CN102702585A - Radial tire carcass ply compound and rubber composition containing environment-friendly resin and preparation method thereof - Google Patents
Radial tire carcass ply compound and rubber composition containing environment-friendly resin and preparation method thereof Download PDFInfo
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- CN102702585A CN102702585A CN2012102072880A CN201210207288A CN102702585A CN 102702585 A CN102702585 A CN 102702585A CN 2012102072880 A CN2012102072880 A CN 2012102072880A CN 201210207288 A CN201210207288 A CN 201210207288A CN 102702585 A CN102702585 A CN 102702585A
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Abstract
The invention relates to the technical field of rubber, in particular to a radial tire carcass ply compound and rubber composition containing environment-friendly resin, which is characterized by taking 100 weight parts of dienes elastomers as the basis and further comprising 50-60 wieght parts of black carbon, 3-5 weight parts of methylene donors, 1-1.5 weight parts of environment-friendly resin, 4-6 weight parts of sulphur, 1-2 weight parts of cobalt salt, and 1-2 weight parts of accelerant, wherein the environment-friendly resin is obtained through R-modified resorcinol, R mainly consists of styrene, and the dienes elastomers adopt one type from smoke sheet rubber, standard rubber and synthetic polyisoprene rubber, or the mixture of multiple types. According to the invention, the rubber production cost is greatly reduced; and most important of all, on the premise of satisfying basic physical properties of the tire carcass rubber, such as tensile strength, percentage elongation, and resilience, the adhesive force between the rubber and the steel carcass ply can be ensured.
Description
Technical field
The present invention relates to the rubber technology field, specifically a kind of radial-ply tyre carcass glue rubber combination that contains environmental protection type resin and preparation method thereof.
Background technology
As everyone knows, in the manufacturing process of all-steel radial tyre, carcass sizing material and carcass steel cord bonding of crucial importance, wherein initial, the aging back bounding force of bonding glue material is high, is the most important request for utilization of sizing material binding system.Traditional resorcinol-formaldehyde adhesion system uses Resorcinol and hexa methoxy melamine to be used, and smolders and mass defect such as bloom because Resorcinol distils down at mixing and processing conditions easily, and production, environmental protection and worker health are caused many harm.
Summary of the invention
The object of the invention is exactly in order to overcome the deficiency of above-mentioned prior art; A kind of radial-ply tyre carcass glue rubber combination that contains environmental protection type resin and preparation method thereof is provided; Improved in the production in the past; Because " smoldering ", sizing material " bloom " and the low problem of material use efficiency of using the Resorcinol product to cause have bigger advantage to environment protection, health of human body, simultaneously the production cost that lowers sizing material is very helpful; Under the prerequisite that satisfies requirements such as basic physicals of carcass sizing material such as tensile strength, elongation, resilience, the most important thing is to guarantee the bounding force of carcass sizing material and steel curtain.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of radial-ply tyre carcass glue rubber combination that contains environmental protection type resin,
Diene elastomer with 100 weight parts is a benchmark, also comprises,
The carbon black of 50～60 weight parts,
The methylene radical donor of 3～5 weight parts,
The environmental protection type resin of 1～1.5 weight part, environmental protection type resin is obtained by R modification Resorcinol, and R is mainly vinylbenzene,
The sulphur of 4～6 weight parts,
The cobalt salt of 1～2 weight part,
The promotor of 1～2 weight part;
Wherein diene elastomer is selected one or more the mixture in smoke sheet rubber, standard glue, the synthetic polyisoprenes rubber for use.
The preferred N326 carbon black of described carbon black.
The preferred hexamethoxy methyl cyanuramide of described methylene radical donor.
The preferred oil-filled type insoluble sulfur of described sulphur.
The preferred capric acid cobalt of described cobalt salt or cobalt naphthenate or cobalt boracylate.
A kind ofly produce said a kind of method that contains the radial-ply tyre carcass glue of environmental protection type resin, comprise the following steps, its component ratio by weight:
one section is mixing: the closed-smelting machine rotor rotating speed is 50 rev/mins, floating weight pressure 0.7MPa.100 parts of 20# mark glue were dropped into the banburying unit room mixing 35～38 seconds; Drop into 50～60 parts of N326,7～10 parts of zinc oxide, 4020,1～1.5 part of environmental protection type resin of 1～2 part of anti-aging agent, 1～2 part of new cobalt decanoate or cobalt naphthenate, 0.2～0.4 part of peptizer SJ-103 then; Mixing 40～45 seconds, carried bolt 6～8 seconds, mixing then 30～35 seconds; Binder removal, dump temperature are controlled at below 165 ℃.
(2) park: the rubber master batch with a section after mixing was parked about 4 hours, guaranteed that sizing material is cooled to room temperature.
(3) two-stage mixing: the closed-smelting machine rotor rotating speed is 60 rev/mins, and floating weight pressure is 0.7MPa; One section rubber master batch is dropped into Banbury mixer, mixing 40～45 seconds, carry and fasten 6～8 seconds, binder removal after mixing again 40～45 seconds, dump temperature is controlled at below 165 ℃.
(4) park: the rubber master batch behind the two-stage mixing was parked about 4 hours, guaranteed that sizing material is cooled to room temperature.
(5) three-stage mixing: three-stage mixing closed-smelting machine rotor rotating speed is 25 rev/mins, and floating weight pressure is 0.6MPa.Two sections rubber master batch of 170 parts, 4～6 parts sulphur HD-OT20,1～2 part promotor (mixture of DZ or DZ and NS), 3～5 parts methylene radical donor RA, 0.2～0.4 part anti-scorching agent CTP are dropped into the banburying unit room; Mixing 40～45 seconds; Carried bolt then 7～8 seconds, mixing again 55～60 seconds, binder removal; Dump temperature is controlled at below 100 ℃, can make the radial-ply tyre carcass glue that contains environmental protection type resin.
The invention has the beneficial effects as follows; Improved in the production in the past; Because " smoldering ", sizing material " bloom " and the low problem of material use efficiency of using the Resorcinol product to cause have bigger advantage to environment protection, health of human body, simultaneously the production cost that lowers sizing material is very helpful; Under the prerequisite that satisfies requirements such as basic physicals of carcass sizing material such as tensile strength, elongation, resilience, the most important thing is to guarantee the bounding force of carcass sizing material and steel curtain.
Description of drawings
Fig. 1 is the thermogenesis performance figure of sizing material of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done further description:
Traditional Resorcinol product, flue gas is bigger during refining glue, and environmental pollution is serious, to site operation personnel's health generation threat.Simultaneously, owing to the volatilization of Resorcinol, reduced the utilization ratio of material.The used environmental protection type resin of the present invention, its free phenol content is in 3%, and good thermal stability, has improved problem of environment pollution caused greatly, has improved the utilization ratio of material.
Rubber components is a diene elastomer, can be one or more the mixture in smoke sheet rubber, standard glue or the synthetic polyisoprenes rubber, is preferably Thailand or Malaysia and produces 20# standard glue.When selecting 20# standard glue for use, its plasticity initial value should not be lower than 30, and plasticity retention(percentage) is not less than 40, mooney viscosity ML
℃Be no more than 80.
The methylene radical donor is not special to be limited; Can be the product of six ethoxyl methyl melamines, hexamethoxy methyl cyanuramide or vulkacit H class; Be preferably hexamethoxy methyl cyanuramide and WHITE CARBON BLACK material modified-tackiness agent RA, contain 65% hexamethoxy methyl cyanuramide and 35% WHITE CARBON BLACK in this product.
The preferential N375 of carbon black component, N375 are not special to be limited, but suggestion use be used for tire industry and National standard in the product of top grade article requirement.
Powder sulphur component is oil-filled type high thermal stability sulphur HD-OT20, and the place of production is a U.S. FLEXSYS company.
The cobalt salt adhesive component, not special the qualification, preferential new cobalt decanoate or cobalt naphthenate, neodecanoic acid cobalt salt cobalt contents is 20.0-21.0% (CN20.5 of U.S. shepherd company), naphthenic acid cobalt salt cobalt contents is 9.5-10.5% (Zibo Hong Wei RC-N10 of company).
Vulcanization accelerator selects the sulphenamide series products, or their mixture, and this series products can make diene rubber composition have the characteristic of stable inhibition scorching, and gives suitable vulcanization rate, sizing material course of processing safety, and cross-linked rubber has preferable performance.For example suitable promotor has, N tert butyl benzothiazole 2 sulfenamide (accelerator NS), N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ) and N, N '-dicyclohexyl-2-[4-morpholinodithio sulphenamide (accelerator DZ).
In the traditional mode of production, the methylene acceptor that uses is the Resorcinol product.For making things convenient for description effect, reference examples has been used the predispersion (R-80) of Resorcinol, contains 80% Resorcinol and 20% colloid in this product, and the place of production is a Lay mattress chemical company.
Zinc oxide requires the product into indirect method production, and its zinc oxide content (in dry product) should be more than 99.7%, and burning decrement is below 0.2%, and the place of production is Weifang Long Da company.
Anti-aging agent, preferred N-(1,3-diformazan butyl)-N '-diphenyl-para-phenylene diamine (4020), the place of production is a Shandong Sheng Ao company.
Scorch retarder, preferred N-cyclohexylthiophthalimide (CTP), the place of production is a Shandong Yanggu Hua Tai company;
Peptizer SJ-103 contains 60% pentachlorothiophenol and 40% mineral substance.
Embodiment
1. below in conjunction with embodiment the present invention is elaborated, but the present invention is not limited to these embodiment.
2. use above-mentioned environmental protection type resin as methylene acceptor, make all-steel meridian tire carcass sizing material, it is characterized in that using the method for three-stage mixing, comprise following mixing step:
(2) park: the rubber master batch with a section after mixing was parked about 4 hours, guaranteed that sizing material is cooled to room temperature.
(3) two-stage mixing: the closed-smelting machine rotor rotating speed is 60 rev/mins, and floating weight pressure is 0.7MPa; One section rubber master batch is dropped into Banbury mixer, mixing 40～45 seconds, carry and fasten 6～8 seconds, binder removal after mixing again 40～45 seconds, dump temperature is controlled at below 165 ℃.
(4) park: the rubber master batch behind the two-stage mixing was parked about 4 hours, guaranteed that sizing material is cooled to room temperature.
(5) three-stage mixing: three-stage mixing closed-smelting machine rotor rotating speed is 25 rev/mins, and floating weight pressure is 0.6MPa.Two sections rubber master batch of 170 parts, 4～6 parts sulphur HD-OT20,1～2 part promotor (mixture of DZ or DZ and NS), 3～5 parts methylene radical donor RA, 0.2～0.4 part anti-scorching agent CTP are dropped into the banburying unit room; Mixing 40～45 seconds; Carried bolt then 7～8 seconds; Mixing again 55～60 seconds, binder removal, dump temperature were controlled at below 100 ℃.
More than can obtain the present invention--radial tyre body rubber compsn.
The sizing material that will make according to above method is used for the production of all-steel meridian tire.Sizing material is in mixing and rolling processing process, and the glue cigarette obviously reduces, and obtains operating worker's favorable comment.Because the Resorcinol distillation that the glue cigarette is mainly in the sizing material binding system produces flue gas; When Resorcinol distils crystallization easily attached to equipment and calendering cord surface; Be prone to adhere to its surface viscosity of cord surface influence, so increase with this kind environment-friendly resin calendering back cord surface viscosity.
3. prescription cooperates table (each material content unit: weight part)
| The material name | Reference examples | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 20# marks glue | 100.0 | 100.0 | 100.0 | 100.0 |
| Carbon black wet method N326 | 57.0 | 57.0 | 57.0 | 57.0 |
| Insoluble sulfur HDOT20 | 5.00 | 5.00 | 5.00 | 4.60 |
| Resorcinol R-80 | 1.00 | |||
| Environmental protection type resin | 1.00 | 1.50 | 1.20 | |
| Tackiness agent RA | 3.00 | 3.00 | 4.50 | 5.00 |
| Cobalt naphthenate RC-N10 | 1.50 | 1.5 | 1.5 | |
| New cobalt decanoate CN20.5 | 0.75 | |||
| Accelerator DZ | 1.30 | 1.3 | 0.8 | 1.3 |
| Accelerator NS | 0.5 | |||
| Other material | - | - | - | - |
4. the dynamic heat build up improved performance of sizing material, differently strained scanning sizing material hysteresis loss contrast (probe temperature 70 degree), accompanying drawing 1 can find out that the thermogenesis performance of sizing material that the present invention produces (three kinds of embodiment sizing materials) is starkly lower than the sizing material of reference examples.
5. the time of scorch of sizing material prolongs, and has increased processing safety, has reduced because of processing to make sizing material getting up early sulfurized risk.Sizing material improves in the flowability of initial vulcanization step simultaneously, helps being penetrated into the structure the inside of steel cord, to the promoter action that is bonded with of sizing material and steel curtain.
6. sizing material satisfies the required physicals of carcass sizing material, and the present invention's performance of sizing material in one's power slightly is superior to the sizing material of ordinary production, and especially tensile strength, the elongation of sizing material are superior to normal sizing material in aging back, and advantage is arranged this work-ing life to sizing material and finished tire.
7. select test sizing-1 for use, carry out the production of finished tire.12.00R20-18PR specification carcass sizing material is all used sizing material of the present invention.Produce tire and carry out indoor machine test, a tires speed " L " level is durable to be 95 hours, is 130Km/h 9 minutes at a high speed, and performance is in normal range, is higher than common level.
According to the present invention, can in tire production, reduce " flue gas ", compare with traditional method, bigger active effect is played in environment protection.Because " flue gas " volatilization reduces, the effective rate of utilization of material raises in addition.The bounding force of sizing material of being produced and steel curtain slightly is superior to normal sizing material, and the sizing material time of scorch is long simultaneously, and the process safety performance is good.Test sizing cross-linked rubber dynamic property is good, gives birth to hot low.Test finished product tire performance is superior to usual prodn.
Claims (6)
1. radial-ply tyre carcass glue rubber combination that contains environmental protection type resin is characterized in that:
Diene elastomer with 100 weight parts is a benchmark, also comprises,
The carbon black of 50～60 weight parts,
The methylene radical donor of 3～5 weight parts,
The environmental protection type resin of 1～1.5 weight part, environmental protection type resin is obtained by R modification Resorcinol, and R is mainly vinylbenzene,
The sulphur of 4～6 weight parts,
The cobalt salt of 1～2 weight part,
The promotor of 1～2 weight part;
Wherein diene elastomer is selected one or more the mixture in smoke sheet rubber, standard glue, the synthetic polyisoprenes rubber for use.
2. according to the said radial-ply tyre carcass glue rubber combination that contains environmental protection type resin of claim 1, it is characterized in that the preferred N326 carbon black of said carbon black.
3. according to the said radial-ply tyre carcass glue rubber combination that contains environmental protection type resin of claim 1, it is characterized in that the preferred hexamethoxy methyl cyanuramide of said methylene radical donor.
4. according to the said radial-ply tyre carcass glue rubber combination that contains environmental protection type resin of claim 1, it is characterized in that the preferred oil-filled type insoluble sulfur of said sulphur.
5. according to the said radial-ply tyre carcass glue rubber combination that contains environmental protection type resin of claim 1, it is characterized in that the preferred capric acid cobalt of said cobalt salt or cobalt naphthenate or cobalt boracylate.
6. produce the said method that contains the radial-ply tyre carcass glue of environmental protection type resin of claim 1 for one kind, comprise the following steps, its component ratio by weight:
(2) park: the rubber master batch with a section after mixing was parked about 4 hours, guaranteed that sizing material is cooled to room temperature;
(3) two-stage mixing: the closed-smelting machine rotor rotating speed is 60 rev/mins, and floating weight pressure is 0.7MPa; One section rubber master batch is dropped into Banbury mixer, mixing 40～45 seconds, to carry and fasten 6～8 seconds, binder removal after mixing again 40～45 seconds, dump temperature are controlled at below 165 ℃;
(4) park: the rubber master batch behind the two-stage mixing was parked about 4 hours, guaranteed that sizing material is cooled to room temperature;
(5) three-stage mixing: three-stage mixing closed-smelting machine rotor rotating speed is 25 rev/mins, and floating weight pressure is 0.6MPa; Two sections rubber master batch of 170 parts, 4～6 parts sulphur HD-OT20,1～2 part promotor (mixture of DZ or DZ and NS), 3～5 parts methylene radical donor RA, 0.2～0.4 part anti-scorching agent CTP are dropped into the banburying unit room; Mixing 40～45 seconds; Carried bolt then 7～8 seconds, mixing again 55～60 seconds, binder removal; Dump temperature is controlled at below 100 ℃, can make the radial-ply tyre carcass glue that contains environmental protection type resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012102072880A CN102702585A (en) | 2012-06-21 | 2012-06-21 | Radial tire carcass ply compound and rubber composition containing environment-friendly resin and preparation method thereof |
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| CN2012102072880A CN102702585A (en) | 2012-06-21 | 2012-06-21 | Radial tire carcass ply compound and rubber composition containing environment-friendly resin and preparation method thereof |
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| CN102702585A true CN102702585A (en) | 2012-10-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327316A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch in steel cord adhesive |
| CN113150409A (en) * | 2021-04-30 | 2021-07-23 | 中国科学院长春应用化学研究所 | Rubber composition for all-steel radial tire body and preparation method thereof |
| CN115594896A (en) * | 2022-11-03 | 2023-01-13 | 北京彤程创展科技有限公司（Cn） | Rubber composition, rubber product and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751077A (en) * | 2003-02-18 | 2006-03-22 | 茵迪斯佩克化学公司 | Modified resorcinol resins and applications thereof |
| CN101235166A (en) * | 2008-01-04 | 2008-08-06 | 华奇（张家港）化工有限公司 | Resorcin phenolic resin modified rubber composition |
-
2012
- 2012-06-21 CN CN2012102072880A patent/CN102702585A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751077A (en) * | 2003-02-18 | 2006-03-22 | 茵迪斯佩克化学公司 | Modified resorcinol resins and applications thereof |
| CN101235166A (en) * | 2008-01-04 | 2008-08-06 | 华奇（张家港）化工有限公司 | Resorcin phenolic resin modified rubber composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327316A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch in steel cord adhesive |
| CN104327316B (en) * | 2014-11-03 | 2017-03-29 | 怡维怡橡胶研究院有限公司 | A kind of application of rubber masterbatch prepared by continuous way in steel cord adhesive glue |
| CN113150409A (en) * | 2021-04-30 | 2021-07-23 | 中国科学院长春应用化学研究所 | Rubber composition for all-steel radial tire body and preparation method thereof |
| CN115594896A (en) * | 2022-11-03 | 2023-01-13 | 北京彤程创展科技有限公司（Cn） | Rubber composition, rubber product and application |
| CN115594896B (en) * | 2022-11-03 | 2023-11-21 | 北京彤程创展科技有限公司 | Rubber composition, rubber product and application |
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Application publication date: 20121003 |