CN100415814C - Rubber composition containing silica and method for production therof - Google Patents
Rubber composition containing silica and method for production therof Download PDFInfo
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- CN100415814C CN100415814C CNB2004800246006A CN200480024600A CN100415814C CN 100415814 C CN100415814 C CN 100415814C CN B2004800246006 A CNB2004800246006 A CN B2004800246006A CN 200480024600 A CN200480024600 A CN 200480024600A CN 100415814 C CN100415814 C CN 100415814C
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Abstract
A rubber composition containing silica which is produced by a process comprising co-coagulating a mixture of a rubber latex and silica to provide a slurry of a crumb rubber containing silica, reducing the water content of the slurry to 80 wt % or less by filtration, and then dewatering the resultant slurry by means of a dewatering device having compressing function, followed by drying. According to the present invention, a rubber composition containing silica with improved silica dispersibility can be provided.
Description
Technical field
The present invention relates to the novel composition and method of making the same that contains silica rubber, specifically, relate to excellences such as wearability and low burnup, what be suitable as tire tread contains the silica rubber composition.
Background technology
All the time, as the reinforcement packing material of rubber, carbon black, silicon-dioxide have obtained widespread use, usually, extensively adopt the drying process of kneading devices such as using Banbury, kneader and rubber mix.In recent years, it is found that: the rubber combination that is filled with silicon-dioxide be filled with the sooty rubber combination and compare, can be free painted, and it is low in the pollution of the environment, anti-drawing crack excellence, moreover, also can realize low burnup and the high ground property of pasting simultaneously, be subjected to people's attention with elastomeric material as tire tread.But silica sphere is covered by silanol group usually, has very strong self coagulation, and therefore the affinity of shortcoming and rubber is difficult to make its good distribution in rubber.
In order to improve the dispersiveness of silicon-dioxide in diene series rubber, the someone has proposed to make rubber obtain diene rubber composition with the so-called damp process that silicon-dioxide solidifies by diene series rubber latex is mixed with SiO 2 slurry.For example, in order to make diene series rubber latex and SiO 2 slurry uniform mixing, disclosing positively charged ions such as using alkyl trimethyl ammonium salt is the method (United States Patent (USP) the 4th of organic surface active agent or cationic resin, 482, No. 657 communiques, TOHKEMY 2001-213971 communique), to use positively charged ion be the method (TOHKEMY 2002-241507 communique) etc. of material and the aqueous electrolyte liquid that contains polyvalent metal salt.Also disclose with silane coupling agent and handled, the organic solvent solution of hydrophobic silicon-dioxide with diene series rubber latex or diene series rubber mixed, made its method of solidifying altogether (Japanese kokai publication hei 10-231381 communique).
But, for silicon-dioxide is distributed in the diene series rubber, though these methods mix than by the mixing of drying process, but in the dehydration of in step thereafter, adopting, the drying means, the drying of rubber combination needs the energy, time, and the reinforcement of gained diene rubber composition or wearability, the low burnup when the tire tread, for the subsides ground on wet and slippery road surface property to improve effect not enough.
Summary of the invention
What the object of the present invention is to provide that the dispersiveness of silicon-dioxide is improved contains silica rubber composition, the cross moulding product of this rubber combination and the preparation method of this rubber combination.
The inventor etc. have carried out research in depth for solving above-mentioned technical task, found that: the mixture of rubber latex and silicon-dioxide is solidified altogether, obtain containing the slurry of silica particle, by filtering, making its water ratio is below the prescribed value, then, it is also dry with specific dewatering unit dehydration, use obtain thus contain the silica rubber composition, low burnup in the time of can improving its physical strength, moulding tire or in the subsides on wet and slippery road surface ground property, and finished the present invention according to this understanding.
Promptly, the present invention can provide and contain the silica rubber composition, said composition is that the mixture with rubber latex and silicon-dioxide solidifies altogether, obtain containing the slurry of silica particle, by filtering, making its water ratio is below 80% weight, then, gets with the dewatering unit dehydration after drying with compression function.
The silica rubber composition that contains of the present invention can also contain the cationic material.
Of the present invention containing in the silica rubber composition, preferred above-mentioned silicon-dioxide is 40-230m by the specific surface area of the determining adsorption of bromination trimethylammonium cetyltrimethyl ammonium (CTAB)
2/ g.
The silica rubber composition that contains of the present invention can also contain linking agent.
The silica rubber composition that contains of the present invention can further contain organopolysiloxane or polyethers based polymer.
The silica rubber composition that contains of the present invention can contain the silane coupling agent again.
The water ratio that contains the silica rubber composition of the present invention is below 5% weight.
The invention provides the cross moulding product that will contain the containing silica rubber composition cross moulding of above-mentioned linking agent and obtain.
The invention provides and contain silica rubber preparation of compositions method, the method includes the steps of: rubber latex is mixed with the aqueous dispersions of silicon-dioxide, obtain the step (A) of the mixture of rubber latex and silicon-dioxide; Rubber in the said mixture is solidified altogether with silicon-dioxide, obtain containing the step (B) of the slurry of silica particle; Filter above-mentioned slurry, obtaining water ratio is the step (C) of the following micelle of 80% weight; Use has the dewatering unit of compression function, the step (D) that above-mentioned filtered micelle is dewatered; And to above-mentioned through the dehydration micelle carry out exsiccant step (E).
Of the present invention containing in the silica rubber preparation of compositions method, above-mentioned dewatering unit preferably uses the forcing machine with barrel, and wherein the inside of barrel is provided with screw rod.
Of the present invention containing in the silica rubber preparation of compositions method, the interior pressure that preferably makes above-mentioned extruder barrel is carried out the dehydration of above-mentioned filtered micelle through the interim state that improves when running well.
Of the present invention containing in the silica rubber preparation of compositions method, preferably or midway at the start of run of above-mentioned forcing machine, partly or entirely interim inaccessible with the micelle spout of above-mentioned forcing machine.
Of the present invention containing in the silica rubber preparation of compositions method, preferred filling weighting material in above-mentioned forcing machine makes the part or all of obturation of micelle spout.
Of the present invention containing in the silica rubber preparation of compositions method, preferred above-mentioned weighting material uses the material of any material at least that contains rubber, resin and ice.
Of the present invention containing in the silica rubber preparation of compositions method, preferably by decompression operation or/and heating operation carries out the drying of the micelle of above-mentioned dehydration.
Of the present invention containing in the silica rubber preparation of compositions method, the preferably drying of operating the micelle that carries out above-mentioned dehydration by squeeze operation and pressure release.
The accompanying drawing summary
Fig. 1 is the dehydration of using in the present embodiment of solidifying micelle, the explanatory view of exsiccant device.
The preferred plan that carries out an invention
(containing the silica rubber composition)
The silica rubber composition that contains of the present invention is that mixture with rubber latex and silicon-dioxide solidifies altogether, by filtering, the water ratio that makes the slurry that contains silica particle that obtains is below 80% weight, then, dewater with the dewatering unit with compression function, drying forms then.
(rubber)
The employed rubber of above-mentioned rubber latex can suitably be selected according to the target purposes, has specifically: natural rubber, synthetic polyisoprene, divinyl rubber, styrene butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, styrene butadiene-isoprene copolymer rubber, butadiene-isoprene copolymer glue, acrylonitrile-styrene-diene series rubbers such as butadiene copolymer rubber; Neoprene; Isoprene-isobutylene rubber; Acrylic rubber etc.These rubber can have hydroxyl, carboxyl, alkoxysilyl, amino and epoxy group(ing) etc.These rubber may be used alone, or two or more kinds may be used in combination.Wherein, particularly when being used for the tire purposes, consider tyre performances such as wearability, low burnup, preferably use diene series rubbers such as natural rubber, synthetic polyisoprene, divinyl rubber, styrene butadiene copolymer rubber.
Above-mentioned rubber can pass through methods such as emulsion polymerization, solution polymerization process, suspension polymerization, gaseous polymerization and obtain with latex, organic solvent solution, slurry or solid state respectively, but among the present invention, except using the material that obtains with latex, can also use the material of making latex by the dissolving of phase conversion method or pulverizing-again etc.Wherein, effectively disperse the preferred latex that obtains by emulsion polymerization that uses in order to make silicon-dioxide.
When obtaining above-mentioned rubber by letex polymerization, can adopt known emulsion polymerization, employed emulsifying agent of letex polymerization and polymerization starter also can use known material.Molecular weight regulator for example can use thio-alcohols such as uncle's lauryl mercaptan, n-dodecyl mercaptan, tetracol phenixin, Thiovanic acid, diterpene, terpinolene, γ-terpinene class etc.
The temperature of letex polymerization can suitably be selected according to the kind of employed polymerization starter, is generally 0-100 ℃, preferred 0-60 ℃.Polymerization methods can be any-modes such as successive polymerization, batchwise polymerization.
Consider that from the angle of the gelation that prevents polymkeric substance the polymerisation conversion when polyreaction stops is preferably below 85% weight, more preferably the scope of 50-80% weight.Polyreaction stops normally when reaching the polymerisation conversion of afore mentioned rules, is undertaken by add polymerization terminator in polymerization system.The example of polymerization terminator has: amine compounds such as diethyl hydroxylamine or azanol; Quinone such as quinhydrones or benzoquinones based compound; Sodium Nitrite, company's two thiocarbamate ester sodium etc.
Preferably after stopping, polyreaction in reaction soln, adds antiaging agent between the latex coagulation to making.Particularly use forcing machine to carry out the dehydration of micelle and when dry,, preferably add the antiaging agent of necessary amount from preventing to shear the viewpoint of the deterioration that causes with barrel.Here, described barrel is provided with screw rod in inside.It is antiaging agent that ageing-resistant example has phenol such as 2,6 di tert butyl 4 methyl phenol, 3-(3 ', 3 '-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, styrenated phenol; 2, two (octylsulfo the methyl)-sulphur such as 6-methylphenol of 4-are antiaging agent; (1, the 3-dimethylbutyl)-N '-amine such as phenyl-Ursol D are antiaging agent to N-; 2,2,4-trimethylammonium-1, quinoline such as 2-dihydroxyl quinoline are antiaging agent; Quinhydrones is an antiaging agent; Phosphorus is antiaging agent etc.
These antiaging agents may be used alone, or two or more kinds may be used in combination.With respect to 100 parts by weight of rubber, these ageing-resistant additions are generally the 0.05-10.0 weight part, preferred 0.08-6.0 weight part, more preferably 0.1-4.0 weight part.In addition, polyreaction preferably as required, is removed unreacted monomer after stopping from gained latex.
Each monomeric consumption can suitably be selected in the letex polymerization, so that the amount of each monomeric unit is desirable content in the polymkeric substance.When using the styrene copolymerized diene series rubber of styrene butadiene copolymer rubber, styrene butadiene-isoprene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber etc., this vinylbenzene amount is below 60% weight, below preferred 50% weight.When using the acrylonitrile compolymer diene series rubber, this vinyl cyanide amount is below 60% weight, below preferred 55% weight.Vinylbenzene amount or vinyl cyanide amount are too much, and then heat generation increases, and low temperature brittleness is poor.
Mooney viscosity (the ML of employed rubber among the present invention
1+4, 100 ℃) be preferably the scope of 10-250, the more preferably scope of 30-200.
Among the present invention, can mix extending oil in the rubber.Extending oil can use normally used material in the rubber industry, and petroleum line softeners such as paraffin series, aromatics system, naphthene series are arranged; Department of botany's tenderizer; Lipid acid etc.When using petroleum line softener, the content of preferred polycyclic aromatic is lower than 3%.This content can be measured by the method (inspection method of Institute of Petroleum(IP) (THEINSTITUTE PETROLEUM)) of IP346.
(silicon-dioxide)
The silicon-dioxide that uses among the present invention is not particularly limited.For example, can use usually the dry type silicon-dioxide that silicon tetrachloride burnt in oxyhydrogen flame and obtain, the wet silicon dioxide that silicate base is obtained with the acid neutralization, with the alkoxide of silicon such as tetramethoxy-silicane or tetraethoxysilane hydrolysis and the sol-gel method silicon-dioxide that obtains, the colloid silica that the dealkalize of the silicate base aqueous solution obtained by electrodialysis etc. in acid or alkaline water-containing organic solvent.These silicon-dioxide can be independent, also can will be used in combination more than 2 kinds.Among the present invention, the wet silicon dioxide of preferred productive rate excellence, the wherein precipitated silica that especially preferably obtains without gel.
Preferred above-mentioned silicon-dioxide is 40-230m through the specific surface area of bromination trimethylammonium cetyltrimethyl ammonium (CTAB) determining adsorption
2/ g, more preferably 50-180m
2/ g, most preferably 60-120m
2/ g.
Preferred above-mentioned silicon-dioxide is through the specific surface area (S of determination of nitrogen adsorption
BET) be 50-250m
2/ g, more preferably 60-190m
2/ g, most preferably 70-140m
2/ g.
The preferred dibutyl phthalate oil number of above-mentioned silicon-dioxide (being designated hereinafter simply as oil number) is 100-250ml/100g, more preferably 110-210ml/100g, most preferably 120-180ml/100g.
Among the present invention, use when having the silicon-dioxide of above-mentioned specific surface area and oil number, gained contains the tensile strength of silica rubber composition, the excellences such as wearability of cross moulding product, reinforcement or low burnup excellence when therefore using as tire.
The median size of silicon-dioxide is not particularly limited, and can suitably determine according to the target purposes.The scope of usually preferred 0.1-50 μ m.Making above-mentioned median size is more than the 0.1 μ m, can prevent that the dispersion that the self coagulation because of silicon-dioxide causes is bad, and gained contains the hardness excellence of silica rubber composition.And make above-mentioned median size is below the 50 μ m, and then the good dispersion of silicon-dioxide in rubber can obtain enough reinforcement or low burnup.Wherein, when being used for tire, the median size of preferred silicon-dioxide is 1 μ m-30 μ m.
Adjusting for the silicon-dioxide particle diameter is not particularly limited, and can use known method.For example, use jet mill, ball milling, nara mill, microballoon mill etc., suitably be adjusted to and obtain the wet comminuting method of doing of target grain size; Use dispersion machine, homogenizer, high-pressure homogenizer, colloidal mill etc., suitably be adjusted to the methods such as case of wet attrition method that can obtain target grain size.In addition, when regulating the particle diameter of silicon-dioxide, can in water, organic solvent or rubber latex or in their mixing solutions, regulate by the case of wet attrition method.
(cationic material)
In order further to improve the dispersiveness of silicon-dioxide, the silica rubber composition that contains of the present invention can further contain the cationic material.The cationic material can use United States Patent (USP) the 4th, 482, the cationic material of No. 657 records etc., but in order to be suitable for dehydration of the present invention described later, drying means, from operating the preferred cationic polymer.
The cationic polymer shows that the polymer of cationic get final product so long as ionization takes place when being dissolved in water, can be without any use restrictedly.Specifically, representational for example have a polymer that has the amino and quaternary ammonium hydroxide of primary-uncle on high polymer main chain or side chain.Described cationic polymer for example preferably makes has the compound that primary-uncle monomer polymerization amino or its ammonium alkali and quaternary ammonium hydroxide obtains.In the scope of harmless above-mentioned effect, can also be the compound that obtains with other monomer copolymerization.
Among the present invention, particularly make monomer polymerization and the compound that obtains is good to the reinforcement of gained diene rubber composition with uncle and quaternary ammonium hydroxide, thus preferred.
Among the present invention, specifically provide the preferred cation polymer, polymine is arranged, polyvinylamine, polyvinyl pyridine, polyamine sulfone (Port リ ア ミ Application ス Le ホ Application), PAH, the polydiene propyl methylamine, polyamide-amide, the polyacrylate and amino alkyl ester, the polymethyl acrylic acid aminoalkyl ester, poly-aminoalkyl group acrylamide, poly-epoxy group(ing) amine, polymeric amide-polyamine, polyester-polyamine, dicyan diamide formaldehyde condensation products, polyalkylene polyamine dicyan diamide condenses, epichlorohydrin dialkylamine condenses etc. and their ammonium salt, also has diallyl dimethyl ammoniumchloride, polymethacryl methyl chlorine etc. has the polymer of quaternary amine alkali.Wherein special preferably polyethylene imines, PAH, polydiene propyl methylamine, poly-epoxy group(ing) amine, epichlorohydrin dialkylamine condenses and their ammonium salt.
The high molecular weight-average molecular weight of above-mentioned cationic is preferred 1,000-1,000,000, more preferably 2,000-900,000, most preferably 3,000-800,000.Above-mentioned weight-average molecular weight is more than 1,000, then containing in the silica rubber composition at gained, the reinforcement property improvement effect of tensile strength or wearability etc. increases, and above-mentioned weight-average molecular weight is 1,000, below 000, the favorable dispersity of silicon-dioxide in rubber then.
The value of the cation equivalent molecular weight that calculates by the high molecular colloidal titration of above-mentioned cationic is preferably below 200, more preferably below 180, most preferably below 150.
These cationic polymers can separately or be used in combination of two or more.With respect to 100 weight part silicon-dioxide, the combined amount of these cationic materials in rubber combination is the 0.1-7.5 weight part, preferred 0.5-7 weight part, more preferably 1-6 weight part.
(preparation method)
Among the present invention, preferred above-mentioned rubber latex and the mixture of silicon-dioxide are rubber latex is mixed with the aqueous dispersions of silicon-dioxide and to obtain.The silicon-dioxide of rubber in the above-mentioned rubber latex in silica aqueous dispersion solidifies, and what can obtain like this that the dispersiveness of reinforcement and low burnup excellence, silicon-dioxide is improved contains the silica rubber composition, thereby preferred.
That is, the silica rubber preparation of compositions method that contains of the present invention is characterised in that and comprises following steps: rubber latex is mixed with the aqueous dispersions of silicon-dioxide, obtain the step (A) of the mixture of rubber latex and silicon-dioxide; Rubber in the said mixture is solidified altogether with silicon-dioxide, obtain containing the step (B) of the slurry of silica particle; Filter above-mentioned slurry, obtaining water ratio is the step (C) of the following micelle of 80% weight; Use has the dewatering unit of compression function, the step (D) that above-mentioned filtered micelle is dewatered; And to above-mentioned through the dehydration micelle carry out exsiccant step (E).
Step (A) is the step of mixed silica in above-mentioned rubber latex, it is characterized in that: silicon-dioxide is made aqueous dispersions, mix with this rubber latex.In this step (A), the more preferably silicon-dioxide that for example silicate base and sour neutralization reaction is obtained drying not is scattered in the water with the form of paste-like or wet pie, and the aqueous dispersions of preparation silicon-dioxide mixes it with rubber latex.Like this, without drying step, by adopting silicon-dioxide is scattered in method in the water, make the selectivity of spendable silicon-dioxide broaden, therefore the self coagulations that the thermal contraction of silicon-dioxide causes in the time of can avoiding drying in addition etc. can improve the dispersiveness of silicon-dioxide in rubber.
In the aforesaid method, the process of mixing above-mentioned cationic material has following method:
(1) with rubber latex with after silica aqueous dispersion is mixed, with the cationic material directly or make the method for aqueous solution, the perhaps method of the mixed solution of mixed rubber latex and silica aqueous dispersion in the aqueous solution of ionic substance on the sunny side;
(2) silicon-dioxide is mixed in water with the cationic material, make aqueous dispersions, to the method for mixed rubber latex wherein;
(3) with rubber latex, silica aqueous dispersion and cationic material while blended method etc.
Wherein, the excellences such as elasticity of the micelle of the method for above-mentioned (2) can be dewatered effectively by method of the present invention, and are the most preferred.
Rubber concentrations in the above-mentioned rubber latex is not particularly limited, and can suitably set according to purpose, purposes.Be generally 1-80% weight, preferred 3-55% weight, the scope of preferred especially 5-30% weight.When this scope, control the particle diameter of micelle when solidifying etc. easily.
In the above-mentioned steps (A), the combined amount of silica aqueous dispersion in rubber latex is not particularly limited, can suitably determine according to the target purposes, with respect to the rubber in the 100 parts by weight of rubber latex, preferred silica weight is the 10-120 weight part, more preferably 20-100 weight part, most preferably 30-90 weight part.In the time of in above-mentioned scope, it is good that gained contains the reinforcement or the low burnup of silica rubber composition.Break away from above-mentioned scope, then the gained micelle does not have the rubber proterties, and during with method of the present invention dehydration, becomes pasty state, and the low tendency of dewatering efficiency is arranged.
The preferred usually 1-40% weight of using of silica concentration in the above-mentioned aqueous dispersions.When this scope, the flowability of the aqueous dispersions of silicon-dioxide improves, and what solidify altogether is controlled good, can be contained the silica rubber composition uniformly.
Step (B) is characterised in that: the rubber latex that obtains in the use step (A) and the mixture of silicon-dioxide, and make the rubber in the rubber latex solidify (solidifying altogether) with silicon-dioxide, obtain containing silica particle.As mentioned above, by when taking in silicon-dioxide, rubber being solidified, can further improve the dispersiveness of silicon-dioxide in rubber like this, in this step (B), the pH of system is preferably 3.5-11.0 when solidifying, the addition surplus of rubber latex, and then pH rises, therefore preferred acid and/or the salt of adding is regulated pH.The example of acid and salt has: mineral acids such as sulfuric acid, phosphoric acid, hydrochloric acid, organic acids such as formic acid, acetate, butyric acid, acid such as Lewis acid such as Tai-Ace S 150; Salt such as sodium-chlor, calcium chloride etc.
When mixing extending oil in the rubber combination of the present invention, preferably in solidifying beginning forward direction system, add the fat liquor that extending oil emulsification is obtained, more preferably mix with rubber latex in advance.
Preferred 10 ℃-90 ℃ of temperature of solidification, more preferably 20 ℃-80 ℃.The method of solidifying altogether is not particularly limited, and adopts the diverting device with routines such as propeller type stirrer, dispersion machine, homogenizers to carry out the blended method usually.
Step (C) is characterised in that: with the slurry that contains silica particle that obtains in the step (B), promptly the mixture that contains the micelle (saccharoid or block) of silicon-dioxide and solidification liquid (aqueous solution) is with filtrations such as sieves, remove the part of solidification liquid thus in advance, the water ratio of the micelle after obtaining filtering is that 80% weight is following, preferred 75% weight following, the more preferably following micelle of 65% weight.
The above-mentioned slurry that contains silica particle is filtered, a part of removing solidification liquid in advance, making the water ratio of the micelle after the filtration is below the prescribed value, can improve the dewatering efficiency of following step like this.The water ratio of the micelle after the filtration is generally more than 40% weight.
Step (D) is characterised in that: use the micelle of dewatering unit after to the filtration of step (C) gained with compression function to dewater.
The dewatering unit that use has a compression function dewaters to the micelle that above-mentioned water ratio is adjusted to after the filtration below the prescribed value, the silicon-dioxide dispersiveness can be brought up to the level that present method had not realized thus, as a result, the low burnup in the time of can making gained contain the silica rubber composition to have physical strength, tire building, paste excellent characteristic such as ground property.
(dewatering unit) with compression function
The dewatering unit with compression function that uses in the step (D) is so long as have and can get final product by compressing the device that above-mentioned filtered micelle extrudes the function of solidification liquid, be not particularly limited, for example can use to have the device that inside is provided with the barrel (compressing micelle between barrel wall and screw flight) of screw rod; The device of extruding type (micelle is sealed in the die cavity of certain volume and compresses); Has the device of roller (make between the roller of micelle by a fixed gap and compress) etc.Particularly above-mentioned dewatering unit preferably uses the forcing machine with barrel, and the inside of wherein said barrel is provided with screw rod.Have forcing machine that inside is provided with the barrel of screw rod and can use single screw extrusion machine with barrel or dehydration slit, twin screw extruder etc., the inside of wherein said barrel is provided with screw rod and can heats.
In the step (D), in these dewatering units, add above-mentioned filtered micelle, dewater.The temperature of the micelle that adds is not particularly limited, can be identical with temperature of solidification, also can cool off, identical with envrionment temperature.The dehydration of micelle can be carried out said apparatus combination more than 2 kinds.
When using forcing machine to carry out step (D), the interior pressure that preferably makes extruder barrel is carried out the dehydration of above-mentioned filtered micelle through the interim state that improves when running well in above-mentioned forcing machine.Like this, and moisture micelle is directly carried out warm air drying or vacuum drying situation is compared, can be with the moisture content (water ratio) of low-yield reduction micelle.
Like this, when dewatering in forcing machine, the method for the interim state that improves is not particularly limited when reaching than normal operation for the interior pressure that makes extruder barrel, preferably makes the partly or entirely method of interim obturation of forcing machine micelle spout.The interim inaccessible operation of above-mentioned micelle spout is preferably carried out in the initial stage of micelle dehydrating step.Also can carry out in the stage midway of micelle dehydrating step.
Make the partly or entirely interim inaccessible of micelle spout, reach the state that temporarily improves when the inner pressure ratio that makes extruder barrel runs well, then solidifying micelle becomes compressed state along extruding direction, can prevent the micelle that causes because of the shearing force of screw rod etc. in forcing machine in the pasty state.Can effectively remove the moisture in the micelle thus.
In above-mentioned, make the partly or entirely interim inaccessible method of the micelle spout of forcing machine preferably weighting material is filled near the method the micelle spout in the forcing machine.According to this method, can wait the inaccessible degree of regulating the micelle spout by the kind or the loading level of weighting material.The filling of weighting material can be about to carry out before the dehydration at micelle, and preferably the block service that is undertaken by filling carried out at the initial stage of dehydrating step.
In above-mentioned, inaccessible employed weighting material preferably uses at least a material that contains rubber, resin and ice.
The rubber that is used for weighting material has: rubber such as styrene butadiene rubbers, divinyl rubber, synthetic polyisoprene, isoprene-isobutylene rubber, ethylene-propylene-elastoprene, acrylonitrile-butadiene rubber, acrylic rubber, hydrogenated acrylonitrile-divinyl rubber, Viton, organo-silicone rubber; Be mixed with the rubber combination of fillers such as carbon black or silicon-dioxide etc. in these rubber.
Rubber as weighting material can use and the rubber that contains the silica rubber identical type that dewaters with the inventive method.
The resin that is used for weighting material has: high styrene resin, polystyrene, shock resistance polystyrene, vinyl cyanide styrene butadiene resin, polycarbonate, acrylic resin, polyethylene terephthalate, polyethylene, polypropylene, vinyl chloride resin, cyclic olefine resin; Be mixed with the resin combination of fillers such as glass fibre or carbon fiber etc. in these resins.These rubber or resin etc. may be used alone, or two or more kinds may be used in combination.
The shape of these weighting materials or size are without limits.So long as getting final product of can adding by the dog-house of forcing machine, can be according to wanting inaccessible degree suitably to select.For example rubber can use micelle, and resin can use particle etc., the combinations of substances of different shapes or size can be used.
The method of filling above-mentioned weighting material to forcing machine for example has forcing machines of packing into such as above-mentioned micelle, toner, resin particles, does not seal spout, extrudes these weighting materials according to ordinary method.When the weighting material that is added sprays approximately, stop the running of forcing machine, like this, can weighting material residually be arranged near the ejiction opening usually, under this state, add and contain silica particle, the forcing machine that turns round once more dewaters.
When weighting material is ice, begin to extrude micelle when residual ice does not dissolve as yet near spout.
After dewatering with above-mentioned dewatering unit, the preferred 0-50% weight of the water ratio of micelle, more preferably 3-40% weight, preferred especially 5-30% weight.Water ratio is too high, then shows to fail effectively to dewater, and when micelle was pasty state, drying step afterwards was difficult to carry out.Just the preferred 20-180 of temperature ℃ of the micelle after the dehydration, more preferably 40-150 ℃, preferred 60-130 ℃ especially.Can effectively dewater when this scope, reinforcement such as the tensile strength of gained rubber combination or wearability, the low burnup when making tire are good.
Step (E) is that the micelle that dewaters in the step (D) is carried out the exsiccant step.Preferably by the micelle after the above-mentioned dehydration is further implemented reduce pressure, drying is carried out in one of at least operation in the heating, centrifugal and compression, more preferably implements one of them of decompression or heating at least, most preferably implements both.These operations can be undertaken by above-mentioned dewatering unit accessory device, also can carry out in addition.
The micelle of one of them operation at least by above-mentioned heating, decompression, centrifugal and compression after to dehydration carries out the exsiccant concrete grammar to be had: the micelle after (1) will dewater place decompression down and/or heating carry out exsiccant method, (2) down and operate and carry out exsiccant method etc. by the micelle after dewatering being implemented alternately squeeze operation and pressure release.
The method of above-mentioned (1) has vacuum-drying or warm air drying.When micelle being carried out drying by this method, preferably with stapling machine or pulverizer etc. to the back fine chopping of micelle adhered to one another of dewatering, carry out drying by vacuum-drying or warm air drying after pulverizing, can shorten the time of drying of micelle thus.With vacuum drier or the hot-air drier when dry preferred 50-200 of drying temperature ℃, more preferably 60-150 ℃, preferred 70-120 ℃ especially.But drying temperature is efficient drying when this scope, can prevent the deterioration, ignition of gained rubber combination etc., and tensile strength, wearability etc. are good.
By vacuum drier or hot-air drier micelle is carried out dried water ratio and be preferably below 5% weight, more preferably below 3% weight, below preferred especially 1% weight.Dried water ratio is too high, and Zhuan Dai building rubber compound deposits yields dewfall then may coking when mixing various mixture with forcing machine etc. in rubber combination.
The method of above-mentioned (2) has: the micelle after will dewatering is supplied with forcing machine, by it is expanded the liquid that remains in the micelle is discharged during discharge, carry out the exsiccant method, wherein said forcing machine for example can be be used to dewater same, have a forcing machine that inside is provided with the barrel of screw rod.Here, expansion is meant compresses micelle in barrel, when being expelled to outside the barrel, makes the extremely acute release of pressure, makes micelle exsiccant method by heat insulation expansion thus.
The method of the method for above-mentioned (1) and (2) combination is had: the micelle after will dewater is supplied with has pressures partially and the part that reduces pressure, and has the forcing machine that inside is provided with the barrel of screw rod, thus the method for dry micelle.Reinforcement such as the tensile strength that contains the silica rubber composition that is obtained by these methods, wearability, low burnup are good.
The preferred 80-220 of drying temperature when carrying out drying ℃ with above-mentioned forcing machine, more preferably 100-200 ℃, preferred 120-180 ℃ especially.Drying temperature is when this scope, but efficient drying can prevent the deterioration, ignition of gained rubber combination etc., and reinforcement such as tensile strength, wearability, low burnup are good.
The dry employed forcing machine of above-mentioned micelle preferably has the screw rod that can prevent that near the micelle of die head is detained.Specifically, the preferred Japan that uses opens the screw rod that the screw thread of putting down in writing in the flat 1-83522 communique extends to screw head in fact, and perhaps using the screw head of Japanese kokai publication sho 62-21518 communique record is the screw rod of non-rotational symmetry type.That also preferred this forcing machine possesses is little with the gap of screw head, have the die head that has the inner chamber that front end attenuates towards outlet side.Have the forcing machine of above-mentioned screw rod or die head by use, even dry back viscosity uprise contain silica particle, also can discharge from die head effectively, drying efficiency is improved.
The forcing machine that is used to dewater can be an one with being used for the exsiccant forcing machine, also can directly connect, and can also separate, and the micelle of dehydration is packed into is used for the exsiccant forcing machine.Among the present invention, the forcing machine that is used to dewater and when being used for the exsiccant forcing machine and being one is with " micelle spout " use as the forcing machine that is used to dewater of the screw rod of drying zone and drying zone intersection and the space between the barrel.
The water ratio that carries out dried micelle with above-mentioned forcing machine is preferably below 10% weight, more preferably below 5% weight, below preferred especially 3% weight.After the forcing machine drying, can further carry out drying with vacuum drier or hot-air drier, water ratio is reduced.
Below preferred 5% weight of the water ratio that contains the silica rubber composition that finally obtains by aforesaid method, more preferably below 3% weight, below preferred especially 1% weight.Dried water ratio is too high, and Zhuan Dai building rubber compound deposits yields dewfall then may produce burnt the paste when mixing various mixture with forcing machine etc. in rubber combination.
Among the present invention, the dried silica rubber composition that contains can be with acquisitions such as block, sheet and particulate state, in order to reduce the living load of dry back when mixing various mixture, preferably obtains with sheet or particulate state.
Among the present invention, when using above-mentioned forcing machine in the drying step, can in dry forward direction micelle, add organopolysiloxane or polyethers based polymer.The water ratio of micelle is low, viscosity increased then, but, the viscosity of micelle is reduced by adding organopolysiloxane or polyethers based polymer, the living load of forcing machine reduces.These organopolysiloxane preferred degree of polymerization are 3-10,000, preferably have functional groups such as methoxyl group, hydroxyl, amino, alkoxyl group, epoxy group(ing), carbonyl, sulfenyl, alkylsulfonyl, itrile group.The polyethers based polymer is the polymkeric substance that main chain has ehter bond, for example is preferably the polymkeric substance of oxirane compounds such as epoxide, epihalohydrins, unsaturated epoxide, and molecular weight is 100-10,000,000.They can be independent, also can will be used in combination more than 2 kinds.
About addition, get final product so long as in the scope of the living load that can reduce forcing machine, add, with respect to 100 weight part silicon-dioxide, the scope of preferred 0.1-50 weight part.Addition means is not particularly limited, get final product so long as before carrying out drying step, add by forcing machine, the method that is added with extruder barrel by drying is arranged, the method of adding in the micelle after dehydration, by the method that dehydration adds with extruder barrel, the method for adding in the micelle before dehydration, the method for in being total to coagulation step, adding, the method of in rubber latex, adding in advance, method of in the aqueous dispersions of silicon-dioxide, adding etc. in advance.In order accurately to add, add in the aqueous dispersions of preferred rubber latex before solidifying altogether in advance or silicon-dioxide.
Among the present invention, can also the mixed silanes coupling agent in the rubber combination.By the mixed silanes coupling agent, can further improve reinforcement and low burnup.Silane coupling agent for example has vinyltriethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, 3-eight sulfo-s-1-propyl-triethoxysilicane, two (3-(triethoxysilyl) propyl group) tetrasulfide, two (3-(triethoxysilyl) propyl group) disulphide etc.; γ-trimethoxy-silylpropyl dimethyl thiocarbamoyl tetrasulfide, γ-tetrasulfide classes such as trimethoxy-silylpropyl benzothiazole tetrasulfide etc.These silane coupling agents can be separately separately or will be used in combination more than 2 kinds.With respect to 100 weight part silicon-dioxide, the combined amount of silane coupling agent is preferably the 0.1-20 weight part, more preferably 0.5-15 weight part, most preferably 1-10 weight part.
Among the present invention, can also mix silylating agent in the rubber combination.By mixing silylating agent, can further improve reinforcement and low burnup.The example of silylating agent has: chlorosilane cpds such as phenyl-trichloro-silicane, diphenyl dichlorosilane, trimethylchlorosilane, TERT-BUTYL DIMETHYL CHLORO SILANE; Alkoxysilane compound containing trialkylsilyl group in molecular structure such as phenyltrimethoxysila,e, phenyl triethoxysilane, isobutyl-Trimethoxy silane, dimethoxydiphenylsilane, vinyl three ('beta '-methoxy) silane, γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan; Silazane compounds such as hexamethyldisilazane; N-trimethyl silyl ethanamide, N, ethanamides such as N-(two trimethyl silyl) ethanamide; N, urea classes such as N-(two trimethyl silyl) urea etc.These silylating agents can use separately, also can will be used in combination more than 2 kinds arbitrarily.In these silylating agents, especially preferably use chlorosilane cpd, alkoxysilane compound containing trialkylsilyl group in molecular structure, silazane compound.
With respect to 100 weight part silicon-dioxide, the preferred 0.1-20 weight part of the combined amount of silylating agent, more preferably 0.5-15 weight part, most preferably 1-10 weight part.
Above-mentioned silane coupling agent and silylating agent can mix in any stage such as above-mentioned coagulation step front and back, dehydrating step front and back, specifically, the method that is pre-mixed in the above-mentioned silica aqueous dispersion is arranged, be pre-mixed the method in the mixture of cationic material and silicon-dioxide, be mixed into the method in the rubber latex, blended method when solidifying altogether joining dehydration with in the extruder barrel and the blended method, is mixed into method in the micelle after the dehydration etc.Can also add and mix when mixing in roller or Banbury described later.Can also be with them in a small amount of gradation mixing of all stages.
For accurate interpolation, preferably before solidifying altogether, add in advance in the aqueous dispersions of rubber latex or silicon-dioxide.For reinforcement or the low burnup of further improving rubber combination, add particularly preferably in adding in the cationic polymer silica aqueous dispersion before.In addition, the mixing temperature when silane coupling agent and silylating agent are mixed with the aqueous dispersions of silicon-dioxide is generally 10-100 ℃, preferred 40-90 ℃, more preferably 60-80 ℃, mixing time is generally 0.1-180 minute, and preferred 0.5-150 minute, more preferably 1-120 minute.
Silane coupling agent and silylating agent and above-mentioned organopolysiloxane etc. are same, have the effect of the viscosity reduction that makes rubber combination.Thereby when using above-mentioned forcing machine as drying installation, the load in the time of can making it mixing reduces, and can reduce power, therefore preferably mixes add micelle in drying installation before.
In the scope of harmless effect of the present invention, the strengthening agent such as mixed carbon black that contains in the silica rubber composition suitably of the present invention; Weighting agents such as talcum powder, lime carbonate, aluminium hydroxide; Antiaging agent; Promoting agent; Mixtures such as softening agent.
Carbon black for example can use furnace black, Shawinigan black, thermal black, thermally oxidized black, graphite etc.Wherein preferred especially furnace black.Can mixed carbon black, support the carbon-silicon-dioxide two-phase filler of silicon-dioxide at carbon blacksurface, with this as strengthening agent.With respect to 100 parts by weight of rubber, the preferred 20-200 weight part of the total amount of strengthening agent can use according to desirable concentration.Can also mix and the silicon-dioxide that contains different specific surface areas of the employed silicon-dioxide of silica rubber composition or oil number of the present invention.
(cross moulding product)
The silica rubber composition that contains of the present invention can pass through mixed cross-linker, and cross moulding is made and is fit to the cross moulding product that tire is used.The example of linking agent has: sulphur such as powder sulphur, precipitated sulfur, colloid sulphur, insoluble sulphur, polymolecularity sulphur; Halogenation such as sulfur monochloride, sulfur dichloride sulphur; Organo-peroxide such as dicumyl peroxide, di-t-butyl peroxide; P-benzoqui(o)none dioxime, p, p '-benzoquinones dioximes such as dibenzoyl benzoquinones dioxime; Triethylenetetramine (TETA), hexamethylene-diamine carbamate, 4,4 '-methylene-bis-organic multicomponent amine compound such as Ortho-Chloro aniline; Has the alkyl phenolic resin of methylol etc.Wherein preferred sulphur.These linking agents are can be separately independent or will be used in combination more than 2 kinds.With respect to 100 parts by weight of rubber, the preferred 0.3-10 weight part of the combined amount of linking agent, more preferably 0.5-5 weight part.
Can be used in combination crosslinking accelerator, activator of crosslinking in the above-mentioned linking agent.The example of crosslinking accelerator has: N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, N-oxyethylene group-2-[4-morpholinodithio sulphenamide, N-oxyethylene group-2-[4-morpholinodithio sulphenamide, N, and N '-di-isopropyl-sulphenamides such as 2-[4-morpholinodithio sulphenamide are crosslinking accelerator; Guanidines such as diphenylguanidine, di-o-tolyl guanidine, o-tolyl guanidine are crosslinking accelerator; Thiocarbamides such as diethyl thiourea are crosslinking accelerator; Thiazoles such as 2-mercaptobenzothiazole, bisbenzothiazole based bisulfide, 2-mercaptobenzothiazole zinc salt are crosslinking accelerator; Thiuram such as tetramethylthiuram monosulfide, tetramethyl-thiuram disulfide is a crosslinking accelerator; Dithiocarbamic acid such as Sodium dimethyldithiocarbamate 40min, zinc diethyldithiocarbamate is a crosslinking accelerator; Xanthogenic acid such as Good-Rite Nix, zinc isopropyl xanthate, zinc butyl xanthate are crosslinking accelerator etc.Can be separately separately or will be used in combination more than 2 kinds with these crosslinking accelerators, preferably containing sulphenamide is the material of crosslinking accelerator.With respect to 100 parts by weight of rubber, the preferred 0.3-10 weight part of the combined amount of crosslinking accelerator, more preferably 0.5-5 weight part.
Activator of crosslinking for example can use senior lipid acid such as stearic acid or zinc oxide etc.It is the following materials of 5 μ m that zinc oxide preferably uses the high granularity of surfactivity, and it is the active zinc white of 0.05-0.2 μ m or the zinc white of 0.3-1 μ m etc. that its example has granularity.Zinc oxide can be that dispersion agent or lubricant carry out surface treatment with amine.These activator of crosslinking can be separately separately or will be used in combination more than 2 kinds.The blending ratio of activator of crosslinking can suitably be selected according to the kind of activator of crosslinking.With respect to 100 parts by weight of rubber, the combined amount of higher fatty acid is preferably the 0.3-10 weight part, more preferably the 0.5-5 weight part.With respect to 100 parts by weight of rubber, the combined amount of zinc oxide is preferably the 0.1-5 weight part, more preferably the 0.5-2 weight part.
Be not particularly limited for cross-linking method, can be according to selections such as the shape of cross moulding product, sizes.Can carry out crosslinked in the time of with moulding by in mould, filling crosslinking-type rubber composition and heating; Also the unvulcanized rubber composition of moulding in advance can be heated, make it crosslinked.The preferred 120-200 of crosslinking temperature ℃, more preferably 100-190 ℃, most preferably 120-180 ℃.
Of the present inventionly contain the tire material that the silica rubber composition for example can be used for tire tread, undertread, carcass, sidewall, tyre bead portion etc.; Elastomeric materials such as flexible pipe, window frame, belt, sole, Shockproof rubber, trolley part, shock-absorbing rubber; Resin reinforcing rubber materials such as shock resistance polystyrene, ABS resin etc.Wherein, preferably as the tire material, preferred especially tire tread as low burnup tire.
Embodiment
In order further to specify the present invention, provide following examples and comparative example describes, but the present invention is not subjected to the qualification of these embodiment.If no special instructions, " part " and " % " is weight basis.Various rerum naturas in embodiment and the comparative example are measured by following method.
(evaluation of physical property)
(1) the median diameter value of the volume reference of use scattering of light diffraction-type particle size distribution device (コ-Le -company's manufacturing, LS-230) mensuration is as the median size of silicon-dioxide.
(2a) specific surface area (S that obtains by bromination trimethylammonium cetyltrimethyl ammonium (CTAB) absorption
CTAB) adopt the wet cake of the silicon-dioxide moisture eliminator (120 ℃) of packing into is carried out drying, the value that draws according to the method for ASTM D3765-92 record then.The method of ASTM D3765-92 record is to measure sooty (S
CTAB) method, so the present invention is the method for some improvement in addition.That is, do not use carbon standard product ITRB (83.0m
2/ g), prepare the CTAB reference liquid separately, carry out the dioctylis sulfosuccinas natricus standardizing of solution thus, with each CTAB1 molecule at the absorption sectional area of silica sphere as 35 square angstroms, by the adsorptive capacity calculated specific surface area of CTAB.This is that therefore, even identical specific surface area, the adsorptive capacity of CTAB also has difference because carbon black is different with the condition of surface of silicon-dioxide.
(2b) specific surface area (S that obtains by nitrogen adsorption method
BET) be that the wet cake of the silicon-dioxide moisture eliminator (120 ℃) of packing into is carried out drying, the ア サ Star プ 2010 that uses マ イ Network ロ メ リ テ イ Network ス company to make then measures the nitrogen adsorptive capacitys, adopts the value of pressing 1 method under 0.2 relatively.
(3) oil number is obtained by JIS K6220.
(4) the styrene units amount in the multipolymer is measured according to JIS K6383 (index method).
(5) the silicon-dioxide containing ratio uses apparatus for thermal analysis TG/DTA (the Seiko electronic industry is made TG/DTA 320), measures dry sample the combustion residue rate after the thermolysis and the weight-loss ratio when being warming up to 150 ℃ in air, calculates with following formula.It among the embodiment amount (part, weight standard) that is scaled with respect to 100 parts by weight of rubber.Condition determination be in air with 20 ℃ of/minute intensifications of heat-up rate, keep for 600 ℃ carrying out in 20 minutes arriving temperature.
Silicon-dioxide containing ratio (%)=combustion residue rate/[100-(to 150 ℃ time weight-loss ratio)] * 100
(6) hardness uses the Duro-A hardness tester to measure according to JIS K6253.This characteristic is 100 with exponential representation with standard model.
(7) 100%, 300% modulus is measured by JIS K6251 tensile stress test method(s).And calculate 300% when stretching stress (MPa) and the ratio of the stress (MPa) during 100% stretching.This characteristic is 100 with index (reinforcement sex index) expression with standard model.Its value is big more, then represents the silicon-dioxide good dispersion, physical strength or reinforcement excellence.
(8) tan δ and G ' (10 ℃) use the RDA-II that レ オ メ ト リ Star Network ス company makes, tan δ and G ' under measuring-10 ℃ under the condition of 0.5% torsion, 20Hz.This characteristic is with exponential representation.This tan δ (10 ℃) value is big more and/or G ' (10 ℃) is more little, and the subsides ground property that then is presented at wet and slippery road surface is excellent more.
(9) tan δ (60 ℃) uses the RDA-II that レ オ メ ト リ Star Network ス company makes, the tan δ under measuring 60 ℃ under the condition of 0.5% torsion, 20Hz.This characteristic is with exponential representation.This tan δ (60 ℃) value is more little to show that then low burnup is excellent more.
(10) RDA-II that uses レ オ メ ト リ Star Network ス company to make, the deformation dependency of Young's modulus under 0.05% to the 10% scope torsion when under the condition of 1Hz, measuring 50 ℃.Obtain the G ' value under 10% torsion and the poor AG ' of the G ' value under 0.1% torsion.This characteristic is with exponential representation.This value is more little, then shows the good dispersion of silicon-dioxide, low burnup excellence.
(rubber preparation example 1)
In the voltage-resistant reactor of band stirrer, add 200 parts of deionized waters, 1.5 parts of RA rosin acids, 2.1 parts of fatty acid soaps and following monomer: 72 parts of 1,3-butadienes, 28 parts of vinylbenzene, 0.20 part of uncle's lauryl mercaptan.Making temperature of reactor is 10 ℃, adds following polymerization starter in reactor: 0.03 part of diisopropyl benzene hydrogen peroxide, 0.04 part of rongalite and 0.01 part of sodium ethylene diamine tetracetate and 0.03 part of ferric sulfate, initiated polymerization.Polymerisation conversion reaches at 45% o'clock, adds 0.05 part of uncle's lauryl mercaptan, and reaction is continued.Polymerisation conversion reaches at 70% o'clock, adds 0.05 part of diethyl hydroxylamine, makes reaction terminating.
Then, remove unreacted monomer by wet distillation, then with respect to 100 parts of polymkeric substance, with 0.8 part of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl and 0.12 part 2, two (n-octyl the sulphomethyl)-6-methylphenols of 4-are made 30% aqueous emulsion, add as antiaging agent, obtain polymer latex (R1).Then, take out the part of polymer latex (R1), be adjusted to pH 3-5, with sodium-chlor polymer latex is solidified at 50 ℃ simultaneously, obtain glue granulous polymkeric substance with sulfuric acid.With the hot air dryer drying of gained micelle shaped polymer, obtain solid rubber with 80 ℃.The vinylbenzene amount of gained rubber is 23.5%, and mooney viscosity is 52.
(rubber preparation example 2)
Below with the quantitative change of each composition of in reactor, packing into or adding being, in addition according to carrying out polyreaction: 57.5 parts of 1,3-butadienes, 42.5 parts of vinylbenzene, 0.12 part of uncle's lauryl mercaptan (initial add-on), 0.1 part of diisopropyl benzene hydrogen peroxide, 0 06 parts of rongalites, 0.014 part of sodium ethylene diamine tetracetate, 0.02 part of ferric sulfate with the same method of preparation example 1.
Then, remove unreacted monomer by wet distillation, then with respect to 100 parts of polymkeric substance, with 0.21 part of N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D and 0.14 part 2,2,4-trimethylammonium-1, the 2-dihydroquinoline is made 60% aqueous emulsion, adds as antiaging agent, obtains polymer latex (R2).Then, take out the part of polymer latex (R2), with respect to the polymkeric substance in 100 parts of polymer latex Ruzhongs, with fatty acid soaps Enerthene1849A (manufacturing of Block リ テ イ Star シ ユ ペ ト ロ リ ア system company) is made 66% aqueous emulsion, add 37.5 parts as extending oil.Then it is adjusted to pH3-5 with sulfuric acid, with sodium-chlor the polymer latex that contains extending oil is solidified at 60 ℃ simultaneously, obtain glue granulous polymkeric substance.With the hot air dryer drying of gained micelle shaped polymer, obtain solid rubber with 80 ℃.The vinylbenzene amount of gained rubber is 35.0%, and mooney viscosity is 49.
(silicon-dioxide preparation example 1)
1m to the band thermoswitch
3Add 201L sodium silicate aqueous solution (SiO in the reactor
2Concentration: 10g/L, mol ratio: SiO
2/ Na
2O=3.41), be warming up to 95 ℃.Then with 77L22% sulfuric acid and 455L sodium silicate aqueous solution (SiO
2Concentration: 90g/L, mol ratio: SiO
2/ Na
2O=3.41) added simultaneously with 140 minutes.After the slaking 10 minutes, with 15 minutes adding 16L 22% sulfuric acid.Above-mentioned reaction is that reacting liquid temperature is kept 95 ℃, on one side often stirring reaction liquid carry out on one side, the pH that finally obtains reaction solution is 2.9 SiO 2 slurry.It is filtered with filter-pressing device, and washing obtains the solid-state part of silicon-dioxide and is 25% the wet cake (A) of silicon-dioxide.The part of the wet cake (A) of gained silicon-dioxide is dry, the BET specific surface area (S of gained SiO 2 powder
BET) be 121m
2/ g, CTAB specific surface area (S
CTAB) be 110m
2/ g, oil number is 170ml/100g.
(silicon-dioxide preparation example 2)
The add-on of sodium silicate aqueous solution is 150L, in addition with preparation example 1 similarly, use reaction vessel and sodium silicate aqueous solution, be warming up to uniform temp.Then, make the add-on of 22% sulfuric acid and sodium silicate aqueous solution be respectively 78L and 461L, the joining day is 190 minutes, and 22% vitriolic add-on is 15L, in addition similarly carries out with preparation example 1, obtains pH and be 3.1 SiO 2 slurry.Similarly obtaining the solid-state part of silicon-dioxide with preparation example 1 is the wet cake (B) of 27% silicon-dioxide.The part of the wet cake (B) of gained silicon-dioxide is dry, the BET specific surface area (S of gained SiO 2 powder
BET) be 100m
2/ g, CTAB specific surface area (S
CTAB) be 93m
2/ g, oil number is 165ml/100g.
(silicon-dioxide preparation example 3)
The add-on of sodium silicate aqueous solution is 201L, and is in addition identical with preparation example 1, uses reaction vessel and sodium silicate aqueous solution, is warming up to 90 ℃.Then, temperature of reaction is remained on 90 ℃, in addition, the add-on of 22% sulfuric acid and sodium silicate aqueous solution and joining day are all identical with preparation example 1, add 22% sulfuric acid of same amount again, obtain pH and be 3.0 SiO 2 slurry.Similarly obtaining the solid-state part of silicon-dioxide with preparation example 1 is the wet cake (C) of 25% silicon-dioxide.The part of the wet cake (C) of gained silicon-dioxide is dry, the BET specific surface area (S of gained SiO 2 powder
BET) be 135m
2/ g, CTAB specific surface area (S
CTAB) be 125m
2/ g, oil number is 175ml/100g.
(silicon-dioxide preparation example 4)
The add-on of sodium silicate aqueous solution is 224L, is warming up to 90 ℃, and is in addition identical with preparation example 1, uses reaction vessel and sodium silicate aqueous solution.Then, make the add-on of 22% sulfuric acid and sodium silicate aqueous solution be respectively 76L and 452L, the joining day is 125 minutes, and making 22% vitriolic add-on again is 17L, make reacting liquid temperature keep 90 ℃, in addition similarly obtaining pH with preparation example 1 is 3.2 SiO 2 slurry.With preparation example 1 similarly, obtain the solid-state part of silicon-dioxide and be 24% the wet cake (D) of silicon-dioxide.The part of the wet cake (D) of gained silicon-dioxide is dry, the BET specific surface area (S of gained SiO 2 powder
BET) be 150m
2/ g, CTAB specific surface area (S
CTAB) be 138m
2/ g, oil number is 177ml/100g.
(silicon-dioxide preparation example 5)
The add-on of sodium silicate aqueous solution is 305L, is warming up to 80 ℃, and is in addition identical with preparation example 1, uses reaction vessel and sodium silicate aqueous solution.Then, make the add-on of 22% sulfuric acid and sodium silicate aqueous solution be respectively 75L and 444L, the joining day is 90 minutes, making 22% vitriolic add-on again is 18L, make reacting liquid temperature keep 80 ℃, in addition with preparation example 1 similarly, obtain pH and be 3.2 SiO 2 slurry.With preparation example 1 similarly, obtain the solid-state part of silicon-dioxide and be 24% the wet cake (E) of silicon-dioxide.The part of the wet cake (E) of gained silicon-dioxide is dry, the BET specific surface area (S of gained SiO 2 powder
BET) be 300m
2/ g, CTAB specific surface area (S
CTAB) be 275m
2/ g, oil number is 250ml/100g.
(silica aqueous dispersion preparation example 1)
Mix pure water in the wet cake (A) of the silicon-dioxide that in above-mentioned silicon-dioxide preparation example 1, obtains, making concentration of silicon dioxide is 15%, two (3-(triethoxysilyl) propyl group) tetrasulfides of 1% are made 10% aqueous solution, join in the silicon-dioxide, use homogenizer to stir 10 minutes down for 50 ℃ in temperature.Then, (weight-average molecular weight is 20,000 to add the cationic polymer in silicon-dioxide, the cation equivalent molecular weight that is calculated by colloidal titration is 146 polydiene propyl group ammonio methacrylate) 3% aqueous solution, making the cationic polymer is 3%, mixed 20 minutes with homogenizer, obtain silica aqueous dispersion (I).The pH of this aqueous dispersions is 3.5, and silica concentration is 13%, and the median size of silicon-dioxide is 17 μ m in the aqueous dispersions.
(silica aqueous dispersion preparation example 2)
Add pure water in the wet cake (B) of the silicon-dioxide that in above-mentioned silicon-dioxide preparation example 2, obtains, making concentration of silicon dioxide is 15%, and (weight-average molecular weight is 20,000 to add the cationic polymer, the cation equivalent molecular weight that is calculated by colloidal titration is 162 polydiene propyl group ammonio methacrylate) 3% aqueous solution, making it is 3% with respect to silicon-dioxide, mixed 20 minutes with homogenizer, obtain silica aqueous dispersion (II).The pH of this aqueous dispersions is 3.5, and the median size of silicon-dioxide is 16 μ m in the aqueous dispersions.
(silica aqueous dispersion preparation example 3)
Add pure water in the wet cake (C) of the silicon-dioxide that in above-mentioned silicon-dioxide preparation example 3, obtains, making concentration of silicon dioxide is 15%, and 3% aqueous solution of adding cationic polymer (identical) with preparation example 1, making it is 3.5% with respect to silicon-dioxide, in addition identical with preparation example 2, obtain silica aqueous dispersion (III).The pH of this aqueous dispersions is 3.4, and the median size of silicon-dioxide is 15 μ m in the aqueous dispersions.
(silica aqueous dispersion preparation example 4)
The silicon-dioxide that obtains in silicon-dioxide preparation example 4 wets and adds pure water in the cake (D), making concentration of silicon dioxide is 15%, and 3% aqueous solution of adding cationic polymer (identical) with preparation example 1, making it is 4% with respect to silicon-dioxide, in addition identical with preparation example 2, obtain silica aqueous dispersion (IV).The pH of this aqueous dispersions is 3.4, and the median size of the silicon-dioxide in the aqueous dispersions is 16 μ m.
(silica aqueous dispersion preparation example 5)
The silicon-dioxide that obtains in silicon-dioxide preparation example 5 wets and adds pure water in the cake (E), making concentration of silicon dioxide is 15%, and 3% aqueous solution of adding cationic polymer (identical) with preparation example 1, making it is 5% with respect to silicon-dioxide, in addition identical with preparation example 2, obtain silica aqueous dispersion (V).The pH of this aqueous dispersions is 3.2, and the median size of silicon-dioxide is 14 μ m in the aqueous dispersions.
(silicon-dioxide and rubber solidify altogether micelle preparation example 1)
The SBR latex (solid-state part is 23%) that obtains in 720 parts of rubber preparation examples 1 is diluted warming while stirring to 50 ℃ with 2000 parts of pure water.Then, under agitation in the latex of above-mentioned dilution, add 600 parts of silica aqueous dispersion (I), generate the mixture of silicon-dioxide and rubber.The pH of mixed solution is 7.5.Then, add 10% sulfuric acid in above-mentioned mixed solution, SBR latex is solidified fully, obtain containing the slurry that solidifies micelle, this solidifies micelle is the rubber that contains silicon-dioxide.The final pH of mixed solution (slurry) is 6.5.The temperature of mixed solution keeps 50 ℃ and carries out.The washing gained solidifies micelle, reclaims with 40 purpose wire nettings, obtains solidifying micelle (A).At 120 ℃, this was solidified micelle (A) dry 3 hours, measure water ratio by the weight-loss ratio before and after it, the result is 61%.Take out this part of solidifying micelle (A) and make its drying, measure the silicon-dioxide containing ratio, the result is 47 parts with respect to 100 parts of SBR.
(silicon-dioxide and rubber solidify altogether micelle preparation example 2)
Making silica aqueous dispersion (II) is 520 parts, in addition similarly implements with (silicon-dioxide and rubber solidify altogether micelle preparation example 1), obtains containing the slurry that solidifies micelle, and this solidifies micelle for containing silica rubber.The final pH of mixed solution (slurry) is 6.7.The washing gained solidifies micelle, with 40 purpose wire nettings recovery, obtain water ratio and be 58% solidify micelle (B).Take out this part of solidifying micelle (B) and make its drying, measure the silicon-dioxide containing ratio, the result is 47 parts with respect to 100 parts of SBR.
(silicon-dioxide and rubber solidify altogether micelle preparation example 3)
With fatty acid soaps 62 parts of extending oil Enerthene1849A (manufacturing of Block リ テ イ Star シ ユ ペ ト ロ リ ア system company) and 5 parts of polysiloxane FZ3704 (Japanese ユ ニ カ-company makes) are made 66% aqueous emulsion, it is mixed with the SBR latex (solid-state part is 23%) that obtains in 720 parts of rubber preparation examples 2.This mixed solution is diluted with 2000 parts of pure water, be warming up to 60 ℃.Then, under agitation in the latex of above-mentioned dilution, add 750 parts of silica aqueous dispersion (III), in above-mentioned mixed solution, add 10% sulfuric acid then, SBR latex is solidified fully, obtain containing the slurry that solidifies micelle, this solidifies micelle for containing silica rubber.The final pH of mixed solution (slurry) is 6.8.The temperature of mixed solution keeps 60 ℃ and carries out.The washing gained solidifies micelle, with 40 purpose wire nettings recovery, obtain water ratio and be 65% solidify micelle (C).Take out this part of solidifying micelle (C) and make its drying, measure the silicon-dioxide containing ratio, the result is 68 parts with respect to 100 parts of SBR.
(silicon-dioxide and rubber solidify altogether micelle preparation example 4)
Making silica aqueous dispersion (IV) is 520 parts, does not add polysiloxane, in addition similarly implements with (silicon-dioxide and rubber solidify altogether micelle preparation example 3), obtains containing the slurry that solidifies micelle, and this solidifies micelle for containing silica rubber.The final pH of mixed solution (slurry) is 6.6.The washing gained solidifies micelle, with 40 purpose wire nettings recovery, obtain water ratio and be 62% solidify micelle (D).Take out this part of solidifying micelle (D) and make its drying, measure the silicon-dioxide containing ratio, the result is 47 parts with respect to 100 parts of SBR.
(silicon-dioxide and rubber solidify altogether micelle preparation example 5)
Preparation silica aqueous dispersion (V) is in addition similarly implemented with (silicon-dioxide and rubber solidify altogether micelle preparation example 2), obtains containing the slurry that solidifies micelle, and this solidifies micelle for containing silica rubber.The final pH of mixed solution (slurry) is 6.6.The washing gained solidifies micelle, with 100 purpose wire nettings recovery, obtain water ratio and be 81% solidify micelle (E).Take out this part of solidifying micelle (E) and make its drying, measure the silicon-dioxide containing ratio, the result is 46 parts with respect to 100 parts of SBR.
Embodiment 1
In the present embodiment, the dehydration, the exsiccant device that solidify micelle use forcing machine 2 shown in Figure 1.Forcing machine 2 has the barrel 4 that is made of 12 cartridge unit.The cartridge unit of No 1-6 constitutes drying zone, and the cartridge unit of No.7-12 constitutes drying zone.The cartridge unit of No.1 is to supply with the feed unit of the slurry that contains silica particle.The cartridge unit of No.3 and No.6 is the dewatering unit of discharging by the water of slurry dewatering, and the dehydration slit separation is 0.25mm.The cartridge unit of No.8 and No.10 is to remove the exhaust unit with discharge slots of contained humidity in the micelle by heated volatile, and discharge slots is spaced apart 2.0mm.Cartridge unit beyond above-mentioned is the standard cell of drum.The unit of barrel 4 constitutes as shown in table 1.
[table 1]
In the present embodiment, in the zone in each district of correspondence, use the screw rod 6 that for example disposes screw element as follows and kneading disk.
Drying zone: BBBAABAAABAACAAABAAAB
Drying zone: AAAEAAABAAABEAABAAABAAAB.
Employed screw element and kneading disk are as shown in table 2.
[table 2]
For will dewater, the dried silica rubber composition that contains extrudes with the shape of regulations such as linearity, forcing machine 2 is connected with die head 8 in the downstream of No.12 barrel section one side.
In the present embodiment, with the screw rod 6 of 250rpm rotation forcing machine 2.Drying zone is heated to 115 ℃, drying zone is heated to 160 ℃ of enforcements.
Before the embodiment operation, use Nipol SBR1502 (Japanese ゼ オ Application company make) to turn round, forcing machine 2 inside are cleaned.There is same SBR to adhere in the kneading disk, but, will plays former state and be positioned over this for its weighting material as the micelle spout (space between drying zone and drying zone intersection screw rod and the barrel) of inaccessible forcing machine 2 is used.
Place like this, can be just the micelle spout of forcing machine 2 is inaccessible temporarily with SBR from forcing machine 2 start of run, the result can make and press state high through than normal operation the time in the barrel of micelle spout side of forcing machine 2.
Carry out following embodiment operation then.The above-mentioned micelle (A) that solidifies is added by the supplying opening of above-mentioned forcing machine 2, dewater under these conditions, drying.By the temperature that exports the rubber combination (A1) of discharging is 157 ℃, and water ratio is 0.6%.During discharge be shaped as about diameter 5mm, length is the band shape about 20mm.Carry out following operation in the part that does not have above-mentioned weighting material (SBR) to sneak into.
Silane coupling agent (Si69, デ グ Star サ company make), paraffin, stearic acid, zinc white (granularity 0.4 μ m, zinc white #1: this village chemical company makes), antiaging agent (ノ Network ラ Star Network 6C: imperial palace newly developed company makes) are mixed with opening rubber mixing machine at 50 ℃, make gained rubber combination (A1) be the proportional quantity shown in the table 3, then use mixing 2 minutes of Banbury (the smart machine-processed ラ ボ プ ラ ス ト ミ Le type 100C of Japan stirs type B-250).Temperature during mixing the end is 150 ℃.Then with 50 ℃ opening rubber mixing machine with sulphur and crosslinking accelerator (CBS:N-cyclohexyl-2-[4-morpholinodithio sulphenamide and DPG: diphenylguanidine) mixing, take out with sheet then.160 ℃ of press vulcanizations 15 minutes, the preparation test film was measured each rerum natura with the gained rubber combination.The result is as shown in table 4.
Comparative example 1
With 80 ℃ the above-mentioned micelle (A) that solidifies is carried out warm air drying, the water ratio with 0.3% obtains rubber combination (A2).With the proportioning of gained rubber combination (A2) according to table 3, prepare test film similarly to Example 1, measure each rerum natura.The result is as shown in table 4.
[table 3]
| (part) | |
| Rubber combination (solidifying micelle) | 148 |
| Silane coupling agent | 1.2 |
| Stearic acid | 2.0 |
| Paraffin | 1.0 |
| Zinc white | 3.0 |
| Antiaging agent | 2.0 |
| Sulphur | 1.8 |
| Accelerator CBS | 1.7 |
| Vulkacit D PG | 0.9 |
[table 4]
| No. | Embodiment 1 | Comparative example 1 |
| Rubber combination (solidifying micelle) | A1 | A1 |
| tanδ-10℃ | 103 | 100 |
| G′-10℃ | 84 | 100 |
| tanδ60℃ | 85 | 100 |
| ΔG’ | 65 | 100 |
| Hardness | 98 | 100 |
| 100% modulus | 100 | 100 |
| 300% modulus | 109 | 100 |
| 300%/100% modular ratio | 109 | 100 |
Embodiment 2
The device that solidifies the micelle dehydration uses screw rod total length L=890mm, drying zone 482mm, and the compression ratio of drying zone is 1.45 times, and narrow crack is the single screw extrusion machine of 0.25mm at interval.The screw rod of single screw extrusion machine rotates with 100rpm, and outlet vertebra type opening degree (being installed on the tapered hub and the interval of housing outlet on the screw rod) is 1.5mm, drying zone is heated to 36 ℃ implements to dewater.
Before the embodiment operation, add NipolSBR1502 as weighting material (Japanese ゼ オ Application company make) and extrude, discharge at whole outlet tapered sections (green stock spout) of this SBR and shut down before by forcing machine 2 to the inside of forcing machine 2.Carry out following embodiment operation.
With above-mentioned supplying opening adding of solidifying micelle (B), dewater under these conditions by above-mentioned forcing machine.By the temperature that exports the rubber combination (B1) of discharging is 74 ℃, and water ratio is 10.8%.During discharge be shaped as about diameter 5mm, length is the band shape about 20mm.(B1) carries out warm air drying to the gained rubber combination, and the water ratio with 0.3% obtains rubber combination (B2).Carry out following operation in the part of not sneaking into above-mentioned weighting material (SBR).
Prepare test film similarly to Example 1, make gained rubber combination (B2), measure each rerum natura for the proportional quantity shown in the table 5.The result is as shown in table 6.
Comparative example 2
The above-mentioned micelle (B) that solidifies is carried out warm air drying with 80 ℃, and the water ratio with 0.4% obtains rubber combination (B3).Similarly to Example 2, (B3) prepares test film according to the proportional quantity shown in the table 5 with the gained rubber combination, measures each rerum natura.The result is as shown in table 6.
[table 5]
| (part) | |
| Rubber combination (solidifying micelle) | 147 |
| Silane coupling agent | 2.0 |
| Stearic acid | 2.0 |
| Paraffin | 1.0 |
| Zinc white | 3.0 |
| Antiaging agent | 2.0 |
| Sulphur | 1.8 |
| Accelerator CBS | 1.7 |
| Vulkacit D PG | 0.9 |
[table 6]
| No. | Embodiment 2 | Comparative example 2 |
| Rubber combination (solidifying micelle) | B2 | B3 |
| tanδ-10℃ | 101 | 100 |
| G′-10℃ | 92 | 100 |
| tanδ60℃ | 90 | 100 |
| ΔG’ | 78 | 100 |
| Hardness | 99 | 100 |
| 100% modulus | 98 | 100 |
| 300% modulus | 105 | 100 |
| 300%/100% modular ratio | 106 | 100 |
Embodiment 3
Use the single screw extrusion machine that uses among the embodiment 2, make above-mentioned micelle (C) dehydration of solidifying after the same method.By the temperature that exports the rubber combination (C1) of discharging is 77 ℃, and water ratio is 16.2%.During discharge be shaped as about diameter 5mm, length is the band shape about 20mm.Use the twin screw extruder that uses among the embodiment 1 that gained rubber combination (C1) is carried out drying.As follows, use the screw rod that disposes screw element and kneading disk, not to rubber combination (C1) applying load, in fact only carry out drying operation at drying zone.
Drying zone: BBBAABBBBBBAAAABBB
Drying zone: AAADAAABAAABEAABAAABAAAB.
Screw rod with 250rpm rotation forcing machine.Drying zone is heated to 115 ℃, drying zone is heated to 145 ℃ of enforcements.Carry out drying similarly to Example 1.By the temperature that exports the rubber combination (C2) of discharging is 148 ℃, and water ratio is 0.3%.During discharge be shaped as about diameter 5mm, length is the band shape about 20mm.
Prepare test film similarly to Example 1, make gained rubber combination (C2), measure each rerum natura for the proportional quantity shown in the table 7.The result is as shown in table 8.
Comparative example 3
The above-mentioned micelle (C) that solidifies is carried out warm air drying with 80 ℃, and the water ratio with 0.4% obtains rubber combination (C3).Similarly to Example 3, (C3) prepares test film according to the proportioning shown in the table 7 with the gained rubber combination, measures each rerum natura.The result is as shown in table 8.
[table 7]
| (part) | |
| Rubber combination (solidifying micelle) | 210.5 |
| Silane coupling agent | 2.0 |
| Stearic acid | 2.0 |
| Paraffin | 1.0 |
| Zinc white | 3.0 |
| Antiaging agent | 2.0 |
| Sulphur | 1.8 |
| Accelerator CBS | 1.7 |
| Vulkacit D PG | 1.6 |
[table 8]
| No. | Embodiment 3 | Comparative example 3 |
| Rubber combination (solidifying micelle) | C2 | C3 |
| tanδ-10℃ | 102 | 100 |
| G′-10℃ | 82 | 100 |
| tanδ60℃ | 87 | 100 |
| ΔG’ | 63 | 100 |
| Hardness | 98 | 100 |
| 100% modulus | 99 | 100 |
| 300% modulus | 109 | 100 |
| 300%/100% modular ratio | 110 | 100 |
With 50 ℃ opening rubber mixing machine, gap 3mm by 8 times, dewaters the above-mentioned micelle (D) that solidifies.The water ratio of gained sheet rubber combination (D1) is 49%.(D1) carries out warm air drying with the gained rubber combination, and the water ratio with 0.7% obtains rubber combination (D2).
(the ノ Network loses Star Network 6C: the manufacturing of imperial palace newly developed company) mixing 2 minutes, make gained rubber combination (D2) be the proportional quantity shown in the table 9 with carbon black (シ-ス ト 7HM, East Sea カ-ボ Application company makes), silane coupling agent (Si69, デ グ Star サ company make), paraffin, stearic acid, zinc white (granularity 0.4 μ m, zinc white #1: this village chemical company makes), antiaging agent with Banbury (Japan machine-processed ラ ボ プ ラ ス ト ミ Le type 100C of essence stirs type B-250).Temperature during mixing the end is 150 ℃.
Then sulphur and crosslinking accelerator (N cyclohexyl 2 benzothiazole sulfenamide and diphenylguanidine) is mixing with 50 ℃ opening rubber mixing machine, take out with sheet then.160 ℃ of press vulcanizations 15 minutes, the preparation test film was measured each rerum natura with the gained rubber combination.The result is as shown in table 10.
Comparative example 4
The above-mentioned micelle (D) that solidifies is carried out warm air drying with 80 ℃, and the water ratio with 0.6% obtains rubber combination (D3).Similarly to Example 4, (D3) prepares test film according to the proportioning shown in the table 9 with the gained rubber combination, measures each rerum natura.The result is as shown in table 10.
[table 9]
| (part) | |
| Rubber combination (solidifying micelle) | 184.5 |
| Carbon black | 23 |
| Silane coupling agent | 3.5 |
| Stearic acid | 2.0 |
| Paraffin | 1.0 |
| Zinc white | 3.0 |
| Antiaging agent | 2.0 |
| Sulphur | 1.8 |
| Accelerator CBS | 1.7 |
| Vulkacit D PG | 0.9 |
[table 10]
| No. | |
Comparative example 4 |
| Rubber combination (solidifying micelle) | D2 | D3 |
| tanδ-10℃ | 101 | 100 |
| G′-10℃ | 96 | 100 |
| tanδ60℃ | 97 | 100 |
| ΔG’ | 90 | 100 |
| Hardness | 100 | 100 |
| 100% modulus | 101 | 100 |
| 300% modulus | 104 | 100 |
| 300%/100% modular ratio | 103 | 100 |
Comparative example 5
Use the forcing machine of embodiment 1, using the same method adds the above-mentioned micelle (E) that solidifies.By the temperature that exports the rubber combination (E1) of discharging is 151 ℃, and water ratio is 72%, and it is shaped as pasty state.Dewater fully, therefore do not implement physical property measurement.
Comparative example 6
Use the single screw extrusion machine of embodiment 2, using the same method adds the above-mentioned micelle (E) that solidifies.By the temperature that exports the rubber combination (E1) of discharging is 34 ℃, and water ratio is 79%, and it is shaped as pasty state.Dewater fully, therefore do not implement physical property measurement.
Comparative example 7
Use the opening rubber mixing machine of embodiment 4, use the same method to add and above-mentionedly solidify micelle (E), though dewater, by under 2 times the state, it is shaped as pasty state, can't more operate.The water ratio of this moment is 79%, dewaters fully, does not therefore implement physical property measurement.
Investigate
More than, among the embodiment 1-4, to have and solidify micelle with the dewatering unit dehydration with compression function of the present invention after the filtration of the following water ratio of prescribed value, tan δ (10 ℃) value that gained contains the silica rubber composition is big, G ' (10 ℃) is little, therefore compare with the comparative example of the dewatering type that does not have compression function, in the subsides ground on wet and slippery road surface property excellence.Tan δ (60 ℃), Δ G ' are littler than comparative example in addition, and the silicon-dioxide excellent dispersion is hanged down the burnup excellence as can be known.
300% modulus is big, and it compares increase with the ratio of 100% modulus with comparative example, silicon-dioxide excellent dispersion as can be known, reinforcement excellence.And, in drying step, use drying installation with compression function, these characteristics are better.
Among the comparative example 5-7, used water ratio surpass 80% solidify micelle (E), therefore fail effectively to dewater.And among the embodiment 1-4, using water ratio is to solidify micelle (A)-(D) below 80%, so the dewatering efficiency height, can well dewater.
Industrial applicability
The present invention can provide cross moulding product that contain silica rubber composition, this rubber composition that the dispersiveness of silica is improved and the preparation method of this rubber composition.
Claims (14)
1. silica containing rubber combination, said composition is that the mixture with rubber latex and silicon-dioxide solidifies altogether, obtain the slurry of silica containing micelle, by filtering, making its water ratio is below 80% weight, then dewater with the dewatering unit with compression function, dry then and obtain, wherein said dewatering unit with compression function is selected from has the device that barrel and barrel inside are provided with the device of screw rod and have roller.
2. the silica containing rubber combination of claim 1, said composition also contains the cationic material.
3. the silica containing rubber combination of claim 1, wherein said silicon-dioxide are that the specific surface area of the determining adsorption of CTAB is 40-230m by bromination trimethylammonium cetyltrimethyl ammonium
2/ g.
4. the silica containing rubber combination of claim 1, said composition also contains linking agent.
5. the silica containing rubber combination of claim 1, said composition also contains organopolysiloxane or polyethers based polymer.
6. the silica containing rubber combination of claim 1, said composition also contains silane coupling agent.
7. the silica containing rubber combination of claim 1, its water ratio is below 5% weight.
8. the preparation method of silica containing rubber combination, the method includes the steps of:
The aqueous dispersions of rubber latex and silicon-dioxide is mixed, obtain the step (A) of the mixture of rubber latex and silicon-dioxide;
Rubber in the described mixture is solidified altogether with silicon-dioxide, obtain containing the step (B) of the slurry of silica particle;
Filter described slurry, obtaining water ratio is the step (C) of the following micelle of 80% weight;
Use has the dewatering unit of compression function, and to the step (D) that described filtered micelle dewaters, wherein said dewatering unit with compression function is selected from has the device that barrel and barrel inside are provided with the device of screw rod and have roller;
And to described through the dehydration micelle carry out exsiccant step (E).
9. the preparation method of the silica containing rubber combination of claim 8, wherein make describedly to have the interior pressure of dewatering unit that barrel and barrel inside is provided with screw rod, the micelle after the described filtration is dewatered through the interim state that improves when running well.
10. the preparation method of the silica containing rubber combination of claim 9 is wherein at the start of run of described dewatering unit or midway, inaccessible temporarily with the part or all of micelle spout of described dewatering unit.
11. the preparation method of the silica containing rubber combination of claim 10, filling weighting material in described dewatering unit wherein is with part or all of micelle spout obturation.
12. the preparation method of the silica containing rubber combination of claim 11, wherein said weighting material uses the material that contains any material at least in rubber, resin and the ice.
13. the preparation method of the silica containing rubber combination of claim 8, wherein by decompression operation or/and the micelle of heating operation after to described dehydration carries out drying.
14. the preparation method of the silica containing rubber combination of claim 8 wherein carries out drying by squeeze operation and pressure release operation to the micelle after the described dehydration.
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| WO2010123072A1 (en) * | 2009-04-24 | 2010-10-28 | 株式会社ブリヂストン | Rubber composition and pneumatic tire |
| FR2981076B1 (en) * | 2011-10-11 | 2013-11-01 | Michelin Soc Tech | METHOD FOR PREPARING A MASTER MIXTURE OF DIENE ELASTOMER AND SILICA |
| CN102977429A (en) * | 2012-12-19 | 2013-03-20 | 利安隆（天津）化工有限公司 | Compound antioxidant for producing emulsion-polymerized styrene butadiene rubber and application thereof |
| JP6120949B2 (en) * | 2013-03-25 | 2017-04-26 | 有限会社Ｅｔｉｃ | Rubber composition comprising emulsion polymerization conjugated diene polymer and silica suspension and method for producing the same |
| EP3406664B1 (en) * | 2016-01-19 | 2020-08-05 | Bridgestone Corporation | Rubber composition and tire |
| SG11201903665UA (en) * | 2016-11-04 | 2019-05-30 | Zeon Corp | Rubbery polymer extrusion dryer, method of drying rubbery polymer, and method of manufacturing rubbery polymer |
| CN108180739B (en) * | 2018-02-12 | 2023-08-15 | 郭永广 | Be applicable to emulsion pad drying processing device |
| CN111349274B (en) * | 2018-12-20 | 2022-04-26 | 万向新元科技股份有限公司 | Natural rubber/white carbon black composite material and preparation method and application thereof |
| CN111849042B (en) * | 2020-08-04 | 2022-04-19 | 诺博橡胶制品有限公司 | Rubber material for rubber shaft sleeve and preparation method thereof |
| CN112265996B (en) * | 2020-10-23 | 2021-05-07 | 广州市飞雪材料科技有限公司 | Low RDA friction type silicon dioxide and preparation method thereof |
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| CN1170421A (en) * | 1994-12-22 | 1998-01-14 | 卡伯特公司 | Latex compositions and films produced therefrom |
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| JP2001213971A (en) * | 2000-02-02 | 2001-08-07 | Tokuyama Corp | Method for manufacturing rubber comprising precipitated silicic acid |
| CN1405222A (en) * | 2001-07-27 | 2003-03-26 | 普利司通株式会社 | Natural rubber master batch and its producing method, and natural rubber composition |
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|---|---|---|---|---|
| CN1170421A (en) * | 1994-12-22 | 1998-01-14 | 卡伯特公司 | Latex compositions and films produced therefrom |
| CN1197084A (en) * | 1996-12-18 | 1998-10-28 | Dsm共聚物公司 | Compatibilized silica and polymer silica-reinforced masterbatches and process for preparation |
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Effective date of registration: 20090807 Address after: Tokyo, Japan, Japan Patentee after: Nippon Zeon Co., Ltd. Address before: Tokyo, Japan Co-patentee before: Tokuyama Co., Ltd. Patentee before: Japanese Swiss company |
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