WO2017073194A1 - Composition de caoutchouc anti-vibration et caoutchouc anti-vibration - Google Patents

Composition de caoutchouc anti-vibration et caoutchouc anti-vibration Download PDF

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WO2017073194A1
WO2017073194A1 PCT/JP2016/077131 JP2016077131W WO2017073194A1 WO 2017073194 A1 WO2017073194 A1 WO 2017073194A1 JP 2016077131 W JP2016077131 W JP 2016077131W WO 2017073194 A1 WO2017073194 A1 WO 2017073194A1
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group
parts
mass
component
carbon atoms
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PCT/JP2016/077131
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Japanese (ja)
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渡辺　健太郎
武司 福住
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日信化学工業株式会社
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Priority to CN201680063007.5A priority Critical patent/CN108350233A/zh
Priority to JP2017547667A priority patent/JP6525062B2/ja
Publication of WO2017073194A1 publication Critical patent/WO2017073194A1/fr

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    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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
    • F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
    • F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
    • F16F15/04—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means
    • F16F15/08—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems using elastic means with rubber springs ; with springs made of rubber and metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes

Definitions

  • the present invention relates to an anti-vibration rubber composition that provides an anti-vibration rubber capable of suppressing abnormal noise generated in an anti-vibration rubber product used in vehicles such as automobiles, and an anti-vibration rubber using the same. More specifically, the present invention relates to an anti-vibration rubber composition and an anti-vibration rubber that are suitable for applications such as an automobile stabilizer bush and a rear suspension bush.
  • anti-vibration rubber for automobiles, for example, anti-vibration rubber that is used by inserting metal parts such as stabilizer bushes and rear suspension bushes, contact between the mounting bracket and the surface of the rubber bush when starting, sudden braking, and turning left and right Abnormal noise occurs in the area, and countermeasures are required.
  • Patent Documents 1 and 2 International Publication No. 2011/021641, JP-A-10-245451.
  • the method of sticking the Teflon sheet is expensive in terms of materials and processes, and the method of adding wax is insufficient in reducing the friction coefficient.
  • the method of adding silicone oil has an excellent effect in reducing the friction coefficient, but has a problem that the compatibility with the rubber component is poor, the kneading processability is extremely inferior, and mass production is difficult. ing.
  • Patent Document 2 discloses acrylic silicone oil, but a change with time due to bleeding on the coating surface occurred, and it was not possible to maintain the use for a long time.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide an anti-vibration rubber composition that provides an anti-vibration rubber capable of reducing the friction coefficient of the surface, and an anti-vibration rubber using the same. .
  • the present inventors have found that the specific silicone acrylic graft copolymer resin has good compatibility with the rubber, does not excessively bleed on the rubber surface, and is moderate.
  • the anti-vibration rubber comprising a cured product of the anti-vibration rubber composition containing the silicone acrylic graft copolymer resin in the rubber component is known to have a function as a self-lubricant component.
  • the present inventors have found that the friction reducing effect is maintained when used for a part, and have completed the present invention.
  • the present invention provides the following anti-vibration rubber composition and anti-vibration rubber.
  • Rubber component 100 parts by mass
  • Silicone acrylic which is a polymer of a mixture containing 50 to 99 parts by mass of polyorganosiloxane represented by the following general formula (1) and 50 to 1 parts by mass of an acrylate monomer or methacrylic acid ester monomer
  • Graft copolymer resin An anti-vibration rubber composition comprising 1 to 30 parts by mass.
  • R 1 is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, an acryloxy group or a methacryloxy group.
  • X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group or hydroxyl group having 1 to 20 carbon atoms
  • Y is X or — [O —Si (X) 2 ] d
  • X is the same or different group, and at least two of X and Y are hydroxyl groups
  • Z is an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
  • A is a positive number from 0 to 1,000
  • b is a positive number from 100 to 10,000
  • c is a positive number from 1 to 10
  • d is a positive number from 1 to 1,000.
  • (II) silicone acrylic graft copolymer resin (I) 100 parts by mass of the polyorganosiloxane represented by the general formula (1), (Ii) 1 to 100 parts by mass of an acrylic ester monomer or a methacrylic ester monomer; (Iii) a mixture of 0.01 to 20 parts by mass of a functional group-containing monomer copolymerizable therewith, and (i) the component and (ii) and (iii) the sum of the components are in a mass ratio of 50
  • the anti-vibration rubber composition according to [1] which is an emulsion graft polymer of a mixture in a ratio of 50 to 99: 1.
  • component (iii) is selected from methacrylic acid, acrylic acid, acrylic amide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate Anti-vibration rubber composition.
  • (Ii) The vibration-insulating rubber composition according to any one of [2] to [6], wherein the component is an acrylic ester or methacrylic ester having an alkyl group having 1 to 10 carbon atoms.
  • the polyorganosiloxane represented by the formula (1) is a cyclic organosiloxane, ⁇ , ⁇ -dihydroxysiloxane oligomer, ⁇ , ⁇ -dialkoxysiloxane oligomer or alkoxysilane, and a silane coupling agent represented by the following general formula (2)
  • the vibration-insulating rubber composition according to any one of [1] to [7], which is a polymer of R 3 (4-ef) R 4 f Si (OR 5 ) e (2) (Wherein R 3 is a mercapto group, an acryloxy group or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group, R 4 is an alkyl group having 1 to 4 carbon atoms, and R 5 is carbon.
  • An anti-vibration rubber comprising a crosslinked product of the anti-vibration rubber composition according to any one of [1] to [8].
  • the anti-vibration rubber according to [9] which is for vehicle parts.
  • the anti-vibration rubber composition of the present invention contains a specific silicone acrylic graft copolymer resin in the rubber component, so that when the anti-vibration rubber made of the cured product of the composition is used for a part such as a stabilizer bush, the friction is obtained. The reduction effect is maintained for a long time.
  • the anti-vibration rubber composition of the present invention contains (I) a rubber component and (II) a silicone acrylic graft copolymer resin. Below, each component is explained in full detail.
  • (I) rubber component includes butadiene rubber (BR), styrene butadiene rubber (SBR), nitrile rubber (NBR), isoprene rubber (IR), diene rubber such as chloroprene rubber (CR), ethylene propylene, and the like.
  • Olefin rubbers such as rubber (EPR, EPDM), butyl rubber (IIR), halogenated butyl rubber such as brominated butyl rubber (Br-IIR), other polyurethane rubber, acrylic rubber, fluoro rubber, silicone rubber, chlorosulfonated polyethylene, etc. Examples thereof include synthetic rubbers, natural rubbers and the like, and these can be used alone or in combination of two or more.
  • the silicone acrylic graft copolymer resin is a polymer of a polyorganosiloxane represented by formula (1) and an acrylate monomer or a methacrylic acid ester monomer, preferably (i) the following general formula A mixture of the polyorganosiloxane represented by (1) and (ii) (meth) acrylic acid ester monomer, or (i), (ii) and (iii) a functional group-containing monomer copolymerizable therewith. It is obtained by emulsion graft polymerization of a mixture with a monomer.
  • polyorganosiloxane is represented by the following general formula (1).
  • R 1 is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, an acryloxy group or a methacryloxy group.
  • X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group or hydroxyl group having 1 to 20 carbon atoms
  • Y is X or — [O —Si (X) 2 ] d
  • X is the same or different group, and at least two of X and Y are hydroxyl groups
  • Z is an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
  • A is a positive number from 0 to 1,000
  • b is a positive number from 100 to 10,000
  • c is a positive number from 1 to 10
  • d is a positive number from 1 to 1,000. .
  • R 1 is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl Group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group, cycloheptyl group and other cycloalkyl groups, vinyl group, allyl group Alkenyl groups such as phenyl group, tolyl group and naphthyl group, alkenyl aryl groups such as vinylphenyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, vinylbenzyl
  • R 2 is a mercapto group, an acryloxy group or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group. Specifically, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, a vinyl group and the like are preferable.
  • X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and is an unsubstituted or substituted monovalent group having 1 to 20 carbon atoms.
  • the hydrocarbon group are the same as those exemplified for R 1.
  • Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a hexyloxy group. , Heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group and the like.
  • X is preferably a hydroxyl group, a methyl group, a butyl group, or a phenyl group.
  • Y is the same or different group represented by X or — [O—Si (X) 2 ] d —X.
  • d is a positive number of 1 to 1,000, preferably 1 to 200. Further, in the present invention, from the viewpoint of crosslinkability, it has at least 2, preferably 2 to 4 hydroxyl groups in X and Y, and has at both ends. preferable.
  • Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, preferably a hydroxyl group or a methyl group.
  • a is greater than 1,000, the strength of the resulting cured product will be insufficient, so a positive number from 0 to 1,000, preferably a positive number from 0 to 200, and b being less than 100, If it is greater than 10,000, the tear strength of the resulting cured product will be reduced, so a positive number of 100 to 10,000, preferably a positive number of 1,000 to 5,000.
  • c is a positive number of 1 to 10, and if it exceeds 10, gelled particles are easily formed during the reaction.
  • the arrangement of the repeating units may be a block or random.
  • Such (i) polyorganosiloxane is preferably used in the form of an emulsion, and a commercially available product may be used or synthesized. In the case of synthesis, it can be carried out by a known emulsion polymerization method. For example, it may have a halogen atom such as a fluorine atom, a (meth) acryloxy group, a carboxyl group, an alkoxy group, an alkenyloxy group, a hydroxyl group or an amino group.
  • a halogen atom such as a fluorine atom, a (meth) acryloxy group, a carboxyl group, an alkoxy group, an alkenyloxy group, a hydroxyl group or an amino group.
  • a good cyclic organosiloxane, ⁇ , ⁇ -dihydroxysiloxane oligomer, ⁇ , ⁇ -dialkoxysiloxane oligomer, alkoxysilane, and the like, and a silane coupling agent represented by the following general formula (2) are used. It can be easily synthesized by emulsifying and dispersing in water and then adding a catalyst such as an acid as necessary to carry out a polymerization reaction.
  • R 3 (4-ef) R 4 f Si (OR 5 ) e (2)
  • R 3 is a mercapto group, an acryloxy group or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group
  • R 4 is an alkyl group having 1 to 4 carbon atoms
  • R 5 is carbon.
  • Equation is an alkyl group of 1 to 4, e is 2 or 3, f is 0 or 1, and e + f is 2 or 3.
  • cyclic organosiloxane examples include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1.
  • silane coupling agent examples include vinyl silanes such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl methyl dimethoxy silane, vinyl methyl diethoxy silane; ⁇ - ( (Meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxypropyltripropoxysilane, ⁇ - (meth) acryloxypropyltriisopropoxysilane, ⁇ - (meta ) Acryloxypropyl tributoxysilane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, ⁇ - (meth) acryloxypropylmethyldipropoxysilane, ⁇ Acrylic silanes such as (meth) acryloxypropyl
  • an oligomer obtained by condensation polymerization of these may be more preferable because generation of alcohol is suppressed.
  • (meth) acryloxy represents acryloxy or methacryloxy.
  • These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of cyclic organosiloxane, ⁇ , ⁇ -dihydroxysiloxane oligomer, ⁇ , ⁇ -dialkoxysiloxane oligomer or alkoxysilane. The use of 01 to 5 parts by mass is more preferable.
  • a polyorganosiloxane having a siloxane unit of c in formula (1) is obtained, and the effect of grafting the monomer of component (ii) or (iii) is obtained.
  • a known polymerization catalyst may be used as the catalyst used for the polymerization.
  • strong acids are preferable, and hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid are exemplified.
  • Preferred is dodecylbenzenesulfonic acid having emulsifying ability.
  • the amount of the acid catalyst used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of cyclic organosiloxane, ⁇ , ⁇ -dihydroxysiloxane oligomer, ⁇ , ⁇ -dialkoxysiloxane oligomer or alkoxysilane, More preferably, it is 0.2 to 2 parts by mass.
  • surfactant used for the polymerization examples include anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, aliphatic soap, alkyl phosphate and the like. However, those which are easily soluble in water and do not have a polyethylene oxide chain are preferred. More preferred are N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps and alkyl phosphates, and particularly preferred are sodium lauroyl methyl taurine, sodium myristoyl methyl taurine and sodium lauryl sulfate.
  • anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, aliphatic soap, alkyl phosphate and the like.
  • anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N
  • the amount of the anionic surfactant used is 0.1 to 20 parts by mass with respect to 100 parts by mass of the cyclic organosiloxane, ⁇ , ⁇ -dihydroxysiloxane oligomer, ⁇ , ⁇ -dialkoxysiloxane oligomer or alkoxysilane.
  • the amount is preferably 0.5 to 10 parts by mass.
  • the polymerization temperature is preferably 50 to 75 ° C.
  • the polymerization time is preferably 10 hours or more, more preferably 15 hours or more. Further, it is particularly preferable to age at 5 to 30 ° C. for 10 hours or longer after polymerization. Further, the pH of the obtained polymerization solution is preferably 6-8.
  • acrylic acid ester monomer or methacrylic acid ester monomer (hereinafter sometimes referred to as acrylic component or (meth) acrylic acid ester monomer) is a hydroxyl group, an amide group, a carboxyl group.
  • Acrylic acid ester monomer or methacrylic acid ester monomer having no functional group such as a group, preferably an acrylic acid ester or methacrylic acid ester having an alkyl group having 1 to 10 carbon atoms, and further an acrylic component polymer A monomer having a glass transition temperature (hereinafter sometimes referred to as Tg) of 40 ° C. or higher, preferably 60 ° C. or higher is preferred.
  • Tg glass transition temperature
  • Examples of such monomers include methyl methacrylate, isopropyl methacrylate, ethyl methacrylate, Examples include cyclohexyl methacrylate.
  • the upper limit of Tg is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.
  • the glass transition temperature can be measured based on JIS K7121.
  • the polyorganosiloxane of formula (1) obtained as described above preferably has 2 to 10 crosslinking points, preferably 2 to 6 crosslinking points per mole of the polymer.
  • (Ii) Graft with component Polymerization can be derived.
  • the functional group-containing monomer copolymerizable with the component (ii) includes a functional group such as an unsaturated bond including a carboxyl group, an amide group, a hydroxyl group, a vinyl group, and an allyl group.
  • a functional group such as an unsaturated bond including a carboxyl group, an amide group, a hydroxyl group, a vinyl group, and an allyl group.
  • monomers such as methacrylic acid, acrylic acid, acrylic amide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and these are copolymerized By doing so, it becomes possible to improve the compatibility.
  • the (II) silicone acrylic graft copolymer resin according to the present invention is first prepared from (ii) the polyorganosiloxane obtained as described above, and (ii) a (meth) acrylic acid ester monomer, preferably (ii) ) And (iii) a mixture of this and a copolymerizable functional group-containing monomer is subjected to emulsion graft polymerization.
  • the mass ratio of the polyorganosiloxane of formula (1) to the (meth) acrylic acid ester monomer in the graft polymerization is 50:50 to 99: 1, preferably 70:30 to 99: 1. It is. If the silicone component is less than 50 by mass ratio, sufficient vibration isolation may not be obtained and abnormal noise may occur.
  • examples of the radical initiator used for graft polymerization include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen persulfate, t-butyl hydroperoxide, and hydrogen peroxide.
  • persulfates such as potassium persulfate and ammonium persulfate
  • aqueous hydrogen persulfate aqueous hydrogen persulfate
  • t-butyl hydroperoxide examples of the radical initiator used for graft polymerization
  • a redox system using a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, tartaric acid, saccharides and amines can also be used.
  • the amount of the radical initiator used is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass, based on the total amount of the components (ii) and (iii).
  • the surfactant already contained in the emulsion when the polyorganosiloxane is already prepared can be sufficiently graft-polymerized, but for the purpose of improving the stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps, alkyl phosphates and the like can be added. Moreover, nonionic emulsifiers, such as polyoxyethylene lauryl ether and polyoxylene tridecyl ether, can also be added.
  • the amount used in the case of adding the surfactant is preferably 0.1 to 5% by mass of the total amount of the components (ii) and (iii).
  • a chain transfer agent can be added to adjust the molecular weight and graft ratio of the graft polymer.
  • the graft polymerization temperature is preferably 25 to 55 ° C, more preferably 25 to 40 ° C.
  • the polymerization time is preferably 2 to 8 hours, more preferably 3 to 6 hours.
  • the silicone acrylic graft copolymer resin thus obtained is a polymer in which the component (ii) and the component (iii) are randomly grafted to the component (i).
  • the silicone acrylic graft copolymer resin obtained above is preferably 30 to 50% by mass as a solid content in the emulsion.
  • the viscosity (25 ° C.) of the emulsion is preferably 10 to 5,000 mPa ⁇ s or less, and more preferably 50 to 1,000 mPa ⁇ s.
  • the viscosity can be measured with a rotational viscometer.
  • the average particle size of this emulsion is preferably 1 ⁇ m or less, and preferably 0.1 ⁇ m (100 nm) to 0.3 ⁇ m (300 nm).
  • the pH is preferably 6-8.
  • the average particle size can be measured by a laser diffraction / scattering particle size distribution measuring device.
  • the obtained silicone acrylic graft copolymer resin is in the form of an emulsion, for example, after concentrating the dispersion by a method such as heat dehydration, filtration, centrifugation, decantation, etc., and then washing with water as necessary. Water is removed by heat drying under normal pressure or reduced pressure, spray drying in which the dispersion is sprayed in an air stream, heat drying using a fluidized heat medium, etc., and then once dried and powdered. The drying temperature is preferably 60 to 105 ° C. When the obtained powder is slightly agglomerated, it may be pulverized by appropriately using a pulverizer such as a jet mill, a ball mill, or a hammer mill.
  • a pulverizer such as a jet mill, a ball mill, or a hammer mill.
  • the solvent is preferably an alcohol organic solvent or a hydrocarbon organic solvent, and examples thereof include lower alcohols having 1 to 4 carbon atoms and aliphatic hydrocarbons having 5 to 20 carbon atoms. More preferred are ethanol, isopropyl alcohol, hexane, and isododecane.
  • 100 parts by mass of powder is collected in a beaker, and the solvent is added at least 5 times its mass, stirred for several hours, and suction filtered. After that, it is more effective to wash with the same solvent or with a solvent that dissolves in water such as alcohol. In this case, it is usually performed at room temperature (25 ° C.), but it may be heated in some cases.
  • the filtered powder When washed, it is re-dried to form powder, but the filtered powder may be simply dried at a temperature of 40 ° C. or higher and 200 ° C. or lower for several hours with a dryer, or a fluid dryer or the like may be used. .
  • the silicone acrylic graft copolymer resin thus obtained preferably has an average particle size of 15 ⁇ m or less, particularly 0.1 to 10 ⁇ m.
  • the weight average molecular weight of the silicone acrylic graft copolymer resin is preferably 50,000 to 500,000. If it is less than 50,000, precipitation on the rubber compound surface may become severe, and if it exceeds 500,000, the friction reducing effect may be insufficient.
  • the weight average molecular weight is measured in terms of dimethylsilicone molecular weight from a kinematic viscosity measurement value at 25 ° C. obtained by mixing an emulsion and isopropyl alcohol (IPA), extracting and drying 1 g of the oil in 100 mL of toluene.
  • IPA isopropyl alcohol
  • the blending amount of the silicone acrylic graft copolymer resin is 1 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the (I) rubber component. If it is less than 1 part by mass, the effect of reducing friction is poor, and if it exceeds 30 parts by mass, it may precipitate on the surface of the rubber compound and an appropriate effect may not be exhibited.
  • the anti-vibration rubber composition of the present invention contains, in addition to the above essential components, a vulcanizing agent conventionally used as an additive for rubber (0.1) to 10 parts by mass with respect to 100 parts by mass of the rubber component. Mass parts can be included.
  • a vulcanizing agent conventionally used as an additive for rubber (0.1) to 10 parts by mass with respect to 100 parts by mass of the rubber component. Mass parts can be included.
  • the vulcanizing agent include sulfur and peroxides, and other compounds and resins can be used as long as they have a vulcanizing effect.
  • the anti-vibration rubber composition of the present invention further comprises a vulcanization accelerator, a reinforcing agent, a vulcanization aid, a softening agent, a processing aid, an antiaging agent, a filler and the like in (I) 100 parts by mass of the rubber component.
  • a vulcanization accelerator e.g., a vulcanization accelerator
  • a reinforcing agent e.g., a vulcanization aid
  • a softening agent e.g., a processing aid
  • an antiaging agent e.g., a filler and the like
  • filler e.g., a filler and the like in (I) 100 parts by mass of the rubber component.
  • Each can be blended in an amount of 0.1 to 10 parts by mass.
  • the reinforcing agent and filler include inorganic fillers such as carbon black, acetylene black, graphite, silica, calcium carbonate, talc, and clay.
  • vulcanization accelerator examples include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thiurams such as tetraethylthiuram monosulfide, thioureas, guanidines such as diphenylguanidine, thiazoles such as mercaptobenzothiazole and dibenzothiazyl disulfide, Select one or more of higher fatty acids such as stearic acid, such as sulfenamides such as cyclohexylbenzothiazole sulfenamide, butylbenzothiazole sulfenamide, dithiocarbamate such as zinc dimethyldithiocarbamate, etc.
  • vulcanization aid examples include ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triallyl isocyanuric acid ester, zinc white, magnesium oxide, zinc oxide and the like.
  • Antiaging agents include aromatic secondary amines, bisphenols, polyphenols, imidazoles, thioureas, waxes and the like.
  • a vulcanization accelerator and a vulcanization aid it is particularly preferable to use a vulcanization accelerator and a vulcanization aid in order to accelerate vulcanization.
  • the anti-vibration rubber composition of the present invention is obtained by kneading, extrusion molding, injection molding and the like of these components with a usual processing apparatus such as a roll, a Banbury mixer, a kneader, etc., to obtain a rubber molded product having a desired shape. .
  • the anti-vibration rubber can be obtained by vulcanizing this rubber composition by a known method. At this time, the rubber composition can be vulcanized by heating at about 120 to 250 ° C. for 1 to 60 minutes.
  • the molded product depends on the shape of the object, but when covering the shaft of an automobile, the vehicle part is obtained by vulcanizing and molding into a desired shape such as a cylinder and inserting the object. Can do.
  • the obtained anti-vibration rubber molded article is excellent in releasability from the mold.
  • the anti-vibration rubber of the present invention obtained as described above can be used as a protective member for vehicle parts, and can be preferably used for an inset bush such as a stabilizer bush. It can be used for a part that touches and receives rotational force or load.
  • the weight average molecular weight was measured in terms of dimethylsilicone molecular weight based on a kinematic viscosity measurement value at 25 ° C. in which emulsion and IPA were mixed, 1 g of the oil was dried after extraction and dissolved in 100 mL of toluene.
  • This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 55 ° C. for 24 hours, aged at 10 ° C. for 24 hours, and then 10 g of 10% by weight aqueous sodium carbonate solution. Neutralized to pH 6.8.
  • This emulsion had a non-volatile content (solid content) of 45.4% by mass after drying at 105 ° C. for 3 hours, and the polyorganosiloxane in the emulsion was a non-flowable soft gel.
  • MMA methyl methacrylate
  • silicone acrylic graft copolymer resin emulsion having a nonvolatile content of 44.5% by mass and a pH of 6.8.
  • the emulsion was adjusted to a concentration of 10 to 30% by mass and spray-dried (100 ° C.) to obtain a silicone acrylic graft copolymer resin powder.
  • the obtained silicone acrylic graft copolymer resin had an average particle size of 0.2 ⁇ m and a weight average molecular weight of about 300,000.
  • a silicone acrylic graft copolymer resin was prepared in the same manner as in Production Example 1 except that 55.5 g of MMA was replaced with 611.4 g of MMA, 16.5 g of t-butyl hydroperoxide and 11 g of L-ascorbic acid as a reducing agent were used. Got. The obtained silicone acrylic graft copolymer resin had an average particle size of 0.2 ⁇ m and a weight average molecular weight of about 300,000.
  • Table 1 shows the reaction ratio between polyorganosiloxane and (meth) acrylic acid ester.
  • Examples 1 to 4 Comparative Examples 1 to 4
  • the silicone acrylic graft copolymer resins obtained in Production Examples 1 to 3 and Comparative Production Examples 1 and 2, natural rubber, butadiene rubber, and carbon black are blended in the amounts shown in Table 2, and additives are blended in the amounts described below.
  • anti-vibration rubber compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared.
  • Additives are 3 parts by weight of aroma-based process oil, 5 parts by weight of zinc white 3, 1 part by weight of stearic acid, 2 parts by weight of wax, anti-aging agent N-phenyl-N ′-(1,3-dimethylbutyl)- 2 parts by mass of p-phenylenediamine 6C (manufactured by Ouchi Shinsei Chemical Co., Ltd.), 2 parts by mass of anti-aging agent RD (manufactured by Ouchi Shinsei Chemical Co., Ltd.), 1.5 parts by mass of sulfur, vulcanization accelerator CZ ( 1.5 parts by mass of Ouchi Shinsei Chemical Co., Ltd.) and 0.5 parts by mass of the vulcanization accelerator tetramethylthiuram monosulfide TS (Ouchi Shinsei Chemical Co., Ltd.).
  • the anti-vibration rubber composition was molded into a shape having a through-hole and vulcanized at 150 ° C. for 30 minutes to produce an anti-vibration rubber.
  • a metal stabilizer bar was loaded into the through hole, the vibration-proof rubber was clamped, the stabilizer bar was twisted ⁇ 10 degrees, and the presence or absence of abnormal noise at that time was confirmed in an environment of 25 ° C.

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Abstract

La présente invention concerne une composition de caoutchouc anti-vibration dans laquelle il est possible de réduire le coefficient de frottement de la surface de caoutchouc anti-vibration, et le caoutchouc anti-vibration dans lequel cette dernière est employée. Une composition de caoutchouc anti-vibration caractérisée en ce qu'elle contient (I) 100 parties en masse d'un constituant de caoutchouc, et (II) de 1 à 30 parties en masse d'une résine de copolymère greffée au silicone-acrylique qui est un polymère d'un mélange comprenant de 50 à 99 parties en masse d'un polyorganosiloxane indiqué par la formule générale (1) et de 1 à 50 parties en masse de monomères d'ester d'acide acrylique ou de monomères d'ester d'acide méthacrylique. (R1 est un groupe hydrocarbure monovalent ; R2 est un groupe mercapto, un groupe acryloxy ou un groupe alkyle substitué par un groupe méthacryloxy, ou un groupe vinyle ; X est un groupe hydrocarbure monovalent, un groupe alcoxy, ou un groupe hydroxyle ; Y est X ou -[O-Si(X)2]d-X ; et deux ou plusieurs parmi X et Y sont des groupes hydroxyle. Z est un groupe alkyle, un groupe alcoxy, ou un groupe hydroxyle. a prend la valeur de 0 à 1 000, b la valeur de 100 à 10 000, c la valeur de 1 à 10, et d la valeur de 1 à 1 000.)
PCT/JP2016/077131 2015-10-27 2016-09-14 Composition de caoutchouc anti-vibration et caoutchouc anti-vibration WO2017073194A1 (fr)

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WO2020175300A1 (fr) * 2019-02-28 2020-09-03 日信化学工業株式会社 Composition d'émulsion de résine de silicone (méth)acrylique, agent de traitement de tissu contenant ladite composition et tissu traité avec ledit agent de traitement de tissu
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US20220275134A1 (en) * 2021-02-26 2022-09-01 Nissin Chemical Industry Co., Ltd. Vinyl acetate-silicone copolymer resin and method for producing same

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