composition of tire is especially contacted with ground simultaneously also differs, for the different use environment of tire
And handling characteristicss, design corresponding tire product, reach optimal using effect, such as, winter tire, because winter weather becomes
Cold, and often snowy road, situations such as ice road, so if in winter still using summer tire with regard to danger close, summer, tire was in winter
When tyre surface can be hardening, the contact defective tightness with ground for the sizing material, the handling and safety of tire will substantially reduce.So, one
As for the material composition that adopts of different kinds of tyre different, adjust for different environment, realize acquisition and be best suitable for concrete ring
The tire in border.
Content of the invention
The technical problem to be solved be to provide a kind of be applied to the use of the highway four seasons for rainy day performance
The preferably rubber composition of tyre tread part, the glass transition temperature of the recipe requirements sizing material of this tread rubber composition
At -25 DEG C, and the fissipation factor tan δ at 0 DEG C is higher than 0.5.
For solving above-mentioned technical problem, present invention offer is a kind of to be applied to the more preferable for rainy day performance of highway four seasons use
Tread rubber composition, it includes butadiene-styrene rubber, butadiene rubber and various filler.
Wherein, described filler include white carbon, zinc oxide, stearic acid, White carbon black dispersant, silane coupler, environment protection oil,
Ancient Malong indene polymerization resin, static protective agent, age resistor, accelerator and sulfur.
Wherein, described butadiene-styrene rubber be crude rubber Mooney viscosity between 45-65, styrene-content is in 40% about fill
Oily solution polymerized butadiene styrene rubber.
Wherein, described butadiene rubber is higher than 96% polybutadiene rubber for cis-content.
Wherein, described white carbon selects specific surface area in 150-170m2Not the comprising according to sedimentation method technique manufacture of/g
The high-dispersion white carbon black of crystalline silica.
Wherein, described White carbon black dispersant is the mixture of unsaturated high molecular weight fatty acid and ester.
Wherein, described silane coupler is si69, entitled double-[γ-(triethoxysilicane) propyl group] tetrasulfide of chemistry.
Wherein, described environment protection oil is tdae oil.
Wherein, described Gu Malong indene polymerization resin is the high-purity resin of 100 DEG C of softening point.
Wherein, described static state protective agent is the mixture of 56%-66% linear paraffin and 34%-44% branched paraffin.
Wherein, described age resistor is p phenylenediamine type antioxidant 4020.
Wherein, described accelerator is sulfenamide accelerator and two kinds of guanidines.
Wherein said sulfur is common Cosan, industrial 200 mesh.
Wherein, in described tread rubber composition, the weight portion of each composition is respectively 135 parts of butadiene-styrene rubber, butadiene rubber 10
Part, 120 parts of white carbon, 2 parts of zinc oxide, 1 part of stearic acid, 3 parts of White carbon black dispersant, 19.2 parts of silane coupler, environment protection oil 14
Part, 8 parts of ancient Malong indenes, static 2 parts of protective agent, 2 parts of age resistor, 1.8 parts of sulfenamide accelerator cbs, guanidines
1.6 parts of dpg and 1.8 parts of sulfur.
Present invention also offers the preparation method of above-mentioned tread rubber composition, comprising:
The first step, banburying；
Second step, mixing；
3rd step, refining glue, obtain tread rubber composition.
Wherein, the described first step is specially further and divides butadiene-styrene rubber, butadiene rubber, zinc oxide, stearic acid, white carbon
Powder, silane coupler, ancient Malong indene polymerization resin, static protective agent and age resistor put into banbury, turn in rotating speed 30-55/
10-60s is kneaded under the speed of minute.
Wherein, described second step is specially further and adds white carbon, mixing to the mixture that first step banburying obtains
Add after 1min environment protection oil mixing 1min, then between 135 DEG C -140 DEG C constant temperature mixing 1min, finally temperature be 150
DEG C when dumping, obtain rubber master batch.
Wherein, described 3rd step is specially further and adopts once-through method rubber mixing technique, and the rubber master batch that second step is obtained is discharged to
After mill, carry out thin logical cooling using 2-4mm roll spacing under 10-50 rev/min of speed and supplement mixing, knead 1-5min,
It is subsequently adding vulcanization aid and is sent to secondary mill, then knead 8-15min under 10-50 rev/min of speed, 2-4mm roll spacing,
It is then passed to two roller bottom sheet machines, obtain rubber composition.
Beneficial effects of the present invention:
Provided by the present invention for the tread rubber composition of rainy day tire, rubber is from modified the containing intermingle with of molecule chain end
Butadiene-styrene rubber system, it has the following advantages: 1) wetland is functional；2) process safety is good, and curingprocess rate is fast；3) ageing resistace
Excellent.The anti-slippery of tread rubber composition can be improved using this rubber, from the high-dispersion white carbon black of high surface area, simultaneously
Using White carbon black dispersant, give full play to the effect of white carbon, and improve with reference to highly purified Gu Malong indene resin anti-further
Wet and slippery performance.
Specific embodiment
The present invention provide a kind of be applied to the highway four seasons use for the more preferable tread rubber composition of rainy day performance, its
Including butadiene-styrene rubber, butadiene rubber and various filler.
Described filler includes white carbon, zinc oxide, stearic acid, White carbon black dispersant, silane coupler, environment protection oil, ancient horse
Imperial indene polymerization resin, static protective agent, age resistor, accelerator and sulfur.
Described zinc oxide is indirect process zinc oxide.
Described silane coupler is si69, entitled double-[γ-(triethoxysilicane) propyl group] tetrasulfide of chemistry of si69,
Preferably Nanjing dawn produces.
Described environment protection oil is the little aromatic naphtha of polycyclic aromatic hydrocarbon content, is also tdae oil, is the oil processing, holy for the German Chinese
The tdae oil that company produces, its trade mark is vivatec 500.
Described butadiene-styrene rubber be crude rubber Mooney viscosity between 45-65, styrene-content 40% about oil-filled molten
The trade mark that poly- butadiene-styrene rubber, preferably Asahi Chemical Industry produce is the butadiene-styrene rubber of tufdene 4850.
Described butadiene rubber is the polybutadiene rubber that cis-content is higher than 96%, preferably br9000.
Described white carbon selects specific surface area in 150-170m2/ g according to sedimentation method technique manufacture do not comprise crystallize two
The high-dispersion white carbon black of 165 specifications that the high-dispersion white carbon black of silicon oxide, preferably Rhodia produce, specially 1165mp.
Described White carbon black dispersant is the ultra-flow 700s of performance additives company, chemical composition
Mixture for unsaturated high molecular weight fatty acid and ester.
Described Gu Malong indene polymerization resin is the high-purity resin of 100 DEG C of softening point, can be purchased from the market, and the such as trade mark is
The ancient Malong indene polymerization resin of novares c 100.
Static protective agent is the mixture of 56%-66% linear paraffin and 34%-44% branched paraffin, it is preferred to use Rhein
Paraffin and the mixture of microwax that chemical (Qingdao) company produces, entitled antilux111.
Described sulfur adopts common sulfur, industrial 200 mesh.
Age resistor can be p phenylenediamine type antioxidant, preferably the 4020 of Jiangsu Sheng'Ao Chemical Technology Co., Ltd.
The preferred Shandong of the described sulfenamide accelerator cbs that still Shun produces, chemical name is n- cyclohexyl -2- benzo thiophene
Azoles sulfenamide.
The dpg of described guanidines preferred Huangyan, Zhejiang East Zhejiang province rubber chemicals company limited production, chemical name is n,
N'- diphenylguanidine.
In described tread rubber composition, the weight portion of each composition is respectively butadiene-styrene rubber 96.25 weight portion～150 weight
Part, butadiene rubber 5 weight portion～15 weight portion, white carbon 100 weight portion～120 weight portion, zinc oxide 1.5 weight portion～3 weight
Amount part, stearic acid 0.5 weight portion～2 weight portion, White carbon black dispersant 1 weight portion～4 weight portion, silane coupler 16 weight portion
～19.2 weight portions, environment protection oil 12 weight portion～20 weight portion, ancient Malong indenes 5 weight portion～8 weight portion, static protective agent 1.5
Weight portion～2.5 weight portion, age resistor 1.5 weight portion～2.5 weight portion, sulfenamide accelerator cbs 1 weight portion～2 weight
Amount part, guanidines dpg 1 weight portion～2 weight portion and and sulfur 1 weight portion～3 weight portion.
In described tread rubber composition, the weight portion of each composition is respectively 135 parts of butadiene-styrene rubber, 10 parts of butadiene rubber, white
120 parts of white carbon black, 2 parts of zinc oxide, 1 part of stearic acid, 3 parts of White carbon black dispersant, 19.2 parts of silane coupler, 14 parts of environment protection oil, Gu
8 parts of Malong indenes, static 2 parts of protective agent, 2 parts of age resistor, 1.8 parts of sulfenamide accelerator cbs, guanidines dpg 1.6
Part and 1.8 parts of sulfur.
Present invention also offers the preparation method of above-mentioned tread rubber composition, comprising:
The first step, banburying；
Second step, mixing；
3rd step, refining glue, obtain tread rubber composition.
The described first step further be specially by butadiene-styrene rubber, butadiene rubber, zinc oxide, stearic acid, White carbon black dispersant,
Silane coupler, ancient Malong indene polymerization resin, static protective agent and age resistor put into banbury, in 30-55 rev/min of rotating speed
60s is kneaded under speed.
Still more preferably 55 revs/min of rotating speed in the described first step, mixing time is preferably 60s.
Wherein, described second step is specially further and adds white carbon, mixing to the mixture that first step banburying obtains
Add after 1min environment protection oil mixing 1min, then between 135 DEG C -140 DEG C constant temperature mixing 1min, finally temperature be 150
DEG C when dumping.
Described 3rd step is specially further and adopts once-through method rubber mixing technique, and the rubber master batch that second step is obtained is discharged to mill
Afterwards, carry out thin logical cooling using 2-4mm roll spacing under 10-50 rev/min of speed and supplement mixing, knead 1-5min, Ran Houjia
Enter vulcanization aid and be sent to secondary mill, then knead 8-15min, Ran Houchuan under 10-50 rev/min of speed, 2-4mm roll spacing
It is delivered to two roller bottom sheet machines, obtain rubber composition.
Hereinafter embodiments of the present invention are described in detail using embodiment, whereby to the present invention how application technology means
To solve technical problem, and reach realizing process and fully understanding and implement according to this of technique effect.
The preparation of embodiment 1 rubber composition
Butadiene rubber br9000 that butadiene-styrene rubber 13.5kg, 1kg Qilu Petrochemical for tufdene 4850 for the trade mark is produced,
Zinc oxide 0.2kg, stearic acid 0.1kg, White carbon black dispersant 0.3kg, silane coupler si-691.92kg, the trade mark are novares
Paraffin and the mixture of microwax that ancient Malong indene polymerization resin 0.8kg, 0.2kg Rhein chemistry (Qingdao) company of c100 produces
Static protective agent, entitled antilux111 and 0.2kg antioxidant 4020 puts into banbury, in 55 revs/min of speed of rotating speed
Lower mixing 60s；The mixture that banburying obtains adds the high-dispersion white carbon black 1165mp of 165 specifications of 12kg Rhodia production
Mixing 1min, then reduction of speed to 20 revs/min, the tdae oil 1.4kg being subsequently added the production of German Han Sheng company kneads 1min again,
The dumping in 155 DEG C of temperature；The rubber master batch of acquisition is discharged to after mill, low speed under 30 revs/min of speed, 2.5mm roll spacing
Mixing 2min, adds sulfur 0.18kg, 0.18kgn- cyclohexyl -2-[4-morpholinodithio sulfenamide cbs and 0.16kg diphenylguanidine
Dpg, is then delivered to secondary mill, then in 20 revs/min of speed, under 3mm roll spacing, low speed mixing 11min, then transmits
To two roller bottom sheet machines, obtain rubber composition.
Embodiment 2 rubber composition 2
By butadiene-styrene rubber 10.5kg, 3kg butadiene rubber br9000 for tufdene 4850 for the trade mark, zinc oxide 0.2kg, hard
Fat acid 0.1kg, 1.92kg silane coupler si-69, the trade mark be novares c100 ancient Malong indene polymerization resin 0.8kg,
The paraffin that 0.2kg Rhein chemistry (Qingdao) company produces static protective agent, entitled antilux111 with the mixture of microwax
Put into banbury with 0.2kg antioxidant 4020, knead 60s under the speed of 55 revs/min of rotating speed；The mixture that banburying obtains adds
Enter the high-dispersion white carbon black 1165mp mixing 1min of 165 specifications of 12kg Rhodia production, be subsequently added the German Chinese holy public
The tdae oil 2.4kg that department produces kneads 1min again, the dumping in 155 DEG C of temperature；The rubber master batch of acquisition is discharged to after mill, 30
Rev/min speed, under 2.5mm roll spacing low speed mixing 2min, add sulfur 0.18kg, 0.18kgn- cyclohexyl -2- benzo
Thiazolesulfenamide cbs and 0.16kg diphenylguanidine dpg, is then delivered to secondary mill, then in 20 revs/min of speed, 3mm
Roll spacing, lower low speed kneads 11min, is then passed to two roller bottom sheet machines, obtains rubber composition.
Compliance test result
Table 1 is the physical property table of compositionss, conditions of vulcanization: 150 DEG C of * 40min
Table 1 Main physical performance
| Formula number | Embodiment 1 | Embodiment 2 |
| Hardness (shore a) | 68 | 70 |
| 100% stretches (mpa) surely | 2.3 | 2.6 |
| 300% stretches (mpa) surely | 14.36 | 13.35 |
| Elongation at break (%) | 380 | 348 |
| Tensile strength (mpa) | 16.52 | 17.43 |
| Resilience % | 28 | 35 |
The dynamic mechanical table of table 2 compositionss, dma test condition: -75 DEG C of -65 DEG C of temperature scannings.Moved using prunus mume (sieb.) sieb.et zucc. Teller
State Mechanical Analyzer is tested.
Table 2 dynamic mechanical
It is shown in Table 3 using the test chamber machine tool capability test that above-mentioned formula a and b manufactures experimently tire, trial-production specification is according to 225/
45rf17 executes.
Table 3 machine tool capability test result
| Indoor performance is tested | a | b |
| High speed performance | Pass through | Pass through |
| Endurance quality | Pass through | Pass through |
All above-mentioned this intellectual properties of primary enforcement, do not set this new product of enforcement limiting other forms
And/or new method.Those skilled in the art will be using this important information, and the above is changed, to realize similar execution feelings
Condition.But, all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention is made with other forms, appoints
What those skilled in the art possibly also with the disclosure above technology contents changed or be modified as equivalent variations etc.
Effect embodiment.But every without departing from technical solution of the present invention content, according to the present invention technical spirit to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of be applied to the highway four seasons use for the more preferable tread rubber composition of rainy day performance it is characterised in that: bag
Include butadiene-styrene rubber, butadiene rubber and various filler.
2. tread rubber composition as claimed in claim 1 it is characterised in that: described filler includes white carbon, zinc oxide, hard
Fat acid, White carbon black dispersant, silane coupler, environment protection oil, ancient Malong indene polymerization resin, static protective agent, age resistor, promotion
Agent and sulfur.
3. tread rubber composition as claimed in claim 1 or 2 it is characterised in that: described butadiene-styrene rubber for rubber Mooney glue
Degree between 45-65, styrene-content 40% about oil-filled solution polymerized butadiene styrene rubber.
4. the tread rubber composition as described in claims 1 to 3 it is characterised in that: described butadiene rubber is that cis-content is high
In 96% polybutadiene rubber.
5. the tread rubber composition as described in Claims 1-4 it is characterised in that: described white carbon is existed from specific surface area
150-170m2The high-dispersion white carbon black not comprising crystalline silica according to sedimentation method technique manufacture of/g.
6. the tread rubber composition as described in claim 1 to 5 it is characterised in that: respectively become in described tread rubber composition
The weight portion dividing is respectively butadiene-styrene rubber 96.25 weight portion～150 weight portion, butadiene rubber 5 weight portion～15 weight portion, Linesless charcoal
Black 100 weight portion～120 weight portions, zinc oxide 1.5 weight portion～3 weight portion, stearic acid 0.5 weight portion～2 weight portion, Linesless charcoal
Black dispersant 1 weight portion～4 weight portion, silane coupler 16 weight portion～19.2 weight portion, environment protection oil 12 weight portion～20 weight
Amount part, ancient Malong indenes 5 weight portion～8 weight portion, static protective agent 1.5 weight portion～2.5 weight portion, age resistor 1.5 weight portion
～2.5 weight portions, accelerator cbs 1 weight portion～2 weight portion, accelerator dpg 1 weight portion～2 weight portion and and sulfur 1 weight
Amount part～3 weight portion.
7. the preparation method of tread rubber composition described in claim 1 to 6 is it is characterised in that include:
The first step, banburying；
Second step, mixing；
3rd step, refining glue, obtain tread rubber composition.
8. tread rubber composition as claimed in claim 7 preparation method it is characterised in that: the described first step is concrete further
Be by butadiene-styrene rubber, butadiene rubber, zinc oxide, stearic acid, White carbon black dispersant, silane coupler, ancient Malong indene polymerization resin,
Static protective agent and age resistor put into banbury, knead 10-60s under the speed of 30-55 rev/min of rotating speed.
9. as described in claim 7 or 8 tread rubber composition preparation method it is characterised in that: described second step is further
It is specially and adds white carbon to the mixture that first step banburying obtains, after mixing 1-10min, add environment protection oil to knead 1- again
30min, the dumping when temperature is for 130-160 DEG C.
10. as described in claim 7 to 9 tread rubber composition preparation method it is characterised in that: described 3rd step is further
It is specially and adopts once-through method rubber mixing technique, the rubber master batch that second step is obtained is discharged to after mill, adds sulfur, accelerator,
Under 10-50 rev/min of speed, low speed mixing 1-5min, is then delivered to secondary mill, then in 10-50 rev/min of speed
Degree lower low speed mixing 8-15min, is then passed to two roller bottom sheet machines, obtains rubber composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610726420.7A CN106366377A (en) | 2016-08-25 | 2016-08-25 | Tread rubber composition for rain tires and production method for same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610726420.7A CN106366377A (en) | 2016-08-25 | 2016-08-25 | Tread rubber composition for rain tires and production method for same |
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| Publication Number | Publication Date |
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| CN106366377A true CN106366377A (en) | 2017-02-01 |
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ID=57878478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610726420.7A Pending CN106366377A (en) | 2016-08-25 | 2016-08-25 | Tread rubber composition for rain tires and production method for same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330704A (en) * | 2019-06-28 | 2019-10-15 | 华南理工大学 | A kind of high-performance tread rubber composition of Han quaternary phosphine styrene resin |
| WO2023238153A1 (en) * | 2022-06-08 | 2023-12-14 | Tvs Srichakra Limited | A tire tread rubber composition using eggshell powder as a biofiller and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924771A (en) * | 2012-11-23 | 2013-02-13 | 青岛森麒麟轮胎有限公司 | High wet-skid resistance low rolling resistance prescription |
| CN103073761A (en) * | 2012-12-31 | 2013-05-01 | 特拓(青岛)轮胎技术有限公司 | Production method of tire tread with low rolling resistance |
| CN103073755A (en) * | 2012-12-31 | 2013-05-01 | 特拓(青岛)轮胎技术有限公司 | Rubber composition for producing wet-skid resistant tire tread |
| CN105623018A (en) * | 2016-03-22 | 2016-06-01 | 中策橡胶集团有限公司 | Super-low rolling resistance wheel tread rubber, rubber mixing method thereof, and tire |
-
2016
- 2016-08-25 CN CN201610726420.7A patent/CN106366377A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924771A (en) * | 2012-11-23 | 2013-02-13 | 青岛森麒麟轮胎有限公司 | High wet-skid resistance low rolling resistance prescription |
| CN103073761A (en) * | 2012-12-31 | 2013-05-01 | 特拓(青岛)轮胎技术有限公司 | Production method of tire tread with low rolling resistance |
| CN103073755A (en) * | 2012-12-31 | 2013-05-01 | 特拓(青岛)轮胎技术有限公司 | Rubber composition for producing wet-skid resistant tire tread |
| CN105623018A (en) * | 2016-03-22 | 2016-06-01 | 中策橡胶集团有限公司 | Super-low rolling resistance wheel tread rubber, rubber mixing method thereof, and tire |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330704A (en) * | 2019-06-28 | 2019-10-15 | 华南理工大学 | A kind of high-performance tread rubber composition of Han quaternary phosphine styrene resin |
| CN110330704B (en) * | 2019-06-28 | 2020-06-05 | 华南理工大学 | High-performance tread rubber composition containing quaternary phosphonium styrene resin |
| WO2023238153A1 (en) * | 2022-06-08 | 2023-12-14 | Tvs Srichakra Limited | A tire tread rubber composition using eggshell powder as a biofiller and its preparation |
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