WO2005098123A1 - コード被覆用組成物、それを用いたゴム補強用コード、およびそれを用いたゴム製品 - Google Patents
コード被覆用組成物、それを用いたゴム補強用コード、およびそれを用いたゴム製品 Download PDFInfo
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- WO2005098123A1 WO2005098123A1 PCT/JP2005/005564 JP2005005564W WO2005098123A1 WO 2005098123 A1 WO2005098123 A1 WO 2005098123A1 JP 2005005564 W JP2005005564 W JP 2005005564W WO 2005098123 A1 WO2005098123 A1 WO 2005098123A1
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- rubber
- latex
- cord
- mass
- coating
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Classifications
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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
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D115/00—Coating compositions based on rubber derivatives
- C09D115/005—Hydrogenated nitrile rubber
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
- D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- 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
-
- 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
-
- 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
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
Definitions
- the present invention relates to a cord coating composition, a rubber reinforcing cord using the same, and a rubber product using the same.
- a reinforcing material for rubber products such as a rubber belt
- a cord using a reinforcing fiber such as a glass fiber peramide fiber
- toothed belts used for driving camshafts of internal combustion engines of automobiles are required to have high dimensional stability in order to maintain appropriate timing.
- high strength, high strength and high elasticity have been required to drive injection pumps that can be driven not only by camshafts, to transmit power to industrial machines, and to use in applications where power is high and loads are high. .
- Japanese Patent Application Laid-Open No. 63-270877 proposes a composition containing a resorcinol formaldehyde condensate and a tolyl group-containing highly saturated polymer rubber having an iodine value of 120 or less as main components.
- Japanese Patent Application Laid-Open No. 6-212572 proposes a treating agent containing, as main components, a resorcinol-formaldehyde water-soluble condensate and a -tolyl group-containing highly saturated copolymer rubber latex having an iodine value of 120 or less.
- the nitrile group-containing highly saturated copolymer rubber latex is obtained by subjecting a nitrile group-containing unsaturated copolymer obtained by an emulsion polymerization method to hydrogen treatment.
- JP-A-8-120573 discloses a resorcinol-formaldehyde water-soluble condensate, A treating agent containing a -tolyl group-containing highly saturated polymer having a nitrogen value of 120 or less and a methacrylate has been proposed.
- Japanese Patent Application Laid-Open No. 8-333564 proposes an adhesive composition in which resorcinol formaldehyde resin and an aromatic epoxy resin are mixed with a latex of a carboxyl group-containing highly saturated tolyl rubber! You.
- the above-described conventional treatment agent improves the heat resistance of the reinforcing cord.
- the temperature at which rubber belts are used ranges from low to high temperatures. Bending fatigue resistance and dimensional stability at room temperature are also important properties required for reinforcing cords.
- High heat resistance is obtained by using a treating agent containing a -tolyl group-containing highly saturated polymer having an iodine value of 120 or less.
- the conventional treating agent is not sufficiently resistant to a decrease in adhesive strength due to rubbing of the fibers constituting the reinforcing cord and a deterioration due to abrasion.
- the treatment agent using butyl pyridine butadiene styrene terpolymer latex has good bending fatigue resistance and dimensional stability at room temperature, which is strong against abrasion deterioration due to rubbing of fibers constituting the reinforcing cord. It is. However, in a high-temperature atmosphere, the polymer hardens due to thermal degradation, so that the bending fatigue resistance may decrease.
- the cord coating composition of the present invention has a ratio of the latex of the first rubber, the phenol resin, and the water-soluble condensate of resorcinol formaldehyde to the solid content. But,
- the first rubber power is a -tolyl group-containing highly saturated polymer rubber having an iodine value of 120 or less
- the water-soluble condensate is a novolak-type condensate.
- the “solid content” means a component excluding a solvent and a dispersion medium.
- the rubber reinforcing cord of the present invention includes a reinforcing fiber and a coating formed so as to cover the reinforcing fiber, wherein the coating is a coating formed of a cord coating composition.
- the ratio of the latex of the first rubber, the phenol resin, and the water-soluble condensate of resonoresin formaldehyde to the solid content is as follows:
- the first rubber power is a -tolyl group-containing highly saturated polymer rubber having an iodine value of 120 or less, and the water-soluble condensate is a novolak-type condensate.
- the rubber product of the present invention is a rubber product reinforced with the rubber reinforcing cord of the present invention.
- the composition (adhesive) of the present invention By using the composition (adhesive) of the present invention to form a coating of a reinforcing cord, rubber serving as a matrix and the reinforcing cord can be strongly bonded.
- the reinforcing cord covered with the composition has excellent dimensional stability and resistance to bending fatigue at room temperature and high temperature. Therefore, the reinforcing cord of the present invention is suitable for applications in which a bending stress is applied under a wide range of temperature conditions, for example, a reinforcing cord for an automobile timing belt.
- FIG. 1 is a view schematically showing one example of a rubber product of the present invention.
- composition of the present invention for coating a cord comprises a latex of a first rubber, a phenol resin, and a water-soluble condensate of resorcinol formaldehyde, the proportion of which is based on the solid content. 0/0
- the first rubber is a highly saturated polymer rubber having an iodine value of 120 or less and containing a nitrile group (one CN).
- a water-soluble condensate of resorcinol formaldehyde (hereinafter sometimes referred to as “RF condensate”) is a novolak-type condensate.
- the iodine value of the first rubber is 120 or less from the viewpoint of heat resistance of the coating composition.
- the preferred iodine value is 0-100, more preferably 0-50.
- the iodine value is a value obtained in accordance with K0070-1992 of Japanese Industrial Standard (JIS).
- the proportion of the first rubber in the solid content of the coating composition is in the range of 30 to 95% by mass, preferably 40 to 90% by mass, and particularly preferably 60 to 85% by mass. % Range. If the ratio is less than 30% by mass, the heat resistance of the cord is not sufficiently improved. When this proportion exceeds 95% by mass, the relative proportion of the RF condensate, which is an essential component, is reduced, so that the adhesion to rubber is reduced.
- the first rubber latex may be one type of rubber latex or a latex obtained by mixing a plurality of types of rubber latex. The following can be exemplified as the first rubber.
- Hydrogenated butadiene acrylonitrile copolymer rubber isoprene butadiene atari mouth-tolyl copolymer rubber, isoprene acrylonitrile copolymer rubber;
- These rubbers can be obtained by a usual polymerization technique or a usual hydrogenation method.
- One preferred example of the first rubber latex is a hydrogenated-tolyl rubber latex, for example, Zetpol2020 (trade name, iodine value 28) manufactured by Zeon Corporation.
- Phenol resin is an essential component and is added to prevent abrasion deterioration due to rubbing of cords and to improve the adhesive strength of cords.
- the phenol resin of the present invention may be, for example, a phenol resin obtained by reacting phenol with formaldehyde, or a phenol resin obtained by reacting phenols with formaldehyde. You can.
- the phenolic resin may be a novolak-type phenolic resin obtained by reacting phenol or phenols with formaldehyde with an acid catalyst. Further, the phenol resin may be a resol type phenol resin obtained by reacting phenol or phenols with formaldehyde with an alkali catalyst. The use of nopolak-type phenol resin can suppress the generation of alkali components from the phenol resin.
- the proportion of the phenolic resin in the solid content of the coating composition is in the range of 0.01 to 30% by mass, preferably in the range of 0.03 to 20% by mass, for example, 7% by mass. In the range of -20% by mass. If the proportion of phenol ⁇ is less than 0.01 mass 0/0 adhesion to rubber can not be formed with high coating. On the other hand, when the proportion exceeds 30% by mass, the coating formed by the coating composition becomes too hard, and the bending fatigue resistance of the reinforcing cord is reduced.
- the coating composition of the present invention may contain a polyurethane resin, a urea resin, a melanin resin, and an epoxy resin in addition to the phenol resin.
- the RF condensate is an essential component for obtaining adhesiveness to rubber.
- the ratio of the RF condensate to the solid content of the coating composition is in the range of 2 to 15% by mass, and more preferably in the range of 3 to 12% by mass.
- the ratio of the RF condensate is less than 2% by mass, a film having high adhesiveness to rubber cannot be formed.
- the proportion exceeds 15 mass 0/0, the coating becomes too hard to be formed by the coating composition, flexural fatigue resistance of the reinforcing cords is lowered.
- the RF condensate used in the present invention is a novolak-type addition condensate obtained by reacting resorcin and formaldehyde with an acid catalyst.
- a condensate obtained by reacting resorcinol (R) with formaldehyde (F) at a molar ratio of R: F 2: 1 to 1: 3 is preferable.
- a novolak-type RF condensate has a higher degree of polymerization than a resol-type RF condensate, so that a denser film can be formed. Therefore, by using the novolak type R-F condensate, a film having high environmental resistance can be formed.
- the resole type RF condensate has a large number of hydroxyl groups and an alcohol component remains. For this reason, when glass fibers are used as the reinforcing fibers and a resole type RF condensate is used, the glass fibers are easily eroded at high temperatures! / ⁇ . Therefore, when glass fiber is used as the reinforcing fiber, it is particularly important to use a novolak-type RF condensate.
- the composition of the present invention may include a latex of a second rubber different from the first rubber.
- the latex of the second rubber is not essential, but is preferably included when flexibility of the cord or adhesive strength between cord belts is required.
- the ratio of the second rubber to the solid content of the composition is preferably 60% by mass or less, more preferably 50% by mass or less, for example, 5% by mass or less. % By mass-in the range of 50% by mass. If this ratio exceeds 60% by mass, sufficient heat resistance and bending resistance may not be obtained.
- the second rubber latex includes butadiene styrene copolymer latex, dicarboxylated butadiene styrene copolymer latex, butylpyridine butadiene styrene terpolymer latex, isoprene rubber latex, chloroprene rubber latex, chloros It is at least one type of latex selected from the group consisting of rufonated polyethylene latex and acrylonitrile-butadiene copolymer latex having an iodine value of more than 120.
- the coating composition of the present invention may optionally contain a base for adjusting pH, for example, an ammonia. Furthermore, the coating composition of the present invention may contain a stabilizer, a thickener, an anti-aging agent, and!
- the solvent (dispersion medium) of the composition of the present invention is, for example, water, but may contain alcohols such as methanol, ketones such as methylethyl ketone, etc. after being added to water. .
- the viscosity of the composition can be changed depending on the amount of the solvent.
- the composition of the present invention can be prepared by mixing the above components.
- a cord for reinforcing rubber according to the present invention includes a reinforcing fiber and a coating formed so as to cover the reinforcing fiber.
- the coating is a coating formed from the above-described cord coating composition of the present invention.
- the code coating composition has been described above, and a duplicate description will be omitted.
- the mass of the coating is preferably in the range of 5 to 40% of the mass of the reinforcing fiber, and more preferably in the range of 10 to 35%. If the proportion of the coating is too low, the coating amount of the reinforcing cord by the coating becomes insufficient. On the other hand, if this ratio is too high, it is difficult to control the coating amount of the reinforcing cord with the coating, and it is difficult to obtain a uniform coating. It is necessary to appropriately set the amount of the reinforcing cord covered by the coating depending on the type of fiber. For example, in the case of glass fiber, the weight of the coating is preferably in the range of 5 to 35% of the weight of the reinforcing fiber.
- the reinforcing fiber may be at least one kind of fiber selected from the group consisting of glass fiber, aramide fiber and carbon fiber.
- One of these fibers may be used alone, or a plurality of them may be used as a mixture.
- the reinforcing fibers are not limited to these fibers, and other fibers having the necessary strength for reinforcing the rubber product may be used.
- glass fibers are said to have high bending fatigue resistance and high dimensional stability. Have the advantage.
- a novolak type RF condensate formed by an acid catalyst is used, even when glass fibers are used, deterioration of the glass fibers is small.
- the reinforcing fiber may be a bundle of a plurality of filaments.
- the plurality of filaments may or may not be twisted.
- the reinforcing fiber may be a bundle of a plurality of fibers.
- the plurality of fibers may be twisted or untwisted.
- the reinforcing fiber is glass fiber, usually about 50 to 2000 filaments are bundled to form one glass fiber.
- the glass fibers are bundled, for example, one by one and used.
- the coating may be covered with another coating.
- the other coating is formed to enhance the adhesion between the reinforcing cord and the rubber (matrix rubber) reinforced by the reinforcing cord.
- Other coating materials are selected according to the type of the matrix rubber, and known materials can be applied. For example, a composition containing chlorosulfonated polyethylene (CSM) and a crosslinking agent can be applied.
- CSM chlorosulfonated polyethylene
- crosslinking agent can be applied.
- the excess liquid is removed and the surface of the fibers is coated with the composition.
- the solvent is removed from the composition to form a coating covering the fibers.
- the solvent can be removed by any method, for example, natural drying, drying under reduced pressure, drying by heating and the like.
- the reinforcing fibers may be coated with a sizing agent applied during spinning. Further, a pretreatment agent may be applied to the reinforcing fiber in order to improve familiarity with the coating composition or to improve adhesion to the coating composition.
- a desired number of fibers coated with the coating composition are collected and twisted to obtain a reinforcing cord.
- the apparatus used for the joining and twisting of the reinforcing fibers For example, a ring twisting machine, a flyer single twisting machine, a stranded wire machine and the like can be used.
- the number of twists at that time is preferably set according to the fiber used. For example, in the case of a glass fiber cord, a twist number of 0.25 times Z25 mm-10.0 times Z25 mm is preferable.
- twisting may be performed in several times in accordance with the thickness and specifications of the cord. Twisted There is no limitation on the direction.
- the fiber cord In the case of a glass fiber cord, it is preferable to form the fiber cord by dividing the yarn into two stages. More specifically, it is preferable to make a cord by bundling several glass fibers and twisting them together, and obtain a fiber cord by bundling and twisting a few of these cords.
- the rubber product of the present invention is a rubber product reinforced with the rubber reinforcing cord of the present invention.
- rubber products include, but are not limited to, toothed belts, belts such as V-belts, tires, and rubber hoses.
- the reinforcing cord is embedded in the rubber part of the rubber product or is arranged on the surface of the rubber part. There is no particular limitation on the method of arranging the reinforcing cord. For example, after a reinforcing cord is embedded in a rubber part before vulcanization, the rubber part is vulcanized, so that the rubber part is reinforced with the reinforcing cord.
- the rubber in the rubber portion is not particularly limited, and examples thereof include chloroprene rubber, butyl rubber, butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, ethylene propylene rubber, and hyvalon rubber.
- the rubber reinforcing cord of the present invention is preferably used for reinforcing a rubber portion made of hydrogenated-tolyl rubber.
- FIG. 1 schematically shows an example of the toothed belt of the present invention.
- the toothed belt 10 of FIG. 1 includes a rubber portion 11 and a reinforcing cord 12 embedded in the rubber portion. Note that the configuration shown in FIG. 1 is an example, and the present invention is not limited to this.
- Zetpol2020 (iodine value 28) manufactured by Zeon Corporation was used as the nitrile group-containing highly saturated polymer.
- the phenolic resin used was Yukaresin KE912-1 (Novolac type phenolic resin emulsion) from Yoshimura Oil Chemical Co., Ltd.
- the R—F condensate of Example 15 and Comparative Example 14 were obtained by reacting resorcinol and formaldehyde in a 1: 1 molar ratio in the presence of an acid catalyst. Novolak type condensate was used.
- As the RF condensate of Comparative Example 5 a resole type condensate obtained by reacting resorcinol and formaldehyde at a molar ratio of 1: 1 in the presence of an alkali catalyst was used.
- Examples 1 to 5 A filament of non-alkali glass having a diameter of 9 m was spun and bundled with a sizing agent to obtain a glass fiber of 33.7 tex. Three of these glass fibers were combined, impregnated with the coating composition (solid content 30% by mass) shown in Table 1, and further heat-treated to obtain a glass fiber cord.
- the coating composition was composed of aqueous ammonia (NH OH) for pH adjustment and a solvent.
- the coating amount of the coating composition was adjusted such that the weight of the coating formed thereby was 20% of the weight of the glass fiber.
- Table 1 the mass ratio (% by mass) of the solid content is shown together with the amount (parts by mass) of the yarn composition.
- Example 15 the rubber reinforcing cord of Example 15 was produced.
- a second coating composition (liquid) having a composition shown in Table 2 was further applied to the rubber reinforcing cord obtained in Example 1 and dried to obtain a rubber reinforcing cord of Example 6.
- the coating amount (solid content) of the second coating composition on the reinforcing cord was 5% by mass.
- Two matrix rubber sheets (width 10 mm, length 300 mm, thickness lmm) formed with the composition shown in Table 3 below were prepared.
- One reinforcing cord of the example having a length of 300 mm was arranged on one matrix rubber sheet, and another matrix rubber sheet was stacked thereon.
- the rubber sheet was press-vulcanized at 150 ° C for 20 minutes from both the upper and lower surfaces.
- a strip-shaped test piece was prepared.
- the test piece was repeatedly bent by a bending tester, and the resistance to bending fatigue was evaluated.
- the bending test was performed by bending the test piece by reciprocating 20,000 times.
- the bending test was performed in an atmosphere at room temperature and an atmosphere at 140 ° C.
- the tensile strength (per cord) before and after this bending test was measured.
- the ratio of the tensile strength after the test to the tensile strength before the test was calculated as a strength retention (%). The higher the value of the strength retention, the higher the flex fatigue resistance.
- a reinforcing code having a length of 200 mm was arranged on a matrix rubber sheet having the components shown in Table 2 so as to have a width of 25 mm, and was press-vulcanized at 150 ° C for 20 minutes. A test piece was obtained. Next, the matrix rubber force was also measured by peeling off the reinforcing cord and measuring the adhesive strength. The bond strength is the value for a 25 mm wide specimen. Table 4 shows the results of these evaluations. Table 4 also shows the number (mass per 1000 meters) and diameter of the reinforcing cord, and the strength of the reinforcing cord alone.
- Comparative Examples 1 to 5 the reinforcing cord was manufactured in the same manner as in Example 1 except that the coating composition having the composition shown in Table 5 was used instead of the coating composition having the composition shown in Table 1.
- the coating composition having the composition shown in Table 5 was used instead of the coating composition having the composition shown in Table 1.
- the RF condensate a novolak type was used in Comparative Examples 14 to 14, and a resol type was used in Comparative Example 5.
- the reinforcing cords of Comparative Examples 2 and 3 had low strength retention against bending at high temperatures.
- the reinforcing cords of Comparative Examples 1 and 4 had low dimensional stability.
- the reinforcing cord of the present invention had high strength in both resistance to bending fatigue and dimensional stability.
- the reinforcing cord of Comparative Example 5 when the resol type RF condensate was used, the strength retention against bending at high temperatures was low.
- the reinforcing cord of the present invention had high resistance to bending at room temperature and high temperature and high dimensional stability.
- the rubber reinforced with the reinforcing cord of the present invention has high resistance to bending at room temperature and high temperature and has excellent dimensional stability.
- the present invention can be applied to a composition for forming a film of a rubber reinforcing cord, a rubber reinforcing cord, and a rubber product reinforced thereby.
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2558460 CA2558460C (en) | 2004-03-30 | 2005-03-25 | Composition for cord coating, cord for rubber reinforcement made with the same, and rubber product made with the same |
US10/590,926 US20080107913A1 (en) | 2004-03-30 | 2005-03-25 | Composition for Cord Coating, Cord for Rubber Reinforcement Made with the Same, and Rubber Product Made with the Same |
JP2006512034A JP4328354B2 (ja) | 2004-03-30 | 2005-03-25 | コード被覆用組成物、それを用いたゴム補強用コード、およびそれを用いたゴム製品 |
CN2005800099980A CN1938475B (zh) | 2004-03-30 | 2005-03-25 | 软线覆盖用组合物、使用该组合物的橡胶加强用软线以及使用该软线的橡胶制品 |
BRPI0509308A BRPI0509308B1 (pt) | 2004-03-30 | 2005-03-25 | composição para revestir cordonéis, cordonel para reforço de borracha fabricado com o mesmo, e produto de borracha fabricado com o mesmo |
EP20050721491 EP1731657B1 (en) | 2004-03-30 | 2005-03-25 | Composition for cord coating, cord for rubber reinforcement made with the same, and rubber product made with the same |
DE200560026110 DE602005026110D1 (de) | 2004-03-30 | 2005-03-25 | Zusammensetzung für cordbeschichtung, damit hergestellter cord für gummiarmierung und damit hergestelltes gummiprodukt |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004097958 | 2004-03-30 | ||
JP2004-097958 | 2004-03-30 |
Related Child Applications (1)
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US11/519,133 Continuation US7849814B2 (en) | 2004-03-26 | 2006-09-12 | Plasma generating device |
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EP (1) | EP1731657B1 (ja) |
JP (1) | JP4328354B2 (ja) |
KR (1) | KR100804350B1 (ja) |
CN (1) | CN1938475B (ja) |
BR (1) | BRPI0509308B1 (ja) |
CA (1) | CA2558460C (ja) |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1852463A1 (en) | 2006-03-31 | 2007-11-07 | Sumitomo Rubber Industries, Ltd. | Rubber composition for coating cord |
JP2007291349A (ja) * | 2006-03-31 | 2007-11-08 | Sumitomo Rubber Ind Ltd | コード被覆用ゴム組成物 |
JP2013531101A (ja) * | 2010-06-30 | 2013-08-01 | コーロン インダストリーズ インク | タイヤインナーライナ用フィルム及びその製造方法 |
JPWO2014119280A1 (ja) * | 2013-01-30 | 2017-01-26 | 日本板硝子株式会社 | ゴム製品を補強するための炭素繊維コードおよびそれを用いたゴム製品 |
WO2019181654A1 (ja) * | 2018-03-19 | 2019-09-26 | 日本板硝子株式会社 | ゴム補強用コード及びその製造方法、並びにゴム製品 |
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US8596032B2 (en) * | 2009-10-28 | 2013-12-03 | Nisshinbo Textile, Inc. | Core-sheath type conjugated yarn, knitted fabric, clothing product, and method of producing core-sheath type conjugated yarn |
JP5367006B2 (ja) * | 2011-03-31 | 2013-12-11 | ゲイツ・ユニッタ・アジア株式会社 | 摩擦伝動ベルト |
CN103410004B (zh) * | 2013-08-12 | 2015-05-20 | 浙江尤夫科技工业有限公司 | 一种用于改善帘线耐疲劳性能的一浴浸胶液制备方法 |
CN104108564B (zh) * | 2014-08-15 | 2016-03-30 | 兖矿集团有限公司 | 一种煤矿用织物叠层阻燃输送带 |
KR102229134B1 (ko) * | 2020-08-18 | 2021-03-19 | (주)승신건설 | 탄성 및 내충격성이 우수한 보강용 폴리우레탄 조성물 및 이로 형성된 코팅층을 포함하는 건축 및 토목 자재 |
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- 2005-03-25 BR BRPI0509308A patent/BRPI0509308B1/pt active IP Right Grant
- 2005-03-25 KR KR1020067022158A patent/KR100804350B1/ko not_active IP Right Cessation
- 2005-03-25 WO PCT/JP2005/005564 patent/WO2005098123A1/ja active Application Filing
- 2005-03-25 US US10/590,926 patent/US20080107913A1/en not_active Abandoned
- 2005-03-25 CN CN2005800099980A patent/CN1938475B/zh active Active
- 2005-03-25 DE DE200560026110 patent/DE602005026110D1/de active Active
- 2005-03-25 CA CA 2558460 patent/CA2558460C/en not_active Expired - Fee Related
- 2005-03-25 RU RU2006138058A patent/RU2321608C1/ru active
- 2005-03-25 JP JP2006512034A patent/JP4328354B2/ja active Active
- 2005-03-25 EP EP20050721491 patent/EP1731657B1/en active Active
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1852463A1 (en) | 2006-03-31 | 2007-11-07 | Sumitomo Rubber Industries, Ltd. | Rubber composition for coating cord |
JP2007291349A (ja) * | 2006-03-31 | 2007-11-08 | Sumitomo Rubber Ind Ltd | コード被覆用ゴム組成物 |
CN101045840B (zh) * | 2006-03-31 | 2012-08-29 | 住友橡胶工业株式会社 | 用于涂覆帘线的橡胶组合物 |
JP2013531101A (ja) * | 2010-06-30 | 2013-08-01 | コーロン インダストリーズ インク | タイヤインナーライナ用フィルム及びその製造方法 |
JPWO2014119280A1 (ja) * | 2013-01-30 | 2017-01-26 | 日本板硝子株式会社 | ゴム製品を補強するための炭素繊維コードおよびそれを用いたゴム製品 |
US9752649B2 (en) | 2013-01-30 | 2017-09-05 | Nippon Sheet Glass Company, Limited | Carbon fiber cord for reinforcing rubber product and rubber product using the same |
WO2019181654A1 (ja) * | 2018-03-19 | 2019-09-26 | 日本板硝子株式会社 | ゴム補強用コード及びその製造方法、並びにゴム製品 |
JP6603008B1 (ja) * | 2018-03-19 | 2019-11-06 | 日本板硝子株式会社 | ゴム補強用コード及びその製造方法、並びにゴム製品 |
Also Published As
Publication number | Publication date |
---|---|
CN1938475B (zh) | 2011-11-09 |
JP4328354B2 (ja) | 2009-09-09 |
DE602005026110D1 (de) | 2011-03-10 |
BRPI0509308B1 (pt) | 2016-10-04 |
US20080107913A1 (en) | 2008-05-08 |
CA2558460A1 (en) | 2005-10-20 |
KR100804350B1 (ko) | 2008-02-15 |
EP1731657A1 (en) | 2006-12-13 |
EP1731657B1 (en) | 2011-01-26 |
BRPI0509308A (pt) | 2007-09-04 |
KR20060135917A (ko) | 2006-12-29 |
JPWO2005098123A1 (ja) | 2008-07-31 |
RU2321608C1 (ru) | 2008-04-10 |
CN1938475A (zh) | 2007-03-28 |
EP1731657A4 (en) | 2008-03-26 |
CA2558460C (en) | 2009-02-10 |
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