[go: up one dir, main page]

WO2006101228A1 - Composition de caoutchouc et son procede de fabrication - Google Patents

Composition de caoutchouc et son procede de fabrication Download PDF

Info

Publication number
WO2006101228A1
WO2006101228A1 PCT/JP2006/306124 JP2006306124W WO2006101228A1 WO 2006101228 A1 WO2006101228 A1 WO 2006101228A1 JP 2006306124 W JP2006306124 W JP 2006306124W WO 2006101228 A1 WO2006101228 A1 WO 2006101228A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
rubber composition
composition according
compound
fine particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/306124
Other languages
English (en)
Japanese (ja)
Inventor
Yuko Ikeda
Sirilux Poompradub
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyoto Institute of Technology NUC
Original Assignee
Kyoto Institute of Technology NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyoto Institute of Technology NUC filed Critical Kyoto Institute of Technology NUC
Priority to JP2007509363A priority Critical patent/JP4867015B2/ja
Publication of WO2006101228A1 publication Critical patent/WO2006101228A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Definitions

  • the present invention relates to a rubber composition and a method for producing the same. More specifically, it is possible to obtain a rubber material excellent in wear resistance and fatigue resistance, in which hysteresis loss is small and high stress is exhibited from a low strain region even when fine particles such as silica are filled at a high rate.
  • the present invention relates to a rubber composition and a method for producing the same.
  • Silica is known as a typical white filler mixed with rubber. Many silica particles have a large number of silanol groups on their surface, so the agglomeration force between silica particles is strong and the affinity with rubber is weak. For this reason, the simple kneading method is less effective in improving the mechanical properties as compared with the case where the silica particles are filled with carbon black or the like which is difficult to uniformly disperse in the rubber.
  • Patent Document 1 As a method for improving the dispersibility of silica particles in rubber, an in situ sol-gel method has been proposed.
  • Patent Document 1 and Patent Document 2 uncrosslinked rubber is immersed and swollen in a liquid containing an alkoxysilane compound, and the swollen uncrosslinked rubber is immersed in an aqueous catalyst solution to swell.
  • a method is disclosed in which a polycondensate of a hydrolyzate of an alkoxysilane compound is produced in uncrosslinked rubber, and then crosslinked by adding a crosslinking agent. And, by this method, the silica particles are uniformly dispersed in the rubber, and it is easy to obtain a product with an overall stable reinforcing effect! /
  • Patent Document 1 JP-A-9 48880
  • Patent Document 2 Japanese Patent Laid-Open No. 11-335403
  • the present invention can provide a rubber material having a small hysteresis loss and exhibiting a high stress from a low strain region and having excellent wear resistance and fatigue resistance, such as silica.
  • An object of the present invention is to provide a rubber composition in which fine particles are filled at a higher filling rate and in a more uniform dispersion state, and a method for producing the same.
  • the present inventor has found that fine particles such as silica can be produced at a high rate by using a specific amino compound as a catalyst for the hydrolysis reaction of an alkoxysilane compound. It has been found that a rubber composition that can be filled and has excellent dispersibility can be obtained, and when the rubber composition is further crosslinked, mechanical properties of high stress such as low hysteresis loss and low strain are obtained. As a result, it was found that the rubber material is excellent in wear resistance and fatigue resistance. The present invention has been completed based on these findings.
  • the present invention provides an amino compound having a hydrocarbon group having 5 to 15 carbon atoms or a catalyst comprising an amino compound having a water solubility of 0.001 to 34 gZL at 25 ° C. and normal pressure.
  • the rubber composition is obtained by hydrolyzing and polycondensing an alkoxysilane compound contained in rubber.
  • the rubber is impregnated with or mixed with an alkoxysilane compound, and the rubber contains an alkoxysilane compound; the alkoxysilane compound includes 5 to 15 carbon atoms.
  • a method for producing a rubber composition comprising condensing.
  • an amino compound having a hydrocarbon group having 5 to 15 carbon atoms or 25 By generating fine particles in situ using a catalyst that also has an amino compound power of 0.001 to 34 gZL of water solubility at ° C and normal pressure, the fine particles can be uniformly distributed at a high filling rate.
  • a rubber composition filled in the rubber in a state can be obtained.
  • This rubber composition has greatly improved mechanical properties in which the interaction between rubber and fine particles is strong.
  • the rubber composition of the present invention is crosslinked, the hysteresis loss is small and high stress is exhibited from the low strain region when the fine particles such as silica are filled at a high rate. It is suitable as a material for obtaining a rubber material having excellent properties.
  • the fine particles generated in situ may be referred to as in situ silica.
  • FIG. 1 is a diagram showing a stress-strain curve of a rubber sheet produced by hot pressing.
  • FIG. 2 is a diagram showing a stress-strain curve of a crosslinked rubber sheet.
  • FIG. 3 is a diagram showing a hysteresis curve of the rubber sheet obtained in Example 20.
  • FIG. 4 is a diagram showing a hysteresis curve of the rubber sheet obtained in Example 22.
  • FIG. 5 is a diagram showing a hysteresis curve of a rubber sheet obtained in Comparative Example 6.
  • FIG. 6 is a diagram showing transmission electron microscope images of rubber sheets obtained in Examples 1, 2, 4, 5, and 7 and Comparative Examples 1 to 3.
  • FIG. 7 is a diagram showing stress-strain curves of sheets obtained in Example 23 and Comparative Example 7.
  • FIG. 8 is a diagram showing stress-strain curves of sheets obtained in Examples 24 to 26 and Comparative Examples 8 to 10.
  • FIG. 9 is a diagram showing stress-strain curves of the crosslinked bodies obtained in Example 27 and Comparative Example 11.
  • FIG. 10 is a diagram showing hysteresis curves of the crosslinked bodies obtained in Example 27 and Comparative Example 11.
  • FIG. 11 is a graph showing the temperature distribution of dynamic viscoelasticity of the crosslinked bodies obtained in Example 27 and Comparative Example 11.
  • FIG. 12 is a graph showing the temperature dispersion of tan ⁇ of the crosslinked product obtained in Example 27 and Comparative Example 11.
  • FIG. 13 is a diagram showing stress-strain curves of sheets obtained in Examples 20 and 21 and Comparative Examples 12 and 13.
  • E5 Image of transmission electron microscope photograph of Example 5; E4: Image of transmission electron microscope photograph of Example 4; E2: Image of transmission electron microscope photograph of Example 2; E1: Transmission type of Example 1 E7: Image of transmission electron micrograph of Example 7; C1: Image of transmission electron micrograph of Comparative Example 1; C2: Image of transmission electron micrograph of Comparative Example 2; C3: Image of transmission electron micrograph of Comparative Example 3;
  • the rubber composition of the present invention includes an amino compound having a hydrocarbon group having 5 to 15 carbon atoms or a catalyst comprising an amino compound having a solubility in water at 25 ° C and normal pressure of 0.001 to 34 gZL.
  • an alkoxysilane compound contained in rubber is hydrolyzed and polycondensed.
  • the rubber used in the present invention is not particularly limited as long as it has rubber elasticity; is natural rubber (NR); isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber ( Gen-based synthetic rubbers such as SBR), acrylonitrile-butadiene copolymer rubber (NBR), black-prene rubber (CR), hydrogenated tolyl rubber (hydrogenated NBR); butanolate rubber (IIR), ethylene propylene copolymer rubber (EPM) Olefin-based rubbers such as ethylene-propylene-gene terpolymer rubber (EPDM); 1,2-polybutadiene; trans-polyisoprene; chlorosulfonated polyethylene rubber; fluororubber (FKM); silicone rubber (VMQ, FVMQ) Epoxychlorohydrin rubber (CO, ECO); Polysulfide rubber (T); Urethane rubber (U); Acrylic rubber (ACM); Ester rubber,
  • thermoplastic elastomer can be used. These may be used alone or in combination of two or more.
  • synthetic rubbers suitable for industrial mass production particularly to synthetic rubbers such as IR, and therefore, synthetic rubber materials with excellent wear resistance and fatigue resistance. Can be produced in large quantities.
  • the rubber is not limited to a solid state, and includes a latex in which rubber particles are emulsified and dispersed in water, a rubber solution in which rubber is dissolved in a solvent, and a liquid rubber.
  • the rubber may be uncrosslinked or crosslinked. Even a mixture of them.
  • the alkoxysilane compound used in the present invention is not particularly limited as long as it produces and precipitates fine particles such as silica by a hydrolysis reaction.
  • the alkoxy group constituting the alkoxysilane include a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, Examples thereof include a phenoxy group.
  • the alkoxysilane compound used in the present invention is one in which one or more alkoxy groups are added to silane.
  • silane is preferred.
  • monoalkoxysilane or dialkoxysilane is used, it is preferably used in combination with one having a trifunctional or higher functional alkoxysilyl group.
  • alkoxysilane compound examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetraphenoxysilane.
  • various alkyl alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyljetoxysilane, and various aromatic alkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane.
  • alkoxysilane compounds can be used alone or in combination of two or more. Of these, tetraethoxysilane is preferred from the standpoints that it is excellent in action and effect, has a moderately low hydrolysis reactivity and is easy to handle during production.
  • the alkoxysilane compound is impregnated or mixed with rubber. Therefore, it is contained in rubber.
  • This mixing includes mixing an alkoxysilane compound with a solution in which rubber is dissolved in an organic solvent or latex in which rubber is dispersed in water.
  • the alkoxysilane compound may be used by dissolving it in an organic solvent.
  • the organic solvent in which the alkoxysilane compound is dissolved is not particularly limited. Examples include dioxane, acetone, chloroform, n-hexane, and petroleum ether. These may be used alone or in combination of two or more.
  • the silane coupling agent has a function of controlling the particle size and dispersibility of the fine particles produced by hydrolysis and the interaction with rubber, and it can reduce the mechanical properties to low strain region force and high stress. Since it can be used, it is preferably used.
  • the filler is preferably used because it has an effect to improve the mechanical properties of the rubber.
  • silane coupling agents include silane compounds such as mercaptosilanes, bursilanes, methacryloxysilanes, aminosilanes, glycidoxysilanes, and tetrasulfide silanes.
  • bis (3-triethoxysilylpropyl) disulfide bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylpropyl) tetrasulfide
  • Sulfid type silanes such as bis (3-triethoxysilylpropyl) polysulfide
  • mercaptosilanes such as 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane
  • 3 Aminopropyltriethoxysilane, 3-aminopropyl Aminosilanes such as rutrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane; glycidoxysilanes
  • the silane coupling agent to be used is appropriately selected in consideration of the type of rubber and the crosslinking system.
  • mercaptosilanes, vinyl silanes, or methacryloxysilanes are suitable for peroxide-crosslinked rubbers
  • sulfide-type silanes or mercaptosilanes are suitable for sulfur vulcanized rubbers. Is preferred.
  • the amount of the silane coupling agent is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, particularly preferably 1 to: LO parts by weight with respect to 100 parts by weight of the rubber. is there. If the content is too small, the wear resistance tends to be low, as the coupling effect is not sufficient. On the other hand, if the amount is too large, the processability tends to be deteriorated because a sufficient additive effect cannot be obtained.
  • the filler there are a filler made of inorganic fine particles and a filler made of organic fine particles, and among these, a filler also having an inorganic fine particle force is preferably used.
  • Inorganic fine particles include carbon black; clay; acid aluminum, titanium oxide, zinc oxide, calcium oxide, magnesium oxide; magnesium carbonate, calcium carbonate, zinc carbonate; hydroxide, aluminum, hydroxide, magnesium. ; Cation-based particles other than fine particles obtained by hydrolysis.
  • Examples of the organic fine particles include polystyrene resin particles, acrylic resin particles, and silicone resin particles. Of these, carbon black or cage-based particles other than fine particles obtained by hydrolysis are preferably used.
  • Carbon black is appropriately selected according to the use of the rubber material.
  • examples of carbon black include SAF, ISAF, HAF, FEF, GPF, and SRF.
  • HAF, ISA F and SAF type carbon blacks are preferably used in pneumatic tires and in particular pneumatic tire thread strip applications.
  • the amount of carbon black is preferably 1 to 200 parts by weight, more preferably 1 to 150 parts by weight, and particularly preferably 1 to: LOO parts by weight with respect to 100 parts by weight of rubber.
  • Examples of key particles other than fine particles obtained by hydrolysis include commercially available general-purpose silica VN-3 (Tosoichi), RS-150 (Tosoichi), Perkasil KS 430 (AKZO), BV 3380 and Ultrasil 7000 (Degussa), Zeosil 1165 MP and 1115 MP (Rhodia), Hi-Sil 2000 (PPG), Zeopol 8715, 8741 or 8745 (Huber) and treated precipitated silica such as EP-A-0 735 088 Examples include silica “doped” with aluminum as described in 1.
  • the Ca-based particles other than the fine particles obtained by hydrolysis are, for example, in the form of a composite or mixed oxide with an oxide such as Al, Mg, Ca, Ba, Zn, Zr, and Ti.
  • an oxide such as Al, Mg, Ca, Ba, Zn, Zr, and Ti.
  • the amount of silica particles other than fine particles obtained by hydrolysis is usually 1 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of rubber.
  • the catalyst used in the present invention is an amino compound.
  • the amino compound constituting the catalyst has a hydrocarbon group having 5 to 15 carbon atoms, preferably 6 to 8 carbon atoms, or has a solubility in water at 25 ° C and normal pressure of 0.001 to 34 gZL. , Preferably 0.1 to 20 gZL, more preferably 0.1 to 15 gZL.
  • an amino compound having a carbon number or solubility in water within the above range is used, in situ silica can be filled in rubber at a high rate in a short time and can be uniformly dispersed.
  • the number of hydrocarbon groups bonded to nitrogen is not particularly limited, but monoamines are preferable because they have a high effect of hydrolysis and handleability.
  • An amino compound having a hydrocarbon group with a large number of carbon atoms tends to be poorly soluble in water, so in that case, the solubility is relatively high!
  • Diamine or ammonium salt type compounds may be used!
  • amino compound used in the present invention examples include primary amine RNH, secondary amine RR 'NH,
  • Tertiary amines RR, R, N, tertiary ammonium salts RR, R, N +, quaternary ammonium salts RR'R "R", N + and the like Primary amines are preferred in the present invention.
  • amino compounds include aliphatic amino compounds having a long-chain hydrocarbon group such as n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and the like; alicyclic aminoamines such as cyclohexylamine Compound: aromatic aromatic amino compounds having an aromatic ring such as a phosphorus.
  • n-hexylamine in which n-hexylamine (12 gZL), n-heptylamine (6.79 gZL), or n-octylamine (0.2 gZL) is more preferred, is preferred.
  • Figures in parentheses are water solubility at 25 ° C and normal pressure.
  • the catalyst having an amino compound strength may be used as it is, or may be used by dissolving in water V, or may be used by dissolving in a mixed solvent of water and an organic solvent!
  • the rubber is impregnated with an alkoxysilane compound! / ⁇ is mixed and the rubber contains an alkoxysilane compound; the alkoxysilane compound has 5 or more carbon atoms.
  • Hydrolysis in rubber in the presence of an amino compound having 15 or less hydrocarbon groups or a catalyst composed of an amino compound having a solubility in water at 25 ° C and atmospheric pressure of 0.001 to 34 gZL. It is the method of including.
  • a more specific embodiment of the method for producing the rubber composition of the present invention includes the following method.
  • the rubber is immersed in a liquid alkoxysilane compound or an alkoxysilane compound solution for a predetermined time to swell the rubber and contain the alkoxysilane compound in the rubber. Then, the swollen rubber is immersed in a catalyst solution, the rubber is contained in the catalyst, and alkoxysilane is added. The compound is hydrolyzed and polycondensed to produce fine particles such as silica in the rubber. Then, if necessary, a rubber material in which in situ silica is dispersed and filled can be obtained by removing the unreacted alkoxysilane compound and the like by performing treatment such as air drying and vacuum heat drying. Furthermore, it can be cross-linked as necessary.
  • Rubber is kneaded with a mixer or the like, and the kneaded rubber is mixed with an alkoxysilane compound, a catalyst, and other compounding agents, and the alkoxysilane compound is hydrolyzed in the rubber. Generates fine particles such as silica. If necessary, treatment such as air drying or vacuum heat drying is performed to remove unreacted alkoxysilane compounds and the like, whereby a rubber material in which in situ silica is dispersed and filled can be obtained. Furthermore, it can be cross-linked as necessary.
  • the temperature condition for performing the hydrolysis and polycondensation by causing the catalyst to act is not particularly limited, but is preferably 30 ° C to 50 ° C, most preferably around 40 ° C. In other words, if the temperature is too low, the amount of silica that reacts slowly tends to decrease. If the temperature is too high, a large amount of silica is deposited on the surface of the rubber material, which may cause a problem in the surface condition.
  • a solid uncrosslinked rubber is passed through two rolls to form a sheet having a thickness of about 0.5 to 2 mm (preferably about 1 mm). Molding to obtain an uncrosslinked rubber sheet.
  • This uncrosslinked rubber sheet is immersed in an alkoxysilane compound (eg, tetraethoxysilane [sometimes abbreviated as TEOS]) at about 40 ° C. for 0.5 to 2 hours, and then TEOS is added. Cool to room temperature and continue to immerse for more than 10 hours, swell the uncrosslinked rubber sheet with TEOS, and incorporate TEOS into the rubber sheet.
  • an alkoxysilane compound eg, tetraethoxysilane [sometimes abbreviated as TEOS]
  • the swollen uncrosslinked rubber sheet is immersed in a solution of a catalyst having an amino compound (for example, n-hexylamine) having a hydrocarbon group having 5 to 15 carbon atoms at about 40 ° C for several tens of hours. To do. By this operation, the alkoxysilane compound is hydrolyzed and polycondensed by the catalyst to produce fine particles such as silica in the rubber (ie, in situ).
  • a catalyst having an amino compound for example, n-hexylamine
  • the alkoxysilane compound is hydrolyzed and polycondensed by the catalyst to produce fine particles such as silica in the rubber (ie, in situ).
  • the rubber composition obtained as described above may be directly molded into a desired shape by a known method, or a cross-linked rubber or vulcanizing agent may be mixed and cross-linked to obtain a cross-linked rubber.
  • crosslinking agent or vulcanizing agent examples include vulcanizing agents that form sulfur bonds such as sulfur, sulfur chloride, and organic sulfur-containing compounds; benzoyl peroxide, dicumyl peroxide, di-ter t-butyl peroxide, tert Butyl Tamyl Peroxide, Methyl Ethyl Ketone Peroxide, Cumene Hydride Peroxide, 2, 5 Dimethyl-2,5 Di (tert-butylberoxy) hexane, 2,5 Dimethyl-2,5 Di (Benzyl Peroxy) ) Hexane, 2,5 Dimethyl-2,5 Di (tert-butylperoxy) hexyne-3, or 1,3-bis (tert-butylenoperoxypropynole) benzene, di-tert-butylenoperoxydiisopropylbenzene, tert-butinoleper Oxybenzene, 2,4-dichlorobenzoyl
  • a vulcanization accelerator or a vulcanization acceleration aid for accelerating the crosslinking or vulcanization reaction rate.
  • Vulcanization accelerators include: zinc dimethyldithiocarbamate, zinc jetyldithiocarbamate, zinc butyldithiocarbamate, ethylphenol dithiocarbamate Dithiocarbamates such as zinc oxide, copper dimethyldithiocarbamate; thiurams such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, tetramethyl thiuram monosulfide; N Sulfenamides such as 2-cyclohexyl lu 2-benzodithidyl sulfenamide, N, N'-dicyclohexyl 2-benzothia zolyl sulfenamide, N-tert butyl 2-benzothiazolyl sulfenamide And thiazonores such as dibenzothiazyl disulfide and mercaptobenz
  • the vulcanization acceleration aid metal oxides, fatty acids, amines and the like can be used.
  • the rubber composition of the present invention can be crosslinked or vulcanized according to a known method.
  • Uncrosslinked NR (RSS No. 1) was passed through two rolls to obtain an uncrosslinked NR sheet having a thickness of about 1 mm.
  • the swollen uncrosslinked NR sheet was taken out from the TEOS, and the surface was lightly wiped with a filter paper.
  • the swelling degree of the swollen uncrosslinked NR sheet was about 345 370%.
  • a rubber sheet was obtained in the same manner as in Example 1 except that the concentration of the aqueous catalyst solution and the type of amino compound constituting the catalyst were changed to the formulation shown in Table 1. The results are shown in Table 1.
  • the amino compounds used are all reagents with a purity of 95% or more.
  • Example 6 Same as Example 1 except that the concentration of the aqueous catalyst solution and the type of amino compound constituting the catalyst were changed to the formulation shown in Table 1, and the vacuum drying was changed to 40 ° C and 80 ° C in Example 6 and Comparative Example 4. Thus, a rubber sheet was obtained.
  • the results are shown in Table 1.
  • the amino compounds used in Examples 6 and 7 are reagents with a purity of 95% or more.
  • the cetylamine used in Comparative Example 4 has a purity higher than 95%.
  • cetylamine which has a hydrocarbon group with more than 15 carbon atoms or has a solubility in water at 25 ° C normal pressure of 0.
  • the reaction proceeded in a state where it floated unevenly in low water, and the total content was relatively large, but more silica was produced on the surface.
  • the amount produced was less than that of n-hexylamine, n-heptylamine and n-octylamine.
  • Example 7 the average particle size of in situ silica was determined from transmission electron micrographs.
  • the average particle size of the high content of in situ silica used for transmission electron microscope observation was approximately the same, 45 to 46 nm.
  • a rubber sheet was obtained in the same manner as in Example 6 except that the reaction time was 24 hours according to the formulation shown in Table 2. The results are shown in Table 2.
  • NR uncrosslinked NR
  • RSS No. 1 100 parts by weight of uncrosslinked NR (RSS No. 1) is blended with bis (3-triethoxysilylpropyl) polysulfide [Daiso Cabras 4, hereinafter referred to as “TESPT”] in the amount shown in Table 3.
  • TESPT bis (3-triethoxysilylpropyl) polysulfide
  • Thinning was performed with two rolls to obtain an NR sheet having a thickness of about 1 mm. After immersing this NR sheet in TEOS at 40 ° C for 1 hour, cool the TEOS to 25 ° C and continue further immersion at 25 ° C for 16 hours to swell the NR sheet with TEOS. TEO S was added to The swollen NR sheet was taken out from the TEOS, and the surface was lightly wiped with a filter paper.
  • the swollen NR sheet was immersed for 24 hours in an aqueous catalyst solution of n-xylamine having a concentration of 0.064 mol ZL maintained at 40 ° C.
  • the rubber sheet was taken out from the catalyst aqueous solution and dried under reduced pressure at 40 ° C. and further at 80 ° C. until a constant weight was obtained.
  • a rubber sheet in which in situ silica was dispersed and filled in the rubber was obtained.
  • the silica filling amount and particle size in this rubber sheet were determined, and the results are shown in Table 3.
  • the in situ silica content tended to increase as the TESPT content increased.
  • An NR sheet with a thickness of about lmm mixed with the amount of TESPT or butortris (2-methoxyethoxy) silane (shown as VTM ES in the table) in the amount shown in Table 4 was kept at 40 ° C at a concentration of 0.064 mol / L.
  • a rubber sheet was obtained in the same manner as in Example 13 except that it was immersed in an aqueous catalyst solution having n-hexylamine power for 72 hours. The results are shown in Table 4. System force using TESPT The in-situ silica content and particle size were slightly increased.
  • a rubber sheet was obtained in the same manner as in Example 15 except that the formulation shown in Table 5 was used. The results are shown in Table 5.
  • the in-situ silica content of the system containing the same amount of TESPT was strongly recognized with no significant difference between n-xylamine, n-heptylamine and n-octylamine.
  • FIG. 7 shows the tensile test results of the sheets obtained in Example 23 and Comparative Example 7.
  • FIG. 8 shows the results of the bow I tension test (room temperature, bow I tension speed lOOmmZ min.) Of the sheets obtained in Examples 24-26 and Comparative Examples 8-10.
  • a comparative crosslinked product was obtained with the same composition and processing conditions as in Example 27 except that 71 parts by weight of commercially available silica (VN-3) was kneaded with 100 parts by weight of NR rubber.
  • the network chain density is 7.6 X 10 " 5 mol / c It was m 3.
  • Fig. 9 (1) shows the stress-strain curve (room temperature, tensile rate of 20 mmZ) of the crosslinked product obtained in Example 27.
  • the stress-strain curve of the comparative crosslinked product obtained in Comparative Example 11 is shown in FIG. 9 (2).
  • the in-situ silica-filled NR crosslinked product had a stress immediately after stretching smaller than that of the comparative sample, and the stress increased with elongation.
  • Rubber filled with a high content of insitu silica is obtained by a master notch by a dilution method.
  • FIG. 13 shows the stress-strain curves of Example 20 and Comparative Example 12 (room temperature, tensile speed of lOOmmZ). It can be seen that the cross-linked sheet obtained in Example 20 shows higher stress in the low strain region force than in Comparative Example 12.
  • FIG. 13 shows the stress-strain curves of Example 21 and Comparative Example 13. It can be seen that the cross-linked sheet obtained in Example 21 exhibits a high stress from the low strain region as compared with Comparative Example 13.
  • the present invention is not limited to the above-described embodiments.
  • the catalyst amount, treatment temperature, reaction time, etc. can be changed as appropriate.
  • the amount of packing and the particle size can be adjusted by increasing the amount of catalyst, increasing the treatment temperature, or extending the reaction time.
  • the present invention has the following effects.
  • a large amount of fine particles such as silica can be filled in the rubber.
  • Such a rubber composition can be produced in a short time.
  • Fine particles of lOOnm or less can be uniformly dispersed in the rubber.
  • the content of silica-based fine particles can be varied over a wide range by the master notch method by dilution.
  • Hysteresis loss, dynamic elastic modulus, hardness, stress immediately after elongation is low and stress from the low strain region (strain of about 2) is high compared to the silica kneaded product even if the silica fine content is high
  • the rubber material obtained by the present invention has the above-described effects, for example, vibration-proof rubber, rubber balls, conveyor belts, oil fences, various tires, casters, rollers, sheets, belts, hoses are used. Suitable for so-called light rubber applications in general, such as rubber tiles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

Composition de caoutchouc présentant des pertes par hystérésis réduites, des contraintes élevées même dans une zone de faible déformation, et pouvant donner un caoutchouc avec une excellente résistance à l’usure et à la fatigue. La composition est chargée de fines particules, par ex. de silice, dans une proportion plus élevée et dispersés de manière plus uniforme. Un caoutchouc est imprégné ou mélangé avec un composé d’alcoxysilane. De préférence, en plus du composé d’alcoxysilane, on incorpore également au caoutchouc un agent réticulant, un agent de couplage à base de silane et/ou des charges. Le composé d’alcoxysilane est hydrolysé dans le caoutchouc en présence d’un catalyseur comprenant soit un composé amino ayant un groupe hydrocarboné en C5-15, soit un composé amino ayant une solubilité dans l’eau à 25°C et sous pression normale de 0,001-34 g/L. On obtient ainsi une composition de caoutchouc chargée de particules de silice en grande proportion. Cette composition de caoutchouc est moulée et réticulée pour obtenir un objet réticulé.
PCT/JP2006/306124 2005-03-25 2006-03-27 Composition de caoutchouc et son procede de fabrication Ceased WO2006101228A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007509363A JP4867015B2 (ja) 2005-03-25 2006-03-27 ゴム組成物及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005088412 2005-03-25
JP2005-088412 2005-03-25

Publications (1)

Publication Number Publication Date
WO2006101228A1 true WO2006101228A1 (fr) 2006-09-28

Family

ID=37023874

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/306124 Ceased WO2006101228A1 (fr) 2005-03-25 2006-03-27 Composition de caoutchouc et son procede de fabrication

Country Status (2)

Country Link
JP (1) JP4867015B2 (fr)
WO (1) WO2006101228A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120067249A1 (en) * 2009-04-29 2012-03-22 Henkel Ag & Co. Kgaa Moisture curable polydisulfides
JP2013170268A (ja) * 2012-02-23 2013-09-02 Tokai Rubber Ind Ltd 防振ゴム組成物および防振ゴム部材
JP2015040303A (ja) * 2013-08-20 2015-03-02 ハンコック タイヤ カンパニー リミテッド タイヤトレッド用ゴム組成物及びこれを用いて製造したタイヤ
JP2015514843A (ja) * 2012-04-18 2015-05-21 株式会社ブリヂストン シリカ含有ゴム配合物の製造方法
JPWO2016021448A1 (ja) * 2014-08-07 2017-05-25 バンドー化学株式会社 コンベヤベルト、コンベヤベルトの製造方法、及び、ゴム組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733910A (ja) * 1992-09-10 1995-02-03 Nippon Zeon Co Ltd 金属酸化物含有重合体組成物の製造方法および金属酸化物含有重合体組成物
JPH09302152A (ja) * 1996-05-08 1997-11-25 Sumitomo Rubber Ind Ltd ゴム製品の製造方法
JPH1180377A (ja) * 1997-09-04 1999-03-26 Sumitomo Rubber Ind Ltd ゴム製品の製造方法
JPH11335403A (ja) * 1998-05-26 1999-12-07 Tokai Rubber Ind Ltd ゴム製品の製法およびそれに用いるゴム組成物
JPH11335493A (ja) * 1998-05-26 1999-12-07 Tokai Rubber Ind Ltd ゴム製品の製法
JP2000053806A (ja) * 1998-08-11 2000-02-22 Sumitomo Rubber Ind Ltd ゴム組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3363300B2 (ja) * 1995-05-31 2003-01-08 住友ゴム工業株式会社 ゴム組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733910A (ja) * 1992-09-10 1995-02-03 Nippon Zeon Co Ltd 金属酸化物含有重合体組成物の製造方法および金属酸化物含有重合体組成物
JPH09302152A (ja) * 1996-05-08 1997-11-25 Sumitomo Rubber Ind Ltd ゴム製品の製造方法
JPH1180377A (ja) * 1997-09-04 1999-03-26 Sumitomo Rubber Ind Ltd ゴム製品の製造方法
JPH11335403A (ja) * 1998-05-26 1999-12-07 Tokai Rubber Ind Ltd ゴム製品の製法およびそれに用いるゴム組成物
JPH11335493A (ja) * 1998-05-26 1999-12-07 Tokai Rubber Ind Ltd ゴム製品の製法
JP2000053806A (ja) * 1998-08-11 2000-02-22 Sumitomo Rubber Ind Ltd ゴム組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120067249A1 (en) * 2009-04-29 2012-03-22 Henkel Ag & Co. Kgaa Moisture curable polydisulfides
JP2013170268A (ja) * 2012-02-23 2013-09-02 Tokai Rubber Ind Ltd 防振ゴム組成物および防振ゴム部材
JP2015514843A (ja) * 2012-04-18 2015-05-21 株式会社ブリヂストン シリカ含有ゴム配合物の製造方法
JP2015040303A (ja) * 2013-08-20 2015-03-02 ハンコック タイヤ カンパニー リミテッド タイヤトレッド用ゴム組成物及びこれを用いて製造したタイヤ
JPWO2016021448A1 (ja) * 2014-08-07 2017-05-25 バンドー化学株式会社 コンベヤベルト、コンベヤベルトの製造方法、及び、ゴム組成物

Also Published As

Publication number Publication date
JPWO2006101228A1 (ja) 2008-09-04
JP4867015B2 (ja) 2012-02-01

Similar Documents

Publication Publication Date Title
CN102341471B (zh) 用于对于固化橡胶的改进的金属粘合性和金属粘合保持性的氨基烷氧基改性的硅倍半氧烷粘合剂
JP3826301B2 (ja) 改質炭酸カルシウム及びこれを含むポリマー組成物並びにそれらの製造方法
RU2485148C2 (ru) Смеси на основе бутилового каучука, содержащие трехкомпонентную смешанную систему модификаторов
JP5830950B2 (ja) ゴム組成物およびこれを用いるスタッドレスタイヤ
EP3372638A1 (fr) Composition de caoutchouc et pneu
EP1111004A1 (fr) Composées de butylène élastomères avec liaison chimique entre elastomère de butyl et charge améliorée
JP4157608B2 (ja) ゴム組成物
JP2009262835A (ja) タイヤ
JP2010241983A (ja) ゴム組成物の製造方法
US10899778B2 (en) Silane compound, rubber composition and tire
CN107735443B (zh) 含白色填料的可用胺交联的橡胶组合物
TW542850B (en) Surface-modified siliceous fillers and their use
JP2010185053A (ja) タイヤ
CN1685017A (zh) 沉淀碳酸钙填料的处理方法
CA2393927A1 (fr) Melanges de caoutchouc contenant du butene-1,4-diol (polyether)
WO2006101228A1 (fr) Composition de caoutchouc et son procede de fabrication
JP2011079978A (ja) 変性ジエン系ゴムおよびゴム組成物
JP3583601B2 (ja) 架橋可能なゴム組成物、及びその架橋ゴム弾性体
JP5598365B2 (ja) 変性ジエン系ゴムの製造方法
US11111338B2 (en) Terminal-functionalized polymer and related methods
JP2001192454A (ja) オルガノポリシロキサン、ゴム用配合剤及びそれを用いたゴム組成物並びにタイヤ
JP2008001742A (ja) 空気入りタイヤ
JP2010059411A (ja) シリカ充填ゴムにおける揮発性有機化学物質の発生が少ないアミノアルコキシ変性シルセスキオキサン類
JP6577136B2 (ja) 効率が高められた脱硫剤
JP4687056B2 (ja) 補強性粒子の製造方法、重合体組成物及びその製造方法並びに加硫性ゴム組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2007509363

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06730072

Country of ref document: EP

Kind code of ref document: A1