WO2020195799A1 - Composition d'élastomère et corps moulé - Google Patents

Composition d'élastomère et corps moulé Download PDF

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Publication number
WO2020195799A1
WO2020195799A1 PCT/JP2020/010327 JP2020010327W WO2020195799A1 WO 2020195799 A1 WO2020195799 A1 WO 2020195799A1 JP 2020010327 W JP2020010327 W JP 2020010327W WO 2020195799 A1 WO2020195799 A1 WO 2020195799A1
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elastomer composition
elastomer
molded product
cnt
coefficient
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PCT/JP2020/010327
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English (en)
Japanese (ja)
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慶久 武山
上野　真寛
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日本ゼオン株式会社
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Priority to JP2021508988A priority Critical patent/JPWO2020195799A1/ja
Publication of WO2020195799A1 publication Critical patent/WO2020195799A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to an elastomer composition and a molded product.
  • CNT carbon nanotubes
  • Patent Document 1 by using a composition containing a fibrous carbon nanostructure containing a single-walled CNT in a predetermined ratio with respect to a fluorine-containing elastomer, a molded product such as a sealing member can be used. Techniques have been proposed that sufficiently improve both flexibility and tensile breaking energy at high temperatures and tear strength at high temperatures.
  • the molded product formed by using the elastomer composition has both a high frictional force (that is, having a high friction coefficient) and a small amount of wear (that is, a low wear amount). It is required to combine.
  • the friction coefficient and the amount of wear have a trade-off relationship.
  • the amount of wear also increases, and conversely, when the amount of wear is decreased, the friction coefficient is increased. In some cases, there was a problem that the coefficient of friction decreased.
  • the present inventor has conducted diligent studies for the purpose of solving the above problems. Then, the present inventor has prepared an elastomer composition containing an elastomer and a reinforcing filler in which single-walled carbon nanotubes occupy a predetermined ratio, and the coefficient of variation of the surface resistance when used as a crosslinked sheet is not more than a predetermined value. We have found that if used, it is possible to form a molded product having both a high coefficient of friction and a low amount of wear, and completed the present invention.
  • the present invention is intended to advantageously solve the above problems, and the elastomer composition of the present invention is an elastomer composition containing an elastomer and a reinforcing filler, and the reinforcing filling.
  • the agent contains carbon nanotubes, the proportion of single-walled carbon nanotubes in the reinforcing filler is 90% by mass or more, and the variation coefficient of the surface resistance of the crosslinked sheet obtained by cross-linking the elastomer composition is 20%. It is characterized by the following.
  • the elastomer composition containing the elastomer and the reinforcing filler having a single-layer CNT ratio of the above value or more and having a coefficient of variation of the surface resistance of the crosslinked sheet formed by cross-linking is not more than the above value.
  • the "crosslinked sheet" used for measuring the surface resistivity can be produced by using the method described in the examples of the present specification.
  • the "surface resistivity” can be measured by using the method described in the examples of the present specification.
  • the "coefficient of variation of the surface resistivity” means "a value (%) obtained by dividing the standard deviation of the surface resistivity by the average value and multiplying it by 100". It can be identified using the methods described in the examples herein.
  • the elastomer is a fluorine-containing elastomer. If the elastomer in the elastomer composition is a fluorine-containing elastomer, heat resistance and chemical resistance can be enhanced.
  • the carbon nanotubes preferably have a BET specific surface area of 600 m 2 / g or more.
  • the BET specific surface area of the CNT is equal to or higher than the above value, the high friction coefficient and the low wear amount of the molded product can be compatible with each other at a higher level.
  • the "BET specific surface area” means the nitrogen adsorption specific surface area measured by the BET method, and can be measured by using, for example, a BET specific surface area meter.
  • the elastomer composition of the present invention preferably has an average length of 10 ⁇ m or more of the carbon nanotubes.
  • the average length of CNTs is equal to or greater than the above value, the high coefficient of friction of the molded product and the low amount of wear can be compatible at a higher level.
  • the "average length of carbon nanotubes" in the elastomer composition can be determined by, for example, scanning electron microscope (SEM) observation and image processing.
  • the content of the carbon nanotubes is preferably 0.1 parts by mass or more and 4 parts by mass or less per 100 parts by mass of the elastomer.
  • the ratio of the amount of CNTs to the elastomer in the elastomer composition is within the above range, it is possible to achieve both a high coefficient of friction and a low wear amount of the molded product at a higher level.
  • the elastomer composition of the present invention can further contain a cross-linking agent.
  • the present invention is intended to advantageously solve the above problems, and the molded product of the present invention is characterized in that the above-mentioned elastomer composition is crosslinked.
  • the above-mentioned elastomer composition is crosslinked.
  • the molded product of the present invention can be advantageously used as any of, for example, a belt, a vibration-proof rubber, a rubber roll, and an outsole.
  • an elastomer composition capable of forming a molded product having both a high coefficient of friction and a low amount of wear. Further, according to the present invention, it is possible to provide a molded product having both a high friction coefficient and a low wear amount.
  • the elastomer composition of the present invention can be used for forming the molded product of the present invention.
  • the molded product of the present invention is a crosslinked product formed by using the elastomer composition of the present invention.
  • the elastomeric composition of the present invention contains an elastomer and a reinforcing filler, and optionally further contains a cross-linking agent and other components.
  • the elastomer composition of the present invention contains carbon nanotubes as a reinforcing filler, 90% by mass or more of the reinforcing filler is single-walled carbon nanotubes, and a crosslinked sheet formed by cross-linking the elastomer composition.
  • the coefficient of variation of the surface resistivity of the above is 20% or less.
  • the elastomer composition of the present invention contains a reinforcing filler having a single-layer CNT ratio of the above value or more, and the coefficient of variation of the surface resistance when the crosslinked sheet is formed is the above value or less.
  • the coefficient of friction depends on the volume fraction of the elastomer in the elastomer composition, and the amount of wear depends on the fracture energy of the elastomer composition. Then, the coefficient of friction of the molded product can be increased by reducing the amount of the reinforcing filler added and increasing the volume fraction of the elastomer in the elastomer composition. On the contrary, the amount of wear of the molded product can be reduced by increasing the amount of the reinforcing filler added and increasing the breaking energy of the elastomer composition.
  • the friction coefficient and the wear amount are in a trade-off relationship, and it is generally difficult to achieve both a high friction coefficient and a low wear amount of the molded product.
  • the reinforcing filler contained in the elastomer composition of the present invention is a single-walled CNT having an extremely high reinforcing effect of 90% by mass or more, a sufficiently high fracture energy can be obtained by adding a small amount of the reinforcing filler. Can be obtained. Therefore, it is considered that the amount of wear of the molded body can be reduced while keeping the friction coefficient of the molded body high.
  • the single-walled CNTs in the molded product have good dispersibility. This is because if the single-walled CNTs are not well dispersed in the molded product, a sufficiently high fracture energy cannot be obtained by adding the reinforcing filler containing the single-walled CNTs.
  • the elastomer composition of the present invention has a coefficient of variation of surface resistivity of 20% or less when used as a crosslinked sheet.
  • the coefficient of variation of the surface resistivity can correlate with the degree of dispersion of the conductive CNTs, and the elastomer composition having the coefficient of variation of the surface resistivity of 20% or less when made into a crosslinked sheet is used.
  • the elastomer composition of the present invention it is possible to achieve both a high coefficient of friction and a low wear amount of the molded product.
  • the elastomer contained in the elastomer composition is not particularly limited, and known elastomers can be used. Specifically, acrylonitrile-butadiene rubber (NBR), acrylonitrile-isoprene rubber, acrylonitrile-butadiene-isoprene rubber, styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), natural rubber (NR) , Ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), and their hydrides (hydrided acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-isoprene rubber, hydrogenated acrylonitrile-butadiene-isoprene rubber, hydride styrene-butadiene Examples include rubber, hydride butadiene rubber, isoprene hydride, natural hydride rubber, ethylene-propylene-diene hydride
  • the above-mentioned elastomers include those having a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group introduced therein.
  • a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group introduced therein.
  • One type of these elastomers may be used alone, or two or more types may be used in combination.
  • the elastomer contained in the elastomer composition is preferably a fluorine-containing elastomer from the viewpoint of excellent heat resistance and chemical resistance.
  • fluorine-containing elastomer examples include ethylene tetrafluoroethylene-propylene rubber (FEPM), vinylidene fluoride rubber (FKM), ethylene tetrafluoroethylene-perfluoromethyl vinyl ether rubber (FFKM), and tetrafluoroethylene rubber (TFKM). TFE) and the like.
  • fluorine-containing elastomer vinylidene fluoride rubber (FKM) and ethylene tetrafluoride-propylene rubber (FEPM) are preferable, and vinylidene fluoride rubber (FKM) is more preferable.
  • vinylidene fluoride rubber is a fluororubber containing vinylidene fluoride as a main component and having excellent heat resistance, oil resistance, chemical resistance, solvent resistance, processability, and the like.
  • the FKM is not particularly limited, and is, for example, a binary copolymer composed of vinylidene fluoride and hexafluoropropylene, a ternary copolymer composed of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, and vinylidene fluoride. Hexafluoropropylene, tetrafluoroethylene, and a quaternary copolymer composed of a sulfide site monomer.
  • Examples of commercially available products include “Viton (registered trademark)” of The Chemours Company, Inc. and “Daiel (registered trademark) G” of Daikin Industries, Ltd. Of these, a quaternary copolymer composed of vinylidene fluoride, hexafluoropyrene, tetrafluoroethylene, and a vulcanized site monomer is preferable.
  • the quaternary copolymer is available as, for example, a commercially available product "Viton GBL-600S” (manufactured by Chemers Co., Ltd.).
  • tetrafluoroethylene-propylene rubber is a fluororubber based on an alternating copolymer of tetrafluoroethylene and propylene, and has excellent heat resistance, chemical resistance, polarity solvent resistance, steam resistance, and the like.
  • the FEPM is not particularly limited, but for example, a binary copolymer composed of tetrafluoroethylene and propylene, a ternary copolymer composed of tetrafluoroethylene, propylene and vinylidene fluoride, and a cross-linking point between tetrafluoroethylene and propylene. Examples thereof include a ternary copolymer composed of a monomer.
  • Examples of commercially available products of the binary copolymer composed of tetrafluoroethylene and propylene include "Afras (registered trademark) 100" and “Afras 150" of AGC Inc.
  • As a commercially available product of a ternary copolymer composed of tetrafluoroethylene, propylene and vinylidene fluoride for example, "Afras 200" of AGC Inc. can be mentioned.
  • As a commercially available product of a ternary copolymer composed of tetrafluoroethylene, propylene and a cross-linking point monomer for example, "Afras 300" of AGC Inc. can be mentioned.
  • the content ratio of the elastomer in the elastomer composition is preferably 85% by mass or more, more preferably 88% by mass or more, preferably 95% by mass or less, and 92% by mass or less. Is more preferable.
  • the content ratio of the elastomer in the elastomer composition is within the above-mentioned range, the high friction coefficient and the low wear amount of the molded product formed by using the elastomer composition can be compatible with each other at a higher level.
  • the reinforcing filler is a filler that can be added to the elastomer composition to improve the strength (particularly, fracture energy) of the molded product obtained by cross-linking the elastomer composition. It should be noted that the reinforcing filler usually does not substantially participate in the crosslinking reaction of the elastomer when the elastomer composition is subjected to the crosslinking reaction, and its shape (cylindrical, particulate) even in the molded product after crosslinking. It is a component that contributes to the improvement of the strength of the molded product by retaining the above.
  • the reinforcing filler does not include, for example, a substance corresponding to a cross-linking agent or a cross-linking aid described later. Further, in the present invention, the reinforcing filler does not include the non-reinforcing filler described later, which is blended for the purpose of increasing the amount and processability.
  • the elastomer composition of the present invention it is necessary to use CNTs containing single-walled CNTs as the reinforcing filler.
  • the elastomer composition of the present invention may contain a reinforcing filler other than CNT.
  • the elastomer composition of the present invention preferably contains only CNT as the reinforcing filler.
  • the CNT as the reinforcing filler is not particularly limited as long as the ratio of the single-walled CNTs in the entire reinforcing filler can be 90% by mass or more, and may be a CNT composed of only the single-walled CNTs. However, it may be a mixture of single-walled CNTs and multi-walled CNTs. When a mixture of single-walled CNTs and multi-walled CNTs is used, the mixture needs to contain 90% by mass or more of single-walled CNTs.
  • the average diameter (Av) of the CNTs is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 15 nm or less, and more preferably 10 nm or less.
  • the average diameter (Av) of the CNTs is 0.5 nm or more, the CNTs can be well dispersed and arranged in the molded product. Further, when the average diameter (Av) of CNT is 15 nm or less, the physical properties of the molded product can be further improved. Therefore, when the average diameter (Av) of the CNT is within the above range, it is possible to achieve both a high coefficient of friction and a low wear amount of the molded product at a higher level.
  • the CNT shows an upwardly convex shape in the t-plot obtained from the adsorption isotherm. Above all, it is more preferable that the CNT is not opened and the t-plot shows an upwardly convex shape.
  • adsorption is a phenomenon in which gas molecules are removed from the gas phase to the solid surface, and is classified into physical adsorption and chemisorption according to the cause. Then, in the nitrogen gas adsorption method used for acquiring the t-plot, physical adsorption is used. Normally, if the adsorption temperature is constant, the number of nitrogen gas molecules adsorbed on the CNT increases as the pressure increases.
  • the horizontal axis plots the relative pressure (the ratio of the pressure P in the adsorption equilibrium state to the saturated vapor pressure P0), and the vertical axis plots the amount of nitrogen gas adsorbed, which is called the "isotherm”. Nitrogen gas adsorption while increasing the pressure. The case where the amount is measured is called “adsorption isotherm", and the case where the amount of nitrogen gas adsorbed while reducing the pressure is called “desorption isotherm”.
  • the t-plot is obtained by converting the relative pressure into the average thickness t (nm) of the nitrogen gas adsorption layer in the adsorption isotherm measured by the nitrogen gas adsorption method. That is, the average thickness t of the nitrogen gas adsorption layer corresponding to the relative pressure is obtained from a known standard isotherm obtained by plotting the average thickness t of the nitrogen gas adsorption layer with respect to the relative pressure P / P0, and the above conversion is performed.
  • t-plot of CNT t-plot method by de Boer et al.
  • the growth of the nitrogen gas adsorption layer is classified into the following processes (1) to (3). Then, the slope of the t-plot changes due to the following processes (1) to (3).
  • the plot In the t-plot showing an upwardly convex shape, the plot is located on a straight line passing through the origin in the region where the average thickness t of the nitrogen gas adsorption layer is small, whereas when t is large, the plot is the straight line. The position is shifted downward from.
  • the CNT having such a t-plot shape has a large ratio of the internal specific surface area to the total specific surface area of the CNT, indicating that a large number of openings are formed in the CNT.
  • the bending point of the t-plot of CNT is preferably in the range satisfying 0.2 ⁇ t (nm) ⁇ 1.5, and is in the range satisfying 0.45 ⁇ t (nm) ⁇ 1.5. It is more preferable, and it is further preferable that the range satisfies 0.55 ⁇ t (nm) ⁇ 1.0.
  • the position of the bending point of the t-plot is within the above range, the characteristics of the CNT are further improved, so that the high friction coefficient and the low wear amount of the molded product can be compatible with each other at a higher level.
  • the "position of the bending point" is the intersection of the approximate straight line A of the process (1) described above and the approximate straight line B of the process (3) described above in the t-plot.
  • the ratio (S2 / S1) of the internal specific surface area S2 to the total specific surface area S1 obtained from the t-plot is preferably 0.05 or more, more preferably 0.06 or more. It is more preferably 0.08 or more, and more preferably 0.30 or less.
  • S2 / S1 is 0.05 or more and 0.30 or less, the characteristics of CNT can be further improved, so that a high friction coefficient and a low wear amount of the molded product can be compatible at a higher level.
  • the measurement of the adsorption isotherm of CNT, the creation of the t-plot, and the calculation of the total specific surface area S1 and the internal specific surface area S2 based on the analysis of the t-plot can be performed by, for example, "BELSORP (BELSORP), which is a commercially available measuring device. It can be carried out using "registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).
  • the CNT a CNT in which the ratio (3 ⁇ / Av) of the value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ ) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20 and less than 0.80 is used. It is preferable to use a CNT having a 3 ⁇ / Av of more than 0.25, more preferably to use a CNT having a 3 ⁇ / Av of more than 0.40, and further using a CNT having a 3 ⁇ / Av of more than 0.50. Is particularly preferred.
  • the "average diameter of CNT (Av)” and “standard deviation of CNT diameter ( ⁇ : sample standard deviation)” are the diameters (outer diameters) of 100 CNTs randomly selected using a transmission electron microscope, respectively. ) Can be measured and obtained.
  • the average diameter (Av) and standard deviation ( ⁇ ) of the CNTs may be adjusted by changing the manufacturing method and manufacturing conditions of the CNTs, or by combining a plurality of types of CNTs obtained by different manufacturing methods. You may.
  • the CNT has a BET specific surface area of 600 m 2 / g or more, more preferably 800 m 2 / g or more, preferably 2000 m 2 / g or less, and 1600 m 2 / g or less. It is more preferable to have.
  • the BET specific surface area of the single-walled CNT is 600 m 2 / g or more, the physical properties of the molded product can be further improved. Further, when the BET specific surface area of the single-walled CNT is 2000 m 2 / g or less, it can be satisfactorily dispersed in the molded product. Therefore, if the BET specific surface area is within the above range, the high friction coefficient and the low wear amount of the molded product can be compatible with each other at a higher level.
  • the average length of CNTs contained in the elastomer composition of the present invention is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and even more preferably 20 ⁇ m or more.
  • the average length of CNTs as a reinforcing filler is 10 ⁇ m or more, the reinforcing effect of CNTs (particularly, single-walled CNTs) is sufficiently large, so that high fracture energy can be obtained with a small amount of CNTs. Therefore, it is possible to achieve both a high coefficient of friction and a low wear amount of the molded product at a higher level.
  • the upper limit of the average length of CNTs is not particularly limited, but is usually 800 ⁇ m or less.
  • the average length of the CNTs contained in the elastomer composition can be determined as, for example, the average length of 100 CNTs after removing the elastomer from the elastomer composition.
  • the method for removing the elastomer from the elastomer composition is not particularly limited. For example, after burning the elastomer in the elastomer composition, a solvent is added to the obtained ash to elute the CNTs, and the CNTs are applied to the surface of the observation substrate to make the individual CNTs observable. be able to. A scanning electron microscope (SEM) or known image processing can be used for CNT observation.
  • SEM scanning electron microscope
  • the raw material compound and the carrier gas are supplied on the substrate having the catalyst layer for CNT production on the surface, and the CNT is obtained by the chemical gas phase growth method (CVD method).
  • CVD method chemical gas phase growth method
  • efficient production can be achieved by forming a catalyst layer on the surface of the base material by a wet process.
  • the carbon nanotubes obtained by the super growth method may be referred to as "SGCNT".
  • the proportion of single-walled carbon nanotubes in the reinforcing filler is 90% by mass or more, assuming that the total amount of the reinforcing filler contained in the elastomer composition is 100% by mass. It is necessary, and it is preferable that it is 92% by mass or more. If the proportion of the single-walled carbon nanotubes in the reinforcing filler is less than 90% by mass, it is not possible to achieve both a high coefficient of friction and a low wear amount of the molded product.
  • the elastomer composition of the present invention preferably contains CNT in an amount of 0.1 part by mass or more, more preferably 0.2 part by mass or more, and preferably 0.4 part by mass or more per 100 parts by mass of the elastomer. More preferably, it contains 0.5 parts by mass or more, particularly preferably 4 parts by mass or less, more preferably 3 parts by mass or less, further preferably 2.5 parts by mass or less, and 2 parts by mass or less. It is more preferably contained, and it is particularly preferable to contain 1 part by mass or less.
  • the content of CNT in the elastomer composition is 0.1 part by mass or more per 100 parts by mass of the elastomer, a sufficiently high fracture energy can be obtained, so that the amount of wear of the molded product can be reduced.
  • the content of CNT in the elastomer composition is 4 parts by mass or less per 100 parts by mass of the elastomer, the volume fraction of the elastomer in the elastomer composition can be sufficiently increased, so that the friction of the molded product The coefficient can be increased.
  • Reinforcing filler other than CNT examples include carbon-based fillers other than CNT (for example, carbon black, graphene, graphite), silica and the like.
  • the elastomer composition of the present invention preferably does not contain a carbon-based filler other than carbon nanotubes and silica, for example. , Carbon black, graphene, graphite and silica are preferably not included.
  • the "elastomer composition containing an elastomer and a reinforcing filler" of the present invention contains "elastomer and carbon nanotubes" from the viewpoint of achieving both a high friction coefficient and a low wear amount of the molded product at a higher level.
  • the elastomer composition contains carbon nanotubes other than carbon nanotubes and does not contain silica.
  • an elastomer composition containing elastomer and carbon nanotubes and not containing carbon black, graphene, graphite and silica. is preferable.
  • the carbon black that can be used as the reinforcing filler is not particularly limited, and a known carbon black that can be used in the elastomer composition can be used. Specific examples include furnace black, acetylene black, thermal black, channel black, and Ketjen black. In addition, these carbon blacks can be used individually by 1 type or by mixing 2 or more types. Further, the particle size and structure of carbon black are not particularly limited.
  • the silica that can be used as the reinforcing filler is not particularly limited, and known silica that can be used in the elastomer composition can be used. Specific examples thereof include colloidal silica, wet silica, amorphous silica, fumed silica, silica sol, and silica gel. In addition, these silicas can be used individually by 1 type or a mixture of 2 or more types. Further, the surface of silica may be modified with functional functional groups such as hydrophilicity and hydrophobicity.
  • the cross-linking agent that can be optionally contained in the elastomer composition of the present invention is not particularly limited.
  • the cross-linking agent a known cross-linking agent capable of cross-linking the elastomer contained in the elastomer composition can be used.
  • the cross-linking agent for example, sulfur, a peroxide-based cross-linking agent, triallyl isocyanurate, or the like can be used.
  • these cross-linking agents can be used individually by 1 type or in combination of 2 or more type.
  • the amount of the cross-linking agent to be blended in the elastomer composition of the present invention is not particularly limited, but is preferably 1 part by mass or more and more preferably 3 parts by mass or more with respect to 100 parts by mass of the elastomer. It is more preferably 5 parts by mass or more, more preferably 10 parts by mass or less, and further preferably 7 parts by mass or less.
  • the elastomer composition of the present invention may contain components other than the above components (other components).
  • the elastomer composition may contain a known filler (non-reinforcing filler) other than the reinforcing filler described above.
  • the elastomer composition may also contain known additives such as cross-linking aids and antioxidants.
  • the filler other than the reinforcing filler is not particularly limited, and for example, clay, talc, calcium carbonate, barium sulfate and the like can be used.
  • the cross-linking aid is not particularly limited, and for example, zinc oxide or stearic acid can be used.
  • the antioxidant is not particularly limited, and an amine-based antioxidant, an imidazole-based antioxidant, or the like can be used.
  • the other components may be used alone or in combination of two or more.
  • the blending amount of the other components can be any amount as long as the expression of the desired effect is not inhibited.
  • the coefficient of variation of the surface resistivity of the crosslinked sheet obtained by cross-linking the elastomer composition needs to be 20% or less, preferably 17% or less. More preferably, it is 14% or less.
  • the coefficient of variation of the surface resistivity of the crosslinked sheet is more than 20%, the single-walled CNTs are likely to aggregate in the crosslinked sheet (molded article). Therefore, the dispersibility of the single-layer CNT in the crosslinked sheet (molded body) cannot be improved, and the high friction coefficient and the low wear amount of the molded body cannot be compatible with each other.
  • the lower limit of the coefficient of variation of the surface resistivity of the crosslinked sheet is not particularly limited, but may be, for example, 0.1% or more, 1% or more, or 5.9% or more. be able to.
  • the coefficient of variation of the surface resistivity of the crosslinked sheet can be adjusted by changing the method for preparing the elastomer composition. For example, it can be adjusted by changing the number of passes of the bead mill dispersion treatment in the step of preparing the rubber kneaded product (elastomer composition). More specifically, the coefficient of variation of the surface resistivity of the crosslinked sheet can be reduced by increasing the number of passes of the bead mill dispersion treatment.
  • elastomer composition for example, the above-mentioned elastomer, a reinforcing filler in which single-walled CNTs occupy a predetermined ratio, a cross-linking agent as an optional component, and other components are mixed or mixed at a desired blending ratio. It can be prepared by kneading.
  • the elastomer composition comprises a step of obtaining a mixture (master batch) of the elastomer and CNT (master batch preparation step), and a reinforcing filler other than CNT, which is an optional component of the obtained mixture (master batch). It is preferable to prepare the mixture through a step of kneading the cross-linking agent and other components (kneading step).
  • a cross-linking agent and other components other than CNT By premixing the elastomer and CNT in the absence of a reinforcing filler, a cross-linking agent and other components other than CNT, aggregation of CNT in the elastomer is suppressed and dispersed well, and a predetermined cross-linking is performed. The coefficient of variation of the surface resistivity of the sheet can be reduced.
  • Preparation of the masterbatch can be performed using any mixing method capable of dispersing CNTs in the elastomer. Then, in the master batch, for example, CNT is added to an elastomer solution obtained by dissolving the elastomer in an organic solvent or an elastomer dispersion liquid obtained by dispersing the elastomer in a dispersion medium, and further, a high-speed emulsification / dispersion device or a wet jet mill is used. It is preferable to prepare a slurry by dispersing CNT using the above or the like, and then removing the organic solvent or the dispersion medium from the dispersion treatment solution as the obtained slurry.
  • the elastomer composition is crosslinked by changing the number of passes of the dispersion treatment (the number of times the dispersion target passes through a dispersion device such as a high-speed emulsion dispersion device or a wet jet mill).
  • the coefficient of variation of the surface resistivity of the sheet can be adjusted.
  • the number of passes is preferably 2 or more, and more preferably 3 or more, from the viewpoint of satisfactorily dispersing CNTs.
  • the upper limit of the number of passes is not particularly limited, but can be, for example, 20 or less from the viewpoint of masterbatch preparation efficiency.
  • a coagulation method for example, a casting method or a drying method can be used.
  • a casting method for example, a casting method or a drying method.
  • the reinforcing filler is composed of only CNT, it is not necessary to add a reinforcing filler other than CNT, and in the present invention, it is preferable not to add a reinforcing filler other than CNT. Further, an elastomer may be additionally added in the kneading step.
  • the molded product of the present invention can be obtained by cross-linking the above-mentioned elastomer composition of the present invention. Since the molded product of the present invention is formed by cross-linking the above-mentioned elastomer composition of the present invention, it is possible to achieve both a high coefficient of friction and a low amount of wear.
  • the preferable range of the above-mentioned CNT content per 100 parts by mass of the elastomer in the molded product is the same as the above-mentioned range in the above-mentioned elastomer composition of the present invention. Further, the molded product of the present invention is obtained by cross-linking the elastomer composition of the present invention as described above.
  • the molded product of the present invention is a molded product obtained by cross-linking an elastomer and an elastomer composition containing a reinforcing filler, wherein the reinforcing filler contains carbon nanotubes and the reinforcing filler is filled.
  • a molded product for example, a crosslinked sheet
  • the proportion of the single-layer carbon nanotubes in the agent is 90% by mass or more and the variation coefficient of the surface resistance is 20% or less.
  • the conditions for cross-linking the elastomer composition of the present invention to obtain a molded product include the shape of the desired molded product, the type and blending amount of the elastomer contained in the elastomer composition, and optionally included in the elastomer composition. It can be appropriately determined according to the type and blending amount of the cross-linking agent and other components.
  • the temperature at the time of crosslinking can be 140 ° C. to 250 ° C.
  • the pressure can be 1 MPa to 20 MPa
  • the time can be 1 minute to 180 minutes.
  • the molded product of the present invention is formed by cross-linking the elastomer composition of the present invention, it has both a high coefficient of friction and a low amount of wear. Therefore, for example, it can be advantageously used as any of a belt, a vibration-proof rubber, a rubber roll, and an outsole.
  • the method for producing the molded product of the present invention is not particularly limited as long as the elastomer composition of the present invention can be molded in a desired shape, and a known method can be adopted. Specifically, for example, the elastomer composition is put into a mold, the cross-linking of the elastomer composition is allowed to proceed in the mold, and then various processing is performed to prepare a molded product having a desired shape. can do.
  • the surface resistivity ( ⁇ / sq.) Of the crosslinked sheet is changed at the measurement location. While measuring 10 times. The mean value and standard deviation were obtained from the measured values at 10 points, and the obtained standard deviation was divided by the mean value and multiplied by 100 to obtain the coefficient of variation (%) of the surface resistivity.
  • the cross-linking conditions temperature, pressure, heating time, etc.
  • JIS K6300-2 2001 at an arbitrary temperature and time using a vulcanization tester.
  • the friction speed is 100 mm / s, and the contact pressure.
  • a friction test was performed at 0.2 MPa (load 0.8 N). The coefficient of friction during wear was measured using a load cell, and the wear size was determined as the displacement in the thickness direction by a differential transformer placed above the rubber test piece. The larger the coefficient of friction, the higher the frictional force of the molded product. Then, from the friction coefficient ( ⁇ A ) obtained as described above and the friction coefficient ( ⁇ B ) of the crosslinked sheet of Comparative Example 2 containing 30 parts of carbon black as a reinforcing filler per 100 parts of the elastomer. The coefficient of friction index was calculated by the following formula. The larger the coefficient of friction index, the higher the frictional force of the molded product.
  • Example 1 ⁇ Preparation of carbon nanotubes> As the CNT containing 90% or more of the single-walled CNT, a single-walled CNT (manufactured by Zeon Nanotechnology, "ZEONANO SG101", SGCNT) was used. In the measurement with a Raman spectrophotometer, the spectrum of radial breathing mode (RBM) was observed in the low wavenumber region of 100 to 300 cm -1 , which is characteristic of single-walled CNTs.
  • the BET specific surface area of SGCNT measured using a BET specific surface area meter (BELSORP (registered trademark) -max manufactured by Nippon Bell Co., Ltd.) was 1325 m 2 / g (unopened).
  • the diameter and length of 100 randomly selected SGCNTs were measured using a transmission electron microscope, and the average diameter (Av), standard deviation ( ⁇ ) and average length of the SGCNTs were determined.
  • the average diameter (Av) is 3.5 nm
  • the standard deviation ( ⁇ ) multiplied by 3 (3 ⁇ ) is 2.1 nm
  • their ratio (3 ⁇ / Av) is 0.6
  • the average was 450 ⁇ m.
  • the t-plot of SGCNT was measured using "BELSORP (registered trademark) -mini" manufactured by Nippon Bell Co., Ltd., the t-plot was bent in an upwardly convex shape.
  • a bead mill (Nanomill NM-G1.4L manufactured by Asada Iron Works Co., Ltd.) and zirconia beads (Vickers hardness: 1250, dispersion media filling rate: 52%, average diameter of dispersion media: 0.5 mm) are used as dispersion media. Then, under the conditions of a peripheral speed of 15 m / s and a discharge rate of 65 g / min, a fluorine-containing elastomer dissolution solution containing SGCNT was subjected to 4-pass dispersion treatment at a temperature of 45 ° C.
  • the obtained dispersion treatment liquid (slurry) was added dropwise to 4000 g of isopropyl alcohol and coagulated to obtain a black solid. Then, the obtained black solid was dried under reduced pressure at 60 ° C. for 12 hours to obtain a mixture (master batch) of the fluorine-containing elastomer and SGCNT. [Kneading] Then, using an open roll at 20 ° C., 13 g (fluorine-containing elastomer: 12.5 g, SGCNT: 0.5 g) of the above-mentioned mixture (master batch) and a fluorine-containing elastomer (manufactured by Chemers, Viton GBL-) were used.
  • Zinchua two types of Zinchua
  • triallyl isocyanurate as a first cross-linking agent
  • 2 g of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as a second cross-linking agent is kneaded, and the roll interval is adjusted to 2 mm.
  • Example 2 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. ⁇ Preparation of elastomer composition> [Preparation of mixture (masterbatch)] A mixture (masterbatch) was prepared in the same manner as in Example 1.
  • the amount of the mixture (master batch) of the fluorine-containing elastomer and SGCNT is 13 g to 26 g (fluorine-containing elastomer: 25 g, SGCNT: 1 g), and the amount of the fluorine-containing elastomer (Viton GBL-600S manufactured by Chemers) is 87.5 g.
  • a rubber kneaded product (elastomer composition) was prepared in the same manner as in Example 1 except that the amount was changed from 75 g to 75 g.
  • Example 3 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. ⁇ Preparation of elastomer composition> [Preparation of mixture (masterbatch)] A mixture (masterbatch) was prepared in the same manner as in Example 1.
  • the amount of the mixture (masterbatch) of the fluorine-containing elastomer and SGCNT is 13 g to 52 g (fluorine-containing elastomer: 50 g, SGCNT: 2 g), and the amount of the fluorine-containing elastomer (Viton GBL-600S manufactured by Chemers) is 87.5 g.
  • a rubber kneaded product (elastomer composition) was prepared in the same manner as in Example 1 except that the amount was changed from 50 g to 50 g.
  • Example 1 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. ⁇ Preparation of elastomer composition> Without preparing a mixture (master batch), 15 g of carbon black (Cancarb, Thermax N-990) was used instead of 13 g of the mixture (master batch) of the fluorine-containing elastomer and SGCNT, and the fluorine-containing elastomer (Kemers) was used. The amount of Viton GBL-600S) was changed from 87.5 g to 100 g, and the kneading operation was performed. Other than that, a rubber kneaded product (elastomer composition) was prepared in the same manner as in Example 1.
  • Example 2 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. ⁇ Preparation of elastomer composition> A rubber kneaded product (elastomer composition) was prepared in the same manner as in Comparative Example 1 except that the amount of carbon black (Cancarb, Thermax N-990) was changed from 15 g to 30 g.
  • the amount of carbon black Cancarb, Thermax N-990
  • Example 3 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. ⁇ Preparation of elastomer composition> [Preparation of mixture (masterbatch)] A mixture (masterbatch) was prepared in the same manner as in Example 1. [Kneading] A rubber kneaded product (elastomer composition) was prepared in the same manner as in Example 1 except that 30 g of carbon black (Cancarb, Thermax N-990) was further added.
  • Example 4 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. ⁇ Preparation of elastomer composition> [Preparation of mixture (masterbatch)] A mixture (masterbatch) was prepared in the same manner as in Example 1. [Kneading] A rubber kneaded product (elastomer composition) was prepared in the same manner as in Example 3 except that 30 g of carbon black (Cancarb, Thermax N-990) was further added.
  • Example 5 A molded product (crosslinked sheet) was prepared in the same manner as in Example 1 except that the elastomer composition prepared as follows was used, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
  • ⁇ Preparation of elastomer composition> [Preparation of mixture (masterbatch)] A mixture (masterbatch) was prepared in the same manner as in Example 2 except that the number of passes of the bead mill dispersion treatment was changed from 4 passes to 1 pass. [Kneading] A rubber kneaded product (elastomer composition) was prepared by kneading in the same manner as in Example 2 except that the mixture (masterbatch) obtained as described above was used.
  • FKM indicates vinylidene fluoride rubber
  • CB indicates carbon black
  • ZnO indicates zinc oxide (two types of zinc oxide)
  • TAIC indicates triallyl isocyanurate
  • PH 2,5-dimethyl-2,5-di (t-butylperoxy) hexane.
  • Comparative Example 1 using an elastomer composition containing a reinforcing filler having a single-layer CNT ratio of less than a predetermined value and having a coefficient of variation of the surface resistance of the crosslinked sheet larger than the predetermined value, the molded product It can be seen that both a high coefficient of friction and a low amount of wear cannot be achieved at the same time. Further, in Comparative Examples 2 to 4 using the elastomer composition containing the reinforcing filler in which the ratio of the single layer CNT is less than a predetermined value, the high friction coefficient and the low wear amount of the molded product cannot be compatible with each other. I understand.
  • Comparative Example 5 using an elastomer composition in which the coefficient of variation of the surface resistivity of the crosslinked sheet is larger than a predetermined value, it can be seen that the high friction coefficient and the low wear amount of the molded product cannot be compatible with each other.
  • an elastomer composition capable of forming a molded product having both a high coefficient of friction and a low amount of wear. Further, according to the present invention, it is possible to provide a molded product having both a high friction coefficient and a low wear amount.

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Abstract

Le but de la présente invention est de fournir une composition d'élastomère capable de former un corps moulé qui permet d'obtenir à la fois un coefficient de frottement élevé et une faible perte d'abrasion. Une composition élastomère selon la présente invention contient un élastomère et une charge de renforcement. La charge de renforcement contient des nanotubes de carbone; la proportion de nanotubes de carbone à paroi simple dans la charge de renforcement est de 90 % en masse ou plus; et le coefficient de variation de la résistivité de surface d'une feuille réticulée formée par réticulation de la composition d'élastomère est de 20 % ou moins.
PCT/JP2020/010327 2019-03-28 2020-03-10 Composition d'élastomère et corps moulé WO2020195799A1 (fr)

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