WO2018135793A1 - Composite de caoutchouc silicone et son procédé de préparation - Google Patents

Composite de caoutchouc silicone et son procédé de préparation Download PDF

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WO2018135793A1
WO2018135793A1 PCT/KR2018/000422 KR2018000422W WO2018135793A1 WO 2018135793 A1 WO2018135793 A1 WO 2018135793A1 KR 2018000422 W KR2018000422 W KR 2018000422W WO 2018135793 A1 WO2018135793 A1 WO 2018135793A1
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silicone rubber
rubber composite
carbon nanotubes
weight
carbon black
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PCT/KR2018/000422
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English (en)
Korean (ko)
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장형식
김평기
김세현
조동현
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주식회사 엘지화학
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Priority claimed from KR1020170177247A external-priority patent/KR102294859B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18741204.4A priority Critical patent/EP3546524A4/fr
Priority to US16/471,510 priority patent/US10995216B2/en
Priority to CN201880005078.9A priority patent/CN110177840B/zh
Publication of WO2018135793A1 publication Critical patent/WO2018135793A1/fr

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    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • 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
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
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    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio

Definitions

  • the present invention relates to a silicone rubber composite having a uniform surface resistance and volume resistance and a method of manufacturing the same.
  • Silicon refers to a polymer in which silicon (Si) containing an organic group and oxygen are connected to each other by chemical bonds. That is, the polymer formed by the silicon to which the organic group is bonded is connected by the siloxane bond (Si-O-Si), which does not exist in nature but is completely artificially synthesized.
  • Silicone rubber means a siloxane polymer processed from silicon as a raw material, and is made by adding various prescriptions such as silica to it.
  • Silicone rubber is classified into high temperature cure (HTV) and natural cure at room temperature (RTV), which harden when heat is greatly applied according to the curing temperature.
  • HTV high temperature cure
  • RTV room temperature
  • HCR solid silicone rubber
  • LSR liquid silicone rubber
  • RTV room temperature curing silicone rubber
  • Silicone rubber is characterized by heat resistance, cold resistance, weather resistance, conductivity, steam resistance, oil resistance, flame retardancy, radiation resistance, and non-toxicity, depending on the manufacturing method and filler added, and thus requires a high degree of reliability and stability. Widely used in automobiles and their applications. In addition, silicone rubber has been widely used in the high electric and electronic industry due to its excellent electrical properties. Silicone rubber having excellent elasticity is excellent enough not to be designed in consideration of elasticity when used in parts requiring elasticity.
  • Silicone rubber is not chemically similar to general organic rubber, but in terms of its properties, silicone rubber and general organic rubber are similar in that they have expansion and contraction, elasticity and repulsion, and flexibility. However, once physical and chemical external forces are applied, they have different characteristics. General rubber has better physical properties than silicone rubber at room temperature, but properties such as tensile strength, elongation and wear resistance are easily destroyed by high temperature, low temperature or chemicals. However, silicone rubbers do not cause significant changes in their original properties over much wider temperature ranges and chemicals.
  • Silicone rubber has a unique chemical structure, has a low carbon ratio in the molecule, and exhibits excellent resistance to arc (ARC) and corona discharge under high voltage. Therefore, it is widely used as a general insulating material. It can be used as an insulator even under conditions. In addition, it is possible to manufacture a conductive silicone rubber by adding a conductive filler such as special carbon black.
  • the problem to be solved by the present invention is to provide a silicone rubber composite composition for a silicone rubber composite having a uniform surface resistance and volume resistance.
  • Another object of the present invention is to provide a conductive silicone rubber composite composition with improved mechanical properties.
  • Another object of the present invention is to provide a silicone rubber composite prepared from the silicone rubber composite composition.
  • the present invention also provides a method for producing the silicone rubber composite.
  • a silicone rubber composite composition comprising a solid silicone rubber and carbon nanotubes having a length / diameter (L / D) value of 500 or more.
  • the length / diameter (L / D) value of the carbon nanotubes may be 5000 or less.
  • the carbon nanotubes are compressed or uncompressed and may have a bulk density of 25 kg / m 3 or more immediately before being blended with the solid silicone rubber.
  • the carbon nanotubes may include 0.2 to 10 parts by weight based on 100 parts by weight of the silicone rubber.
  • the carbon black may further include 5 to 15 parts by weight based on 100 parts by weight of the silicone rubber.
  • the carbon nanotubes and carbon black are included in a 1: 5 to 1:20 weight ratio, the total content of the carbon nanotubes and carbon black is 10 parts by weight or more based on 100 parts by weight of the solid silicone rubber 15 It may be up to parts by weight.
  • the solid silicone rubber may be in a solid or semi-solid state with no fluidity of jelly or contemplation.
  • the present invention also provides a silicone rubber composite prepared from the silicone rubber composite composition described above.
  • the specific gravity of the silicone rubber composite may be 1.18 or less.
  • the hardness of the silicone rubber composite may be 60 or more.
  • the surface resistance of the silicone rubber composite is 10 ⁇ 7 ⁇ / sq. It may be:
  • the volume resistance of the silicone rubber composite may be 20 ⁇ ⁇ cm or less.
  • the elongation of the silicone rubber composite may be 300% or more.
  • the present invention also comprises the steps of preparing a mixture by adding carbon nanotubes or carbon nanotubes and carbon black to a solid silicone rubber;
  • the carbon nanotubes provide a method for producing a silicone rubber composite having a length / diameter (L / D) of 500 or more.
  • the present invention uses carbon nanotubes having a specific length / diameter (L / D) value as a conductive filler instead of carbon black, which should be added to give high conductivity to the insulating silicone rubber, so that even in a much smaller content
  • mechanical properties such as elongation and hardness of silicone rubber composites can also provide improved silicone rubber composites.
  • carbon nanotubes having a specific length / diameter (L / D) value and carbon black are added together as conductive fillers, and exhibit low surface resistance and volume resistance compared to carbon black alone, thereby significantly improving the conductivity of the composite material.
  • L / D length / diameter
  • FIG. 1 schematically illustrates the distribution of carbon black and / or carbon nanotubes in a composite.
  • Figure 2 shows the sluffing properties of the silicone rubber composite according to the Examples and Comparative Examples.
  • Insulating silicone rubber used a carbon-based conductive material such as carbon black as a filler to impart conductivity.
  • carbon black In order to obtain sufficient conductivity using such carbon black, 10 wt% or more of carbon black must be mixed.
  • the carbon black is added in a large amount, there is a problem in that the dispersibility in the manufacturing process and the sloughing of the manufactured molded product occur.
  • the surface resistance reaches 10 ⁇ 6 to 10 ⁇ 7 ⁇ / sq. And it is difficult to obtain sufficient electrical conductivity.
  • the present invention provides a silicone rubber composite composition using a carbon nanotube having a specific L / D value as a conductive filler, thereby providing a silicone rubber composite exhibiting excellent conductivity with a significantly smaller content than when carbon black is used. can do.
  • the present invention provides a silicone rubber composite composition
  • a silicone rubber composite composition comprising a solid silicone rubber and carbon nanotubes having a length / diameter (L / D) value of 500 or more.
  • the solid phase means a solid or semi-solid state having no fluidity of jelly or contemplation.
  • the solid silicone rubber may be HCR (High Consistency Rubber) silicone, or may be prepared in a solid phase by adding other additives such as silica and a catalyst to a liquid siloxane polymer.
  • the length / diameter (L / D) value of the carbon nanotube may be 500 or more, or 600 or more, or 700 or more, or 800 or more, or 900 or more, or 1000 or more, 5000 or less, or Up to 4000, or up to 3000, or up to 2000.
  • the higher the L / D value the more the contact point of the carbon nanotubes may be increased, which is more desirable to exhibit high electrical conductivity at a lower content.
  • the L / D value is too large, the bulk density may be large, resulting in poor workability. .
  • the carbon nanotubes are compressed or uncompressed in pellet form and may have a bulk density of 25 kg / m 3 or more immediately before blending with the solid silicone rubber. It may be preferable to compress for workability, but in this case, the bulk density is preferably 300 kg / m 3 or less in view of workability.
  • the bulk density after compression may preferably be 50-200 kg / m 3 or 80-180 kg / m 3 or 100-160 kg / m 3 .
  • the carbon nanotubes may be included in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the solid silicone rubber, and preferably 0.5 to 5 parts by weight or 0.5 to 3 parts by weight or 0.5 to 2 parts by weight. We can include vice.
  • the present invention can exhibit high conductivity even with a much smaller content than when carbon black is used as the conductive filler.
  • a composite material containing carbon nanotubes as a conductive filler has a carbon nanotube content required to exhibit a level of conductivity equal to or higher than that of a composite material using carbon black as a conductive filler. Only 20.
  • the composite according to the present invention when the carbon nanotubes include 0.2 to 1.5 parts by weight based on 100 parts by weight of the solid silicone rubber, 10 ⁇ 7 ⁇ / sq. Or 10 ⁇ 3 ⁇ / sq. Hereinafter, preferably 10 ⁇ 2 ⁇ / sq. The following surface resistance can be shown.
  • the volume resistance of the composite according to the present invention may be 20 ⁇ ⁇ cm or less, preferably 10 ⁇ ⁇ cm or less.
  • the composite composition according to the present invention can reduce the sloughing phenomenon of the composite (degree of buried when the composite material is rubbed on paper). This may mean that the carbon nanotubes are firmly bound to the silicone rubber composite, and that the carbon nanotubes are not contained in an excessive amount so that the carbon nanotubes are saturated. Can be.
  • the sluffing phenomenon is a phenomenon in which the conductive filler is detached by friction with other accessories, which may cause product defects, and may cause problems when applied to the product by being buried in black. Can be prevented.
  • the silicone rubber composite according to the present invention may have a hardness equivalent to that of the carbon black, even though the carbon nanotube is included in a smaller amount than the carbon black.
  • the hardness of the silicone rubber composite according to the present invention may be 60 or more, preferably 60 to 80, as measured by ASTM D2240.
  • the silicone rubber composite according to the present invention uses carbon nanotubes, which are lighter materials than carbon black, and is included in a small amount compared to carbon black, so that the specific gravity of the silicone rubber composite does not include a conductive filler. It may not increase significantly compared to the specific gravity of the rubber, it is possible to lighten the composite material.
  • the specific gravity of the silicone rubber composite according to the present invention may be 1.17 or more, 1.18 or less, preferably 1.17 to 1.178.
  • the silicone rubber composite according to the present invention by adding a small amount of carbon nanotubes, the elongation can be improved compared to the case of using carbon black, preferably exhibits elongation of 300% or more, more preferably 350% or more Elongation can be indicated.
  • the silicone rubber composite is the most preferable form in which the hardness and conductivity are improved compared to the silicone rubber while maintaining other characteristics of the silicone rubber such as elongation, which is a characteristic required as a rubber.
  • the carbon black added as a conventional conductive filler should contain a large amount of carbon black to improve conductivity, from which the hardness of the composite may increase rapidly, and the elongation decreases rapidly as the hardness increases. There have been disadvantages. In the present invention, the conductivity may be remarkably improved even by adding a small amount of carbon nanotubes, and thus the hardness may not be greatly increased, and thus the elongation may be closer to that of silicone rubber.
  • It may be prepared by a method comprising the step of curing and compression molding the formulation containing the curing agent.
  • the solid silicone rubber may be a commercially available HCR silicone rubber. Or, preparing a liquid siloxane polymer; And
  • It may be a solid silicone prepared by adding other additives such as silica and a catalyst to the liquid siloxane polymer.
  • the catalyst may be platinum (Pt) or a platinum-based compound
  • the platinum-based compound may be a chloroplatinic acid or chloroplatinic acid compound containing phosphorus alcohol, ether, aldehyde, vinylsilane, and phosphate-based platinum (Pt ⁇ P (CH 3 ) 3 ⁇ 4 , Pt ⁇ P (C 4 H 9 ) 3 ⁇ 4 , Pt ⁇ P (OCH 3 ) 3 ⁇ 4 , Pt ⁇ P (OC 6 H 5 ) 3 ⁇ 3 , Pt ⁇ P ( C 6 H 5 ) 3 ⁇ 3 , Pt ⁇ P (OC 6 H 5 ) 3 ⁇ 4 , Pt ⁇ P (C 6 H 5 ) 3 ⁇ 4 , Pt ⁇ P (C 6 H 5 ) 3 ⁇ 4 , Pt ⁇ P (C 6 H 5 ) (C 2 H 5 ) 2 ⁇ 4 , Pt ⁇ P (OC 6 H 5 ) (OC 2 H 5
  • a curing agent is added in the curing step of the mixture, and the curing agent for curing the silicone rubber composite composition is included for the purpose of forming a crosslink of silicone rubber.
  • the curing agent may include an organic peroxide.
  • the organic peroxide may include at least one of an alkyl-based and acyl-based organic peroxide capable of radical generation by pyrolysis in a range of 75 ° C to 220 ° C.
  • the alkyl curing agent may be 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, dicumyl peroxide, di-tert-butylperoxide, 2,5- Dimethyl-2,5-di-tert-butylperoxyhexane, di-tert-butylcumylperoxide, di-tert-butylperoxyisopropylbenzene, butyl 4,4-di-tert-butylperoxyvalate, tert-butylperoxy 2-ethylhexyl carbonate and the like.
  • the acyl curing agent may include a peroxide curing agent such as di-2,4-dichlorobenzoyl peroxide, benzoyl peroxide, and parachlorobenzoyl peroxide.
  • the organic peroxide curing agent may be included 0.1 to 5 parts by weight based on 100 parts by weight of the solid silicone rubber. Easy crosslinking and hardening in the above ranges may be excellent in mechanical properties and heat resistance. For example, 0.5 parts by weight to 5 parts by weight may be included. Other examples may include 0.5 parts by weight to 3 parts by weight.
  • the present invention uses carbon nanotubes as fillers instead of carbon black, which should add high content to give conductivity to the silicone rubber having insulation, so that electrical conductivity equal to or higher than that of high content of carbon black is added even at low content. It is possible to provide a silicone rubber composite, which can significantly reduce the sluffing phenomenon. Such silicone rubber composites are suitable for application to electrical and electronic trays, sheets, keypads, game machines, mobile phone covers, and various electrical and electronic components.
  • the silicone rubber composite according to the present invention may further add other additives in a range that does not affect the physical properties and properties of the composite.
  • a solid silicone rubber and carbon-based additives are included, and the carbon-based additives include carbon nanotubes and carbon black in a weight ratio of 1: 5 to 1:20, but the total of the carbon-based additives It provides a silicone rubber composite composition having a content of 10 parts by weight to 15 parts by weight with respect to 100 parts by weight of the solid silicone rubber.
  • the effects of both carbon black and carbon nanotubes can be obtained.
  • spherical carbon blacks must be adjacent to each other to have conductivity.
  • the carbon nanotubes are linear particles, which are conductive if there is a point of contact with each other.
  • the linear carbon nanotubes are mixed with the spherical carbon black to connect the broken portions between the carbon blacks.
  • the carbon nanotubes and carbon black may be added in a weight ratio of 1: 5 to 1:20, and more preferably in a weight ratio of 1:10 to 1:20.
  • the total content of the carbon nanotubes and carbon black is preferably contained in an amount of 10 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the solid silicone rubber, and more preferably, the carbon nanotubes may be contained in the solid silicone. It may be included in 0.2 to 5 parts by weight based on 100 parts by weight of rubber, preferably 0.2 to 3 parts by weight, the carbon black may be included in 5 to 15 parts by weight based on 100 parts by weight of the solid silicone rubber, Preferably, the carbon black may be included in 5 to 10 parts by weight.
  • the conductivity can be further improved, it is possible to provide a composite having a more even conductivity.
  • the surface resistance of the silicone rubber composite is 10 ⁇ 2 ⁇ / sq. It may be less than, preferably 50 ⁇ / sq. It may be less than or equal to, the variation in surface resistance in the composite material may be less than or equal to 3.
  • the volume resistance of the silicone rubber composite may be 20 ⁇ ⁇ cm or less, preferably 10 ⁇ ⁇ cm or less, and the variation of the volume resistance in the composite may be 1 or less.
  • the present invention uses carbon nanotubes as fillers instead of carbon black, which should add high content to give conductivity to the insulating silicone rubber, thereby reducing the sluffing phenomenon (the degree of bleeding when the composite material is rubbed onto the paper).
  • a silicone rubber composite having low electrical content and high electrical conductivity.
  • Such silicone rubber composites are suitable for application to electrical and electronic trays, sheets, keypads, game machines, mobile phone covers, and various electrical and electronic components.
  • the physical property measurement method used in the Example is as follows.
  • Specific gravity According to ASTM D 792, the specific gravity value was calculated by measuring the mass of the product and the volume when it was soaked in water.
  • Shore A hardness was measured on a silicone rubber composite sheet molded according to ASTM D 2240.
  • the front and rear surfaces of the molded silicone rubber composite sheet were measured 10 times using Mitsubishi Loresta (4-probe type) equipment.
  • Elongation was measured by the method of ASTM D412 Type C, a standard measurement method.
  • Example 1 (0.5% by weight of carbon nanotube)
  • CNT / silicone rubber mixture dough was prepared by adding 2500 g of HCR silicone rubber, which is a solid silicone rubber, and 12.5 g of carbon nanotubes having an L / D value of 1000 or more into a Kneader apparatus, mixing and kneading at a temperature of 50 ° C. for 10 minutes.
  • the CNT / silicone rubber mixture batter was dispersed by adding a peroxide curing agent in a two-roll mill. After the compression molding by applying a load of 2,000 Kgf at 170 °C temperature conditions for 5 minutes in the molding molding to prepare a silicone rubber composite sheet.
  • Example 2 carbon nanotube 1% by weight
  • HCR silicone rubber which is a solid silicone rubber
  • carbon nanotubes having an L / D value of 1000 or more were added to a Kneader apparatus, followed by mixing and kneading at a temperature of 50 ° C. for 10 minutes to prepare a CNT / silicone rubber mixture dough.
  • the CNT / silicone rubber mixture batter was dispersed by adding a peroxide-based curing agent in a two-roll mill. After the compression molding by applying a load of 2,000 Kgf at 170 °C condition for 5 minutes in the molding molding to prepare a silicone rubber composite sheet.
  • Example 3 carbon nanotube 1% by weight
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 2, except that carbon nanotubes having an L / D value of 500 were used.
  • Example 4 carbon nanotube 1% by weight
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 2, except that carbon nanotubes having an L / D value of 5000 were used.
  • HCR silicone rubber which is a solid silicone rubber
  • a peroxide-based curing agent in a two-roll mill. After the compression molding by applying a load of 2,000 Kgf at 170 °C condition for 5 minutes in the molding molding to prepare a silicone rubber composite sheet.
  • the carbon black (CB) / silicone rubber mixture batter was dispersed by adding a peroxide-based curing agent in a two-roll mill. After the compression molding by applying a load of 2,000 Kgf at 170 °C temperature conditions for 5 minutes in the molding molding to prepare a silicone rubber composite sheet.
  • a silicone rubber composite sheet was manufactured in the same manner as in Comparative Example 2, except that 250 g instead of 125 g of Denka Acetylene Black was added.
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 2, except that carbon nanotubes having an L / D value of 200 were used.
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 2, except that carbon nanotubes having an L / D value of 400 were used.
  • a silicon rubber composite sheet was manufactured in the same manner as in Example 2, except that carbon nanotubes having an L / D value of 6000 were used.
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 2, except that carbon nanotubes having an L / D value of 22000 were used.
  • the silicone rubber composite according to the present invention has a specific gravity almost similar to that of the silicone rubber not containing carbon nanotubes, whereas the silicone rubber composite including carbon black as a filler The share increases by more than 1.7%.
  • the silicone rubber composite according to the present invention significantly reduced the surface resistance despite the inclusion of carbon nanotubes in a content of 1/10 or less than carbon black, the hardness is also equivalent to the silicone rubber containing a large amount of carbon black filler Appeared. Therefore, it can be seen that the carbon nanotube silicone rubber composite according to the present invention can provide a silicone rubber composite having low light weight, high hardness, and high conductivity.
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 1, except that 50 g of carbon nanotubes having an L / D value of 1000 or more were used.
  • Example 6 carbon nanotube 3% by weight
  • a silicone rubber composite sheet was manufactured in the same manner as in Example 1, except that 75 g of carbon nanotubes having an L / D value of 1000 or more were used.
  • a silicone rubber composite sheet was manufactured in the same manner as in Comparative Example 2, except that 375 g of Denka Acetylene Black was used.
  • Table 2 shows the results of measurement of specific gravity, hardness, elongation, surface resistance and volume resistance for the composites of Comparative Examples 1, 2 and 8 and Examples 5 and 6.
  • the silicone rubber composite according to the present invention is similar in hardness to a case containing a large amount of carbon black, but in elongation, carbon black is used based on elongation of silicone rubber itself (Comparative Example 1). It shows less reduction than that.
  • the present invention includes a much smaller amount of carbon nanotubes compared to the case where carbon black is added, which is more advantageous for maintaining the physical properties of the silicone rubber itself. That is, compared to the case of using carbon black (Comparative Examples 2 and 3), the addition of a much smaller amount of carbon nanotubes significantly reduces the surface resistance and volume resistance of the silicone rubber composite and improves mechanical properties. have.
  • Example 7 carbon nanotube 1% by weight + carbon black 10% by weight
  • the CNT / CB / silicone rubber mixture batter was dispersed by adding a peroxide-based curing agent in a two-roll mill. Thereafter, compression molding was performed by applying a load of 2,000 kgf at a temperature of 170 ° C. for 5 minutes in the molding molding to prepare a silicone rubber composite sheet.
  • Example 8 (2% by weight of carbon nanotubes + 10% by weight of carbon black)
  • the CNT / CB / silicone rubber mixture batter was dispersed by adding a peroxide-based curing agent in a two-roll mill. Thereafter, compression molding was performed under a load of 2,000 kgf at a temperature of 170 ° C. for 5 minutes in a molding molding to prepare a silicone rubber composite sheet.
  • Example 9 (0.5% by weight of carbon nanotubes + 10% by weight of carbon black)
  • the CNT / CB / silicone rubber mixture batter was dispersed by adding a peroxide-based curing agent in a two-roll mill. Thereafter, compression molding was performed under a load of 2,000 kgf at a temperature of 170 ° C. for 5 minutes in a molding molding to prepare a silicone rubber composite sheet.
  • HCR silicone rubber 2500g HCR silicone rubber, a solid silicone rubber, 25g of carbon nanotubes with an L / D value of 1000 or more, and 375g of denka acetylene black were added to a Kneader apparatus, mixed and kneaded at 50 ° C. for 10 minutes, and the CNT / CB / Silicone rubber mixture dough was prepared.
  • the CNT / CB / silicone rubber mixture batter was dispersed by adding a peroxide-based curing agent in a two-roll mill.
  • the silicone rubber composite sheet was then prepared by compression molding at a load of 2,000 kgf at a temperature of 170 ° C. for 5 minutes in molding molding.
  • Example 7 (CB 10 wt% + CNT 1 wt%) 36 6.9
  • Example 8 (CB 10 wt% + CNT 2 wt%) 14 2.8
  • Example 9 (CB 10 wt% + CNT 0.5 wt%) 10 ⁇ 4 10 ⁇ 3 Comparative Example 1 (Ref.) > 10 ⁇ 13 - Out of resistance measurement range Comparative Example 2 CB 10wt% 10 ⁇ (6 ⁇ 7) 10 ⁇ (5 ⁇ 6) Comparative Example 9 (CB 15 wt% + CNT 1 wt%) - - Not mixed
  • the composite of Example 7 exhibits a value with a very small variation in surface resistance and volume resistance, which means that the conductivity of each of the composites is very uniform.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un composite de caoutchouc silicone utilisant un nanotube de carbone comme charge au lieu de noir de carbone, qui doit être ajouté en une quantité élevée pour conférer la conductivité à un caoutchouc silicone ayant une propriété d'isolation, et par conséquent le nanotube est doué, même à faible quantité, de conductivité au moins dans le cas où une quantité élevée de noir de carbone est utilisée.
PCT/KR2018/000422 2017-01-23 2018-01-09 Composite de caoutchouc silicone et son procédé de préparation WO2018135793A1 (fr)

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EP18741204.4A EP3546524A4 (fr) 2017-01-23 2018-01-09 Composite de caoutchouc silicone et son procédé de préparation
US16/471,510 US10995216B2 (en) 2017-01-23 2018-01-09 Silicone rubber composite and method for producing same
CN201880005078.9A CN110177840B (zh) 2017-01-23 2018-01-09 硅橡胶复合材料及其制备方法

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KR10-2017-0010431 2017-01-23
KR20170010432 2017-01-23
KR20170010429 2017-01-23
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KR10-2017-0010432 2017-01-23
KR20170010431 2017-01-23
KR10-2017-0177247 2017-12-21
KR1020170177247A KR102294859B1 (ko) 2017-01-23 2017-12-21 실리콘 고무 복합재 및 이의 제조방법

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