Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/0005—Pretreatment of tyres or parts thereof, e.g. preheating, irradiation, precuring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • B60C19/00—Tyre parts or constructions not otherwise provided for
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
  • C01B11/04—Hypochlorous acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/12—Incorporating halogen atoms into the molecule
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/126—Halogenation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
  • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
  • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
  • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C66/00—General aspects of processes or apparatus for joining preformed parts
  • B29C66/01—General aspects dealing with the joint area or with the area to be joined
  • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
  • B29C66/026—Chemical pre-treatments
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C66/00—General aspects of processes or apparatus for joining preformed parts
  • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
  • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
  • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
  • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
  • B29C66/73755—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being fully cured, i.e. fully cross-linked, fully vulcanized
  • B29C66/73756—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being fully cured, i.e. fully cross-linked, fully vulcanized the to-be-joined areas of both parts to be joined being fully cured
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/0005—Pretreatment of tyres or parts thereof, e.g. preheating, irradiation, precuring
  • B29D2030/0011—Surface activation of tyres or parts thereof, e.g. by plasma treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2030/00—Pneumatic or solid tyres or parts thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
  • B32B2250/248—All polymers belonging to those covered by group B32B25/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
• • 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
  • C08J2307/00—Characterised by the use of natural 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
  • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • 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
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2421/00—Presence of unspecified rubber
  • C09J2421/006—Presence of unspecified rubber in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2421/00—Presence of unspecified rubber
  • C09J2421/008—Presence of unspecified rubber in the pretreated surface to be joined
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2463/00—Presence of epoxy resin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2475/00—Presence of polyurethane

Definitions

• the present invention relates to a vulcanized rubber surface treatment agent, a method for manufacturing an adhesive structure, an adhesive structure, and a tire.
• Patent Document 1 describes (1) a primer containing a halogenated polyolefin as a main component, (2) a rubber-based adhesive mainly containing a halogenated rubber, and (3) a urethane-based adhesive on a rubber surface. It is disclosed that the adhesive can be adhered firmly and stably by sequentially applying the adhesive and then sandwiching it with other members.
• Patent Document 1 The technique of Patent Document 1 is to develop adhesiveness by heat-bonding. Therefore, especially in the case of a large tire, it is difficult to work in the mounted state. Considering that tire repairs are often performed on-site, it is desirable that the vulcanized rubber members can be firmly bonded to each other without the need for heating.
• Patent Document 1 since the organic solvent is applied to the rubber surface, there is a possibility of causing rubber deterioration.
• an object of the present invention to provide a vulcanized rubber surface treatment agent which enables the vulcanized rubbers to be firmly adhered to each other without requiring heating and has a small influence of rubber deterioration.
• Another object of the present invention is to provide a method for producing an adhesive structure capable of producing an adhesive structure in which vulcanized rubbers are firmly adhered to each other without requiring heating.
• the gist structure of the present invention that solves the above problems is as follows.
• the vulcanized rubber surface treatment agent of the present invention is a vulcanized rubber surface treatment agent used for adhering vulcanized rubbers to each other. It is a hypochlorous acid aqueous solution having a pH value of 2 or more and 7 or less and an effective chlorine concentration of 100 ppm or more and 13000 ppm or less.
• the method for producing an adhesive structure of the present invention is a method for producing an adhesive structure for obtaining an adhesive structure in which a first vulcanized rubber and a second vulcanized rubber are adhered to each other.
• the first coating step of coating the surface of the first vulcanized rubber with a hypochlorous acid aqueous solution having a pH value of 2 or more and 7 or less and an effective chlorine concentration of 100 ppm or more and 13000 ppm or less.
• the first vulcanized rubber and the second vulcanized rubber via the hypochlorite aqueous solution applied in the first coating step and the adhesive applied in the second coating step.
• Adhesion process and It is characterized by including.
• the adhesive structure of the present invention is an adhesive structure in which a first vulcanized rubber and a second vulcanized rubber are bonded via an adhesive layer.
• the adhesive layer contains a urethane compound and / or an epoxy compound and contains.
• the first vulcanized rubber and the second vulcanized rubber are characterized in that at least a part of the surface in contact with the adhesive layer is chloroylated.
• the tire of the present invention is characterized by including the above-mentioned adhesive structure.
• a vulcanized rubber surface treatment agent which enables the vulcanized rubbers to be firmly adhered to each other without requiring heating and has a small influence of rubber deterioration. Further, according to the present invention, it is possible to provide a method for producing an adhesive structure capable of producing an adhesive structure in which vulcanized rubbers are firmly adhered to each other without requiring heating. Further, according to the present invention, it is possible to provide an adhesive structure in which vulcanized rubbers are firmly adhered to each other and have excellent fatigue resistance, and a tire provided with the adhesive structure.
• the vulcanized rubber surface treatment agent of one embodiment of the present invention (hereinafter, may be referred to as "surface treatment agent of the present embodiment") is used for the purpose of adhering vulcanized rubbers to each other.
• the surface treatment agent of the present embodiment is characterized by being a hypochlorous acid aqueous solution having a pH value of 2 or more and 7 or less and an effective chlorine concentration of 100 ppm or more and 13000 ppm or less.
• hypochlorous acid aqueous solution having a pH value of 2 or more and 7 or less
• hypochlorous acid is generally present in a molecular (HClO) state.
• the present inventors have diligently studied a method for improving the adhesiveness of vulcanized rubbers to each other.
• a method for improving the adhesiveness of vulcanized rubbers to each other prior to adhering the vulcanized rubbers to each other using an adhesive, at least one of the vulcanized rubbers is surface-treated with a hypochlorite aqueous solution without the need for heating. It has been found that high adhesiveness can be exhibited.
• the hypochlorous acid aqueous solution is usually used for sterilization, deodorization and the like. Therefore, it can be said that the fact that the adhesiveness between the vulcanized rubbers is improved by using the hypochlorous acid aqueous solution as the surface treatment agent for the vulcanized rubbers is a new and surprising discovery.
• the surface treatment agent of the present embodiment is an aqueous solution (does not contain an organic solvent), it has a small adverse effect on the environment and the influence of deterioration of the vulcanized rubber in direct contact is sufficiently small. Therefore, the adhesive structure obtained by sandwiching the adhesive while applying the surface treatment agent of the present embodiment to the surface of the vulcanized rubber can not only have high adhesiveness but also significantly withstand deformation and strain. Can (has high fatigue resistance).
• hypochlorous acid aqueous solution has an advantage that it can be easily prepared using a commercially available raw material.
• hypochlorous acid aqueous solution When the hypochlorous acid aqueous solution is applied to the surface of the vulcanized rubber, it is considered that an oxidation (chloroization) reaction of the olefin portion occurs on at least a part of the surface of the vulcanized rubber.
• hypochlorous acid that exists as a molecule (HClO) in an aqueous solution is required to some extent, and the polarity of the vulcanized rubber surface cannot be sufficiently increased only by being present as an ionic state. Further, whether hypochlorous acid in the aqueous solution exists as a molecular state or an ionic state can be determined by the pH value of the aqueous solution. If the pH value is 7 or less, it is considered that sufficient hypochlorous acid molecules are present to increase the polarity of the vulcanized rubber surface.
• hypochlorous acid aqueous solution as the surface treatment agent of the present embodiment can be used, for example, in the method for producing an adhesive structure described later.
• the pH value of the hypochlorous acid aqueous solution as the surface treatment agent of the present embodiment is 2 or more and 7 or less. If the pH value is less than 2, a large amount of chlorine gas is released, which makes it difficult to keep the pH within a predetermined range of the effective chlorine concentration. Further, if the pH value is more than 7, it is not possible to obtain a sufficient effect of improving the adhesiveness between the vulcanized rubbers. Further, the pH value of the hypochlorous acid aqueous solution is more preferably 4 or more from the viewpoint of stability.
• the effective chlorine concentration of the hypochlorous acid aqueous solution as the surface treatment agent of the present embodiment is 100 ppm or more and 13000 ppm or less. If the effective chlorine concentration is less than 100 ppm, it is not possible to obtain a sufficient effect of improving the adhesiveness between the vulcanized rubbers. Further, when the effective chlorine concentration exceeds 13000 ppm, the adhesiveness between the vulcanized rubbers deteriorates, and there is a risk to the health of the human body. From the same viewpoint, the effective chlorine concentration of the aqueous hypochlorous acid solution is preferably 200 ppm or more, more preferably 300 ppm or more, preferably 8000 ppm or less, and preferably 4000 ppm or less. It is more preferably 1000 ppm or less, further preferably 500 ppm or less.
• the effective chlorine concentration of the hypochlorous acid aqueous solution can be adjusted by the dilution ratio of the hypochlorite such as sodium hypochlorite dissolved in water to obtain the aqueous solution.
• the pH value of the hypochlorous acid aqueous solution can be reduced, for example, by adding hydrochloric acid to the hypochlorous acid aqueous solution, and can be adjusted by the addition ratio of hydrochloric acid.
• the pH value of the aqueous solution obtained by dissolving sodium hypochlorite in water is about 9 to 10.
• a first vulcanized rubber and a second vulcanized rubber are bonded to each other. It is a method of manufacturing an adhesive structure for obtaining an adhesive structure. And, specifically, the manufacturing method of this embodiment The first coating step of coating the surface of the first vulcanized rubber with a hypochlorous acid aqueous solution having a pH value of 2 or more and 7 or less and an effective chlorine concentration of 100 ppm or more and 13000 ppm or less.
• Adhesion process and It is characterized by including. According to the manufacturing method of the present embodiment, it is possible to manufacture an adhesive structure in which vulcanized rubbers are firmly adhered to each other without requiring heating. In addition, the adhesive structure manufactured by the manufacturing method of the present embodiment can significantly withstand deformation and strain (has high fatigue resistance).
• the vulcanized rubber (first vulcanized rubber and second vulcanized rubber) can be produced by vulcanizing a rubber composition containing a rubber component.
• the rubber component include diene-based rubber components such as natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, chloroprene rubber, ethylene-propylene-diene copolymer, and acrylonitrile-butadiene rubber.
• the rubber component may be one kind alone or a combination of two or more kinds.
• the vulcanized rubber and the rubber composition used for producing the vulcanized rubber may be a filler such as carbon black, a vulcanizing agent such as sulfur, a vulcanization accelerator, a vulcanization accelerating aid, depending on the purpose.
• a filler such as carbon black
• a vulcanizing agent such as sulfur
• a vulcanization accelerator such as sulfur
• a vulcanization accelerator such as sulfur
• a vulcanization accelerator such as sulfur
• a vulcanization accelerator such as sulfur
• a vulcanization accelerating aid an appropriate amount of additives such as zinc black, an antioxidant, an antioxidant, a foaming agent, a plasticizer, a lubricant, a tackifier, and an ultraviolet absorber can be contained.
• the vulcanization conditions are not particularly limited.
• the vulcanized rubber may include members other than rubber, such as a fiber member and a metal member, depending on the purpose.
• anti-aging agent examples include aromatic secondary amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphite ester-based anti-aging agents, and the like.
• aromatic secondary amine-based antiaging agent examples include N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (6PPD) and N-isopropyl-N'-phenyl-.
• IPPD p-phenylenediamine
• DPPD N, N'-diphenyl-p-phenylenediamine
• DNPD N, N'-di-2-naphthyl-p-phenylenediamine
• N- (3-methacryloyloxy- 2-Phenylenediamine-based antiaging agents such as 2-hydroxypropyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine; p- (p-toluenesulfonylamide) diphenylamine , 4,4'-Bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine (CD), octylated diphenylamine (ODPA), diphenylamine-based antiaging agents such as styrenated diphenylamine; N-phenyl-1-naphthylamine (PAN),
• the p-phenylenediamine-based antioxidant is preferable as the aromatic secondary amine-based antioxidant, and the p-phenylenediamine-based antioxidant has a structure having no double bond other than the phenylenediamine moiety. It is preferable to have the following general formula (1): A p-phenylenediamine-based compound represented by [in the formula, R 1 and R 2 are independently monovalent saturated hydrocarbon groups] is more preferable. R 1 and R 2 may be the same or different, but are preferably the same from a synthetic point of view.
• the monovalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 6 and 7 carbon atoms.
• R 1 and R 2 in the general formula (1) are independently chain- or cyclic with 1 to 20 carbon atoms from the viewpoint of further improving the ozone resistance of the hydrocarbon rubber and / or the rubber composition. It is preferably a monovalent saturated hydrocarbon group.
• Examples of the monovalent saturated hydrocarbon group include an alkyl group and a cycloalkyl group.
• the alkyl group may be linear or branched, and the cycloalkyl group may be further an alkyl group as a substituent. Etc. may be combined.
• Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1,2-dimethylbutyl group, and 1,3-.
• cycloalkyl group examples include a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, and among these, a cyclohexyl group is preferable.
• the p-phenylenediamine compound represented by the general formula (1) may be supported on any carrier.
• the p-phenylenediamine-based compound represented by the general formula (1) may be supported on an inorganic filler such as silica or calcium carbonate.
• the p-phenylenediamine-based compound represented by the above general formula (1) may form a masterbatch together with the rubber component used for the vulcanized rubber.
• the p-phenylenediamine-based compound represented by the above general formula (1) may be used as a salt with an organic acid.
• the organic acid used for the salt is not particularly limited, and examples thereof include stearic acid.
• the concentration of the aromatic secondary amine-based antioxidant is preferably 1% by mass or less in the first vulcanized rubber and the second vulcanized rubber. Since the aromatic secondary amine-based antiaging agent may have an unintended effect on the adhesiveness between vulcanized rubbers, by suppressing the concentration to 1% by mass or less, the vulcanized rubbers adhere to each other. The sex can be kept high enough.
• the concentration of each component in the vulcanized rubber can usually be calculated from the component composition (blending ratio) of the rubber composition used for producing the vulcanized rubber.
• the above concentration may be satisfied at least on the surface layer of the vulcanized rubber.
• the first vulcanized rubber and the second vulcanized rubber are aromatic secondary amine-based anti-aging in the region at a depth of 10 ⁇ m from the surface in contact with the adhesive (in a later bonding step).
• the concentration of the agent is preferably 1% by mass or less.
• the concentration in the depth region of 10 ⁇ m from the surface of the vulcanized rubber can be measured, for example, by gas chromatography of the surface wipe.
• the concentration of the aromatic secondary amine-based antiaging agent on the surface layer of the vulcanized rubber is determined by, for example, treating the surface of the vulcanized rubber with an organic solvent such as acetone (for example, impregnating it with a waste cloth or the like and wiping it off). Therefore, it can be reduced.
• the concentration of the aromatic secondary amine-based antioxidant in the first vulcanized rubber and the second vulcanized rubber (or their surface layer) shall be 0.6% by mass or less. Is more preferable, 0.3% by mass or less is further preferable, and 0% by mass may be used.
• the first vulcanized rubber and the second vulcanized rubber may be independent vulcanized rubber members, or they may be located at any two positions in the same vulcanized rubber member. You may. Further, the first vulcanized rubber and the second vulcanized rubber may have the same rubber type, the member shape, and the contents of various additives, respectively, or may be different from each other.
• a hypochlorous acid aqueous solution having a pH value of 2 or more and 7 or less and an effective chlorine concentration of 100 ppm or more and 13000 ppm or less is applied to the surface of the first vulcanized rubber.
• the adhesive surface of the vulcanized rubber is treated with an aqueous solution (organic solvent-free), so that rubber deterioration is sufficiently suppressed.
• the coating amount is not particularly limited, and the coating may be applied so as to cover the surface to be adhered.
• the coating method is not particularly limited.
• hypochlorous acid aqueous solution used in the first coating step preferably has a pH value of 4 or more and 7 or less.
• hypochlorous acid aqueous solution it is preferable to apply the hypochlorous acid aqueous solution to the surface of the second vulcanized rubber as well as the first vulcanized rubber.
• the adhesive is applied to the surface of the hypochlorous acid aqueous solution coated in the first coating step.
• the coating amount is not particularly limited, and the coating may be applied so as to cover the hypochlorous acid aqueous solution on the surface of the first vulcanized rubber.
• the coating method is not particularly limited.
• the adhesive is not particularly limited and can be appropriately selected according to the purpose.
• the adhesive may be used alone or in combination of two or more.
• the adhesive it is preferable to use an adhesive that can develop adhesiveness at room temperature, and from the viewpoint of developing sufficiently high adhesiveness, a urethane-based adhesive and / or an epoxy-based adhesive is used. Is preferable. In this case, the vulcanized rubbers can be more firmly bonded to each other.
• the first vulcanized rubber and the second vulcanized rubber are passed through the hypochlorous acid aqueous solution applied in the first coating step and the adhesive applied in the second coating step. And glue.
• the first vulcanized rubber and the second vulcanized rubber can be bonded by bonding them together via a coating material and appropriately applying pressure.
• the coated surfaces of both vulcanized rubbers may be bonded so as to face each other.
• the drying temperature may be normal temperature.
• the drying time can be, for example, about 2 to 7 days.
• a polishing step of polishing the bonded surface of the first vulcanized rubber and the second vulcanized rubber with a grindstone or the like may be performed in advance.
• the adhesiveness can be further improved by the anchor effect.
• the surfaces of the contact target of the first vulcanized rubber and the second vulcanized rubber are treated with an organic solvent such as acetone in advance, and a predetermined component (for example, aromatic first) on the surface layer is treated.
• a step of reducing the concentration of the secondary amine-based antiaging agent may be performed. This step is particularly useful when the concentration of the aromatic secondary amine-based antiaging agent in the rubber composition used for producing the vulcanized rubber is relatively high.
• a first vulture rubber and a second vulnerable rubber form an adhesive layer. It is an adhesive structure bonded through The adhesive layer contains a urethane compound and / or an epoxy compound, and The first vulcanized rubber and the second vulcanized rubber are characterized in that at least a part of the surface in contact with the adhesive layer is chloroylated.
• the vulcanized rubbers are firmly adhered to each other and have excellent fatigue resistance.
• the adhesive structure of the present embodiment can be preferably manufactured by the above-mentioned manufacturing method of the present embodiment. Further, the adhesive structure of the present embodiment can be preferably produced by using the above-mentioned surface treatment agent of the present embodiment.
• first vulcanized rubber and the second vulcanized rubber are the same as those described above.
• the first vulcanized rubber and the second vulcanized rubber have an aromatic first in a depth region of 10 ⁇ m from the surface in contact with the adhesive layer.
• the concentration of the secondary amine-based antiaging agent is preferably 1% by mass or less.
• the urethane compound and / or the epoxy compound contained in the adhesive layer can be derived from the urethane-based adhesive and / or the epoxy-based adhesive as the adhesive.
• the chlorine group is bonded to a carbon atom constituting a rubber molecule existing on the surface of the vulcanized rubber.
• the rubber molecules existing on the surface in contact with the adhesive layer have a hydroxyl group.
• the hydroxyl group is bonded to a carbon atom constituting a rubber molecule existing on the surface of the vulcanized rubber.
• the tire of one embodiment of the present invention is characterized by comprising the adhesive structure of the present embodiment described above. Since the tire of the present embodiment uses the above-mentioned adhesive structure, it is excellent in fatigue resistance.
• the application location of the adhesive structure in the tire is not particularly limited, and can be appropriately selected depending on the purpose.
• the unvulcanized rubber composition was prepared by sufficiently kneading with the compounding formulations shown in Tables 1 and 2. This rubber composition was vulcanized and molded into a predetermined sheet at 165 ° C. for 10 minutes to prepare a pair of vulcanized rubber sheets (first and second vulcanized rubber sheets).
• the first and second vulcanized rubber sheets used in each example are substantially the same as each other, and are referred to as "first" and "second", respectively, from the viewpoint of convenience.
• the first vulcanized rubber sheet and the second vulcanized rubber sheet were immersed in the above-mentioned surface treatment agent for 1 minute to perform surface treatment. After the immersion, the excess liquid adhering to the surface of the first vulcanized rubber sheet is wiped off, and then the adhesive shown in Tables 1 and 2 is applied to the first vulcanized rubber sheet while using a masking tape having a thickness of 100 ⁇ m as a spacer. It was applied to the surface of a vulcanized rubber sheet (coating thickness: 100 ⁇ m). Next, the coated surface of the first vulcanized rubber sheet was placed on the upper side, and the second vulcanized rubber sheet was placed on the coated surface from above.
• the first and second vulcanized rubber sheets having a length of 60 mm, a width of 30 mm and a thickness of 5 mm were used to prepare an adhesive structure as described above.
• the first and second vulcanized rubber sheets having a length of 50 mm, a width of 10 mm, and a thickness of 5 mm are used, and both sheets are placed in the length direction in order to form a handle portion.
• the adhesive structure was produced as described above by shifting them by 10 mm from each other.
• the adhesive structure produced in each example was subjected to a T-shaped peeling test at a tensile speed of 500 mm / min using a universal material testing machine manufactured by Instron, and the peeling force (N / 25 mm) was measured.
• the results are shown in Tables 1 and 2. If the peeling force is 150 N / 25 mm or more, particularly 220 N / 25 mm or more, it can be recognized that the adhesiveness is good.
• Epoxy adhesive "Fusor” manufactured by LORD * 6
• An ethyl acetate solution of trichloroisocyanuric acid 4% (manufactured by LORD) was used instead of the aqueous solution of hypochlorous acid.
• a vulcanized rubber surface treatment agent which enables the vulcanized rubbers to be firmly adhered to each other without requiring heating and has a small influence of rubber deterioration. Further, according to the present invention, it is possible to provide a method for producing an adhesive structure capable of producing an adhesive structure in which vulcanized rubbers are firmly adhered to each other without requiring heating. Further, according to the present invention, it is possible to provide an adhesive structure in which vulcanized rubbers are firmly adhered to each other and have excellent fatigue resistance, and a tire provided with the adhesive structure.

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• Chemical & Material Sciences (AREA)
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• Polymers & Plastics (AREA)
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• Mechanical Engineering (AREA)
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• 2021
  • 2021-10-12 WO PCT/JP2021/037786 patent/WO2022123894A1/ja not_active Ceased
  • 2021-10-12 CN CN202180081674.7A patent/CN116583574B/zh active Active
  • 2021-10-12 EP EP21902998.0A patent/EP4261262B1/en active Active
  • 2021-10-12 US US18/250,791 patent/US20230399544A1/en not_active Abandoned
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