WO2006078013A1 - ゴム補強用ポリエステル繊維コードおよびその製造方法 - Google Patents
ゴム補強用ポリエステル繊維コードおよびその製造方法 Download PDFInfo
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- WO2006078013A1 WO2006078013A1 PCT/JP2006/300949 JP2006300949W WO2006078013A1 WO 2006078013 A1 WO2006078013 A1 WO 2006078013A1 JP 2006300949 W JP2006300949 W JP 2006300949W WO 2006078013 A1 WO2006078013 A1 WO 2006078013A1
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- Prior art keywords
- polyester fiber
- rubber
- adhesive
- fiber cord
- cord
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Classifications
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/48—Tyre cords
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0042—Reinforcements made of synthetic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
- B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- 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
-
- 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
-
- 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
- D06M15/55—Epoxy resins
-
- 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
- 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
- D06M2101/32—Polyesters
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
Definitions
- Polyester fiber cord for rubber reinforcement and method for producing the same
- the present invention relates to a rubber fiber-reinforced polyester fiber cord used for tires, hoses and belts, and a method for producing the same. More specifically, it is a polyester fiber cord for reinforcing rubber that has remarkably improved heat-resistant adhesion and heat-resistant strength retention when exposed to a high temperature in rubber during a rubber vulcanization process or during product use.
- the present invention relates to a rubber fiber-reinforced polyester fiber cord suitable for a radial tire cap ply cord and a method for producing the same.
- Polyester fibers have excellent strength, elastic modulus, and thermal dimensional stability, and thus have conventionally been widely used as reinforcing materials for rubber products such as tires, hoses, and belts.
- polyester fiber When polyester fiber is used as a reinforcing material embedded in rubber products, it deteriorates under high temperature conditions. The chemical thermal degradation is affected by various additives that are blended in the rubber itself and in the rubber.
- the rubber contains a vulcanization accelerator such as thiuram, sulfenamide, or guadin, an anti-aging agent, and polyester fibers that have been subjected to high-temperature treatment in the rubber are mainly used.
- polyester fiber When a polyester fiber is decomposed by amine or hydrolyzed, a decrease in strength caused by molecular chain breakage results in a decrease in adhesion between rubber and the fiber layer.
- polyester fiber when polyester fiber is used as a rubber reinforcing fiber, it has disadvantages, but it has high strength, high elastic modulus, excellent thermal dimensional stability, and improved fatigue resistance and adhesion.
- it has recently been used as the carcass material for most passenger car radial tires.
- the heat generated during high-speed driving of the tire It is currently used only for carcass materials for passenger cars with relatively small tire sizes that are difficult to resist and chemically deteriorate. Only a small part is used for large tires such as trucks and buses.
- polyester fiber cords are not used for trucks, bus tires, aircraft tires, large passenger car tires and racing car tires.
- Cap ply cords have been used to keep tension on the belt. Since the cap ply cord generates heat more than the carcass part and becomes high temperature, nylon 66 fiber, which is unusable with conventional polyester cords and has excellent adhesion at high temperatures, is used!
- the cap ply cord has a high elastic modulus as a characteristic, it is preferable to use polyester fiber as the fiber material, and the price of the polyester fiber may be low.
- polyester fiber cords that can be used as In order to achieve this, first of all, great improvement in heat-resistant adhesiveness and improvement in heat-resistant strength retention are required.
- Patent Documents 1 to 4 are disclosed as techniques for improving the heat-resistant adhesion of polyester fibers.
- Patent Document 1 describes that a linear aromatic polyester pretreated with a polyepoxide compound is treated with a first treating agent containing a polyepoxide compound and N-methoxymethyl nylon, and then resorcin 'formalin' latex. Discloses a method for treating a polyester fiber treated with a second treating agent comprising an ethylene urea compound and a cresol novolac epoxy compound.
- Patent Document 2 includes treating a linear aromatic polyester fiber with a pretreatment agent including a polyepoxide compound and water-soluble nylon, and then including a polyepoxide compound, a blocked isocyanate compound and a rubber latex. There is disclosed a method for treating a polyester fiber, which is treated with a first treating agent and further treated with resorcin 'formalin' rubber latex with a second treating agent comprising the above-described ethylene urea compound and phenol novolac type epoxy compound.
- Patent Document 3 linear aromatic polyester fibers are treated with a pretreatment agent containing a cresol novolac type epoxy compound and a water-soluble nylon, and then a polyepoxide compound, a blocked isocyanate compound, and The polyester fiber is treated with a first treating agent containing rubber latex, and then treated with a second treating agent comprising the above-mentioned ethylene urea compound and phenol novolac epoxy compound on resorcin / formalin / rubber latex. Disclosure.
- linear aromatic polyester fibers are treated with a pretreatment agent containing an ethylene urea compound and water-soluble nylon, and then treated with a first treatment agent containing an epoxy compound and a rubber latex. Furthermore, a method for treating a polyester fiber is disclosed in which resorcinol / formalin / latex is treated with a second treating agent having the above-mentioned ethylene urea compound and phenol novolac type epoxy compound.
- Patent Document 1 differs in that pretreatment is performed in advance using a pretreatment agent, but pretreatment is not necessary in the present invention, and that the first treatment agent composition does not include the polyvinyl alcohol used in the present invention. .
- Patent Document 2 also differs in that it is pretreated with a pretreatment agent in advance, but pretreatment is not required in the present invention, and that the adhesive composition does not include polybulal alcohol used in the present invention.
- Patent Document 3 and Patent Document 4 are also clearly different techniques, differing in the necessity of a pretreatment agent and not including polyvinyl alcohol, as in the relationship between Patent Document 2 and the present invention.
- Patent Document 1 JP-A 62-21875
- Patent Document 2 Japanese Patent Laid-Open No. 62-27089
- Patent Document 3 Japanese Patent Application Laid-Open No. 62-276083
- Patent Document 4 Japanese Patent Laid-Open No. 62-276084
- the object of the present invention is to improve the heat-resistant adhesion between the polyester fiber and the rubber when exposed to a high temperature and to improve the heat-resistant and strong holding property, which has not been achieved by the above-described conventional technology. It is a polyester fiber cord for reinforcement, and particularly a polyester fiber cord for rubber reinforcement suitable for a cap ply cord of a radial tire and a method for producing the same.
- the rubber fiber-reinforced polyester fiber cord of the present invention mainly has the following configuration. That is, a polyester fiber cord for rubber reinforcement having two adhesive layers, an inner layer and an outer layer, and the inner layer portion of the adhesive layer has an oxygen transmission rate measured at 50% RH under the condition of lOcc '20 ⁇ mZm. 2) A resin layer comprising a resin layer containing a gas barrier resin having a day atm or less, and the outer layer portion of the adhesive layer comprising a resorcinol formaldehyde initial condensate and a rubber latex as main components.
- the present invention is a polyester fiber cord for rubber reinforcement having an inner and outer two adhesive layers, wherein the inner layer portion of the adhesive layer is composed of a resin layer containing polybulal alcohol,
- the outer layer portion of the adhesive is a polyester fiber cord for reinforcing rubber, characterized in that it comprises a resin layer mainly composed of resorcin 'formaldehyde initial condensate and rubber latex.
- the following (1) to (5) are preferable conditions, and further excellent effects can be expected by applying these conditions.
- An epoxy compound is contained in the adhesive layer in the inner layer portion of the cord.
- the content of the polyvinyl alcohol is in the range of 10 to 50% by weight with respect to the total solid content of the adhesive in the inner layer portion.
- the polysulbu alcohol has a saponification degree of 70 to 90 mol%.
- the amount of the resin adhered to the inner layer portion of the adhesive layer is 0.5 to 10% by weight as a solid content ratio to the fiber weight, and the amount of the resin adhered to the outer layer portion is based on the fiber weight.
- Solid content ratio 1 to: LO weight%.
- the polyester fiber cord for rubber reinforcement is a twisted yarn cord subjected to a lower twist and an upper twist, wherein the lower twist coefficient K force 300 ⁇ K ⁇ 1200, and the upper twist coefficient Repulsion 4
- the following (6) to (11) are preferable conditions, and further excellent effects can be expected by applying these conditions.
- An epoxy compound is contained in the adhesive containing polybulal alcohol used in the first bath.
- the polyvinyl alcohol content in the range of 10-50 wt 0/0 relative to the total solid content of the inner layer portion of the adhesive layer.
- the saponification power of the polybulu alcohol is 70 to 90 mol%.
- the amount of the resin adhered to the inner layer portion of the adhesive layer is 0.5 to 10% by weight as a solid content ratio to the fiber weight, and the amount of the resin adhered to the outer layer portion of the adhesive layer is the fiber.
- the solid content ratio with respect to the weight should be 1 to 10% by weight.
- the invention's effect [0020] According to the polyester fiber cord for reinforcing rubber and the method for producing the same according to the present invention, the heat-resistant adhesiveness and the heat-resistant strength retention property when exposed to a high temperature in rubber for a long time during a rubber calcining process or product use. Is significantly improved.
- the rubber product reinforced with the polyester fiber cord according to the present invention can withstand severe use for a long period of time when used as a tire, belt and hose. In particular, it is suitable as a cap ply cord for a strong radial tire that cannot be applied to conventional polyester fiber cords.
- the polyester fiber used in the present invention is composed of a polyester composed of a dicarboxylic acid and a dallicol component, and particularly preferably polyethylene terephthalate composed of terephthalic acid and ethylene glycol.
- the polyester fiber cord for reinforcing rubber according to the present invention has excellent mechanical properties such as high strength, high toughness, high elastic modulus, low shrinkage, and high fatigue resistance, and in rubber at high temperature for a long time.
- the polyester fiber used in the present invention preferably has the following characteristics because it has excellent chemical durability such as hydrolysis resistance and amine resistance even when exposed.
- Intrinsic viscosity (IV) 0.7 to 1.2, more preferably 0.8 to: L1
- Carboxyl end group (COOH) 10-30eqZt, more preferably 12-25eqZt
- Diethylene glycol (DEG) 0.5 to 1.5, preferably 0.5 to 1.2%
- Dry heat shrinkage (A S) 2.0 to 12.0%, more preferably 3.0 to: LO.O%
- polyester fiber used in the polyester fiber cord for rubber reinforcement of the present invention to have chemical durability in particular, it is advantageous that there is less diethylene glycol having a higher viscosity and fewer carboxyl end groups.
- the polyester used in the present invention is modified with a terminal carboxyl group blocking agent such as a carboxylidimide compound, an epoxy compound, an isocyanate compound and an oxazoline compound in order to reduce carboxy terminal groups. It ’s good quality.
- polyester fiber used in the present invention is subject to restrictions such as fineness, number of filaments, and cross-sectional shape. 200-5000 dtex, 30-: LOOO filament, circular cross-section yarn force is used, 2 50-3000 dtex, 50-500 filament yarn, circular cross-section yarn force is preferred.
- the rubber fiber-reinforced polyester fiber cord of the present invention is obtained by twisting the polyester fiber into a raw cord, and woven the raw cord as it is or directly into a raw fabric, followed by an adhesive treatment.
- Raw cords used for ordinary carcass tire cords are twisted in the S or Z direction, then two or three twisted cords are combined and the normal number of twists is applied in the opposite direction to the twisted cord. It is what.
- the raw cord is used as a warp, cotton yarn is used as the weft yarn, or cotton yarn is cannulated to the polyester fiber to form a weft yarn, and the fabric is woven in a raw fabric.
- the ginger fabric is treated with an adhesive to obtain a dip fabric.
- the bottom twisting force is 4 na
- the bottom twisting cord, or in the same direction as above, 2 or 3 are combined in the opposite direction to the bottom twisting
- the same number of upper twists are applied to form a twisted cord, which is then treated with an adhesive in the form of a cord to form a dip cord.
- the rubber-reinforced polyester fiber cord to which the adhesive of the present invention is applied refers to both the dip anti-dip and the dip cord.
- the polyester fiber cord for rubber reinforcement of the present invention is a rubber fiber polyester fiber cord having two inner and outer adhesive layers, and the inner layer portion of the adhesive layer has a humidity of 50% RH.
- the measured oxygen permeation rate is lOcc '20 ⁇ mZm 2 ' dayatm or less, and the outer layer of the adhesive layer is resorcinol formaldehyde initial condensation.
- the inner layer portion of the adhesive layer applied to the polyester fiber cord for rubber reinforcement of the present invention mainly means an adhesion portion of the adhesive component of the first bath in the present invention two-bath dipping method described later, The surface of the polyester cord and a part that penetrates into the cord.
- the outer layer portion of the adhesive layer is a portion overcoated on the inner layer portion of the adhesive layer. There is also a boundary where a part of the adhesive component is mixed.
- the rubber fiber-reinforced polyester fiber cord of the present invention is a rubber fiber-reinforced polyester fiber cord having two inner and outer adhesive layers, and the inner layer portion of the adhesive layer is polyvinyl chloride.
- the resin layer is made of a resin layer containing alcohol, and the outer layer portion of the adhesive layer is made of a resin layer mainly composed of resorcinol formaldehyde initial condensate and rubber latex.
- the inner layer portion of the adhesive layer that is, the code side portion is composed of a resin layer containing gas noble resin, and the gas noble resin has a humidity of 50.
- the oxygen permeation rate measured under% RH conditions must be lOcc 20 ⁇ m / m2 day atm or less, preferably 8cc '20 m / m2 'day' atm or less, more preferably 6cc • Must be 20 ⁇ m / m2 ⁇ day ⁇ atm or less. If it exceeds lOcc ⁇ 20 ⁇ m / m2 ⁇ day-at m, the adhesion between the cord and rubber may decrease after exposure to high temperatures.
- Gas noble resin is a resin having an effect of preventing gas permeation, and specific examples thereof include ethylene butyl alcohol resin, salty vinylidene resin, polyacrylonitrile resin, and polybule. Alcohol resin, nylon resin, polyester resin, etc. are mentioned.
- the adhesive layer containing gas nobulous resin forms a film on the surface of the polyester fiber, and the resorcin 'formaldehyde initial condensate, which is the main component of the outer layer of rubber and adhesive, and rubber latex are heated at high temperatures.
- Low molecular weight amine compounds and water molecules generated by time-exposure and pyrolysis can be prevented from penetrating into the polyester fiber cord, and thermal decomposition of the polyester can be suppressed. As a result, it is possible to obtain an epoch-making effect that not only the decrease in strength of the polyester fiber cord can be suppressed, but also the decrease in adhesion can be suppressed.
- the polyester fiber cord for reinforcing rubber according to the present invention also has an inner layer portion of the adhesive layer, that is, a cord-side partial force and a resin layer force including polybulal alcohol.
- the resin layer containing polyvinyl alcohol forms a film on the surface of the polyester fiber, and the resorcin / formaldehyde initial condensate, which is the main component of the outer layer of the rubber and adhesive layer, and rubber latex are exposed to heat for a long period of time. It is possible to prevent low molecular weight amine compounds and water molecules produced by decomposition from penetrating into the polyester fiber cord, and to suppress thermal decomposition of the polyester. As a result, it is possible to obtain an epoch-making effect that not only a decrease in the strength of the polyester fiber cord but also a decrease in the adhesiveness can be suppressed.
- the polyester fiber cord of the present invention comprises a polybulol alcohol layer adhered to the surface layer portion of the cord, and a resorcin / formaldehyde initial compaction adhered to the outer layer thereof. It is a feature of the polyester fiber cord for reinforcing rubber of the present invention that the compound and the rubber latex component form each layer, and the effect of the present invention can be obtained thereby. That is, the polyester fiber cord for reinforcing rubber of the present invention exhibits an adhesion reaction between polyester fiber, resorcin 'formaldehyde initial condensate and rubber latex, and an adhesion reaction between resorcin / formaldehyde initial condensate, rubber latex and rubber. Inhibition of penetration of low molecular weight amine compounds and water molecules into the polyester cord by the poly (vinyl alcohol) component without hindering is achieved, and as a result, improvement in heat-resistant adhesion and heat-resistant and strong retention is achieved.
- the polybulal alcohol used in the present invention is produced, for example, by saponifying a polybull ester obtained by polymerizing a bullester. Also, modified polyvinyl alcohol obtained by graft copolymerizing unsaturated carboxylic acid or derivative thereof, unsaturated sulfonic acid or derivative thereof, a-olefin with 2 to 30 carbon atoms, etc. in a proportion of less than 5 mol% on the main chain of polyvinyl alcohol. By saponifying a modified polyvinyl ester copolymerized with alcohol, butyl ester and unsaturated carboxylic acid or derivative thereof, unsaturated sulfonic acid or derivative thereof, ex-olefin having 2 to 30 carbon atoms, etc.
- Examples thereof include modified polyvinyl alcohol to be produced, and unmodified or modified polyvinyl alcohol obtained by crosslinking a part of hydroxyl groups with aldehydes such as formalin, butyraldehyde, and benzaldehyde.
- aldehydes such as formalin, butyraldehyde, and benzaldehyde.
- Examples of the bull esters include vinyl acetate, formate, propionate, butyrate, pivalate, versatic acid, lauric acid, stearic acid, and benzoic acid. Of these, butyl acetate is particularly preferable.
- the comonomer used in the modified polybutyl alcohol is mainly copolymerized for the purpose of modifying the polybulal alcohol.
- olefins such as ethylene, propylene, 1-butene and isobutene; acrylic acid and its salts ; Methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylate
- Acrylic esters such as decyl and octadecyl acrylate; methacrylic acid and its salts; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, meth
- the polybulal alcohol used in the present invention preferably has a saponification degree of 70 to 90 mol%, more preferably 70 to 80 mol%. If it is less than 70 mol%, the adhesiveness of the reactive functional group may be insufficient, and if it exceeds 90 mol%, the solubility will be poor, resulting in disadvantages in the manufacturing process, and poor adhesion when wet. There are times.
- the degree of saponification indicates the ratio of units that can be converted to vinyl alcohol units by actual saponification among units that can be converted into butyl alcohol units by saponification.
- the saponification degree of PVA was measured by the method described in JIS.
- a preferred embodiment of the rubber-reinforced polyester fiber cord of the present invention is that the resin layer containing the polyvinyl alcohol contains an epoxy compound.
- Epoxy compounds that can be used in the present invention are those having two or more epoxy groups in one molecule.
- the compound having two or more epoxy groups in the molecule includes, for example, a glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group in the molecule, and a compound power having an amino group in the molecule.
- a glycidylamine type epoxy resin obtained from a compound having a carboxyl group in the molecule, the glycidyl ester type epoxy resin obtained, and the cycloaliphatic epoxy resin obtained from the compound having an unsaturated bond in the molecule
- heterocyclic epoxy resins such as triglycidyl isocyanate, or epoxy resins in which two or more types selected from these forces are mixed in the molecule.
- glycidyl ether type epoxy resin examples include bisphenol A type epoxy resin obtained by reaction of bisphenol A and halogen-containing epoxides such as epichlorohydrin, bisphenol F and the halogen-containing epoxide.
- Bisphenol F-type epoxy resin obtained by reaction with alcohol biphenyl-type epoxy resin obtained by reaction of biphenyl with the halogen-containing epoxide, obtained by reaction of resorcinol with the halogen-containing epoxide
- Resorcinol-type epoxy resin bisphenol S-type epoxy resin obtained by reaction of bisphenol S with the halogen-containing epoxides
- polyethylene which is a reaction product of polyhydric alcohols with the halogen-containing epoxides
- Glycol type epoxy resin Epoxy obtained by acidifying unsaturated bonds such as propylene glycol type epoxy resin, bis- (3,4-epoxy-6-methinoreigecyclohexenolemethinole) adipate, 3,4 epoxycyclohexene epoxide
- the epoxy compound that can effectively improve the heat-resistant adhesion of the polyester fiber cord for rubber reinforcement is an aromatic polyepoxide compound.
- the aromatic polyepoxide compound is a compound having at least one aromatic ring and at least two epoxy groups in the molecule among the polyepoxide compounds.
- Specific examples of such aromatic polyepoxide compounds include polyhydric phenols and halogen-containing epoxides such as epochlorohydrin.
- glycidyl ethers of phenol rosins represented by the following formula are most preferable.
- X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms
- n represents an integer of 1 to 5.
- the aromatic polyepoxide compound is usually used as an emulsion or dispersion.
- the aromatic polyepoxide compound is dissolved as it is or in a small amount of a solvent as necessary, and a known emulsifying agent such as sodium alkylbenzenesulfonate, What is necessary is just to emulsify or disperse
- the inner layer portion of the adhesive layer of the polyester fiber cord for rubber reinforcement of the present invention that is, the main component of the cord side portion is polyvinyl alcohol force, and the viewpoint power for improving heat-resistant adhesion may also include an epoxy compound.
- the rubber latex is further contained as the third component, the effect can be further improved.
- Examples of the rubber latex that can be used in the present invention include natural rubber latex, butadiene rubber latex, styrene 'butadiene' rubber latex, and vinylopyridine styrene.
- a modified vinylpyridine / styrene / butadiene rubber latex obtained by copolymerizing an ethylenically unsaturated acid with a butylpyridine / styrene / butadiene rubber latex may be used alone or in combination with another. I like it.
- Examples of the ethylenically unsaturated acid used herein include acrylic acid, methacrylic acid, crotonic acid, kaycin acid, itaconic acid, fumaric acid, maleic acid, butenetricarboxylic acid, and the like.
- Monoalkyl esters of unsaturated dicarboxylic acids such as monoethyl ester, fumaric acid monobutyl ester and maleic acid monobutyl ester, and sulfoethyl sodium acrylate, sulfopropyl sodium methacrylate, acrylic propane sulfone
- unsaturated sulfonic acids such as acids or alkali salts thereof.
- the carboxyl group may be introduced into the latex by copolymerizing an ethylenically unsaturated acid ester monomer or an ethylenically unsaturated acid anhydride monomer and then hydrolyzing it.
- ethylenically unsaturated acid ester monomers and ethylenically unsaturated acid anhydride monomers include acrylic acid, methacrylic acid, crotonic acid, cinnamate, itaconic acid, fumaric acid, maleic acid, and butenetricarboxylic acid.
- unsaturated carboxylic acid compounds, triesters, and maleic anhydrides are exemplified, and one or a combination of two or more of these can be used.
- the main component of the inner layer portion of the adhesive layer of the polyester fiber cord for reinforcing rubber according to the present invention also has a polybutyl alcohol power, and further contains an epoxy compound and rubber latex to improve the effect. Further, the effect can be further enhanced by containing a blocked polyisocyanate compound and / or an ethyleneimine compound as the fourth component.
- Blocked polyisocyanate compound usable in the present invention and Z or ethylene
- amine compounds include polyisocyanate compounds such as tolylene diisocyanate, metaphenol-diisocyanate, diphenol-methanemethane diisocyanate, hexamethylene diisocyanate, and triphenyl-nomethanemethane triisocyanate.
- Phenols such as phenol, cresol and resorcin; A reactant.
- aromatic polyisocyanate compounds blocked with ⁇ -strength prolatatam and aromatic ethylene urea compounds such as diphenylmethane diethylene urea can be preferably used.
- the rubber fiber-reinforced polyester fiber cord of the present invention has a force that the inner layer portion of the adhesive layer, that is, the cord side also has an adhesive force including polyvinyl alcohol. It is 10 to 50% by weight, preferably 20 to 40% by weight. If it is less than 10% by weight, the heat-resistant adhesiveness when exposed to high temperatures may be insufficient, and if it exceeds 50% by weight, the initial adhesive strength may be insufficient.
- the solid adhesion amount of the inner layer portion of the adhesive layer to the polyester fiber is in the range of 0.5 to 10% by weight, preferably in the range of 1 to 5% by weight with respect to the fiber weight. If the solid content is too low, the adhesiveness is lowered. On the other hand, if the solid content is too high, the cord becomes hard and the fatigue resistance is lowered.
- the main components of the outer layer portion of the adhesive layer of the polyester fiber cord for reinforcing rubber of the present invention are composed of resorcin / formaldehyde initial condensate and rubber latex.
- the resorcin / formaldehyde is preferably prepared using a resorcin / formaldehyde initial condensate obtained by initial condensation in the presence of an alkali catalyst.
- resorcin and formaldehyde are added and mixed in an alkaline aqueous solution containing an alkaline compound such as sodium hydroxide, and the mixture is allowed to stand at room temperature for several hours. It is prepared by a method of preparing a mixed emulsion.
- resorcin 'formaldehyde precondensate one having a molar ratio of resorcin to formaldehyde of 1: 0.3 to 1: 5, preferably 1: 0.75 to 1: 2.0 is used.
- molar ratio of the aldehyde is less than the above range, the treatment cord may become sticky and cause the processing machine to become dirty.On the other hand, if the molar ratio of the formaldehyde is above this range, the adhesiveness is insufficient. become.
- the outer layer portion of the adhesive layer in the polyester fiber cord for reinforcing rubber of the present invention is composed of resorcin 'formaldehyde initial condensate and rubber latex as main components.
- the outer layer adhesive is used together with resorcin' formaldehyde initial condensate.
- W is CH or Sn
- X and Y are Cl, Br, I, H, OH and C to C
- the phenolic compound represented by the above general formula is an initial condensate of a halogenated phenol compound and formaldehyde, an initial condensed particle of sulfur-modified resorcinol and formaldehyde, or an initial condensate of halogenated sulfur-modified resorcinol and formaldehyde. It is a condensate.
- the method for preparing these phenolic compounds is not particularly limited.
- parachlorophenol, orthochlorophenol, parabromophenol, paraiodophenol, orthocresol, paracresol, paratertiary butylphenol and 2, 5 —Dimethylphenol and the like can be mentioned as starting materials, and parachlorophenol, parabromophenol, paracresol, and paratertiary butylphenol are particularly preferred.
- a phenol compound can be obtained by reacting the condensate obtained by reacting in the presence of a recatalyst with formaldehyde in the presence of an alkali catalyst.
- Examples of rubber latex used in the preparation of resorcinol, formaldehyde latex include natural rubber latex, butadiene rubber latex, styrene 'butadiene' rubber latex, bullpyridine 'styrene' butadiene rubber latex, nitrile rubber latex, hydrogenated -Tolyl rubber latex, chloroprene rubber latex, chlorosulfonated rubber latex, ethylene 'propylene' gen rubber latex and the like can be mentioned, and these can be used alone or in combination. Among them, it is preferable to use vinylpyridine 'styrene' butadiene rubber latex alone or in combination with other materials.
- vinyl pyridine 'styrene' butadiene rubber latex is preferably used in combination with a modified bullpyridine 'styrene' butadiene rubber latex obtained by copolymerizing an ethylenically unsaturated acid alone or in combination with another. .
- Examples of the ethylenically unsaturated acid used herein include acrylic acid, methacrylic acid, crotonic acid, kaycin acid, itaconic acid, fumaric acid, maleic acid, butenetricarboxylic acid and other unsaturated rubonic acids and itaconic acids.
- Monoalkyl esters of unsaturated dicarboxylic acids such as monoethyl ester, fumaric acid monobutyl ester and maleic acid monobutyl ester, and sulfoethyl sodium acrylate, sulfopropyl sodium methacrylate, acrylic propane sulfone
- unsaturated sulfonic acids such as acids or alkali salts thereof.
- the carboxyl group may be introduced into the latex by copolymerizing an ethylenically unsaturated acid ester monomer or an ethylenically unsaturated acid anhydride monomer and then hydrolyzing it.
- ethylenically unsaturated acid ester monomers and ethylenically unsaturated acid anhydride monomers include acrylic acid, methacrylic acid, crotonic acid, cinnamate, itaconic acid, fumaric acid, maleic acid, and butenetricarboxylic acid.
- unsaturated carboxylic acid compounds, triesters, and maleic anhydrides are exemplified, and one or a combination of two or more of these can be used.
- the mixing ratio of resorcin / formaldehyde initial condensate and rubber latex in resorcin / formaldehyde / latex is preferably from 1: 3 to 1: 8 in weight ratio of solid content.
- the range of 1: 4 to 1: 6 is more preferable. Outside this range, adhesion may be insufficient.
- the blending ratio of resorcin 'formaldehyde' latex and the above phenolic compound is preferably 10: 1 to LO: 5, more preferably 10: 2 to LO. : 4 to be good. Outside this range, adhesion may be insufficient.
- the solid content adhesion amount of the outer layer adhesive is in the range of 1 to 10% by weight, preferably in the range of 1.5 to 5% by weight. If the solid content is too low, the adhesiveness will decrease, while if the solid content is too high, the cord will become hard and fatigue resistance will decrease, and the solid content will be gummed up in the roll during the process. However, operational stability is poor.
- the polyester fiber cord is a twisted yarn cord subjected to a lower twist and an upper twist, and preferably has a lower twist coefficient K force of 300 ⁇ K ⁇ 1200, more preferably 400 ⁇ ⁇ 1100, more preferably 500 ⁇ 1000. If the lower twisting coefficient is out of the preferred range, the adhesive strength after high temperature exposure may be reduced, and the fatigue resistance in rubber may deteriorate.
- the upper twist coefficient ⁇ is preferably 400 ⁇ 1 ⁇ 1600.
- the polyester fiber cord of the present invention characterized by the above is remarkably improved in heat-resistant adhesion and heat-resistant strength retention when exposed to high temperature for a long time during rubber vulcanization process or rubber product use.
- the rubber product reinforced with the polyester fiber cord according to the present invention can withstand severe use for a long time when used as a tire, belt and hose.
- it is suitable as a cap tire cord for a radial tire that cannot be applied with a conventional polyester fiber cord.
- the polyester fiber cord of the present invention has been able to provide a material suitable as a cap ply cord for the first time by significantly improving the heat-resistant adhesive property and the heat-resistant and strong retaining property.
- the rubber-reinforcing polyester fiber cord of the present invention includes an adhesive containing polyvinyl alcohol in accordance with a method for producing a rubber-reinforcing polyester fiber cord provided with an adhesive by a two-bath dip method. It is obtained by applying resorcin 'formaldehyde initial condensate and rubber latex in the second bath.
- the polyester fiber is twisted in the following manner to form a raw cord having the above-described twist coefficient, and in the same manner, a cord weaving loom is used to form a cord.
- a cord weaving loom is used to form a cord.
- hoses, belts and cap ply cords they are used for the next deribing process without weaving as they are under twisted cords or yarn cords.
- the polyester fiber cord is a twisted cord with a lower twist and an upper twist. It is preferred that 300 ⁇ K ⁇ 1200, more preferably 400 ⁇ 1100, and even more preferably 50 0 ⁇ 1000. If the lower twisting coefficient is out of the preferred range, the adhesive strength after high temperature exposure may be reduced, and the fatigue resistance in rubber may deteriorate. Also, twister The number K is preferably 400 ⁇ 1600, more preferably 600 ⁇ 1400,
- the method of the present invention is a two-bath dipping method in which an adhesive containing polyvinyl alcohol is applied in the first bath, and a resorcin 'formaldehyde initial condensate and a rubber latex are applied in the second bath.
- Polybulol alcohol used as the first bath, an epoxy compound added as the second component, and a rubber latex that is supported as the third component, and a blocked soynate compound that is supported as the fourth component And / or the ethyleneimine compound is the same as described above.
- the present invention does not require the application of a part of the adhesive to the polyester fiber V during the yarn production stage.
- the adhesive is applied at the time of dipping, which is the subject of heat resistance in rubber. Adhesives can be selected in consideration of the properties.
- a rubber fiber-reinforced polyester fiber cord to which an adhesive has been applied is produced by a two-bath dip method, but polyburu alcohol is added in the first bath without applying a part of the adhesive by pretreatment in advance.
- the main component of the cord inner layer portion of the adhesive layer becomes polybulal alcohol and the adhesive layer
- a polyester fiber cord for reinforcing rubber is manufactured so that the main component of the outer layer portion of the cord is a resorcin / formaldehyde initial condensate and a rubber latex power.
- the adhesive component applied in the second bath is the same as described above.
- a method of applying an adhesive containing polyvinyl alcohol is as follows. Polyester fiber raw cord or raw cord cocoon is added to a dip solution prepared by adjusting the adhesive containing polyvinyl alcohol as an aqueous solution or aqueous dispersion. It is performed by dipping, followed by drying and heat treatment.
- the total solid concentration of the dip solution in the first bath is 2 to 20% by weight, preferably 3 to 1. It is preferable to use in the range of 5% by weight. If the solid content concentration is too low, the adhesive surface tension increases, the uniform adhesion to the polyester fiber surface decreases, the adhesiveness decreases due to the decrease in the solid content, and the solid content concentration also decreases. If it is too high, the amount of solid content will be too large, so the cord will become hard and the fatigue resistance may decrease, which is not preferable.
- a dispersant that is, a surfactant in the dip solution of the first bath at 10 wt% or less, preferably 5 wt% or less, based on the total solid content of the dip solution. If it exceeds 10% by weight, the adhesiveness is lowered.
- the solid adhesion amount of the dip liquid in the first bath to the polyester fiber is in the range of 0.5 to 10% by weight, preferably in the range of 1 to 5% by weight, based on the fiber weight. If the solid content is too low, the adhesion will be reduced, while if the solid content is too high, the cord may become stiff and fatigue resistance may be reduced.
- a method such as squeezing with a pressure roller after being immersed in a dip solution, removing force with a scrubber, blowing with pressure air, suction, etc. should be used. Is possible.
- it can also be made to adhere several times.
- the polyester fiber cord to which the dip solution of the first bath was applied was dried at 70 to 150 ° C for 0.5 to 5 minutes, and then heat-treated at 200 to 255 ° C for 0.5 to 5 minutes. In some cases, drying may be omitted.
- the temperature of the heat treatment is less than 200 ° C, the formation of an adhesive film on the fiber and the reaction with the rubber may be insufficient, and the adhesive force may be insufficient. Higher temperatures are undesirable because the coating film of the treatment agent formed on the fiber deteriorates and adhesive strength decreases, and the polyester fiber deteriorates thermally and strength decreases.
- the second bath dip solution containing resorcin 'formaldehyde rubber latex is subsequently adhered.
- the second bath dip liquid containing resorcin, formaldehyde and latex has a solid content of 5 to 30% by weight, preferably 10 to 25% by weight. If it is less than 5% by weight, the amount of solid content of the dip liquid in the second bath may be insufficient, and the adhesive strength may not be sufficient. If the solid content concentration exceeds 30% by weight, the storage stability of the dip solution will deteriorate, and the solid content will decrease. Concentration changes due to aggregation, making it difficult to evenly attach the dip solution to the surface of the polyester fiber cord.
- the solid content of the second bath on the polyester fiber cord is in the range of 1.0 wt% to 10 wt%, and preferably in the range of 1.5 wt% to 5 wt%. If the amount of solid content is too low, the adhesion may be reduced. On the other hand, if the amount of solid content is too high, the cord may become hard and fatigue resistance may be reduced. The roll may cause solid gumming up, resulting in poor operational stability.
- the polyester fiber cord provided with the second bath dip solution is dried at 70 to 150 ° C for 0.5 to 5 minutes and then heat-treated at 200 to 255 ° C for 0.5 to 5 minutes.
- An adhesive film can be formed on the fiber surface, but in some cases, drying can be omitted.
- the temperature of the heat treatment is less than 200 ° C, the formation of the adhesive film on the fiber and the adhesion to the rubber may be insufficient, while at a temperature higher than 255 ° C, it was formed on the fiber. This is not preferable because the coating film of the treatment agent is deteriorated and the adhesive strength is lowered, or the polyester fiber is thermally deteriorated and the strength is lowered.
- the inner layer portion of the adhesive layer that is, the main component of the cord side portion also has polyvinyl alcohol power
- the main component of the outer layer portion of the adhesive layer is Resorcin 'formaldehyde initial condensate and rubber latte Tusca and other polyester fiber cords for rubber reinforcement. It has excellent heat-resistant adhesiveness and heat-resistant strength retention, and has a strong cap that can withstand severe use for a long period of time when used as a rubber material such as conventional tire carcass materials, hoses and belts. It can be suitably used as a ply code.
- the cord shows the strength retention after vulcanization in rubber.
- the cord is under tension in rubber, 170. C, after vulcanization for 3 hours, or after vulcanization for 6 hours, the cord was taken out from the rubber, and the tensile strength at break was determined at a speed of 300 mm / min.
- composition of the rubber compound used for the measurement of T-adhesion strength is as follows.
- Zinc flower 5 (parts by weight)
- Naphthenic acid process oil 3 (parts by weight).
- Blend ratio of butylpyridine styrene butadiene rubber latex (parts by weight)
- Resorcin Z formalin molar ratio of lZl. 4 was mixed in the presence of caustic soda to adjust the solids concentration to 10%, and aging for 2 hours. A condensate was obtained. Next, this initial condensate and bullpyridine styrene butadiene rubber latex (V9625 (manufactured by A & L, Japan)) were mixed at a solid content weight ratio of 100Z30 and aged for 24 hours.
- Polyethylene terephthalate having a viscosity of 0.95 is melt-spun by a conventional method, and two of the lOOdTex multifilament yarns obtained by drawing are twisted with a lower twist of 21 times ZlOcm and an upper twist of 21 times Zl Ocm. The yarn was twisted with a number to obtain an untreated cord.
- the untreated cord was dipped in the inner layer adhesive using a combo treater processor (CA Ritzler), dried at 120 ° C for 2 minutes, and subsequently at 240 ° C for 1 minute. The heat treatment was performed. Subsequently, after immersing in the outer layer adhesive, it was dried at 120 ° C. for 2 minutes, and subsequently heat-treated at 240 ° C. for 1 minute.
- the obtained treated cord had 2.0% solid content of the inner layer adhesive and 3.0% outer layer adhesive.
- Example 5 The same operation as in Example 5 was performed except that the twist coefficient was changed to the values shown in Table 1. The results are also shown in Table 2. 0101 table 1
- KL506 degree of saponification 98-103 600 calfo "xy-modified"
- the rubber product reinforced with the polyester fiber cord according to the present invention can withstand severe use for a long period of time when used as a tire, belt and hose.
- it is suitable as a cap ply cord for radial tires that could not be applied with conventional polyester fiber cords.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2006520485A JP4803033B2 (ja) | 2005-01-21 | 2006-01-23 | ゴム補強用ポリエステル繊維コードおよびその製造方法 |
CN2006800027987A CN101107395B (zh) | 2005-01-21 | 2006-01-23 | 橡胶增强用聚酯纤维帘线及其制造方法 |
EP06712165A EP1842958A4 (en) | 2005-01-21 | 2006-01-23 | POLYESTER FIBER WIRE FOR STRENGTHENING RUBBER AND METHOD FOR PRODUCTION THEREOF |
Applications Claiming Priority (2)
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JP2005013749 | 2005-01-21 | ||
JP2005-013749 | 2005-01-21 |
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WO2006078013A1 true WO2006078013A1 (ja) | 2006-07-27 |
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PCT/JP2006/300949 WO2006078013A1 (ja) | 2005-01-21 | 2006-01-23 | ゴム補強用ポリエステル繊維コードおよびその製造方法 |
Country Status (5)
Country | Link |
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US (1) | US20080121327A1 (ja) |
EP (1) | EP1842958A4 (ja) |
JP (1) | JP4803033B2 (ja) |
CN (1) | CN101107395B (ja) |
WO (1) | WO2006078013A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2008146708A1 (ja) * | 2007-05-25 | 2008-12-04 | Nippon Sheet Glass Company, Limited | ゴム補強用部材およびそれを用いたゴム製品 |
JP2010269675A (ja) * | 2009-05-20 | 2010-12-02 | Bridgestone Corp | 空気入りタイヤ |
WO2018038050A1 (ja) | 2016-08-23 | 2018-03-01 | 株式会社ブリヂストン | 空気入りタイヤ及びその製造方法 |
JP2019131735A (ja) * | 2018-02-01 | 2019-08-08 | 横浜ゴム株式会社 | ゴム組成物およびそれを用いた空気入りタイヤ |
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JP5358424B2 (ja) * | 2009-12-18 | 2013-12-04 | 株式会社ブリヂストン | 空気入りタイヤ |
EP2460649A1 (de) * | 2010-12-02 | 2012-06-06 | Rhein Chemie Rheinau GmbH | Elastomer-Faser-Verbund, Verfahren zur Herstellung und dessen Verwendung |
US8490707B2 (en) | 2011-01-11 | 2013-07-23 | Schlumberger Technology Corporation | Oilfield apparatus and method comprising swellable elastomers |
WO2014091376A1 (en) * | 2012-12-13 | 2014-06-19 | Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi | A dipping material for cord fabrics and a production method thereof |
EP2946948B1 (en) * | 2013-02-28 | 2019-04-24 | Bridgestone Corporation | Pneumatic safety tire |
KR101719190B1 (ko) | 2013-04-26 | 2017-03-23 | 코드사 글로벌 엔두스트리옐 이플릭 베 코드 베지 사나위 베 티카레트 아노님 시르케티 | 코드 직물에 고성능을 제공하는, 레조르시놀-포름알데히드를 포함하지 않는 디핑 재료 |
JP6108943B2 (ja) * | 2013-04-30 | 2017-04-05 | 株式会社ブリヂストン | 接着剤組成物被覆繊維、ゴム部材、空気入りタイヤ及びランフラットタイヤ |
DE102015215149A1 (de) | 2015-08-07 | 2017-02-09 | Contitech Antriebssysteme Gmbh | Antriebsriemen |
JP7188344B2 (ja) * | 2019-09-30 | 2022-12-13 | 横浜ゴム株式会社 | 空気入りタイヤ |
CN111961171B (zh) * | 2020-07-13 | 2022-08-30 | 杭摩新材料集团股份有限公司 | 传输带专用改性树脂及其生产方法 |
JP2022162823A (ja) * | 2021-04-13 | 2022-10-25 | 住友ゴム工業株式会社 | 空気入りタイヤ |
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- 2006-01-23 CN CN2006800027987A patent/CN101107395B/zh not_active Expired - Fee Related
- 2006-01-23 US US11/795,708 patent/US20080121327A1/en not_active Abandoned
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2008146708A1 (ja) * | 2007-05-25 | 2008-12-04 | Nippon Sheet Glass Company, Limited | ゴム補強用部材およびそれを用いたゴム製品 |
JP5290967B2 (ja) * | 2007-05-25 | 2013-09-18 | 日本板硝子株式会社 | ゴム補強用部材およびそれを用いたゴム製品 |
US8962129B2 (en) | 2007-05-25 | 2015-02-24 | Nippon Sheet Glass Company, Limited | Rubber-reinforcing member and rubber product utilizing the same |
JP2010269675A (ja) * | 2009-05-20 | 2010-12-02 | Bridgestone Corp | 空気入りタイヤ |
WO2018038050A1 (ja) | 2016-08-23 | 2018-03-01 | 株式会社ブリヂストン | 空気入りタイヤ及びその製造方法 |
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Also Published As
Publication number | Publication date |
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CN101107395B (zh) | 2010-12-01 |
EP1842958A4 (en) | 2012-10-24 |
CN101107395A (zh) | 2008-01-16 |
EP1842958A1 (en) | 2007-10-10 |
JP4803033B2 (ja) | 2011-10-26 |
JPWO2006078013A1 (ja) | 2008-06-19 |
US20080121327A1 (en) | 2008-05-29 |
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