Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
• • 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
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
  • F16F1/00—Springs
  • F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
  • F16F1/00—Springs
  • F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
  • F16F1/3605—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers characterised by their material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
  • F16F2224/00—Materials; Material properties
  • F16F2224/02—Materials; Material properties solids
  • F16F2224/025—Elastomers

Definitions

• the present invention relates to a rubber composition for anti-vibration rubber and anti-vibration rubber for vehicles.
• the anti-vibration rubber is disposed at a site serving as a source of vibration and noise in order to improve the comfort upon boarding in various vehicles such as automobiles.
• vibration-proof rubber is used as a component such as a torsional damper, an engine mount, and a muffler hanger.
• vibration-proof rubber strength characteristics to support heavy objects such as engines and vibration-proof performance to absorb and suppress the vibration thereof are required, and various techniques have been developed.
• Patent Document 1 a technology for improving the loss property of the vibration-proof rubber by using a specific high loss polymer as a rubber component. Is disclosed.
• an object of the present invention is to provide a rubber composition for anti-vibration rubber excellent in high loss property and a anti-vibration rubber for vehicle excellent in vibration damping performance.
• the rubber component is mainly composed of a diene rubber, and carbon black and a specific type and a specific amount of a resin are contained in the rubber composition, which is not found in conventional rubber compositions for vibration proof rubber It has been found that very high losses can be realized.
• the rubber composition for vibration damping rubber of the present invention comprises a rubber component having a diene rubber, 40 to 120 parts by mass of carbon black with respect to 100 parts by mass of the rubber component And 20 to 80 parts by mass of a resin based on 100 parts by mass of the rubber component,
• the resin is characterized in containing 10 parts by mass or more of a xylene resin with respect to 100 parts by mass of the rubber component.
• the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably 30 m 2 / g or more. It is because the higher loss property can be realized.
• the content of the carbon black is preferably 60 to 120 parts by mass with respect to 100 parts by mass of the rubber component. It is because the higher loss property can be realized.
• the carbon black is preferably ISAF or SAF. It is because the higher loss property can be realized.
• the resin preferably contains 20% by mass or more of a xylene resin. It is because the higher loss property can be realized.
• the content of the resin is preferably 40 to 80 parts by mass with respect to 100 parts by mass of the rubber component. It is because the higher loss property can be realized.
• the anti-vibration rubber for vehicles of the present invention is characterized by using a cross-linked rubber composition for anti-vibration rubber, which is obtained by crosslinking the rubber composition for anti-vibration rubber of the present invention. With the above configuration, excellent vibration damping performance can be realized.
• the rubber composition for vibration damping rubber of the present invention comprises a rubber component having a diene rubber. 40 to 120 parts by mass of carbon black with respect to 100 parts by mass of the rubber component 20 to 80 parts by mass of resin with respect to 100 parts by mass of the rubber component including. And in the rubber composition for vibration proof rubber of the present invention, the resin is characterized by containing 10 parts by mass or more of xylene resin with respect to 100 parts by mass of the rubber component.
• high-grade carbon black is contained in the rubber composition while constituting the rubber component with diene-based rubber as the main component, and further, a certain amount or more of xylene resin (rubber By incorporating a resin containing at least 10 parts by mass with respect to 100 parts by mass of the component in the rubber composition in a larger amount than the usual content, the high loss property which could not be achieved by the conventional vibration-proof rubber was realized .
• high loss property was controlled by the type of rubber component and carbon black.
• the rubber component contained in the rubber composition for anti-vibration rubber of the present invention contains a diene rubber.
• the rubber component may be composed of 100% of diene rubber, but may contain rubber other than diene rubber as long as the object of the present invention is not impaired.
• the content of the diene rubber in the rubber component is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass.
• the type of the diene rubber is not particularly limited, and can be appropriately selected according to the performance required for the rubber composition for vibration damping rubber.
• natural rubber NR
• isoprene rubber IR
• SBR styrene butadiene rubber
• SIBR styrene isoprene butadiene rubber
• EPDM chloroprene rubber
• CR acrylonitrile butadiene rubber
• NBR acrylonitrile butadiene rubber
• IIR butadiene rubber
• BR butadiene rubber
• BR means polybutadiene that is a polymer of 1,3-butadiene, including copolymers of butadiene and other polymers, etc. Not) etc.
• the diene rubber preferably contains at least one selected from natural rubber, isoprene rubber, butadiene rubber, and styrene butadiene rubber among the above-described specific examples. Furthermore, among them, when the rubber component is 100 parts by mass, it is more preferable that the butadiene rubber is 50 parts by mass or more.
• the rubber composition for vibration damping rubber of the present invention further includes a resin containing a xylene resin in addition to the above-described rubber component.
• a resin containing a xylene resin in addition to the above-described rubber component.
• "resin” of this invention is a common resin, and refers to what remove
• the content of the resin is 20 to 80 parts by mass with respect to 100 parts by mass of the rubber component. This is to achieve high loss at a high level.
• the content of the resin is less than 20 parts by mass with respect to 100 parts by mass of the rubber component, sufficient high loss property can not be obtained, while the content of the resin is 100 parts by mass of the rubber component On the other hand, if it exceeds 80 parts by mass, the workability may be deteriorated.
• the content of the resin is preferably 40 to 80 parts by mass with respect to 100 parts by mass of the rubber component.
• the type of the resin may be a xylene resin, and the other resins are not particularly limited.
• resins other than the above-mentioned xylene resin for example, phenol resin, rosin resin, dicyclopentadiene (DCPD) resin, dicyclopentadiene-isoprene copolymer, C5 petroleum resin, C9 petroleum resin, alicyclic petroleum oil
• the resin, petroleum resin (C5-C9 petroleum resin) obtained by copolymerizing C5 fraction and C9 fraction, terpene resin, ketone resin, modified resin of these resins, and the like can be mentioned. These resins may be used alone or in combination of two or more.
• content of the xylene resin in the said resin is 10 mass parts or more with respect to 100 mass parts of said rubber components. If the amount is less than 10 parts by mass with respect to 100 parts by mass of the rubber component, sufficient high loss can not be obtained. Furthermore, it is preferable that the content of the xylene resin in the resin is 20 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of achieving more excellent high loss properties.
• the rubber composition for vibration damping rubber of the present invention further includes carbon black in addition to the above-described rubber component and resin. Physical properties such as strength can be maintained by containing an appropriate amount of carbon black in the rubber composition for vibration damping rubber.
• the content of the carbon black needs to be 40 to 120 parts by mass, preferably 60 to 120 parts by mass, with respect to 100 parts by mass of the rubber component. Even when the high loss property is enhanced by the addition of the resin, excellent high loss property can be realized while maintaining other physical properties such as strength favorably.
• the content of the carbon black is less than 40 parts by mass with respect to 100 parts by mass of the rubber component, there is a possibility that sufficient strength and high loss can not be realized, while 120 with respect to 100 parts by mass of the rubber component If the amount is more than 10 parts by mass, the viscosity of the unvulcanized rubber may be increased to deteriorate the workability.
• the carbon black preferably has a nitrogen adsorption specific surface area (N 2 SA) of 30 m 2 / g or more. Even when the high loss property is enhanced by the addition of the resin, a more excellent high loss property can be realized while maintaining other physical properties such as strength favorably.
• N 2 SA of the carbon black is more preferably 40 m 2 / g or more, more preferably 70m 2 / g or more, particularly not less 100 m 2 / g or more preferable.
• the upper limit of N 2 SA of carbon black is not particularly limited, but is preferably 130 m 2 / g or less from the viewpoint of not deteriorating other physical properties.
• the carbon black N 2 SA can be measured by a single-point method in accordance with ISO 4652-1, for example, after immersing degassed carbon black in liquid nitrogen, the carbon black surface at the time of equilibrium
• the specific surface area (m 2 / g) can be calculated from the measured value by measuring the amount of nitrogen adsorbed to the
• the carbon black preferably has a grade of FEF or higher. Even when the high loss property is enhanced by the addition of the resin, a more excellent high loss property can be realized while maintaining other physical properties such as strength favorably. Further, it is more preferable that the grade of carbon black of FEF or higher is a grade of ISAF or SAF. This is because the strength and high loss can be further improved.
• the rubber composition of the present invention for rubbers, fillers, crosslinking agents other than carbon black, and crosslinking acceleration as long as the object of the present invention is not impaired.
• Additives such as an agent, a crosslinking accelerator, an antiaging agent, an antioxidant, a foaming agent, a plasticizer, a lubricant, a tackifier, and a UV absorber, can be included.
• the contents of the other components described above are not particularly limited.
• the filler is not particularly limited, and fillers such as silica, white carbon, particulate magnesium silicate, calcium carbonate carbonate, magnesium carbonate, clay, and talc can be used as appropriate.
• the rubber composition can be crosslinked.
• the content of the crosslinking agent is preferably 0.4 to 5 parts by mass, and more preferably 0.6 to 3 parts by mass with respect to 100 parts by mass of the rubber component.
• any known crosslinking accelerator may be used without particular limitation.
• thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; N-cyclohexyl-2-benzothiazylsulfenamide, N-t-butyl-2-benzothiazylsulfenamide and the like Sulfenamide-based vulcanization accelerator; guanidine-based vulcanization accelerator such as diphenylguanidine; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetradodecylthiuram disulfide, tetraoctylthiuram disulfide, tetrabenzylthiuram disulfide, Thiuram-based vulcanization accelerators such as pentamethylenethiuram tetrasulfide; dithi
• the crosslinking accelerator may be used alone or in combination of one or more selected from sulfenamides, thiurams, thiazoles, guanidines, dithiocarbamates, etc. In order to adjust the crosslinking behavior (speed), etc., the crosslinking is promoted. It is preferably adopted to combine a thiuram type and / or a thiazole type having a relatively high ability with a guanidine based and / or a sulfenamide type crosslinking accelerator having a relatively medium to low degree of ability to accelerate crosslinking.
• a combination of tetramethylthiuram disulfide and N-cyclohexyl-2-benzothiazylsulfenamide, a combination of tetrabutylthiuram disulfide and N-t-butyl-2-benzothiazylsulfenamide, dibenzo Examples include combinations of thiazyl disulfide and diphenyl guanidine.
• the crosslinking accelerator examples include zinc white (ZnO) and fatty acids.
• the fatty acid may be any saturated or unsaturated, linear or branched fatty acid, and the carbon number of the fatty acid is not particularly limited, and is, for example, a fatty acid having 1 to 30, preferably 15 to 30, carbon atoms More specifically, naphthenic acids such as cyclohexane acid (cyclohexanecarboxylic acid), alkyl cyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acids such as neodecanoic acid), dodecanoic acid, tetradecane Saturated fatty acids such as acids, hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid
• the anti-aging agent may be a known one, and is not particularly limited.
• a phenolic antioxidant, an imidazole antioxidant, an amine antioxidant etc. can be mentioned.
• These antiaging agents can be used alone or in combination of two or more.
• the anti-vibration rubber for vehicles of the present invention is characterized by using a cross-linked rubber composition for anti-vibration rubber, which is obtained by crosslinking the above-mentioned anti-rubber rubber composition of the present invention.
• a cross-linked rubber composition for anti-vibration rubber formed by cross-linking the rubber composition for anti-vibration rubber of the present invention, excellent vibration damping performance can be realized while maintaining the steering stability of the mounted vehicle.
• tan ⁇ at 15 Hz is preferably 0.5 or more, and more preferably 0.6 or more. preferable. This is because a better vibration damping performance can be realized.
• crosslinking (vulcanization) conditions at the time of hardening the said rubber composition for anti-vibration rubbers.
• vulcanization at 140 to 180 ° C. for 5 to 120 minutes can be employed.
• the anti-vibration rubber for vehicles is a cross-linked rubber that is used for the purpose of transmission prevention and shock absorption of vibrations of vehicles (cars, trucks, buses, trains, excavators, etc.) using internal friction. It is a product. Specifically, it is a product used in the above-described vehicle in a state where the above-described crosslinked rubber composition for vibration-proof rubber and a rigid body such as a resin or a metal are in contact with or integrated with each other.
• a non-adhesion type method such as pressing the rubber into the rigid body, or a method using an adhesive on the rigid body The method of making it adhere etc. are mentioned.
• a fluid-containing anti-vibration rubber may be used, in which a fluid is enclosed and the vibration transmission preventing function by the fluid is also used.
• the anti-vibration rubber for a vehicle according to the present invention is preferably an anti-vibration rubber for an automobile, and more preferably an anti-vibration rubber used for an underbody system in an automobile, an engine mount member, and the like. It is because the outstanding vibration damping performance can be realized by the high loss property obtained by the crosslinked rubber composition for vibration damping rubber.
• Examples 1 to 12, Comparative Examples 1 to 2 According to the component composition shown in Table 1, a rubber composition for anti-vibration rubber to be each sample was prepared. Then, the rubber composition for vibration-proof rubber of each sample was subjected to a vulcanization treatment by heating at 155 ° C. for 12 to 26 minutes to prepare a sample of a crosslinked rubber composition for vibration-proof rubber.
• Hardness (Hd) The hardness of each sample of the crosslinked rubber composition for vibration damping rubber was measured in accordance with JIS K 6253 (type A). The measurement results are shown in Table 1. In addition, about the measured hardness, it shows that hardness is so high that a numerical value is large.
• Elongation at break (%) was measured at 23 ° C. in accordance with JIS K 6251 for each sample of the vulcanized rubber composition for vibration damping rubber. The measurement results are shown in Table 1. In addition, about measured breaking elongation, it shows that breaking elongation is so large that a numerical value is large.
• the rubber composition for anti-vibration rubber excellent in high loss property, and the anti-vibration rubber for vehicles excellent in vibration damping performance can be provided.

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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)
• General Engineering & Computer Science (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
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• 2017
  • 2017-08-02 JP JP2017150123A patent/JP7009106B2/ja active Active
• 2018
  • 2018-07-05 CN CN201880050100.1A patent/CN110997788A/zh active Pending
  • 2018-07-05 WO PCT/JP2018/025599 patent/WO2019026537A1/ja not_active Ceased
  • 2018-07-05 US US16/634,912 patent/US20200216643A1/en not_active Abandoned
  • 2018-07-05 EP EP18840452.9A patent/EP3663347B1/en active Active

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