JP2017008244A - Manufacturing method of elastomer composition, elastomer composition, master batch, elastomer mixture and manufacturing method of elastomer mixture - Google Patents

Manufacturing method of elastomer composition, elastomer composition, master batch, elastomer mixture and manufacturing method of elastomer mixture Download PDF

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JP2017008244A
JP2017008244A JP2015126823A JP2015126823A JP2017008244A JP 2017008244 A JP2017008244 A JP 2017008244A JP 2015126823 A JP2015126823 A JP 2015126823A JP 2015126823 A JP2015126823 A JP 2015126823A JP 2017008244 A JP2017008244 A JP 2017008244A
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elastomer
elastomer composition
carbonaceous material
rubber
step
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門田 隆二
Ryuji Kadota
隆二 門田
健三 塙
Kenzo Hanawa
健三 塙
みゆき 冨田
Miyuki Tomita
みゆき 冨田
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昭和電工株式会社
Showa Denko Kk
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Abstract

An object of the present invention is to provide a method for producing an elastomer composition having good heat resistance and the like and a method for producing an elastomer mixture.
The method for producing a masterbatch of the present invention includes a step of dispersing a carbonaceous material in a solvent to produce a carbonaceous material-containing slurry, and an elastomer dissolving step of dissolving the elastomer in the carbonaceous material-containing slurry. And a step of removing the solvent from the elastomer solution.
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Description

  The present invention relates to a method for producing an elastomer composition, an elastomer composition, a masterbatch, an elastomer mixture, and a method for producing an elastomer mixture.

  At present, elastomer products using an elastomer composition are used for various applications. Its usage ranges from general consumer applications such as tires and shoe soles to industrial applications such as packing and O-rings.

  Such an elastomer product is often used after being compressed by taking advantage of its characteristics. Particularly in industrial applications, it is often used for joints (packing, O-ring, etc.) between parts of a device having various parts, and the environment to which the elastomer product is exposed varies depending on the use application of the device. Therefore, there is a demand for elastomer products that can withstand various harsh environments.

As performance required for elastomer products, high heat resistance, high tensile strength, and the like are required.
For example, Patent Document 1 discloses a natural rubber and isoprene rubber containing carbon black with improved tensile strength.
For example, Patent Document 2 discloses an elastomer composition having high plasma resistance.

Japanese Patent No. 5719823 Japanese Patent No. 4600393 JP 2012-76595 A

  However, the present situation is that an elastomer composition having sufficient heat resistance cannot be realized.

  This invention is made | formed in view of the said problem, and aims at obtaining the elastomer composition, masterbatch, and elastomer mixture which have sufficient heat resistance. Moreover, it aims at providing the manufacturing method of the elastomer composition which has sufficient heat resistance.

  As a result of intensive studies, the present inventors have found that increasing the dispersibility of various materials, particularly carbonaceous materials, in the elastomer increases the heat resistance of the elastomer composition and the mixture.

Conventional elastomer compositions are generally prepared from an elastomer compound and other materials by a dry kneading operation. For example, Patent Document 3 describes that an elastomer is produced by adding and mixing other materials to acrylic rubber. For example, Patent Document 1 describes kneading an elastomer composition with an elastomer component and other materials using an oven roll, a Banbury mixer, or the like.
Thus, it was common technical knowledge of those skilled in the art to obtain an elastomer composition by dry kneading while gradually adding other materials to an elastomer. Further, the wet method in which the elastomer is dissolved in a solvent has been avoided by those skilled in the art because the composition of the elastomer may change.

However, the present inventors have found that by using a solution in which the elastomer is dissolved and the carbonaceous material is dispersed, the dispersibility of the carbonaceous material in the obtained elastomer composition can be increased and the heat resistance can be increased. It was. Also, based on the elastomer composition, utilizing the high compatibility of the elastomer components, when another elastomer composition is added and kneaded, the carbonaceous material is homogeneously dispersed and the heat resistance of the resulting elastomer composition is increased. I found that I can do it.
That is, this invention provides the following means in order to solve the said subject.

(1) A method for producing an elastomer composition according to one embodiment of the present invention includes a step of dispersing a carbonaceous material in a solvent to produce a carbonaceous material-containing slurry, and dissolving the elastomer in the carbonaceous material-containing slurry. An elastomer dissolving step, and a step of removing the solvent from the elastomer solution.

(2) The method for producing an elastomer composition according to (1) above may include a pretreatment step in which the elastomer is cut in advance so that the size thereof is 1 to 10 mm.

(3) In the step of dissolving the elastomer of the method for producing an elastomer composition according to the above (1) or (2), while heating the carbonaceous material-containing slurry to a temperature not higher than the temperature at which the elastomer is not decomposed. You may go.

(4) The method for producing an elastomer composition according to any one of (1) to (3), further including a step of applying a shear stress to the elastomer solution before the step of removing the solvent. May be.

(5) In the step of applying the shear stress in the method for producing an elastomer composition according to (4) above, the elastomer solution is heated so that the temperature of the elastomer solution does not become lower than the temperature in the elastomer dissolution step. May be.

(6) In the step of removing the solvent in the method for producing an elastomer composition according to any one of (1) to (5) above, the temperature of the elastomer solution is not lower than the temperature in the elastomer dissolution step. In addition, the elastomer solution may be heated.

(7) In the step of producing the filler-containing slurry of the method for producing an elastomer composition according to any one of (1) to (6), the carbonaceous material having a size of 1 μm or less may be used. Good.

(8) In the method for producing an elastomer composition according to any one of (1) to (7), the carbonaceous material includes carbon black, acetylene black, ketjen black, expanded graphite, and carbon nanotube. It may be at least one selected from the group.

(9) In the method for producing an elastomer composition according to any one of (1) to (8), the elastomer is butyl rubber, fluororubber, nitrile rubber, butadiene rubber, isoprene rubber, natural rubber, chloroprene rubber. Styrene-butadiene rubber, acrylic rubber, ethylene propylene rubber, epichlorohydrin rubber, and at least one rubber selected from the group consisting of copolymers of monomers constituting these elastomers may be used.

(10) An elastomer composition according to an aspect of the present invention is an elastomer composition obtained by the method for producing an elastomer composition according to any one of (1) to (9) above, wherein the elastomer composition The carbonaceous material is contained in the product in an amount of 0.01 to 80% by mass.

(11) The masterbatch which concerns on 1 aspect of this invention uses the elastomer composition obtained by the manufacturing method of the elastomer composition as described in any one of said (1)-(9).

(12) The elastomer mixture which concerns on 1 aspect of this invention contains the elastomer composition obtained by the manufacturing method of the elastomer composition as described in any one of said (1)-(9).

(13) The method for producing an elastomer composition according to one embodiment of the present invention uses the method for producing an elastomer composition according to any one of (1) to (9) above.

  By using the method for producing an elastomer composition and the method for producing an elastomer mixture according to one embodiment of the present invention, an elastomer composition and an elastomer mixture with good heat resistance can be obtained.

Hereinafter, a method for producing an elastomer composition and a method for producing an elastomer mixture to which the present invention is applied will be described in detail.
The materials, dimensions, and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be appropriately modified and implemented without changing the gist thereof.

The definitions of the elastomer composition, master batch, elastomer mixture, and elastomer product in the present invention will be described. The elastomer in the present invention refers to an elastic polymer substance. In general, the elastomer composition is a general term for industrial materials having rubber elasticity including the elastomer itself, a masterbatch, an elastomer mixture, and an elastomer product in a broad sense. In the present invention, the elastomer composition indicates this meaning in a broad sense, but in order to clarify the invention, the elastomer composition, masterbatch, elastomer mixture, and elastomer product are defined as follows.
The elastomer composition means a material in which a carbonaceous material is dispersed in an elastomer. This elastomer composition can function as a masterbatch.
The masterbatch is an aspect of the elastomer composition and is a material that is the basis for producing the elastomer mixture and the elastomer molded article. An elastomer mixture can be obtained by mixing the masterbatch with other elastomer compositions and additives. As the additive, various materials such as a carbonaceous material, a silicon material, a cross-linking agent, and a cross-linking accelerator can be mixed according to the mode of use.
The elastomer mixture means a master batch obtained by adding other elastomers and additives. And an elastomer molded article means what processed the elastomer mixture according to the form of the final product. An elastomer product is an embodiment of an elastomer molded article.

(Method for producing elastomer composition)
The method for producing an elastomer composition according to one embodiment of the present invention includes a step of dispersing a carbonaceous material in a solvent to produce a carbonaceous material-containing slurry, and dissolving the elastomer in the carbonaceous material-containing slurry to prepare an elastomer solution. And a step of removing the solvent from the elastomer solution.

(Production process of carbonaceous material-containing slurry)
First, a carbonaceous material is dispersed in a solvent to produce a carbonaceous material-containing slurry.

  Various materials can be used as the carbonaceous material. For example, a crystalline carbon material and an amorphous carbon material can be used. Specifically, carbon black, acetylene black, furnace black, channel black, thermal black, ketjen black, carbon fiber, carbon nanotube, carbon nanohorn, Graphite, graphene, activated carbon, coke, diamond, glassy carbon, or the like can be used. Here, the amorphous carbon material is carbon whose crystal structure is not observed, and is usually rich in reactivity.

  Solvents include acetates such as methyl acetate, ethyl acetate, and butyl acetate, benzenes such as xylene and trimethylbenzene, ethers such as trichlene and diethyl ether, alcohols, ketones such as methyl ethyl ketone, dichlorobenzene, toluene, Examples include trifluoromethylbenzene, anisole, trifluoromethoxybenzene, pentafluorotoluene, gasoline, and light oil. As will be described later, since the elastomer is added and dissolved in the solvent, a solvent having high solubility of the elastomer is preferable. For example, when adding butyl rubber, it is preferable to use toluene, and when adding fluororubber, it is preferable to use trifluoromethylbenzene.

  A carbonaceous material is dispersed in this solvent. The amount of the carbonaceous material to be dispersed is calculated from the amount of the carbonaceous material desired to be contained in the finally obtained elastomer composition. On the other hand, the solvent to which the carbonaceous material is added is removed when the elastomer composition is obtained. Therefore, it is preferable to prepare an amount of solvent that can sufficiently disperse the carbonaceous material. Here, “sufficiently dispersed” means that 1 or 2 drops are dropped on a glass and covered with a cover glass, and a particle of a carbonaceous material of 1 μm or more in the solvent is not confirmed by an optical microscope of about 500 times. means.

  The carbonaceous material is preferably contained in the elastomer composition in an amount of 0.01 to 80% by mass, more preferably 0.1 to 40% by mass, and further preferably 0.1 to 10% by mass. When the carbonaceous material is suitably dispersed in the elastomer composition, the resulting elastomer composition has improved heat resistance and can further increase tensile strength. When the content of the carbonaceous material in the elastomer composition is within the range, an elastomer composition having a high dispersibility of the amorphous carbon material can be obtained. In particular, when the proportion of the carbonaceous material in the elastomer composition is 10% by mass or less, the dispersibility of the carbonaceous material in the elastomer composition is very high, and the heat resistance can be further improved.

  The carbonaceous material can be dispersed in the solvent by stirring or the like. Further, it is preferable to eliminate the aggregated particles of the carbonaceous material of 1 μm or more in order to improve the dispersibility of the carbonaceous material in the elastomer. Therefore, the aggregated particles may be pulverized using a high-speed rotary pulverizer or a shear stress may be applied to the carbonaceous material using a high-pressure liquid phase jet mill or the like. Moreover, you may remove a big aggregated particle using a sieve. The content of the carbonaceous material contained in the elastomer composition is calculated by measuring the amount from which the aggregates of the carbonaceous material have been removed.

  By obtaining such a step, a carbonaceous material-containing slurry in which the carbonaceous material is sufficiently dispersed in the solvent can be obtained.

(Elastomer pretreatment process)
An elastomer is prepared as a raw material for the elastomer solution. In order to increase the dissolution rate when the elastomer is dissolved in the solvent in the step described later, it is preferable to reduce the size of the elastomer.
The elastomer is preferably about 1 to 10 mm in size. By reducing the size of the elastomer, the solvent can penetrate into the elastomer in a short time when the elastomer is added to the solvent. As a result, the dissolution rate of the elastomer can be increased.

  Elastomers include butyl rubber, fluorine rubber, nitrile rubber, butadiene rubber, isoprene rubber, natural rubber, chloroprene rubber, styrene / butadiene rubber, acrylic rubber, ethylene propylene rubber, epichlorohydrin rubber, and a copolymer of monomers constituting these elastomers. At least one selected can be used. Among these, the isoprene skeleton has good affinity with the carbon material. Therefore, among the above, an elastomer having an isoprene skeleton is preferable, and for example, butyl rubber, isoprene rubber, and natural rubber are preferable. Fluorine rubber, butadiene rubber, chloroprene, and styrene / butadiene rubber are also suitable. These elastomers are dissolved in a solvent to prepare an elastomer solution.

(Elastomer dissolution process)
After the production process of the carbonaceous material-containing slurry is performed, an elastomer dissolution process is performed.

When the elastomer is added to the carbonaceous material slurry, the elastomer swells. This added elastomer may be partly dissolved. In this state, it is preferable to stir for 2 days or more. The elastomer after stirring may not be sufficiently dissolved yet to retain its shape. Therefore, it is preferable that the elastomer is crushed by a high-speed homogenizer to help dissolve the elastomer.
In order to sufficiently dissolve the elastomer, this treatment is preferably performed at a temperature at which the entire elastomer can be dissolved. During this treatment, it is preferable to seal the solvent of the carbonaceous material-containing slurry so that it does not volatilize and to heat it to a temperature below the boiling point of the solvent. If heating is performed with a cooler or the like so that the solvent does not volatilize, the solvent may be heated to a temperature at which the elastomer does not decompose. Here, the temperature at which the elastomer does not decompose means a temperature at which the molecular chain is not broken. A higher temperature is preferable because of high solubility and a high dissolution rate. By heating, the solubility and dissolution rate of the elastomer can be increased. In addition, the dissolved elastomer may re-aggregate at a temperature lower than the saturation solubility. Therefore, it can suppress that an elastomer reaggregates by heating.

In the elastomer dissolving step, the elastomer is sufficiently dissolved in the carbonaceous material-containing slurry.
Here, “sufficient dissolution” means a state in which elastomer particles obtained by dissolving an elastomer are visually observed and elastomer particles cannot be confirmed. If it is difficult to visually discriminate, drop 1 or 2 drops of the elastomer solution on the glass, cover it with a cover glass, and confirm that the elastomer particles cannot be confirmed with an optical microscope (500 times). If the cover glass is tilted or air bubbles may enter and cannot be removed, it is determined that elastomer particles remain.
The amount of the elastomer to be dissolved is such that the carbonaceous material in the elastomer composition has a desired concentration. The amount of solvent used varies with the amount of elastomer. The amount of solvent per gram of elastomer is preferably 3 to 200 ml. If the amount of the solvent is 3 ml or more, the viscosity is easy to stir and mix, and if it is 200 ml or less, the solvent removal in the next step is easy.

The solubility of the elastomer depends on the concentration of the elastomer to be added, the temperature of the solvent, and the solvent species. Examples of the combination of the elastomer and the solvent to be added include the following.
For example, when natural rubber is used, carbon tetrachloride, chloroform, chlorotoluene, cyclohexane, dichlorobenzene, diethyl ether, dioxane, ethylbenzene, ethylene dichloride, fluorobenzene, gasoline, hexane, isopropyl ether, petroleum, propyl acetate, pyridine , Tetrahydrofuran, toluene, trichloroethylene, and xylene are preferably used.

  When using isoprene rubber or butadiene rubber, carbon tetrachloride, chloroform, chlorotoluene, cyclohexane, dichlorobenzene, diethyl ether, dioxane, ethylbenzene, ethylene dichloride, fluorobenzene, gasoline, hexane, isopropyl ether, petroleum, propyl acetate, Pyridine, toluene, trichloroethylene and xylene are preferably used.

  When using styrene rubber, carbon tetrachloride, chloroform, chlorotoluene, cyclohexane, dichlorobenzene, diethyl ether, dioxane, ethylbenzene, ethylene dichloride, fluorobenzene, gasoline, hexane, isopropyl ether, petroleum, propyl acetate, pyridine, tetrahydrofuran It is preferable to use at least one selected from toluene and trichloroethylene.

  When using butyl rubber, at least selected from carbon tetrachloride, chloroform, chlorotoluene, cyclohexane, dichlorobenzene, ethylbenzene, ethylene dichloride, fluorobenzene, gasoline, hexane, petroleum, propyl acetate, tetrahydrofuran, toluene, trichloroethylene and xylene One type is preferably used.

  When chloroprene rubber is used, butyl acetate, carbon tetrachloride, chloroform, chlorotoluene, dichlorobenzene, dioxane, ethylbenzene, ethylene dichloride, isopropyl acetate, methyl isobutyl ketone, piperidine, propyl acetate, pyridine, toluene, trichloroethylene and xylene It is preferable to use at least one selected from

  When epichlorohydrin rubber is used, at least one selected from benzyl alcohol, butyl acetate, chloroform, chlorotoluene, cyclohexanone, dichlorobenzene, dimethylformamide, dimethylformamide, fluorobenzene, methyl ethyl ketone, pyridine, tetrahydrofuran, toluene, and trichloroethylene is used. It is preferable.

  When using a nitrile rubber, it is preferable to use at least one selected from benzyl alcohol, butyl acetate, chloroform, chlorotoluene, cyclohexanone, fluorobenzene, methyl acetate, methyl acetate, methyl ethyl ketone, pyridine, tetrahydrofuran and trichloroethylene.

  When using acrylic rubber, it is preferable to use at least one selected from benzyl alcohol, butyl alcohol, cyclohexanone, methyl ethyl ketone, toluene, trichloroethylene and xylene.

  When using ethylene propylene rubber, it is preferable to use at least one selected from benzene, carbon tetrachloride, chloroform, gasoline, monochlorobenzene, toluene, trichloroethylene and xylene.

  When using fluororubber, it is preferable to use at least one selected from trifluoromethylbenzene, acetone, butyl acetate, cellosolve, cyclohexanone, dimethylformamide, dioxane, ethyl acetate, methyl acetate, methyl ethyl ketone and pyridine.

  The elastomer and the carbonaceous material are preferably mixed as early as possible. It is preferable that the elastomer solution can be prepared in a short time with a small amount of solvent to be used, few steps.

  It is preferable to apply a shear stress to the elastomer solution thus obtained. Examples of the method for applying the shear stress include a method using a jet mill or the like. When applying the shear stress, it is preferable not to lower the temperature of the elastomer solution from the temperature of the elastomer dissolving step. In that case, it is preferable to carry out while heating to the temperature below the boiling point of an elastomer solution. By avoiding the temperature of the elastomer solution from decreasing, it is possible to avoid re-aggregation of the dissolved elastomer and the dispersed carbonaceous material. Further, in an environment where the solvent evaporates, it can be avoided that the solvent evaporates and the carbonaceous material is easily re-aggregated by carrying out at a temperature not higher than the boiling point of the elastomer solution. By performing this step, the proportion of the carbonaceous material that can be dispersed in the elastomer composition can be increased. When the shear stress is not applied, the proportion of the carbonaceous material that can be included in the elastomer composition is about 3% by mass, but can be increased to 40% by mass or more by applying the shear stress. However, if excessive shearing is applied, the molecular chains of the elastomer may be broken, so it is preferable not to apply excessive shearing force.

(Step of removing the solvent)
The elastomer composition is produced by removing the solvent from the elastomer solution thus obtained.
The method for removing the solvent from the elastomer solution may be performed by heating, or may be performed by a decompression process using an evaporator or the like. Further, vacuum drying may be performed.

  The temperature of the elastomer solution is preferably not lowered from the temperature of the elastomer dissolution process. That is, it is preferable to remove the solvent while heating the elastomer solution. In particular, since there is a temperature at which re-aggregation easily occurs due to the elastomer, the temperature is preferably set to a temperature at which re-aggregation is easily performed. The temperature at which reagglomeration tends to occur depends on the amount of elastomer added and the solubility of the elastomer in the solvent. For example, the temperature of the elastomer solution is 60 ° C. or higher for fluoro rubber, and 40 ° C. or higher for butyl rubber. By avoiding a decrease in temperature, it is possible to avoid re-aggregation of dissolved elastomer and dispersed carbonaceous material. In addition, the solvent can be removed in a shorter time when the heating temperature is higher. On the other hand, it is preferable that the heating temperature of the elastomer solution is not higher than the boiling point of the elastomer solution. If the temperature to heat is below a boiling point, the apparatus to be used is simple and handling of an apparatus is also easy. By performing this step, an elastomer composition having high dispersibility of the carbonaceous material can be obtained.

  In the step of removing the solvent, it is preferable to remove the solvent until the solvent contained in the elastomer composition is 200 ppm or less, more preferably 100 ppm or less in terms of mass. If the amount of the solvent contained in the elastomer composition is 200 ppm or less in terms of mass, the solvent does not enter between the molecular chains of the elastomer and the interval is not widened, so that the desired performance can be reliably obtained.

The elastomer composition obtained by such a method has a very high dispersibility of the carbonaceous material.
As a result of forming the elastomer composition into a film and observing with an optical microscope or the like, the number of carbonaceous materials composed of particles of 5 μm or more can be 20 or less per 1 mm 2 in terms of an average film thickness of 10 μm. This measurement can be confirmed by observing the surface of the obtained elastomer composition with an optical microscope.
Since the dispersibility of the carbonaceous material is high, the heat resistance and the tensile strength can be increased even when the amount of the carbonaceous material added is smaller than that of the elastomer composition produced by the conventional kneading method.

The elastomer composition obtained by the above procedure can be used as a masterbatch. A masterbatch can be used to make an elastomer mixture. The elastomer mixture can be obtained by kneading other elastomer compositions and additives to the master batch. Since both the master batch and other elastomer compositions are mainly composed of an elastomer component, the compatibility in kneading is very high. Therefore, the dispersibility of the carbonaceous material in the elastomer mixture can be kept high. An elastomer product can be obtained by molding the obtained elastomer mixture into a desired final product shape.
The elastomer composition, masterbatch, elastomer mixture and elastomer product thus obtained have high heat resistance.

  The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific embodiments, and various modifications can be made within the scope of the gist of the present invention described in the claims. Can be modified or changed.

  Examples of the present invention will be described below. In addition, this invention is not limited only to a following example.

(material)
In the examples and comparative examples, any of the following was used as the elastomer and the carbonaceous material.
Elastomer Fluororubber; G-912 made by Daikin Industries
Butyl rubber; BR01 made by JSR
Chlorinated polyethylene; Eraslen 302NE-X5 from Showa Denko
Chloroprene rubber; Showrene W manufactured by Showa Denko
Carbonaceous material MT carbon; Asahi Thermal expanded graphite manufactured by Asahi Carbon Co .; EC-1500 manufactured by Ito Graphite Industries Co., Ltd.
CB: Aldrich carbon black nanopowder
CNT; carbon nanotube VGCF-H manufactured by Showa Denko KK
Acetylene black; manufactured by Denki Kagaku Kogyo Co., Ltd. acetylene black Ketjen Black; manufactured by Cabot Japan Co., Ltd. Vulcan XC-72
(Heat resistance test)
The heat resistance was confirmed by the thermogravimetric characteristics in the atmosphere using ASC7000S manufactured by NETZSCH. The temperature at which the mass decreased by 10% with respect to the mass before heating was defined as the heat resistant temperature. In Table 1, the heat-resistant temperatures are as follows. No carbonaceous material was added (Comparative Example 1 for Examples 1 to 14, Comparative Example 8 for Example 15, Comparative Example 10 for Example 16, and Example 17). On the other hand, relative temperature is shown on the basis of the heat-resistant temperature in the case of the comparative example 12).

(Tensile test)
A tensile test was performed using a dumbbell-shaped test piece No. 3 defined by JIS K 6251. 50 parts by mass of the master batch, 450 parts by mass of fluororubber (G-912, manufactured by Daikin Industries, Ltd.), 20 parts by mass of the first cross-linking agent (TAIK (registered trademark) manufactured by Nippon Kasei), and the second cross-linking agent (manufactured by Nippon Oil & Fats) 7.5 parts by mass of Perhexa 25B (registered trademark) was mixed, and a sheet (150 mm square) having a thickness of 1 mm was formed at 170 ° C. for 10 minutes. The obtained molded product was subjected to secondary vulcanization at 180 ° C. for 4 hours and punched into a dumbbell-shaped test piece to prepare a test piece. The tensile test conditions were an autograph manufactured by Shimadzu Corporation (model AGS-X 5 kN), a test temperature of 23 ° C., and a tensile speed of 500 ± 50 mm / min. In Table 1, the tensile strength indicates the ratio to the tensile breaking strength when no carbonaceous material is added (Comparative Example 1).

Example 1
Carbon black (MT carbon; Asahi Thermal manufactured by Asahi Carbon Co., Ltd.) was prepared as a carbonaceous material. This carbonaceous material was mixed in trifluoromethylbenzene to prepare a 2% by mass dispersion of the carbonaceous material. At the time of mixing, it processed for 30 minutes at 20000 rpm / min with the high-speed rotary crusher (IKA), and the aggregated particle was grind | pulverized. A shear stress was applied to the treated dispersion under a pressure condition of 150 MPa using a jet mill (Starburst, manufactured by Sugino Machine Co., Ltd.). Finally, the obtained carbonaceous material-containing slurry was passed through a 45 μm sieve to remove aggregated particles.
Then, 30 g of fluororubber was added to 700 ml of carbonaceous material-containing slurry obtained by diluting the obtained 2% by mass dispersion of carbonaceous material with trifluoromethylbenzene (including 0.3 g of carbonaceous material). Prior to adding the fluororubber to the carbonaceous material-containing slurry, the fluororubber was previously cut into approximately 5 mm squares.
The liquid to which the fluororubber was added was stirred at room temperature for 2 days. And after stirring, after confirming that rubber | gum was melt | dissolving visually, it processed for 10 minutes with the ultrasonic homogenizer. The temperature of the elastomer solution at this time rose to 60 ° C. Then, using an evaporator while maintaining the solution temperature at 60 ° C., a part of the solvent was distilled off from the elastomer solution to concentrate the elastomer solution. The temperature at this time was 60 ° C. The obtained master batch was further vacuum-dried at 110 ° C. for 6 hours. Content of the carbonaceous material in a masterbatch was 1.0 mass% with respect to fluororubber. The amount of solvent in the elastomer composition was 50 ppm or less in terms of mass as a result of measurement with a gas chromatograph mass spectrometer (GC-MS).

(Examples 2 to 14)
The difference from Example 1 is that the carbonaceous material, the proportion of the carbonaceous material contained in the masterbatch, and the solvent used were the conditions shown in Table 1.

(Comparative Example 1, Comparative Example 8, Comparative Example 10 and Comparative Example 12)
Fluoro rubber, butyl rubber, chloroprene rubber, and chlorinated polyethylene alone were prepared.

(Comparative Examples 3 to 11)
The carbonaceous material shown in Table 1 was kneaded into an elastomer material by a dry method. As the kneading conditions, a B-type Banbury mixer (manufactured by Kobe Steel Co., Ltd.) was used, and the rotational speed of the rotor was 50 rpm and the kneading time was 2 minutes.

  Table 1 shows the results of the heat resistance temperature of the master batches of Examples 1 to 17 and Comparative Examples 1 to 13 and the tensile strengths of the test pieces obtained by crosslinking the master batches of Example 1, Comparative Example 1 and Comparative Example 2. .

As shown in Table 1, it can be seen that the heat resistance and the tensile strength are increased by adding the carbonaceous material wet.

Claims (13)

  1. A step of dispersing a carbonaceous material in a solvent to produce a carbonaceous material-containing slurry;
    An elastomer dissolving step for dissolving the elastomer in the carbonaceous material-containing slurry;
    A process for removing the solvent from the elastomer solution.
  2.   The manufacturing method of the elastomer composition of Claim 1 including the pre-processing process of the elastomer which cut | disconnects the said elastomer beforehand and makes the size 1-10 mm.
  3.   The method for producing an elastomer composition according to claim 1 or 2, wherein in the elastomer dissolving step, the carbonaceous material-containing slurry is heated to a temperature not higher than a temperature at which the elastomer does not decompose.
  4.   The method for producing an elastomer composition according to any one of claims 1 to 3, further comprising a step of applying a shear stress to the elastomer solution before the step of removing the solvent.
  5.   The method for producing an elastomer composition according to claim 4, wherein in the step of applying the shear stress, the elastomer solution is heated so that the temperature of the elastomer solution does not become equal to or lower than the temperature in the elastomer dissolution step.
  6.   The elastomer composition according to any one of claims 1 to 5, wherein in the step of removing the solvent, the elastomer solution is heated so that the temperature of the elastomer solution does not fall below the temperature in the elastomer dissolution step. Production method.
  7.   The method for producing an elastomer composition according to any one of claims 1 to 6, wherein the carbonaceous material having a size of 1 µm or less is used in the step of producing the carbonaceous material-containing slurry.
  8.   The said carbonaceous material is at least 1 type selected from the group which consists of carbon black, acetylene black, ketjen black, expanded graphite, and a carbon nanotube, The manufacture of the elastomer composition as described in any one of Claims 1-7. Method.
  9.   The elastomer includes butyl rubber, fluorine rubber, nitrile rubber, butadiene rubber, isoprene rubber, natural rubber, chloroprene rubber, styrene-butadiene rubber, acrylic rubber, ethylene propylene rubber, epichlorohydrin rubber, and a copolymer of monomers constituting these elastomers. The method for producing an elastomer composition according to any one of claims 1 to 8, which is at least one rubber selected from the group consisting of:
  10.   It is an elastomer composition obtained by the manufacturing method of the elastomer composition as described in any one of Claims 1-9, Comprising: The elastomer composition which contains the said carbonaceous material 0.01-80 mass% in the said elastomer composition object.
  11.   The masterbatch using the elastomer composition obtained by the manufacturing method of the elastomer composition as described in any one of Claims 1-9.
  12.   The elastomer mixture containing the elastomer composition obtained by the manufacturing method of the elastomer composition as described in any one of Claims 1-9.
  13.   The manufacturing method of the elastomer mixture using the manufacturing method of the elastomer composition as described in any one of Claims 1-9.
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