JP2003221402A - Method for manufacturing rubber filled with silica - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for manufacturing a rubber filled with silica that has high reinforcing properties, high abrasion resistance, and low fuel consumption, and is well dispersed in the rubber in blending with the rubber at a high concentration. <P>SOLUTION: A rubber latex, the silica and a cationic polymer are blended together in the presence of a silane coupling agent, wherein the rubber and the silica are coagulated in the latex. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a silica-filled rubber.
It relates to a manufacturing method. For more information, please refer to
Silica-containing steel with high performance and low fuel consumption
Manufacture of lenbutadiene rubber (hereinafter abbreviated as SBR)
To provide a method for producing silica-filled rubber that can be used for
Is what you do. [0002] 2. Description of the Related Art Silica has been used for reinforcing various rubbers.
Widely used as filler. Generally, Bamba
Kneading equipment such as lee mixer, open roll, kneader
Method of compounding dry silica into rubber using
(Hereinafter referred to as dry kneading). But
However, silica is widely used as a reinforcing agent for rubber.
Surface has silanol groups compared to carbon black.
Covered and has strong self-cohesive properties, into rubber
It was difficult to disperse well. For this reason, silica is used as a reinforcing agent for rubber.
When used, it is used for the complementary purpose of carbon black.
Was often done. In recent years, due to resource conservation and environmental problems,
For tires, achieve both low fuel consumption and high grip
Rubber using silica-based reinforcing agents is required
It was started. However, silica is
Due to such poor dispersibility, it can be highly dispersed in rubber
It was not possible, and improvement was desired. [0005] In order to solve these problems, silica and silica are used.
Various improvements have been made to increase the affinity of the system.
You. For example, a system consisting of diene rubber and silica
A coupling agent, and the coupling effect
For improving the affinity between rubber and silica to improve dispersibility
A method has been disclosed (see Patent Document 1). But above
In order to be effective, the method
It was necessary to use a large amount of the run coupling agent. In addition, the surface of silica has been modified in advance.
Also disclosed is a method for improving dispersibility in rubber using
Have been. For example, natural rubber or diene rubber
Silicon that has been previously surface-treated with an organosilicon compound
Dry kneading of mosquito and silane coupling agent
A method for improving dispersibility has been disclosed (see Patent Document 2).
See). However, even when using the above method, silica
Insufficient dispersion and therefore sufficient coupling effect
And there is room for improvement in reinforcement and wear resistance.
there were. On the other hand, a mixture comprising silica and an organic silicon compound
The mixed solution is mixed with rubber latex, and the rubber and silicone are mixed with acid.
Fine particles containing silica by co-coagulating mosquito
A method for producing rubber is disclosed (Patent Document 3). Only
However, the silica-filled rubber obtained by the above method also
Lica dispersibility is not sufficient, and wear and fuel economy
There was room for improvement. [0008] [Patent Document 1] JP-A-3-252431 [Patent Document 2] JP-A-8-245838 [Patent Document 3] JP-A-2000-103802 [0009] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is as follows.
Is that silica is well dispersed in rubber, and has high reinforcing properties,
Silica-filled with high abrasion resistance and low fuel consumption
Silica-filled rubber that can be easily manufactured
It is to provide a manufacturing method. [0010] Means for Solving the Problems The present inventors have set forth the above object.
We have been conducting diligent research to solve the problem. As a result,
Coprecipitate the rubber and silica in the latex
Operation to obtain coagulated Lica, that is, co-coagulation of rubber and silica
Silica filling using cationic polymer for operation
Silane coupling agent present in rubber manufacturing process
Even if the silane coupling agent is
No effect, co-precipitation of rubber and silica proceeds,
Easily manufactures silica-filled rubber in which silica is well dispersed
I found what I can do. Further, the obtained silica-filled rubber
Is due to the effective action of the silane coupling agent.
Performance, such as high reinforcement, high wear resistance, and low fuel consumption.
Completed the present invention.
I came to. That is, the present invention provides a silane coupling agent
In the presence of rubber latex, silica and cationic high
By mixing molecules, the rubber and silica in the rubber latex are
Method for producing silica-filled rubber characterized by coagulation
It is. [0012] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The rubber latex used in the present invention is a milk latex.
In which rubber is dispersed in a solvent containing an agent and water
If there is no particular limitation, natural rubber latex or milk
Rubber latex obtained by chemical polymerization
What is necessary is just to select suitably according to a use. Rubber properties and silica
Conjugated diene rubber is preferred
Conjugated diene-aromatic vinyl copolymer rubber is more preferred.
New Also, conjugated diene-aromatic containing polar groups
Vinyl copolymers can also be used. In particular,
When using tires, consider the performance of the tires.
In case of using SBR rubber latex,
preferable. Further, process oil is contained in rubber latex.
Mixed with oil-extended rubber latex
it can. The content of rubber in the rubber latex described above is
Without limitation, with silica and a cationic polymer described below
It may be adjusted appropriately according to the mixing form of the
No. Usually, the rubber content is in the range of 10 to 30% by weight.
Is preferred. The silica used in the present invention is a known silica.
Dry silica, wet silica and zo
Rugel silica can be used. Fumed silica
Is generally obtained by burning silicon tetrachloride in an oxyhydrogen flame.
It is. Wet silica neutralizes sodium silicate with acid
Precipitated silica (part of mineral acid or
Is gold that has been neutralized using aluminum sulfate instead
(Including precipitated silica containing a large amount of metal salts) and gel
Mosquito is typical. Furthermore, sol-gel method silica is
Silicon such as tramethoxysilane and tetraethoxysilane
Alkoxide is converted to acidic or alkaline aqueous organic solvent
It is obtained by hydrolysis in water. In the present invention, the silica
Uses wet-process silica with excellent productivity, especially precipitated silica
Preferably. In the present invention, the physical properties of silica are not limited at all.
Not selected, but appropriately selected in consideration of required rubber properties
Just do it. For example, physical properties of the above-mentioned wet silica include:
Considering the use as a filler for rubber, the specific surface
Product is 50-500m²/ G, oil absorption 100-300c
m³/ 100 g is preferred. In the present invention, the specific surface area and the oil absorption
The amount is a value measured by the method described in the Examples below.
You. In the present invention, rubber in rubber latex
The amount of silica to be added is not particularly limited.
Can be selected appropriately according to the intended use.
It is possible to mix at a high filling rate that could not be achieved by the method of
You. For example, when used for tire applications, etc.
Silica compounding amount is 100 weight of rubber in rubber latex
20 to 300 parts by weight per part by weight is preferred. Especially Thailand
When used in rubber applications, the amount of silica
20 to 100 weight per 100 parts by weight of rubber
Parts by weight are preferred, more preferably 30 to 80 parts by weight
Department. The cationic polymer used in the present invention is
Compounds whose active ions become cations when dissolved in water
Is used without any restrictions. For example, a polymer backbone or
Is a polymer having a quaternary ammonium base in the side chain.
It is tabular. In addition, the above active ion forms an anion that forms a salt.
Generally, chlorine ion and bromine ion are used.
You. Examples of the cationic polymer include:
Primary to tertiary ammonium salts and quaternary ammonium salts
Polymer having a hydrophilic group as a tertiary or
Having tertiary and quaternary ammonium salts as hydrophilic groups
However, it is preferable because silica has good dispersibility in rubber.
No. Furthermore, as long as the above effects are not impaired,
Luamide, acrylic acid, acrylate, methacrylic
Copolymerized with other monomers such as luic acid and methacrylic acid
But it's fine. The cationic polymer suitable for the present invention is
Specifically, polyethylene imine, polyvinyl
Amine, polyvinyl pyridine, polyamine sulfone, polyamine
Realylamine, polydiallylmethylamine, polyamido
Doamine, polyaminoalkyl acrylate, polyamido
Methacrylate, polyaminoalkyl acrylate
Lilamide, polyepoxyamine, polyamidepolyamide
, Polyester polyamine, dicyandiamide phor
Marine condensate, polyalkylene polyamine dicyandi
Polymers such as amide condensates and their ammonium salts,
Further, polydiallyl dimethyl ammonium chloride,
Polyvinyl pyridinium chloride, polymethacrylic acid
Quaternary ammonium salts such as ester methyl chloride
Can be mentioned. Of these, polyvinylamine, polya
Lilamine, polydiallylmethylamine, polyepoxy
Amines and their ammonium salts, polydiallyldimethyl
Tilammonium salts and polyvinylpyridinium salts are preferred.
New Weight average molecular weight of the above cationic polymer
Is preferably between 3,000 and 1,000,000
New The weight average molecular weight of the cationic polymer is in the above range
The good dispersibility of silica in the rubber,
Performance of the resulting silica-filled rubber, such as abrasion resistance and fuel economy
It is preferable because it can improve. Silica content in rubber
To improve the dispersibility and obtain higher performance silica-filled rubber
The weight average molecular weight of the cationic polymer is more preferable
5,000 to 800,000, more preferably
Is 10,000 to 500,000. The compounding amount of the cationic polymer is as follows:
0.1 to 20 parts by weight based on 100 parts by weight of silica
Parts by weight, more preferably 0.1 to 10 parts by weight.
preferable. In the present invention, a cationic polymer is used.
To coagulate rubber latex and silica
Silica is easily incorporated into the
Also, silica-filled rubber in which silica is well dispersed in rubber
Obtainable. In addition, if necessary, cationic
And acid such as sulfuric acid and metal salts such as sodium chloride
The rubber may be coagulated together. In the present invention, an important requirement is that silane
It is to carry out the above coagulation in the presence of a purifying agent. Immediately
Silane coupling before or simultaneously with co-coagulation
It is important that a blowing agent is added. Silane coupling
Co-coagulation in the presence of
The coupling agent reliably acts on the system and the resulting seal
Rica-filled rubber has very good silica dispersion and high performance
Rubber can be obtained. Moreover, silane coupling
Agents include rubber latex, silica, and cationic high
Adverse effects on co-coagulation by mixing three molecular components
It was confirmed not to give. The silane coupling agent used in the present invention is
Limited if it is used for ordinary rubber
Not something. Specificization of the above silane coupling agent
Examples of compounds include vinyltrichlorosilane and vinyltoluene.
Limethoxysilane, vinyltriethoxysilane, vinyl
Tris (β-methoxyethoxy) silane, β- (3,4
Poxycyclohexyl) ethyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-gly
Sidoxypropyltriethoxysilane, γ-methacrylo
Xypropyltrimethoxysilane, γ-methacryloxy
Propylmethyldiethoxysilane, γ-methacryloxyp
Ropirtriethoxysilane, N-β (aminoethyl) γ
-Aminopropyltriethoxysilane, N-β (amino
Ethyl) γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) γ-aminopropylmethyl dimethoxy
Sisilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, N-phenyl-
γ-aminopropyltrimethoxysilane, γ-chlorop
Ropirtrimethoxysilane, γ-mercaptopropyl
Limethoxysilane, bis (3-trimethylsilyl propyl
G) tetrasulfide, α-mercaptopropyl tri
Ethoxysilane, α-aminopropyltriethoxysila
, N-phenyl-α-aminopropyltrimethoxy
Run, N-β- (aminoethyl) -γ-aminopropyl
Trimethoxysilane, 3-trimethoxysilylpropyl
-N, N-dimethylthiocarbamoyl-tetrasulfy
De, 2-benzothiazole-3-trimethoxysilyl lp
Ripyl tetrasulfide and the like can be mentioned. In the present invention, the silane coupling agent
The amount of addition is 0.1 to 10 weights per 100 parts by weight of silica.
Parts by weight are preferred. In the present invention, the method of co-coagulation is
It is not limited to. To illustrate the mode, (1) Cationic mixture of rubber latex and silica
A method of co-coagulating by mixing polymers. Also
Is a mixture of cationic latex and rubber latex and silica.
A method of co-coagulation by mixing compounds. (2) A rubber latte is added to the mixture of silica and cationic polymer.
A method of co-coagulation by mixing Also
Is a mixture of silica and cationic polymer in rubber latex.
A method of co-coagulation by mixing compounds. (3) In the solution, a rubber latex, silica,
Co-coagulation by simultaneous mixing of cationic polymer
How to let. And the like. In the present invention, co-coagulation is carried out by the above method.
When carrying out, the mixing method is not particularly limited.
General, such as propeller, disperser, homogenizer, etc.
Mixing method using a simple dispersing device.
You. In the present invention, a screen used for co-coagulation is used.
The average particle size of Rica is not particularly limited,
It may be determined appropriately taking into account the purpose and application, and in general,
The range of 0.1 to 50 μm is suitably adopted. Average particle
By setting the diameter within the above range, the self-aggregating property of silica
Can prevent poor dispersion due to
Therefore, sufficient reinforcement can be obtained. Among them, when used for tire applications, etc.
In this case, adjust the average particle diameter of silica to 0.1 to 30 μm.
Preferably. In the present invention, the particle size of silica is adjusted.
The method can be performed anywhere before co-coagulation.
The adjustment can be performed by a known method without any particular limitation.
You. For example, jet mill, ball mill, nara mill,
The desired particle size can be obtained using
Dry pulverization method appropriately adjusted
Use a homogenizer, high-pressure homogenizer, colloid mill, etc.
And adjust appropriately to obtain the desired particle size.
Can be obtained by a wet grinding method. Also, wet grinding
When the silica particle size is adjusted by the
Medium or rubber latex, or a mixed solution of these
Can be adjusted inside. The properties of the silica used in the present invention are not particularly limited.
Not powdery or bulky, slurryy or wet
Cake-like ones can be used. Among them, in the case of wet silica, drying
Slurry or wet cake
Preferably, it is used. That is, by not passing through the drying step
Avoids the disadvantage of self-aggregation due to drying shrinkage during drying.
Can be opened. In the present invention, co-coagulation is carried out by the above method.
When performing, silica, cationic polymer and silica
And cationic polymer mixture may be used as is.
Water or a suitable organic solvent.
it can. Considering the operability, the system containing silica is suspended
Use as a solution, and use a diluted solution for the cationic polymer.
It is preferred to use In the present invention, co-coagulation is carried out by the above method.
, The silane coupling agent is co-coagulated
Each component or mixture before co-coagulation.
The compound can be added to the
May be added. The silane coupling agent is
Can be used as is, or in water or a suitable solvent
It can be used after dilution. In the present invention, co-coagulation is carried out by the above method.
Beforehand, silica and silane coupling
It is preferred that the agent is kept in contact. Pre-silica
Silane coupling agent
It is possible to reduce the amount of
Rubber can be obtained. In addition, silane must be
Improved operability due to addition of coupling agent
Is preferred. The above silica and the silane coupling agent were
The method of touching is not limited, and is a known dry method.
A treatment method and a wet treatment method can be used. inside that
However, considering the operability, silica is converted to water or an organic solvent.
Disperse into a suspension solution and silane coupling with stirring.
A wet treatment method in which a humectant is added is preferred. Also, a mixture of silica and a cationic polymer
If a silane coupling agent is added to
After contacting the silica with the cationic polymer in advance,
The method of contacting the run coupling agent
After contacting the mosquito with the silane coupling agent, the cationic
Method of contacting polymer, cationic polymer on silica,
Use the method of simultaneously contacting the silane coupling agent
be able to. Among them, silane coupling agents,
Reduce the amount of both thionic polymers added and operate
To obtain high-performance, high-performance rubber,
After contacting Rica with the silane coupling agent, the cation
A method using a method of contacting a conductive polymer is preferable. In the present invention, the pH during co-coagulation is restricted.
It should not be adjusted with acids or alkalis as necessary.
Can be. In addition, the temperature during co-solidification is not particularly limited.
However, 30 ° C to 80 ° C is preferred. In the present invention, a screen obtained by co-coagulation is used.
Rica-filled rubber requires washing, dewatering and drying
Can be adopted as appropriate. The silica packing obtained by the production method of the present invention
The filling rubber may be used as it is or
-As a batch, unfilled silica to a specified concentration
It may be kneaded with the filling rubber. Also, when kneading,
A silane coupling agent may be additionally provided. The silica filler obtained by the production method of the present invention
The filling rubber is used as long as the object of the present invention is not impaired.
Various additives usually used according to the purpose of use, for example, soft
Agent, vulcanizing agent, vulcanization accelerator, anti-aging agent, scorch prevention
Agent, zinc white, stearic acid, carbon black,
Magnesium carbonate, calcium carbonate, clay, glass fiber
Fillers other than silica such as fibers can be appropriately compounded.
You. [0049] DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following, the present invention will be described in detail with reference to the drawings.
Examples and Comparative Examples are shown, but the present invention is not limited to these Examples.
It is not limited at all. In addition, the following example
Various physical properties in Comparative Examples and Comparative Examples were implemented by the following methods.
Was. (1) Specific surface area According to JIS K6220, BET one point method
Was. (2) Oil absorption It was determined according to JIS K6220. (3) Average particle size Light scattering diffraction type particle size distribution analyzer (manufactured by Coal Tar, Inc.
Measure the volume-based median diameter using Coulter LS-230)
And this value was adopted as the average particle size. In addition, measurement
In this case, the refractive index of the dispersion medium (water) was 1.332.
1.458 as the refractive index of silica as a constant at the time of measurement
used. (4) Silica content in silica-filled rubber Thermal analyzer TG / DTA (TG / D manufactured by Seiko Denshi Kogyo)
After thermal decomposition of the dried sample in air using TA320)
Residue rate (%) and weight loss rate (%) up to 150 ° C
The measurement was calculated using the following equation. In the embodiment, the rubber 10
It was described in terms of the amount based on 0 parts by weight. The measurement conditions are
Temperature rise rate 20 ° C / min in air, ultimate temperature 600 ° C,
The test was performed at 600 ° C. for a holding time of 20 minutes. Silica content (%) = Residual combustion rate / (100-150)
Weight loss rate up to ℃) (4) 300% modulus It was measured by the tensile stress test method of JIS K6301. (5) Tensile strength It was measured by the tensile stress test method of JIS K6301. (6) Elongation It was measured by the tensile stress test method of JIS K6301. (7) Wear reduction Using an Akron abrasion tester, after 1000 preliminary rubs
It was determined from the weight and the weight loss after 1000 rubs. (8) Internal loss (tan δ at 60 ° C.) Rheometrics dynamic viscoelasticity measurement device ARES
At 60 ° C. under the conditions of 1% distortion and 15 Hz frequency.
tan δ was measured. The value of this tan δ (60 ° C.) is small.
It shows that it excels in low heat generation (low fuel consumption). What
The silica used in the present invention was synthesized by the following method.
Was. (Silica synthesis method) 10L stainless steel with temperature controller
Sodium silicate aqueous solution (SiO 2)₂Concentration: 1
0 g / L, molar ratio: SiO₂/ Na₂O = 3.41) 2
Then, 624 ml was charged, and the temperature was raised to 90 ° C. Then 22
% 746 ml of sulfuric acid and an aqueous solution of sodium silicate (SiO₂Dark
Degree: 90 g / L, molar ratio: SiO₂/ Na₂O = 3.4
1) 4458 ml was simultaneously charged over 105 minutes. 1
After aging for 0 minutes, 172 ml of 22% sulfuric acid was injected over 15 minutes.
I entered. In the above reaction, the reaction solution temperature was maintained at 90 ° C.
The reaction is performed with constant stirring until the pH of the reaction
A silica slurry of 3.2 was obtained. This is filtered, washed with water,
A silica wet cake was used. The specific surface area of the obtained silica is 203 m²
/ G, and the oil absorption was 200 ml / 100 g. Embodiment 1 Using the silica wet cake synthesized by the above method, the silica concentration
Is mixed with pure water so that the concentration becomes 15%, and the homogenizer is
Stir and pulverize for 10 minutes using an average particle diameter of 16 μm.
An aqueous suspension of silica was obtained. 1 g of 400 g of the obtained aqueous suspension of silica was added.
Γ-mercaptopropyl trimethod adjusted to 0% concentration
5.2 g of an aqueous solution of silane was added, and the temperature was 50 ° C for 5 hours.
Stir the silica water treated with the silane coupling agent
An aqueous suspension was obtained. Then, the obtained silane coupling
Adjusted to 3% concentration in aqueous suspension of silica treated with dispersant
Poly (diallylmethylamine) having a weight average molecular weight of 20,000
Add 56 g of aqueous solution of hydrochloride, stir for 10 minutes,
Silicate treated with coupling agent and cationic polymer
An aqueous suspension of mosquitoes was obtained. Next, the silane coupling agent and the click
400 g of aqueous suspension of silica treated with on-polymer
800 g of pure water was added to the SBR rubber latex (solid content:
480 g were mixed with stirring and co-coagulated.
Was. This coagulated product is filtered, washed with water, dried, and filled with silica.
148 g of rubber (A) was obtained. Silica content, SBR
49.3 parts by weight with respect to 100 parts by weight of the system. Table 1 shows the obtained silica-filled rubber (A).
Silane coupling agent (KBE)
-846, manufactured by Shin-Etsu Chemical Co., Ltd.), paraffin wax,
Stearic acid, zinc white, anti-aging agent (Nocrack 6C,
Ouchi Shinko Chemical Co., Ltd.), vulcanization accelerator (Noxeller C
Z, Ouchi Shinko Chemical Co., Ltd.) and sulfur
Barry mixer (Toyo Seiki Labo Plastomill Model 1
00C, using a mixer type B-250).
Press vulcanization at 160 ° C for 15 minutes to produce test specimens, each physical property
Was measured. Table 2 shows the results. Embodiment 2 In Example 1, γ-mercap adjusted to a concentration of 10%
The addition amount of the aqueous solution of
The same operation as in Example 1 was performed except that the amount was changed to 5.6 g,
152 g of silica-filled rubber (B) was obtained. Silica content
Is 49.8 parts by weight for 100 parts by weight of SBR rubber
there were. The obtained silica-filled rubber (B) was prepared as in Example 1.
Similarly, various additives are blended, kneaded and vulcanized to produce test specimens.
And each physical property was measured. Table 2 shows the results. Embodiment 3 In Example 1, γ-mercaptopropyltrimethoxy
Instead of silane, vinyltriethoxysilane was used
Except for the above, the same operation as in Example 1 was performed to obtain a silica-filled rubber.
(C) 149 g were obtained. Silica content is SBR rubber
It was 50.2 parts by weight based on 100 parts by weight. Obtained
The silica-filled rubber (C) was added in the same manner as in Example 1.
Ingredients, kneading and vulcanizing to make test specimens,
It was measured. Table 2 shows the results. Embodiment 4 In Example 1, γ-mercaptopropyltrimethoxy
Gamma glucidoxypropyl trimethoxy instead of silane
The same operation as in Example 1 was performed except that silane was used.
151 g of silica-filled rubber (D) was obtained. Silica content
Is 48.5 parts by weight for 100 parts by weight of SBR rubber
there were. The obtained silica-filled rubber (D) was prepared in the same manner as in Example 1.
Similarly, various additives are blended, kneaded and vulcanized to produce test specimens.
And each physical property was measured. Table 2 shows the results. Embodiment 5 In Example 1, γ-mercap adjusted to a concentration of 10%
5.2 g of an aqueous solution of topropyltrimethoxysilane and 3%
With a weight average molecular weight of 20,000 adjusted to the concentration of
56 g of an aqueous solution of methylamine hydrochloride was simultaneously added to silica water.
Except that the mixture was stirred at room temperature for 10 hours.
The same operation as in Example 1 was performed to obtain a silica-filled rubber (E) 14
4 g were obtained. Silica content is 100 weight of SBR rubber
48.6 parts by weight per part. The silica charge obtained
Filling rubber (E) is compounded with various additives as in Example 1.
, Kneading and vulcanizing to produce test specimens,
Was. Table 2 shows the results. Embodiment 6 Using the wet cake used in Example 1, the silica concentration was 15%
And mixed with pure water so as to obtain
Stir and pulverize for 0 minute to obtain silica having an average particle size of 16 μm.
An aqueous suspension was obtained. Aqueous suspension of silica 400 obtained
g of γ-mercaptopropyl triad adjusted to a concentration of 10%
5.2 g of an aqueous solution of methoxysilane was added at a temperature of 50 ° C.
The mixture was stirred for 5 hours and treated with the silane coupling agent.
An aqueous suspension of mosquitoes was obtained. Obtained silane coupling agent
Aqueous suspension of silica treated with 800g pure SB
Stir 480 g of R rubber latex (solid content: 22%)
While mixing. Then, to the above mixed solution to a concentration of 3%
Adjusted weight average molecular weight of 20,000
56 g of an aqueous solution of mine hydrochloride was added with stirring and co-coagulated.
I let it. The coagulated product is filtered, washed with water, dried,
153 g of filled rubber (F) was obtained. The silica content is S
48.2 parts by weight for 100 parts by weight of BR rubber
Was. The obtained silica-filled rubber (F) was the same as in Example 1.
, Kneading and vulcanizing to prepare test specimens
Then, each physical property was measured. Table 2 shows the results. Embodiment 7 In Example 1, γ-mercap adjusted to a concentration of 10%
The addition amount of the aqueous solution of
g, amount of SBR rubber latex (solid content: 22%)
The same operation as in Example 1 was performed except that
Thus, 138 g of a silica-filled rubber (G) was obtained. Including silica
The prevalence is 49.2 weight per 100 weight parts of SBR rubber.
Department. Table 1 shows the obtained silica-filled rubber (G).
Paraffin wax, steer, and so on
Phosphoric acid, zinc white, anti-aging agent (Nocrack 6C, Shin Ouchi
Kogaku Chemical Co., Ltd.), vulcanization accelerator (Noxeller CZ, Ouchi
Shinko Chemical Industry Co., Ltd.) and sulfur
Kisa (Toyo Seiki Labo Plastomill Model 100C
After kneading using a mixer type B-250),
To produce test specimens by press vulcanization for 15 minutes
Was. Table 2 shows the results. Comparative Example 1 400 g of the aqueous silica suspension used in Example 1 was added to pure water.
800 g and SBR rubber latex (solid content: 22%) 4
80 g were mixed and stirred. Adjust the mixture to a concentration of 3%.
Attempt co-coagulation by adding the adjusted sulfuric acid aqueous solution with stirring
However, rubber and silica are separated and uniform silica-filled rubber is obtained.
Could not be obtained. Comparative Example 2 Using the wet cake used in Example 1, the silica concentration was 15%
And mixed with pure water so as to obtain
Stir and pulverize for 0 minute to obtain silica having an average particle size of 16 μm.
An aqueous suspension was obtained. Aqueous suspension of silica 400 obtained
g, γ-mercaptopropyl to a concentration of 10%
5.2 g of an aqueous solution of rimethoxysilane was added, and the temperature was 50 ° C.
For 5 hours. Table with the obtained silane coupling agent
800 g of pure water was added to 400 g of the aqueous suspension of surface-treated silica.
g and SBR rubber latex (solid content: 22%) 480 g
Was mixed and stirred. The mixture was adjusted to a concentration of 3%.
A sulfuric acid aqueous solution was added with stirring to try co-coagulation,
The rubber and silica are separated, and a uniform silica-filled rubber is obtained.
Did not. Comparative Example 3 Sulfuric acid is added to the SBR latex used in Example 1 to coagulate
Then, only the SBR rubber was taken out purely. This SBR
100 parts by weight of rubber and silica wet cake used in Example 1
Dried silica 50 parts by weight, silane coupling
Agent (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.), paraffin
Wax, stearic acid, zinc white, anti-aging agent (Nokura
6C, Ouchi Shinko Chemical Co., Ltd.), vulcanization accelerator (Noku
Cellar CZ, Ouchi Shinko Chemical Co., Ltd.) and sulfur
, Bunbury mixer (Labo Plastomi manufactured by Toyo Seiki)
Model 100C mixer type B-250)
After kneading, press vulcanization was performed at 160 ° C for 15 minutes to produce test specimens.
And each physical property was measured. The results are shown in Table 2. Comparative Example 4 In Example 1, the polydiallylmethylamine hydrochloride
Instead, use cetyltrimethylammonium bromide
The same operation as in Example 1 was performed except that the silica
146 g of filling rubber (H) were obtained. Silica content is SB
It was 48.2 parts by weight based on 100 parts by weight of R rubber.
The obtained silica-filled rubber (H) was prepared in the same manner as in Example 1.
Seed additives are compounded, kneaded and vulcanized to produce test specimens, and
Physical properties were measured. Table 2 shows the results. [0064] [Table 1] [0065] [Table 2][0066] As will be understood from the above description, the present invention
Ming's manufacturing method has a high concentration of silica dispersed well in rubber.
Is a method for producing silica-filled rubber, which is obtained by the present invention.
Silica-filled rubber has high reinforcement, high abrasion resistance and
Has low fuel consumption.

Claims (1)

Claims: 1. A rubber latex, silica and a cationic polymer are mixed in the presence of a silane coupling agent,
A process for producing silica-filled rubber, comprising co-coagulating rubber and silica in a rubber latex.