WO2018181631A1 - Adhesive or sizing agent - Google Patents

Adhesive or sizing agent Download PDF

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Publication number
WO2018181631A1
WO2018181631A1 PCT/JP2018/013067 JP2018013067W WO2018181631A1 WO 2018181631 A1 WO2018181631 A1 WO 2018181631A1 JP 2018013067 W JP2018013067 W JP 2018013067W WO 2018181631 A1 WO2018181631 A1 WO 2018181631A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
bonded
sizing agent
rubber
carbon fiber
Prior art date
Application number
PCT/JP2018/013067
Other languages
French (fr)
Japanese (ja)
Inventor
勝朗 塚本
浩晃 塚本
Original Assignee
ジャパンマテックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ジャパンマテックス株式会社 filed Critical ジャパンマテックス株式会社
Priority to JP2018536310A priority Critical patent/JP6456563B1/en
Publication of WO2018181631A1 publication Critical patent/WO2018181631A1/en

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids 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
    • 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

Definitions

  • the present invention relates to an adhesive or a sizing agent, and more specifically, rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.) (hereinafter also simply referred to as rubber material), carbon fibers, and the like
  • rubber products butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.
  • rubber material carbon fibers
  • Organic and inorganic materials can be chemically bonded and bonded at low temperatures, and rubber products and carbon fibers that are bonded and bonded can be easily bonded at the low temperature to easily bond the same or different materials of rubber.
  • -It is related with the adhesive agent or sizing agent which can peel joining.
  • cord materials used for rubber products such as tires and belts are chemically bonded and bonded (in other words, bonded and bonded by functional groups such as OH groups).
  • functional groups such as OH groups.
  • the structure and shape of the side to be deposited and the side to be deposited can be used to physically handle rubber products, regardless of chemical bonding. Are bonded and bonded together.
  • this adhesion / bonding method has a problem that it is very difficult to peel off once it is bonded / bonded, because the side to be bonded and the side to be bonded are firmly bonded / bonded.
  • adhesives or sizing agents including FRP and epoxy resin, which are thermosetting resins are also used for bonding and joining carbon fibers (see, for example, Patent Document 1-2).
  • Carbon fiber is used in various industries such as automobiles and airplanes, but as mentioned above, FRP and epoxy resin, which are thermosetting resins, are also used for bonding and bonding carbon fibers. -It was difficult to recycle the bonded carbon fibers, and many of the used carbon fibers were discarded.
  • Patent Document 1 includes a nanoparticle solution containing a dispersion of transition metal nanoparticles in a solvent and a first fiber sizing agent.
  • An improved fiber sizing agent formulation is described.
  • Ni, Fe, Co, Mo, Cu, Pt, Au, Ag, TiO 2 , ZnO, MnO, SnO and mixtures thereof are used as transition metal nanoparticles.
  • the sizing agent described in Patent Document 1 includes a matrix resin, and an epoxy resin is used as the matrix resin.
  • Patent Document 2 describes a sizing agent for carbon fiber characterized by containing a polymer component and an aromatic nonionic surfactant. ing.
  • the polymer component it is described that an epoxy resin having a hydrophilic group (carbonyl group, hydroxyl group, glycidyl group, amino group, sulfo group, polyethylene group, COOM, SO3M: M is an alkali metal) in the molecule is used. .
  • Patent Document 1 and Patent Document 2 Since the adhesives or sizing agents described in Patent Document 1 and Patent Document 2 use an epoxy resin that is a thermosetting resin as an adhesive component, it is necessary to increase the temperature at the time of bonding of carbon fibers. In addition, there is a problem that the manufacturing cost of the carbon fiber resin tape (that is, the tape of the opened carbon fiber bundle) becomes high. In addition, since an epoxy resin, which is a thermosetting resin, is used, it is difficult to peel off the carbon fibers after bonding the carbon fibers with these adhesives or sizing agents, and it is difficult to recycle the carbon fibers. There was a problem of being.
  • carbon fiber bundles and carbon fiber resin tapes can be bonded and bonded chemically at 60 ° C to 265 ° C, and the bonded and bonded carbon fiber bundles and carbon fiber resin tape can be peeled off.
  • Development of sizing agents or sizing agents is required.
  • rubber products that have been physically bonded and bonded in the past can be chemically bonded and bonded at 60 ° C to 180 ° C, and the bonded and bonded products must be peeled off.
  • a rubber product (such as butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, or silicone rubber) is used at 60 ° C. to 180 ° C. It can be chemically bonded and bonded at 60 ° C, and organic and inorganic materials such as carbon fiber can be bonded and bonded chemically at 60 ° C to 265 ° C.
  • An adhesive or sizing agent that can be easily peeled off and bonded to the same or different materials of rubber by heating at °C to 180 °C or by heating carbon fiber etc. at 60 to 265 °C The purpose is to do.
  • the adhesive or sizing agent is One or more metal oxide sols selected from the group consisting of metal oxide sols of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide; A compound having one or more OH groups selected from the group consisting of potassium persulfate, acetic acid, benzoic acid, phenylphosphonic acid, and benzoyl; It is related with the adhesive agent or sizing agent characterized by being comprised from PVA resin.
  • the invention according to claim 2 relates to the adhesive or sizing agent according to claim 1, wherein the metal oxide sol is made of tin oxide.
  • the invention according to claim 3 relates to the adhesive or sizing agent according to claim 1 or 2, wherein the compound having an OH group is potassium persulfate.
  • the invention according to claim 4 relates to the adhesive or sizing agent according to any one of claims 1 to 3, further comprising an alumina sol.
  • the adhesive or sizing agent is one or more metal oxide sols selected from the group consisting of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide, and persulfuric acid. Since it is composed of a compound having at least one OH group selected from the group consisting of potassium, acetic acid, benzoic acid, phenylphosphonic acid, and benzoyl, and a PVA resin, the OH group contained in the adhesive or sizing agent Accordingly, it is possible to easily bond and bond a rubber product in the range of 60 ° C. to 180 ° C. and carbon fiber and other organic or inorganic materials in the range of 60 ° C. to 265 ° C.
  • the adhesive or sizing agent according to claim 1 since it is chemically bonded and bonded using a PVA resin which is a thermoplastic resin and contains an OH group, The adhesive or sizing agent containing the PVA resin is softened by applying heat or hot water to the carbon fiber, so that the bonded and bonded rubber product and carbon fiber can be easily separated. Therefore, once bonded and bonded rubber products and carbon fibers can be easily recycled.
  • organic and inorganic materials such as rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.) and carbon fiber. After applying the adhesive according to No. 1, organic and inorganic substances such as rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.) and carbon fiber Can be bonded and bonded to materials.
  • the adhesive or sizing agent according to claim 1 it is strong only with other adhesives other than the present invention, such as the same material of rubber materials or carbon fibers or different materials such as rubber materials and carbon fibers.
  • other adhesives other than the present invention, such as the same material of rubber materials or carbon fibers or different materials such as rubber materials and carbon fibers.
  • the adhesive or sizing agent according to claim 1 By impregnating or applying the adhesive or sizing agent according to claim 1 to the materials that could not be bonded / bonded, these materials can be firmly bonded / bonded using other adhesives.
  • the other adhesive and the adhesive or sizing agent according to claim 1 are chemically bonded / bonded, heat is applied to the rubber material or carbon fiber bonded / bonded by the other adhesive.
  • the adhesive or sizing agent according to claim 1 is softened by hot water bathing, and the adhesive force (peeling strength) between the other adhesive and the adhesive or sizing agent according to claim 1 can be reduced, Rubber materials and carbon fibers bonded and bonded with other adhesives can be easily separated. Therefore, it is possible to easily recycle rubber materials, carbon fibers, and the like that are bonded and bonded with other adhesives.
  • the metal oxide sol is a metal oxide sol of tin oxide, and the metal oxide sol of tin oxide is compatible with an adhesive having an OH group or potassium persulfate.
  • the adhesive force of the present invention can be increased, and the effects of claim 1 can be more easily achieved.
  • the compound having the OH group is potassium persulfate having excellent affinity with PVA, PTFE, PI, etc., the handling property of the present invention can be improved, and more The effect of claim 1 can be easily obtained.
  • the adhesive or sizing agent further contains an alumina sol, the effect of any one of claims 1 to 3 can be more easily achieved.
  • the adhesive refers to a substance used for bonding / bonding objects to each other
  • the sizing agent refers to carbon fibers or carbon fibers and other substances among adhesives.
  • the adhesive or sizing agent according to the present invention is composed of one or more metal oxide sols, a compound containing one or more OH groups, and a PVA resin.
  • the metal oxide sol used for the adhesive or sizing agent according to the present invention is at least one selected from the group consisting of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide metal oxide sol. These metal oxide sols contain a large number of OH groups. By using a metal oxide sol containing a large number of OH groups as an adhesive or sizing agent, the number of OH groups contained in the adhesive or sizing agent increases, and the chemical bond strength (adhesive strength) by the OH groups increases. ) Increases, rubber products can be easily bonded and bonded in the range of 60 ° C.
  • the metal oxide sol used for the adhesive or sizing agent according to the present invention is not limited to these, and may be, for example, a metal oxide sol containing a large number of OH groups such as lanthanum oxide, neodymium oxide, cerium oxide, and the like. Anything can be used.
  • the particle size and pH of the metal oxide sol used in the adhesive or sizing agent according to the present invention are not particularly limited, and any particle size or pH that can achieve the effect according to the present invention can be used. Also good.
  • the shape of the metal oxide contained in the metal oxide sol is not particularly limited, and may be any shape such as a plate shape, a column shape, a fiber shape, or a hexagonal plate shape.
  • the metal oxide sol is fibrous, the metal oxide is a fibrous crystal of metal oxide. More specifically, a metal oxide fiber formed from a metal oxide anhydride, a metal oxide hydrate fiber formed from a metal oxide containing a hydrate, and the like can be given.
  • the metal oxide sol (tin oxide, titanium oxide, tantalum oxide, niobium oxide, zirconium oxide, etc.) used for the adhesive or sizing agent according to the present invention
  • Tynock A-6 (TiO 2 wt%: 6, average) Particle size: 20 nm, pH: 12, manufactured by Taki Chemical Co., Ltd.)
  • Tynock AM-15 (TiO 2 wt%: 15, average particle size: 20 nm, pH: 4, manufactured by Taki Chemical Co., Ltd.)
  • Viral Zr-C20 (ZrO 2 % By weight: 20, average particle size: 40 nm, pH: 8, manufactured by Taki Chemical), Viral La-C10 (La 2 O 3 % by weight: 10, average particle size: 40 nm, pH: 8, manufactured by Taki Chemical) Biral Nd-C10 (Nd 2 O 3 wt%: 10, average particle size: 20 nm, pH: 9, manufactured by Taki Chemical), Niedral B-10 (CeO 2 wt
  • the adhesive or sizing agent according to the present invention may further contain an alumina sol in addition to the one or more metal oxide sols.
  • an alumina sol in addition to the one or more metal oxide sols.
  • the adhesive or sizing agent can more easily bond rubber products, carbon fibers, and the like compared to the case where one or more metal oxides are included.
  • the particle diameter and pH of the alumina sol used for the adhesive or sizing agent according to the present invention are not particularly limited, and may be any as long as the effects according to the present invention can be achieved.
  • the shape of the alumina in the alumina sol is not particularly limited, and may be any shape such as a plate shape, a column shape, a fiber shape, or a hexagonal plate shape. Further, when the alumina sol is fibrous, the alumina is a fibrous crystal of alumina. More specifically, examples thereof include alumina fibers formed from anhydrous alumina and alumina hydrate fibers formed from alumina containing hydrates.
  • alumina sol used for the adhesive or sizing agent for example, alumina sol-10A (Al 2 O 3 equivalent weight%: 9.8 to 10.2, particle size nm: 5-15, viscosity 25 ° C., mPa / s: ⁇ 50, pH: 3.4-4.2, manufactured by Kawaken Fine Chemical Co., Ltd., Alumina Sol-A2 (Al 2 O 3 equivalent weight%: 9.8 to 10.2, particle size nm: 10 -20, viscosity 25 ° C., mPa / s: ⁇ 200, pH: 3.4-4.2, manufactured by Kawaken Fine Chemical Co., Ltd., alumina sol-CSA-110AD (Al 2 O 3 equivalent weight%: 6.0-6.
  • the compound containing an OH group used for the adhesive or sizing agent according to the present invention is one or more selected from the group consisting of potassium persulfate, acetic acid, benzoic acid, phenylphosphonic acid, or benzoyl.
  • the number of OH groups contained in the adhesive or sizing agent is increased, and the chemical bonding force (adhesive force) due to the OH groups is increased.
  • Rubber products can be easily bonded and bonded within a temperature range of 180 ° C., and carbon fibers and other organic and inorganic materials can be easily bonded within a temperature range of 60 ° C. to 265 ° C.
  • rubber products bonded and bonded with adhesives or sizing agents are heated in the temperature range of 60 ° C to 180 ° C, or carbon fibers and other organic and inorganic materials are heated in the temperature range of 60 ° C to 265 ° C. It can be easily peeled off. Therefore, rubber products, carbon fibers, and other organic and inorganic materials can be easily recycled.
  • a polyvinyl alcohol (PVA) resin which is a thermoplastic resin as an adhesive component.
  • the PVA resin has the following structural formula and contains many OH groups. Therefore, since it has the characteristics that it is extremely hydrophilic and soluble in hot water, it can bond and join rubber products in the temperature range of 60 ° C to 180 ° C. Carbon fiber resin and the like can be bonded and bonded within a temperature range. Also, since the PVA resin is a thermoplastic resin, once the carbon fiber or the like is bonded and bonded, the bonded or bonded carbon fiber resin or the like is heated again or hot water bath to soften and bond and bond the PVA resin.
  • Carbon fiber resin or the like can be easily peeled off.
  • the PVA resin is stably present in the adhesive even after being blended with the adhesive or the sizing agent, and there is little possibility that the adhesion / bonding force is reduced. Therefore, the adhesive or sizing agent according to the present invention can be used stably over a long period of time.
  • PVA resin that is a thermoplastic resin and contains an OH group as an adhesive or sizing agent
  • Inorganic materials can be easily bonded / bonded and not physically bonded / bonded (that is, not bonded or bonded due to the structure or shape of the applied side and applied side, thermal stress, etc.) Once bonded, it can be easily peeled off.
  • thermoplastic resins such as PP (polypropylene), ABS resin, and 6,6-nylon do not contain OH groups, so they can adhere to rubber products, carbon fibers, and other organic and inorganic substances.
  • PP polypropylene
  • ABS resin polypropylene
  • 6,6-nylon do not contain OH groups, so they can adhere to rubber products, carbon fibers, and other organic and inorganic substances.
  • -PP polypropylene
  • Thermoplastic resins not containing OH groups such as ABS resin and 6,6-nylon, and rubber products, carbon fibers, and other organic and inorganic substances can be bonded and bonded.
  • the adhesive or sizing agent according to the present invention as a binder, those that have conventionally been difficult to bond and join together (for example, those that do not contain an OH group (functional group), etc.) ) Can be bonded / bonded and is not physically bonded / bonded (that is, it is not bonded / bonded due to the structure or shape of the applied side and the applied side, such as fit or thermal stress). It can be easily separated by warm or hot water bathing.
  • the adhesive or sizing agent according to the present invention is composed of one or more metal oxide sols, a compound containing one or more OH groups, and a PVA resin.
  • concentration of these components is not particularly limited, but if the concentration of the adhesive or sizing agent is lower than a predetermined range, there is a possibility that adhesion / bonding may be unintentionally removed.
  • concentration of an adhesive agent or a sizing agent is higher than a predetermined range, there exists a possibility that it may become difficult for an adhesive agent or a sizing agent to osmose
  • the concentration of each component of the adhesive or sizing agent according to the present invention has a preferred range as follows.
  • the concentration of the PVA resin is preferably 0.5 to 30 wt%.
  • the concentration of the metal oxide sol is preferably 0.5 to 16.7 wt%.
  • the concentration ratio between the PVA resin and the metal oxide sol is preferably 3: 1.
  • the concentration of the compound having an OH group is preferably 0.5 to 10 wt%.
  • the adhesive agent or sizing agent concerning this invention may contain other additives etc. in order to modify
  • the additive include a solvent, a tackifier, a plasticizer, a curing agent, and a crosslinking agent.
  • examples include, but are not limited to, diluents, fillers, thickeners, pigments, etc., as long as they are commonly used to modify the properties of adhesives or sizing agents and are obvious to those skilled in the art. Anything can be used.
  • the adhesion / bonding force by the adhesive or sizing agent is further increased.
  • the adhesion / bonding force by the adhesive or sizing agent is further increased.
  • Any adhesive or bonding force can be used, as long as it is obvious to those skilled in the art.
  • the adhesive strength (peeling) of other adhesives to the same material such as rubber materials, carbon fibers, or different materials such as rubber materials and carbon fibers. Strength) can be increased. More specifically, the adhesive or sizing agent according to the present invention is applied or impregnated to the material to be bonded, the other adhesive is applied to the surface of the material to be bonded, and the material to be bonded via the other adhesive These materials can be bonded and bonded together by bringing the surfaces of them into close contact. This effect is caused by chemically bonding the OH group of the adhesive or sizing agent according to the present invention with another adhesive.
  • the adhesive force (peeling strength) of other adhesives can be increased by using the adhesive or sizing agent according to the present invention.
  • the same materials such as rubber materials, carbon fibers, or different materials such as rubber materials and carbon fibers are bonded and joined.
  • the rubber material can be easily bonded and bonded in the temperature range of 60 ° C. to 180 ° C.
  • the carbon fiber and other organic or inorganic materials can be easily bonded in the temperature range of 60 ° C. to 265 ° C.
  • the rubber material bonded / bonded with another adhesive is heated or heated in a temperature range of 60 ° C.
  • the other adhesive means any adhesive other than the adhesive or sizing agent according to the present invention.
  • a carbon fiber bundle composed of a plurality of carbon fibers is immersed in reduced water having a negative oxidation-reduction potential, and the carbon fiber bundle is It consists of a first step of spreading flatly, a second step of immersing the carbon fiber bundle in the adhesive or sizing agent according to the present invention, and a third step of drying the carbon fiber bundle. If you want to add the desired properties to the carbon fiber resin tape, after the third step, there is a fourth step of applying a functional substance such as a heat-resistant, cold-resistant, high-strength pressure-sensitive adhesive or an ultraviolet protection paint to the surface of the carbon fiber. It may be.
  • the carbon fiber bundle is immersed in the water stored in the first tank for a predetermined time.
  • Examples of the carbon fiber bundle include 3K (3,000 bundles), 6K (6000 bundles), 12K (12,000 bundles) and the like of untwisted carbon fibers.
  • the water stored in the first tank is reduced water having a negative redox potential.
  • Ordinary water has a positive oxidation-reduction potential (in the case of tap water: about +400 to +600 mV), but reduced water has a negative oxidation-reduction potential, small water molecule clusters, and excellent penetration.
  • the carbon fiber bundle is naturally expanded without being subjected to physical external forces such as ultrasonic waves by being immersed in such reduced water.
  • the reduced water used in the first step preferably has a redox potential of ⁇ 800 mV or less.
  • the carbon fibers constituting the carbon fiber bundle can be surely spread flat in a short time to obtain a belt-like flat fiber bundle. Further, the obtained belt-like flat fiber bundle is difficult to return to its original state.
  • the production method of the reduced water used in the present invention is not particularly limited, and for example, a gas bubbling method, a method by adding hydrazine, a method by electrolysis, or the like is used.
  • An apparatus for carrying out the method by electrolysis is disclosed by the present applicant in Japanese Patent Application Laid-Open No. 2000-239456, and can be carried out based on this disclosure.
  • ⁇ Second step> The flat fiber bundle obtained by being immersed in reducing water is immersed in an adhesive or a sizing agent in a temperature range of 60 ° C. to 265 ° C. in the second tank.
  • the surface treatment using corona discharge is preferably performed at 5 W ⁇ min / m 2 to 400 W ⁇ min / m 2 , and more preferably at 50 W ⁇ min / m 2 .
  • the flat fiber bundle is immersed in the adhesive, so that one or more metal oxide sols, a compound containing one or more OH groups, and a PVA resin are provided between the spread fibers.
  • Infiltrate sizing agent you may spray an adhesive agent or a sizing agent in the shape of a mist to the carbon fiber (flat fiber bundle) spread flatly by being immersed in reducing water.
  • ⁇ Third step> The spread carbon fiber bundle after being immersed in the adhesive or the sizing agent is taken out from the second layer and then subjected to a drying treatment.
  • the kind of drying apparatus used for the drying process is not particularly limited, and may be a heater heating apparatus, a hot air heating apparatus, a heating apparatus using far infrared rays, or the like. Moreover, you may dry a carbon fiber bundle by natural drying, without using a drying apparatus.
  • the carbon fiber resin tape may be further washed to remove excess adhesive or sizing agent and dried. Excess impurities are removed and the peel strength is improved by leaving the necessary OH groups.
  • the carbon fiber bundle after being dipped in the adhesive or sizing agent is dried, so that one or more metal oxide sols penetrated between the spread fibers and the fibers, and a compound containing one or more OH groups, PVA resin solidifies.
  • the carbon fiber is hardened with an adhesive or a sizing agent in a state where the carbon fiber spreads flat, so that the carbon fiber does not return to its original shape even after a long time, and has a high mechanical strength.
  • a tape is obtained.
  • a fourth step may be performed. From one surface of the carbon fiber resin tape obtained in the third step, for example, an adhesive having one or more physical properties of heat resistance, cold resistance or high strength is applied to the surface of the carbon fiber.
  • an adhesive having one or more physical properties of heat resistance, cold resistance or high strength is applied to the surface of the carbon fiber.
  • polyurethane adhesives, epoxy resin adhesives, silicone rubber adhesives, polytetrafluoroethylene (PTFE) adhesives, etc. are used as pressure sensitive adhesives having one or more physical properties of cold resistance or high strength Can be done.
  • PTFE polytetrafluoroethylene
  • a silicone resin-based paint, an acrylic resin-based paint, a urethane resin-based paint, a fluororesin-based paint, or the like can be used as the ultraviolet ray preventing paint.
  • the fourth step described above is an example, and any step may be used as long as it can add desired characteristics to the carbon fiber resin tape.
  • a comparative test of the adhesive or sizing agent according to the present invention and a conventional adhesive or sizing agent was performed.
  • the peel strength of each adhesive or sizing agent was compared.
  • the peel strength test was conducted according to JIS K 6854-1 (ISO 8510-1) and a 90 ° peel test.
  • the adhesive or sizing agent according to the present invention can adhere and bond the rubber material in the temperature range of 60 ° C. to 180 ° C., and the carbon fiber can be bonded in the temperature range of 60 ° C. to 265 ° C. We were able to bond and join.
  • the adhesive or sizing agent according to the present invention maintains the peel strength even after 2 weeks from the preparation, and can easily bond, bond and peel rubber materials and carbon fibers.
  • the adhesive or sizing agent using a conventional epoxy resin after two weeks has greatly deteriorated the peel strength, making it difficult to bond and join rubber materials and carbon fibers.
  • the components of the adhesive or sizing agent according to the present invention used in Examples 1 to 3 and the concentration of each component are as follows.
  • PVA 5 wt% Niobium metal oxide sol (viral Nb-G6000): 1 wt% Potassium persulfate: 1wt% Water: 93wt%
  • Comparative Examples 1 to 3 a two-component epoxy adhesive (manufactured by Konishi, Bond E set, A agent; epoxy resin 100%, B agent; modified polyamide 100%) was used as a conventional adhesive.
  • the adhesive or sizing agent according to the present invention was uniformly applied by brush to a rubber material having a thickness of 1 mm (purchased from a non-brand rubber plate, Monotaro).
  • the rubber material to which the adhesive or sizing agent according to the present invention is applied and the rubber material to which the adhesive or sizing agent according to the present invention is not applied are brought into close contact with each other, and a flange ( ⁇ 5.5, thickness 2 cm, weight 2. 3 kg) and heated at 60 ° C. for 2 hours while applying a load of about 23 N to bond the rubber materials together.
  • a peel test was performed in accordance with JIS K6854-1 (90 degree peel).
  • Example 2 Open carbon fibers (12K, 150 mm ⁇ 20 mm) are bonded to each other in the same procedure as in Example 1 using the same adhesive or sizing agent according to the present invention as in Example 1, and the same peel test as in Example 1 Carried out.
  • Example 3 A rubber material with a thickness of 1 mm (unbranded rubber plate, purchased as Monotaro) and spread carbon fiber (12K, 150 mm ⁇ 20 mm) were used with the same adhesive or sizing agent according to the present invention as in Example 1. Adhesion was carried out in the same procedure as in Example 1, and a peel test similar to that in Example 1 was performed.
  • bonded rubber material was immersed in hot water of 80 degrees for 30 seconds (hot water bath), and then subjected to a peeling test according to JIS K6854-1 (90 degree peeling).
  • Open carbon fibers (12K, 150 mm ⁇ 20 mm) were bonded together in the same procedure as in Comparative Example 1, and the same peel test as in Comparative Example 1 was performed.
  • ⁇ Comparative Example 3> A rubber material having a thickness of 1 mm (unbranded rubber plate, purchased with Monotaro) and spread carbon fiber (12K, 150 mm ⁇ 20 mm) are bonded in the same procedure as in Comparative Example 1, and the same peeling test as in Comparative Example 1 is performed. Carried out.
  • Table 1 shows the results of the peel tests of Examples 1 to 3 and Comparative Examples 1 to 3.
  • Examples 1 to 3 have a peel strength value of about 0.7 to 1.2, which is lower than that of Comparative Example 1, but the rubber materials are bonded to each other. It is clear that the peel strength is sufficient, and that the peel strength is reduced to half or less by boiling water. On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used. In Comparative Example 2, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength. In addition, even when the hot water bath was used, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
  • Examples 1 to 3 have a peel strength value of about 3.7 to 4.5, which is lower than Comparative Examples 1 and 3, It can be seen that the peel strength is sufficient for bonding, and that the peel strength is reduced to half or less by boiling water. On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used. Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the maximum point test force could not be measured. In addition, even in the case of hot water bath, the maximum point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
  • Examples 1 to 3 have a peel strength value of about 2.2 to 3.7, which is lower than Comparative Examples 1 and 3, but rubber materials and carbon fibers It can be seen that the peel strength is sufficient to bond the film, and that the peel strength is reduced to half or less by boiling water. On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used. Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the average test force could not be measured. In addition, even in the case of hot water bath, the average test force could not be measured because the carbon fiber broke during measurement of the peel strength.
  • the adhesive or sizing agent according to the present invention can bond rubber materials to each other, carbon fibers to each other, and rubber materials to carbon fibers.
  • the adhesive or sizing agent according to the present invention can be easily peeled off by hot water bonding between the rubber materials once bonded, between the carbon fibers, and between the rubber material and the carbon fibers. I found out that it can be recycled.
  • conventional adhesives can bond rubber materials to each other, carbon fibers to each other, and rubber materials to carbon fibers, but once bonded, it is difficult to remove even with a hot water bath. For this reason, it has been found that it is difficult to recycle a material once bonded using a conventional adhesive.
  • Test 2 The rubber material and carbon fiber which apply
  • the components of the adhesive or sizing agent according to the present invention used in Examples 4 to 6 and the concentration of each component are as follows.
  • PVA 5 wt% Niobium metal oxide sol: 1wt% Potassium persulfate: 1wt% Water: 93wt%
  • a two-component epoxy adhesive manufactured by Konishi, Bond E set, agent A; epoxy resin 100%, agent B; modified polyamide 100%
  • Example 4 The adhesive or sizing agent according to the present invention was uniformly applied by brush to a rubber material having a thickness of 1 mm (purchased from a non-brand rubber plate, monotaro), and the applied adhesive or sizing agent according to the present invention was dried. . Drying was performed at 60 ° C. for 30 minutes. In addition, drying was performed using ventilation constant temperature thermostat DN-42 (made by Yamato Scientific Co., Ltd.). Another adhesive was applied to the surface of the rubber material coated with the adhesive or sizing agent according to the present invention using a brush. The rubber materials coated with the adhesive or sizing agent according to the present invention were brought into close contact with each other through other adhesives, and heated at 60 ° C.
  • Example 5 Open carbon fibers (12K, 150 mm ⁇ 20 mm) were bonded together in the same procedure as in Example 4, and the same peel test as in Example 4 was performed.
  • Example 6 A rubber material having a thickness of 1 mm (unbranded rubber plate, purchased with Monotaro) and spread carbon fiber (12K, 150 mm ⁇ 20 mm) were bonded in the same procedure as in Example 4, and the same peel test as in Example 4 was performed. Carried out.
  • Comparative Examples 1 to 3 As Comparative Examples using conventional adhesives, Comparative Examples 1 to 3 were used as in Test 1.
  • Table 2 shows the peel test results of Examples 4 to 6 and Comparative Examples 1 to 3.
  • Examples 4 to 6 have a peel strength value of about 2 to 3.5, which is higher than Comparative Examples 1 and 3. It can be seen that the strength is greatly reduced. On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used. In Comparative Example 2, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength. In addition, even when the hot water bath was used, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
  • the peel strength value is about 11 to 13, which is higher than Comparative Examples 1 and 3, and the peel strength is increased by boiling water. It turns out that it has fallen greatly.
  • Comparative Examples 1 and 3 it can be seen that the peel strength hardly decreases even when the hot water bath is used. Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the maximum point test force could not be measured. In addition, even in the case of hot water bath, the maximum point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
  • Examples 1 to 3 have a peel strength value of about 7 to 11, which is equivalent to Comparative Example 1, higher than Comparative Example 3, It can be seen that the peel strength is greatly reduced. On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used. Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the average test force could not be measured. In addition, even in the case of hot water bath, the average test force could not be measured because the carbon fiber broke during measurement of the peel strength.
  • the adhesive or sizing agent according to the present invention is conventional when the rubber materials, the carbon fibers, and the rubber material and the carbon fibers are bonded to each other through the conventional adhesive. It was found that the adhesive strength of the adhesive can be increased, and the material once adhered can be peeled off by hot water pouring. Therefore, it was found that the material can be adhered more strongly than the case where it is adhered with a conventional adhesive, and can be easily peeled off with a hot water bath, so that the material once adhered can be easily recycled.
  • Example 2 and Comparative Example 2 above the stability of the adhesive or sizing agent according to the present invention was confirmed by a peel test.
  • the peeling test was performed in the same manner as in the above test 1, and was performed according to JISK6854-1 (90 degree peeling).
  • Example 2-1 An adhesive or sizing agent according to the present invention prepared immediately before application to a spread carbon fiber (12K, 150 mm ⁇ 20 mm) was used.
  • Example 2-2 An adhesive or sizing agent according to the present invention prepared two weeks before application to spread carbon fiber (12K, 150 mm ⁇ 20 mm) was used.
  • Comparative Example 2-1 Conventional adhesive (two-part epoxy adhesive (manufactured by Konishi, Bond E set, A agent; epoxy resin 100%) prepared immediately before application to spread carbon fiber (12K, 150 mm ⁇ 20 mm) , B agent; modified polyamide 100%)).
  • Comparative Example 2-2 Conventional adhesive (2-pack epoxy adhesive (Konishi, Bond E set, Agent A; epoxy resin) prepared two weeks before application to spread carbon fiber (12K, 150 mm ⁇ 20 mm) 100%, B agent; modified polyamide 100%)).
  • the adhesive or sizing agent according to the present invention maintained the peel strength even after 2 weeks from the preparation, and was able to easily bond / bond and peel the rubber material and carbon fiber.
  • Conventional adhesives that have passed 2 weeks after preparation have greatly reduced peel strength, making it difficult to adhere and bond rubber products and carbon fibers. From the results of the peeling test, it was found that the adhesive or sizing agent according to the present invention has excellent stability as compared with conventional adhesives.
  • ⁇ Test 4> The peel strength test of the carbon fiber resin tape manufactured using the adhesive or sizing agent according to the present invention was performed.
  • the carbon fiber resin tape used for the peel strength test was manufactured by the above first to third steps, and was cut into 150 mm ⁇ 20 mm.
  • corona treatment was performed, and the corona treatment was performed at 50 W ⁇ min / m 2 .
  • Examples 7 to 12 were used by changing the type of metal oxide sol used for the adhesive or sizing agent.
  • the concentration of each component of the adhesive or sizing agent used in Examples 7 to 12 is as follows.
  • PVA 5 wt% Metal oxide sol: 1wt% Potassium persulfate: 1wt% Water: 97wt%
  • Metal oxide sol Alumina (Alumina sol-10A (Al 2 O 3 equivalent weight%: 9.8 to 10.2, particle size nm: 5-15, viscosity 25 ° C., mPa / s: ⁇ 50, pH: 3.4-4.2, manufactured by Kawaken Fine Chemicals))
  • Metal oxide sol Tin oxide (Cerames S-8 (SnO 2 wt%: 8, average particle size: 8 nm, pH: 10, manufactured by Taki Chemical))
  • Metal oxide sol Zirconium oxide (Viral Zr—C20 (ZrO 2 wt%: 20, average particle size: 40 nm, pH: 8, manufactured by Taki Chemical))
  • Metal oxide sol Titanium oxide (Tynoc A-6 (TiO 2 wt%: 6, average particle size: 20 nm, pH: 12, manufactured by Taki Chemical))
  • Metal oxide sol Titanium oxide (Tynoc AM
  • Comparative Example 4 The carbon fiber resin tape produced in the first step and the third to fourth steps without performing the second step (step of immersing the opened carbon fiber bundle in the adhesive solution) and the corona treatment was used as Comparative Example 4. . In the peeling test, Comparative Example 4 cut to 150 mm ⁇ 20 mm was used.
  • Example 8 had high numerical values in all test forces. In general, a high test force indicates that the adhesiveness is improved, and thus it was found that Example 8 was most excellent from the viewpoint of adhesiveness.
  • the average test force when BIRAL Al-L7 (manufactured by Taki Chemical Co., Ltd.) was used as the alumina sol was 3.03307
  • BIRAL Al-ML15 manufactured by Taki Chemical Co., Ltd.
  • the average test force was 9.86203.
  • the adhesive or sizing agent according to the present invention can easily bond and bond a rubber product in a temperature range of 60 ° C. to 180 ° C., and can be any adherend such as carbon fiber in a temperature range of 60 ° C. to 265 ° C. Can be easily bonded and bonded.
  • the rubber products once bonded and joined can be easily separated by heating them at 60 ° C to 180 ° C, or by heating and hot watering carbon fibers at 60 ° C to 265 ° C.
  • the adherend can be easily recycled. Therefore, the adhesive or sizing agent according to the present invention is suitably used for bonding / bonding all objects to be bonded such as rubber products and carbon fibers.

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Abstract

The purpose of the present invention is to provide an adhesive or a sizing agent, which is capable of chemically bonding/joining rubber products, carbon fibers and the like at low temperatures, while enabling the bonded/joined rubber products or the bonded/joined carbon fibers and the like to be easily separated by heating the rubber products at 60-180°C or by heating the carbon fibers and the like at 60-265°C. An adhesive or a sizing agent according to the present invention is configured of: one or more metal oxide sols selected from the group consisting of metal oxide sols of tin oxide, titanium oxide, tantalum oxide, niobium oxide and zirconium oxide; one or more compounds having an OH group, which are selected from the group consisting of potassium persulfate, acetic acid, benzoic acid, phenylphosphonic acid and benzoyl; and a PVA resin.

Description

接着剤又はサイジング剤Adhesive or sizing agent
　本発明は、接着剤又はサイジング剤に係り、より詳しくは、ゴム製品（ブチルゴム、ウレタンゴム、天然ゴム、ＳＢＲ、合成ゴム、あるいはシリコーンゴム等）（以下、単にゴム材とも称す）や炭素繊維等の有機、無機物質材を低温で化学的に接着・接合することができ、且つ接着・接合されたゴム製品や炭素繊維等を低温で加温することによって容易にゴム同材質、異種材質の接着・接合をはく離することができる接着剤又はサイジング剤に関する。 The present invention relates to an adhesive or a sizing agent, and more specifically, rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.) (hereinafter also simply referred to as rubber material), carbon fibers, and the like Organic and inorganic materials can be chemically bonded and bonded at low temperatures, and rubber products and carbon fibers that are bonded and bonded can be easily bonded at the low temperature to easily bond the same or different materials of rubber. -It is related with the adhesive agent or sizing agent which can peel joining.
　従来から、タイヤやベルト等のゴム製品に用いるコード材（ガラス、ポリエステル、スチール、ケブラー、炭素繊維等）は化学的に接着・接合（言い換えれば、ＯＨ基等の官能基等による接着・接合）できないため、被着する側及び被着される側の構造や形状（例えば、ぎざぎざ、凹凸、焼きばめやしまりばめ等のはめあい等）により、化学的結合によらず、ゴム製品等を物理的に接着・接合している。しかしながら、この接着・接合方法は、被着する側及び被着される側を強固に接着・接合するため、一度接着・接合させると、はく離させることが非常に困難であるという問題があった。
　また、その他の物理的な接着・接合方法として、ゴム製品を熱硬化性樹脂であるエポキシ樹脂や繊維強化プラスチック（ＦＲＰ）等を含む接着剤に含浸し、高温で加熱処理する、あるいはゴム製品を溶かして溶着させる等による接着・接合方法も用いられている。しかしながら、この接着・接合方法は高温での加熱処理が必要であるため、ゴム製品を接着・接合するためには加熱用の大規模な設備が必要となり、接着・接合を容易に実施できないという問題があった。
　また、接着剤として熱硬化性樹脂であるエポキシ樹脂やＦＲＰを使用しているため、接着・接合後に更に熱を加えても樹脂が軟化することはなく、一度接着・接合されたゴム製品をはく離することは非常に困難であり、破砕等の物理的な処理で壊すしかなく、一度接着・接合したゴム製品をリサイクルすることが困難であるという問題があった。
　加えて、エポキシ樹脂やＦＲＰは、接着剤に配合すると接着剤内で化学反応が進んでしまい、１５℃保存で配合後２週間しかその接着性を維持することができず、長期間保存することができないという問題があった。 Conventionally, cord materials (glass, polyester, steel, kevlar, carbon fiber, etc.) used for rubber products such as tires and belts are chemically bonded and bonded (in other words, bonded and bonded by functional groups such as OH groups). Because it is not possible, the structure and shape of the side to be deposited and the side to be deposited (for example, jagged, uneven, fit such as shrink fit and shrink fit) can be used to physically handle rubber products, regardless of chemical bonding. Are bonded and bonded together. However, this adhesion / bonding method has a problem that it is very difficult to peel off once it is bonded / bonded, because the side to be bonded and the side to be bonded are firmly bonded / bonded.
In addition, as another physical bonding / bonding method, rubber products are impregnated with an adhesive containing epoxy resin or fiber reinforced plastic (FRP), which is a thermosetting resin, and heat treatment is performed at a high temperature, or rubber products are Adhesion / joining methods such as melting and welding are also used. However, since this bonding / bonding method requires heat treatment at a high temperature, a large-scale facility for heating is required to bond / bond rubber products, which makes it difficult to perform bonding / bonding easily. was there.
In addition, since epoxy resin or FRP, which is a thermosetting resin, is used as an adhesive, the resin will not soften even if heat is applied after bonding / bonding, and once bonded / bonded rubber products are peeled off. It is very difficult to do this, and it has to be broken only by physical treatment such as crushing, and there is a problem that it is difficult to recycle the rubber product once bonded and bonded.
In addition, when epoxy resin and FRP are blended in an adhesive, the chemical reaction proceeds in the adhesive, and the adhesiveness can only be maintained for two weeks after blending at 15 ° C, and should be stored for a long time. There was a problem that could not.
　叙上のゴム製品と同様に、炭素繊維の接着・接合においても熱硬化性樹脂であるＦＲＰやエポキシ樹脂を含む接着剤又はサイジング剤が用いられている（例えば、特許文献１－２参照）。
　炭素繊維は自動車や飛行機等、様々な産業において用いられているが、叙上の通り、炭素繊維の接着・接合においても熱硬化性樹脂であるＦＲＰやエポキシ樹脂が用いられているため、一度接着・接合した炭素繊維のリサイクルが困難であり、使用された炭素繊維の多くは廃棄されているという問題があった。 Similar to the above rubber products, adhesives or sizing agents including FRP and epoxy resin, which are thermosetting resins, are also used for bonding and joining carbon fibers (see, for example, Patent Document 1-2).
Carbon fiber is used in various industries such as automobiles and airplanes, but as mentioned above, FRP and epoxy resin, which are thermosetting resins, are also used for bonding and bonding carbon fibers. -It was difficult to recycle the bonded carbon fibers, and many of the used carbon fibers were discarded.
　従来の炭素繊維の接着剤又はサイジング剤の例として、例えば、特許文献１には、溶媒中に遷移金属ナノ粒子の分散を含んだナノ粒子溶液と、第１の繊維サイジング剤とを含んで構成された繊維サイジング剤配合剤が記載されている。加えて、遷移金属ナノ粒子としては、Ｎｉ、Ｆｅ、Ｃｏ、Ｍｏ、Ｃｕ、Ｐｔ、Ａｕ、Ａｇ、ＴｉＯ２、ＺｎＯ、ＭｎＯ、ＳｎＯ及びこれらの混合物が用いられることが記載されている。さらに、特許文献１に記載のサイジング剤は、マトリクス樹脂を含み、マトリクス樹脂としてはエポキシ樹脂が用いられることが記載されている。 As an example of a conventional carbon fiber adhesive or sizing agent, for example, Patent Document 1 includes a nanoparticle solution containing a dispersion of transition metal nanoparticles in a solvent and a first fiber sizing agent. An improved fiber sizing agent formulation is described. In addition, it is described that Ni, Fe, Co, Mo, Cu, Pt, Au, Ag, TiO 2 , ZnO, MnO, SnO and mixtures thereof are used as transition metal nanoparticles. Furthermore, it is described that the sizing agent described in Patent Document 1 includes a matrix resin, and an epoxy resin is used as the matrix resin.
　従来の接着剤又はサイジング剤のその他の例として、例えば、特許文献２には、ポリマー成分と芳香族非イオン界面活性剤とを含有してなることを特徴とする炭素繊維用サイジング剤が記載されている。ポリマー成分としては分子中に親水基（カルボニル基、ヒドロキシル基、グリシジル基、アミノ基、スルホ基、ポリエチレン基、ＣＯＯＭ、ＳＯ３Ｍ：Ｍはアルカリ金属）を有するエポキシ樹脂が用いられることが記載されている。 As another example of a conventional adhesive or sizing agent, for example, Patent Document 2 describes a sizing agent for carbon fiber characterized by containing a polymer component and an aromatic nonionic surfactant. ing. As the polymer component, it is described that an epoxy resin having a hydrophilic group (carbonyl group, hydroxyl group, glycidyl group, amino group, sulfo group, polyethylene group, COOM, SO3M: M is an alkali metal) in the molecule is used. .
特許第５５５９８６８号Japanese Patent No. 5559868 特許第５４５５１４１号Patent No. 5455141
　特許文献１及び特許文献２に記載の接着剤又はサイジング剤は、接着成分として熱硬化性樹脂であるエポキシ樹脂を使用しているため、炭素繊維の接着時に高温にする必要があり、炭素繊維束や炭素繊維樹脂テープ（即ち、開繊された炭素繊維束のテープ）の製造コストが高くなるという問題があった。
　加えて、熱硬化性樹脂であるエポキシ樹脂を用いるため、これらの接着剤又はサイジング剤によって炭素繊維を接着した後に、炭素繊維同士をはく離したりすることが困難であり、炭素繊維のリサイクルが困難であるという問題があった。 Since the adhesives or sizing agents described in Patent Document 1 and Patent Document 2 use an epoxy resin that is a thermosetting resin as an adhesive component, it is necessary to increase the temperature at the time of bonding of carbon fibers. In addition, there is a problem that the manufacturing cost of the carbon fiber resin tape (that is, the tape of the opened carbon fiber bundle) becomes high.
In addition, since an epoxy resin, which is a thermosetting resin, is used, it is difficult to peel off the carbon fibers after bonding the carbon fibers with these adhesives or sizing agents, and it is difficult to recycle the carbon fibers. There was a problem of being.
　それゆえに、炭素繊維束や炭素繊維樹脂テープを６０℃～２６５℃で化学的に接着・接合することができ、且つ接着・接合された炭素繊維束や炭素繊維樹脂テープをはく離することができる接着剤又はサイジング剤の開発が求められている。
　加えて、ゴム製品等の従来から物理的に接着・接合されてきたものにおいても、６０℃～１８０℃で化学的に接着・接合することができ、且つ接着・接合されたものをはく離することができる接着剤又はサイジング剤の開発が求められている。 Therefore, carbon fiber bundles and carbon fiber resin tapes can be bonded and bonded chemically at 60 ° C to 265 ° C, and the bonded and bonded carbon fiber bundles and carbon fiber resin tape can be peeled off. Development of sizing agents or sizing agents is required.
In addition, even rubber products that have been physically bonded and bonded in the past can be chemically bonded and bonded at 60 ° C to 180 ° C, and the bonded and bonded products must be peeled off. There is a need to develop adhesives or sizing agents that can be used.
　本発明は、上記したような従来技術の問題点を解決すべくなされたものであって、ゴム製品（ブチルゴム、ウレタンゴム、天然ゴム、ＳＢＲ、合成ゴム、あるいはシリコーンゴム等）を６０℃～１８０℃で化学的に接着・接合することができ、炭素繊維等の有機、無機物質材を６０℃～２６５℃で化学的に接着・接合することができ、且つ接着・接合されたゴム製品を６０℃～１８０℃で加温する、あるいは炭素繊維等を６０℃～２６５℃で加温することによって容易にゴム同材質、異種材質の接着・接合をはく離することができる接着剤又はサイジング剤を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems of the prior art. A rubber product (such as butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, or silicone rubber) is used at 60 ° C. to 180 ° C. It can be chemically bonded and bonded at 60 ° C, and organic and inorganic materials such as carbon fiber can be bonded and bonded chemically at 60 ° C to 265 ° C. Provides an adhesive or sizing agent that can be easily peeled off and bonded to the same or different materials of rubber by heating at ℃ to 180 ℃ or by heating carbon fiber etc. at 60 to 265 ℃ The purpose is to do.
　請求項１に係る発明は、
　接着剤又はサイジング剤であって、
　前記接着剤又はサイジング剤は、
　酸化スズ、酸化チタン、酸化タンタル、酸化ニオブ、および酸化ジルコニウムの金属酸化物ゾルからなる群から選択される一種以上の金属酸化物ゾルと、
　過硫酸カリウム、酢酸、安息香酸、フェニルホスホン酸、およびベンゾイルからなる群から選択される一種以上のＯＨ基を有する化合物と、
　ＰＶＡ樹脂と
から構成されていることを特徴とする、接着剤又はサイジング剤に関する。 The invention according to claim 1
An adhesive or sizing agent,
The adhesive or sizing agent is
One or more metal oxide sols selected from the group consisting of metal oxide sols of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide;
A compound having one or more OH groups selected from the group consisting of potassium persulfate, acetic acid, benzoic acid, phenylphosphonic acid, and benzoyl;
It is related with the adhesive agent or sizing agent characterized by being comprised from PVA resin.
　請求項２に係る発明は、前記金属酸化物ゾルが、酸化スズからなることを特徴とする、請求項１に記載の接着剤又はサイジング剤に関する。 The invention according to claim 2 relates to the adhesive or sizing agent according to claim 1, wherein the metal oxide sol is made of tin oxide.
　請求項３に係る発明は、前記ＯＨ基を有する化合物が、過硫酸カリウムであることを特徴とする、請求項１又は２に記載の接着剤又はサイジング剤に関する。 The invention according to claim 3 relates to the adhesive or sizing agent according to claim 1 or 2, wherein the compound having an OH group is potassium persulfate.
　請求項４に係る発明は、アルミナゾルをさらに含むことを特徴とする、請求項１乃至３のいずれか１項に記載の接着剤又はサイジング剤に関する。 The invention according to claim 4 relates to the adhesive or sizing agent according to any one of claims 1 to 3, further comprising an alumina sol.
　請求項１に係る発明によれば、接着剤又はサイジング剤が、酸化スズ、酸化チタン、酸化タンタル、酸化ニオブ、および酸化ジルコニウムからなる群から選択される一種以上の金属酸化物ゾルと、過硫酸カリウム、酢酸、安息香酸、フェニルホスホン酸、およびベンゾイルからなる群から選択される一種以上のＯＨ基を有する化合物と、ＰＶＡ樹脂とから構成されているため、接着剤又はサイジング剤に含まれるＯＨ基によって、６０℃乃至１８０℃の範囲でゴム製品、６０℃乃至２６５℃の範囲で炭素繊維及びその他の有機物あるいは無機物を容易に接着・接合することができる。それゆえに、ゴム製品を接着・接合させる際にゴム製品を溶かす必要がない。
　加えて、請求項１に係る接着剤又はサイジング剤によれば、熱可塑性樹脂でありＯＨ基を含有するＰＶＡ樹脂を用いて化学的に接着・接合しているため、接着・接合したゴム製品や炭素繊維に熱を加える又は湯せんすることによりＰＶＡ樹脂を含む接着剤又はサイジング剤が軟化して、接着・接合したゴム製品や炭素繊維を容易にはく離できる。それゆえに、一度接着・接合したゴム製品や炭素繊維を容易にリサイクルすることができる。
　さらに、請求項１に係る接着剤又はサイジング剤によれば、ゴム製品（ブチルゴム、ウレタンゴム、天然ゴム、ＳＢＲ、合成ゴム、あるいはシリコーンゴム等）や炭素繊維等の有機、無機物質材に請求項１に係る接着剤をつけた後、任意の添加剤や改質剤を、ゴム製品（ブチルゴム、ウレタンゴム、天然ゴム、ＳＢＲ、合成ゴム、あるいはシリコーンゴム等）や炭素繊維等の有機、無機物質材に接合・接着させることができる。 According to the invention of claim 1, the adhesive or sizing agent is one or more metal oxide sols selected from the group consisting of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide, and persulfuric acid. Since it is composed of a compound having at least one OH group selected from the group consisting of potassium, acetic acid, benzoic acid, phenylphosphonic acid, and benzoyl, and a PVA resin, the OH group contained in the adhesive or sizing agent Accordingly, it is possible to easily bond and bond a rubber product in the range of 60 ° C. to 180 ° C. and carbon fiber and other organic or inorganic materials in the range of 60 ° C. to 265 ° C. Therefore, it is not necessary to melt the rubber product when bonding or joining the rubber product.
In addition, according to the adhesive or sizing agent according to claim 1, since it is chemically bonded and bonded using a PVA resin which is a thermoplastic resin and contains an OH group, The adhesive or sizing agent containing the PVA resin is softened by applying heat or hot water to the carbon fiber, so that the bonded and bonded rubber product and carbon fiber can be easily separated. Therefore, once bonded and bonded rubber products and carbon fibers can be easily recycled.
Further, according to the adhesive or sizing agent according to claim 1, it is claimed for organic and inorganic materials such as rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.) and carbon fiber. After applying the adhesive according to No. 1, organic and inorganic substances such as rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, silicone rubber, etc.) and carbon fiber Can be bonded and bonded to materials.
　さらに、請求項１に係る接着剤又はサイジング剤によれば、ゴム材同士や炭素繊維同士の同材質あるいはゴム材と炭素繊維等の異種材質等、本発明以外の他の接着剤のみでは強固に接着・接合することができなかった材質に、請求項１に係る接着剤又はサイジング剤を含浸あるいは塗布することにより、これらの材質を他の接着剤を用いて強固に接合・接着させることができる。
　加えて、他の接着剤と請求項１に係る接着剤又はサイジング剤は、化学的に接着・接合しているため、他の接着剤によって接着・接合したゴム材や炭素繊維等に熱を加える又は湯せんすることにより請求項１に係る接着剤又はサイジング剤が軟化して、他の接着剤と請求項１に係る接着剤又はサイジング剤間の接着力（はく離強度）を低下させることができ、他の接着剤によって接着・接合したゴム材や炭素繊維等を容易にはく離できる。それゆえに、他の接着剤によって接着・接合したゴム材や炭素繊維等を容易にリサイクルすることができる。 Furthermore, according to the adhesive or sizing agent according to claim 1, it is strong only with other adhesives other than the present invention, such as the same material of rubber materials or carbon fibers or different materials such as rubber materials and carbon fibers. By impregnating or applying the adhesive or sizing agent according to claim 1 to the materials that could not be bonded / bonded, these materials can be firmly bonded / bonded using other adhesives. .
In addition, since the other adhesive and the adhesive or sizing agent according to claim 1 are chemically bonded / bonded, heat is applied to the rubber material or carbon fiber bonded / bonded by the other adhesive. Alternatively, the adhesive or sizing agent according to claim 1 is softened by hot water bathing, and the adhesive force (peeling strength) between the other adhesive and the adhesive or sizing agent according to claim 1 can be reduced, Rubber materials and carbon fibers bonded and bonded with other adhesives can be easily separated. Therefore, it is possible to easily recycle rubber materials, carbon fibers, and the like that are bonded and bonded with other adhesives.
　請求項２に係る発明によれば、前記金属酸化物ゾルが、酸化スズの金属酸化物ゾルであり、酸化スズの金属酸化物ゾルがOH基を有する接着剤や過硫酸カリウムと相性が良いため、本発明の接着力を増加させることができ、より容易に請求項１に記載の効果を奏することができる。 According to the invention of claim 2, the metal oxide sol is a metal oxide sol of tin oxide, and the metal oxide sol of tin oxide is compatible with an adhesive having an OH group or potassium persulfate. The adhesive force of the present invention can be increased, and the effects of claim 1 can be more easily achieved.
　請求項３に係る発明によれば、前記ＯＨ基を有する化合物が、ＰＶＡ、ＰＴＦＥ、ＰＩ等との親和性に優れる過硫酸カリウムであるため、本発明の取り扱い性を向上させることができ、より容易に請求項１に記載の効果を奏することができる。 According to the invention of claim 3, since the compound having the OH group is potassium persulfate having excellent affinity with PVA, PTFE, PI, etc., the handling property of the present invention can be improved, and more The effect of claim 1 can be easily obtained.
　請求項４に係る発明によれば、接着剤又はサイジング剤は、さらにアルミナゾルを含むため、より容易に請求項１乃至３のいずれか１項に記載の効果を奏することができる。 According to the invention of claim 4, since the adhesive or sizing agent further contains an alumina sol, the effect of any one of claims 1 to 3 can be more easily achieved.
　以下、本発明に係る接着剤の好適な実施形態について説明する。
　尚、本明細書において、接着剤とは、物と物とを接着・接合するために使用する物質を言い、サイジング剤とは、接着剤の中でもとりわけ炭素繊維同士あるいは炭素繊維とその他の物質を接着・接合し、場合によっては接着・接合後に加温及び湯せんによりはく離するために使用する物質を言う。
　本発明に係る接着剤又はサイジング剤は、一種以上の金属酸化物ゾルと、一種以上のＯＨ基を含有する化合物と、ＰＶＡ樹脂とから構成される。 Hereinafter, preferred embodiments of the adhesive according to the present invention will be described.
In the present specification, the adhesive refers to a substance used for bonding / bonding objects to each other, and the sizing agent refers to carbon fibers or carbon fibers and other substances among adhesives. A substance used for bonding and joining, and in some cases, for peeling off by heating and hot water after bonding and joining.
The adhesive or sizing agent according to the present invention is composed of one or more metal oxide sols, a compound containing one or more OH groups, and a PVA resin.
　本発明に係る接着剤又はサイジング剤に用いる金属酸化物ゾルは、酸化スズ、酸化チタン、酸化タンタル、酸化ニオブ、および酸化ジルコニウムの金属酸化物ゾルからなる群から選択される一種以上である。
　これらの金属酸化物ゾルはＯＨ基を多数含有している。ＯＨ基を多数含有している金属酸化物ゾルを接着剤又はサイジング剤として用いることにより、接着剤又はサイジング剤に含まれるＯＨ基の数が増加し、ＯＨ基による化学的な結合力（接着力）が増加するため、６０℃乃至１８０℃の範囲でゴム製品、６０℃乃至２６５℃の範囲で炭素繊維及びその他の有機物や無機物を容易に接着、接合することができる。加えて、接着剤又はサイジング剤により接着・接合したゴム製品、炭素繊維、及びその他の有機物や無機物を容易にはく離することができる。それゆえに、容易にゴム製品、炭素繊維、及びその他の有機物や無機物等をリサイクルすることができる。
　尚、本発明に係る接着剤又はサイジング剤に用いる金属酸化物ゾルはこれらに限定されず、例えば、酸化ランタン、酸化ネオジム、酸化セリウム等、ＯＨ基を多数含有している金属酸化物ゾルであれば、いかなるものでも用いることができる。
　また、本発明に係る接着剤又はサイジング剤に用いる金属酸化物ゾルの粒径やｐＨは特に限定されず、本発明に係る効果を奏することができる粒径やｐＨであればいかなるものであってもよい。 The metal oxide sol used for the adhesive or sizing agent according to the present invention is at least one selected from the group consisting of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide metal oxide sol.
These metal oxide sols contain a large number of OH groups. By using a metal oxide sol containing a large number of OH groups as an adhesive or sizing agent, the number of OH groups contained in the adhesive or sizing agent increases, and the chemical bond strength (adhesive strength) by the OH groups increases. ) Increases, rubber products can be easily bonded and bonded in the range of 60 ° C. to 180 ° C., and carbon fibers and other organic and inorganic materials can be easily bonded in the range of 60 ° C. to 265 ° C. In addition, rubber products, carbon fibers, and other organic and inorganic substances bonded and bonded with an adhesive or sizing agent can be easily separated. Therefore, rubber products, carbon fibers, and other organic and inorganic materials can be easily recycled.
The metal oxide sol used for the adhesive or sizing agent according to the present invention is not limited to these, and may be, for example, a metal oxide sol containing a large number of OH groups such as lanthanum oxide, neodymium oxide, cerium oxide, and the like. Anything can be used.
Further, the particle size and pH of the metal oxide sol used in the adhesive or sizing agent according to the present invention are not particularly limited, and any particle size or pH that can achieve the effect according to the present invention can be used. Also good.
　金属酸化物ゾルに含まれる金属酸化物の形状は特に限定されず、板状、柱状、繊維状、六角板状等、いかなる形状であってもよい。
　また、金属酸化物ゾルが繊維状の場合、金属酸化物は、金属酸化物の繊維状結晶である。より具体的には、金属酸化物の無水和物で形成された金属酸化物ファイバー、水和物を含む金属酸化物で形成された金属酸化物水和物ファイバー等が挙げられる。 The shape of the metal oxide contained in the metal oxide sol is not particularly limited, and may be any shape such as a plate shape, a column shape, a fiber shape, or a hexagonal plate shape.
When the metal oxide sol is fibrous, the metal oxide is a fibrous crystal of metal oxide. More specifically, a metal oxide fiber formed from a metal oxide anhydride, a metal oxide hydrate fiber formed from a metal oxide containing a hydrate, and the like can be given.
　本発明に係る接着剤又はサイジング剤に用いる金属酸化物ゾル（酸化スズ、酸化チタン、酸化タンタル、酸化ニオブ、あるいは酸化ジルコニウム等）として、例えば、タイノックＡ－６（ＴｉＯ２重量％：６、平均粒子径：２０ｎｍ、ｐＨ：１２、多木化学製）、タイノックＡＭ－１５（ＴｉＯ２重量％：１５、平均粒子径：２０ｎｍ、ｐＨ：４、多木化学製）、バイラールＺｒ－Ｃ２０（ＺｒＯ２重量％：２０、平均粒子径：４０ｎｍ、ｐＨ：８、多木化学製）、バイラールＬａ－Ｃ１０（Ｌａ２Ｏ３重量％：１０、平均粒子径：４０ｎｍ、ｐＨ：８、多木化学製）、バイラールＮｄ－Ｃ１０（Ｎｄ２Ｏ３重量％：１０、平均粒子径：２０ｎｍ、ｐＨ：９、多木化学製）、ニードラールＢ－１０（ＣｅＯ２重量％：１０、平均粒子径：２０ｎｍ、ｐＨ：８、多木化学製）、セラメースＳ－８（ＳｎＯ２重量％：８、平均粒子径：８ｎｍ、ｐＨ：１０、多木化学製）、バイラールＮｂ－Ｇ６０００（Ｎｂ２Ｏ３重量％：６、平均粒子径：１５ｎｍ、ｐＨ：８、多木化学製）等が挙げられるが、これに限定されず、酸化スズ、酸化チタン、酸化タンタル、酸化ニオブ、あるいは酸化ジルコニウム等、ＯＨ基を多数含有している金属酸化物ゾルであり、当業者に自明のものであれば、いかなるものでも用いることができる。 As the metal oxide sol (tin oxide, titanium oxide, tantalum oxide, niobium oxide, zirconium oxide, etc.) used for the adhesive or sizing agent according to the present invention, for example, Tynock A-6 (TiO 2 wt%: 6, average) Particle size: 20 nm, pH: 12, manufactured by Taki Chemical Co., Ltd.), Tynock AM-15 (TiO 2 wt%: 15, average particle size: 20 nm, pH: 4, manufactured by Taki Chemical Co., Ltd.), Viral Zr-C20 (ZrO 2 % By weight: 20, average particle size: 40 nm, pH: 8, manufactured by Taki Chemical), Viral La-C10 (La 2 O 3 % by weight: 10, average particle size: 40 nm, pH: 8, manufactured by Taki Chemical) Biral Nd-C10 (Nd 2 O 3 wt%: 10, average particle size: 20 nm, pH: 9, manufactured by Taki Chemical), Niedral B-10 (CeO 2 wt%: 10, average particle size) : 20 nm, pH: 8, manufactured by Taki Chemical Co., Ltd.), Cerames S-8 (SnO 2 wt%: 8, average particle size: 8 nm, pH: 10, manufactured by Taki Chemical Co., Ltd.), Viral Nb-G6000 (Nb 2 O 3 (% By weight: 6, average particle size: 15 nm, pH: 8, manufactured by Taki Chemical Co., Ltd.) and the like, but not limited thereto, tin oxide, titanium oxide, tantalum oxide, niobium oxide, zirconium oxide, etc., OH Any metal oxide sol containing a large number of groups can be used as long as it is obvious to those skilled in the art.
　また、本発明に係る接着剤又はサイジング剤は、上記の一種以上の金属酸化物ゾルとは別に、アルミナゾルをさらに含んでいても良い。
　接着剤又はサイジング剤が、上記した一種以上の金属酸化物ゾルとアルミナゾルとを含むことにより、一種以上の金属酸化物を含む場合と比較して、より容易にゴム製品や炭素繊維等を接着・接合することができるうえ、接着・接合したゴム製品や炭素繊維等をより容易にはく離することができる。
　尚、本発明に係る接着剤又はサイジング剤に用いるアルミナゾルの粒径やｐＨは特に限定されず、本発明に係る効果を奏することができるものであれば、いかなるものであってもよい。 Further, the adhesive or sizing agent according to the present invention may further contain an alumina sol in addition to the one or more metal oxide sols.
By including one or more metal oxide sols and alumina sol as described above, the adhesive or sizing agent can more easily bond rubber products, carbon fibers, and the like compared to the case where one or more metal oxides are included. In addition to being able to be joined, it is possible to more easily release rubber products and carbon fibers that are bonded and joined.
In addition, the particle diameter and pH of the alumina sol used for the adhesive or sizing agent according to the present invention are not particularly limited, and may be any as long as the effects according to the present invention can be achieved.
　アルミナゾルのアルミナの形状は特に限定されず、板状、柱状、繊維状、六角板状等、いかなる形状であってもよい。
　また、アルミナゾルが繊維状の場合のアルミナは、アルミナの繊維状結晶である。より具体的には、アルミナの無水和物で形成されたアルミナファイバー、水和物を含むアルミナで形成されたアルミナ水和物ファイバー等が挙げられる。 The shape of the alumina in the alumina sol is not particularly limited, and may be any shape such as a plate shape, a column shape, a fiber shape, or a hexagonal plate shape.
Further, when the alumina sol is fibrous, the alumina is a fibrous crystal of alumina. More specifically, examples thereof include alumina fibers formed from anhydrous alumina and alumina hydrate fibers formed from alumina containing hydrates.
　本発明に係る接着剤又はサイジング剤に用いるアルミナゾルとして、例えば、アルミナゾル－１０Ａ（Ａｌ２Ｏ３換算重量％：９．８～１０．２、粒子の大きさｎｍ：５－１５、粘度２５℃，ｍＰａ／ｓ：＜５０、ｐＨ：３．４－４．２、川研ファインケミカル製）、アルミナゾル－Ａ２（Ａｌ２Ｏ３換算重量％：９．８～１０．２、粒子の大きさｎｍ：１０－２０、粘度２５℃，ｍＰａ／ｓ：＜２００、ｐＨ：３．４－４．２、川研ファインケミカル製）、アルミナゾル－ＣＳＡ－１１０ＡＤ（Ａｌ２Ｏ３換算重量％：６．０～６．４、粒子の大きさｎｍ：５－１５、粘度２５℃，ｍＰａ／ｓ：＜５０、ｐＨ：３．８－４．５、川研ファインケミカル製）、アルミナゾル－Ｆ１０００（Ａｌ２Ｏ３換算重量％：４．８～５．２、粒子の大きさｎｍ：１４００、粘度２５℃，ｍＰａ／ｓ：＜１０００、ｐＨ：２．９－３．３、川研ファインケミカル製）、アルミナゾル－Ｆ３０００（Ａｌ２Ｏ３換算重量％：４．８～５．２、粒子の大きさｎｍ：２０００－４５００、粘度２５℃，ｍＰａ／ｓ：＜１０００、ｐＨ：２．７－３．３、川研ファインケミカル製）等が挙げられるが、これに限定されず、本発明に係る効果を奏することができ、当業者に自明のアルミナゾルであれば、いかなるものでも用いることができる。 As the alumina sol used for the adhesive or sizing agent according to the present invention, for example, alumina sol-10A (Al 2 O 3 equivalent weight%: 9.8 to 10.2, particle size nm: 5-15, viscosity 25 ° C., mPa / s: <50, pH: 3.4-4.2, manufactured by Kawaken Fine Chemical Co., Ltd., Alumina Sol-A2 (Al 2 O 3 equivalent weight%: 9.8 to 10.2, particle size nm: 10 -20, viscosity 25 ° C., mPa / s: <200, pH: 3.4-4.2, manufactured by Kawaken Fine Chemical Co., Ltd., alumina sol-CSA-110AD (Al 2 O 3 equivalent weight%: 6.0-6. 4. Particle size nm: 5-15, viscosity 25 ° C., mPa / s: <50, pH: 3.8-4.5, manufactured by Kawaken Fine Chemical), Alumina Sol-F1000 (Al 2 O 3 equivalent weight%) : 4.8-5.2, grain Size nm: 1400, viscosity 25 ℃, mPa / s: < 1000, pH: 2.9-3.3, manufactured by Kawaken Fine Chemicals), alumina sol -F3000 (Al 2 O 3 in terms of weight percent: 4.8 to 5.2, particle size nm: 2000-4500, viscosity 25 ° C., mPa / s: <1000, pH: 2.7-3.3, manufactured by Kawaken Fine Chemicals) and the like. Any of the alumina sols that can provide the effects of the present invention and are obvious to those skilled in the art can be used.
　本発明に係る接着剤又はサイジング剤に用いるＯＨ基を含有する化合物は、過硫酸カリウム、酢酸、安息香酸、フェニルホスホン酸、あるいはベンゾイルからなる群から選択される一種以上である。
　接着剤又はサイジング剤にこれらの化合物を加えることにより、接着剤又はサイジング剤に含まれるＯＨ基の数が増加し、ＯＨ基による化学的な結合力（接着力）が増加するため、６０℃乃至１８０℃の温度範囲でゴム製品、６０℃乃至２６５℃の温度範囲で炭素繊維及びその他の有機物や無機物を容易に接着・接合することができる。加えて、接着剤又はサイジング剤により接着・接合したゴム製品を６０℃乃至１８０℃の温度範囲で加温する、あるいは炭素繊維及びその他の有機物や無機物を６０℃乃至２６５℃の温度範囲で加温することにより容易にはく離することができる。それゆえに、容易にゴム製品、炭素繊維、及びその他の有機物や無機物等をリサイクルすることができる。 The compound containing an OH group used for the adhesive or sizing agent according to the present invention is one or more selected from the group consisting of potassium persulfate, acetic acid, benzoic acid, phenylphosphonic acid, or benzoyl.
By adding these compounds to the adhesive or sizing agent, the number of OH groups contained in the adhesive or sizing agent is increased, and the chemical bonding force (adhesive force) due to the OH groups is increased. Rubber products can be easily bonded and bonded within a temperature range of 180 ° C., and carbon fibers and other organic and inorganic materials can be easily bonded within a temperature range of 60 ° C. to 265 ° C. In addition, rubber products bonded and bonded with adhesives or sizing agents are heated in the temperature range of 60 ° C to 180 ° C, or carbon fibers and other organic and inorganic materials are heated in the temperature range of 60 ° C to 265 ° C. It can be easily peeled off. Therefore, rubber products, carbon fibers, and other organic and inorganic materials can be easily recycled.
　本発明に係る接着剤又はサイジング剤には、接着成分として熱可塑性樹脂であるポリビニルアルコール（ＰＶＡ）樹脂を用いることが望ましい。
　ＰＶＡ樹脂は以下に示す構造式を有しており、多くのＯＨ基を含有している。それゆえに、親水性が非常に強く、温水に可溶であるという特徴を備えているため、６０℃乃至１８０℃の温度範囲でゴム製品を接着・接合することができ、６０℃乃至２６５℃の温度範囲で炭素繊維樹脂等を接着・接合することができる。
　また、ＰＶＡ樹脂は熱可塑性樹脂であるため、一度炭素繊維等を接着・接合した後、接着・接合した炭素繊維樹脂等を再度加熱あるいは湯せんすることにより、ＰＶＡ樹脂が軟化し、接着・接合した炭素繊維樹脂等を容易にはく離することができる。
　加えて、ＰＶＡ樹脂は、接着剤又はサイジング剤に配合された後でも安定に接着剤中に存在し、接着・接合力が低下する虞が少ない。そのため、本発明に係る接着剤又はサイジング剤は長期間に亘って安定に使用することができる。
　接着剤又はサイジング剤に熱可塑性樹脂でありＯＨ基を含有するＰＶＡ樹脂を用いることにより、従来のように接着・接合時に高温で加熱する必要が無く、ゴム製品、炭素繊維、及びその他の有機物や無機物を容易に接着・接合することができ、且つ物理的な接着・接合でない（即ち、被着する側及び被着される側の構造や形状によるはめあいや熱応力等の接着・接合でない）ため、一度接着した物を容易にはく離することができる。 In the adhesive or sizing agent according to the present invention, it is desirable to use a polyvinyl alcohol (PVA) resin which is a thermoplastic resin as an adhesive component.
The PVA resin has the following structural formula and contains many OH groups. Therefore, since it has the characteristics that it is extremely hydrophilic and soluble in hot water, it can bond and join rubber products in the temperature range of 60 ° C to 180 ° C. Carbon fiber resin and the like can be bonded and bonded within a temperature range.
Also, since the PVA resin is a thermoplastic resin, once the carbon fiber or the like is bonded and bonded, the bonded or bonded carbon fiber resin or the like is heated again or hot water bath to soften and bond and bond the PVA resin. Carbon fiber resin or the like can be easily peeled off.
In addition, the PVA resin is stably present in the adhesive even after being blended with the adhesive or the sizing agent, and there is little possibility that the adhesion / bonding force is reduced. Therefore, the adhesive or sizing agent according to the present invention can be used stably over a long period of time.
By using a PVA resin that is a thermoplastic resin and contains an OH group as an adhesive or sizing agent, there is no need to heat at high temperatures during bonding and bonding as in the past, and rubber products, carbon fibers, and other organic substances Inorganic materials can be easily bonded / bonded and not physically bonded / bonded (that is, not bonded or bonded due to the structure or shape of the applied side and applied side, thermal stress, etc.) Once bonded, it can be easily peeled off.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　また、その他の熱可塑性樹脂であるＰＰ（ポリプロピレン）、ＡＢＳ樹脂、６，６－ナイロン等はＯＨ基を含有していないため、これら単体ではゴム製品、炭素繊維、及びその他の有機物や無機物と接着・接合することはできないが、本発明に係る接着剤又はサイジング剤を結合剤として用いることにより、単体ではゴム製品、炭素繊維、及びその他の有機物や無機物と接着・接合することができないＰＰ（ポリプロピレン）、ＡＢＳ樹脂、６，６－ナイロン等のＯＨ基を含有していない熱可塑性樹脂とゴム製品、炭素繊維、及びその他の有機物や無機物とを接着・接合することができる。即ち、本発明に係る接着剤又はサイジング剤を結合剤として用いることにより、従来では接着・接合することが困難であったもの同士（例えば、ＯＨ基（官能基）を含有していないもの同士等）を接着・接合することができ、且つ物理的な接着・接合でない（即ち、被着する側及び被着される側の構造や形状によるはめあいや熱応力等の接着・接合でない）ため、加温又は湯せんすることにより、容易にはく離することができる。 In addition, other thermoplastic resins such as PP (polypropylene), ABS resin, and 6,6-nylon do not contain OH groups, so they can adhere to rubber products, carbon fibers, and other organic and inorganic substances. -PP (polypropylene) that cannot be bonded but cannot be bonded and bonded to rubber products, carbon fibers, and other organic or inorganic substances by itself using the adhesive or sizing agent according to the present invention as a binder. ), Thermoplastic resins not containing OH groups such as ABS resin and 6,6-nylon, and rubber products, carbon fibers, and other organic and inorganic substances can be bonded and bonded. That is, by using the adhesive or sizing agent according to the present invention as a binder, those that have conventionally been difficult to bond and join together (for example, those that do not contain an OH group (functional group), etc.) ) Can be bonded / bonded and is not physically bonded / bonded (that is, it is not bonded / bonded due to the structure or shape of the applied side and the applied side, such as fit or thermal stress). It can be easily separated by warm or hot water bathing.
　叙上の通り、本発明に係る接着剤又はサイジング剤は、一種以上の金属酸化物ゾルと、一種以上のＯＨ基を含有する化合物と、ＰＶＡ樹脂とから構成されている。
　これらの構成要素の濃度は特に限定されないが、接着剤又はサイジング剤の濃度が所定の範囲より低いと、接着・接合が意図せず外れてしまう虞がある。また、接着剤又はサイジング剤の濃度が所定の範囲より高いと、接着剤又はサイジング剤がゴム製品や炭素繊維等の被接着物に浸透し難くなる虞がある。それゆえに、本発明に係る接着剤又はサイジング剤の各構成要素の濃度には、以下の通りの好適な範囲がある。
　ＰＶＡ樹脂の濃度は、０．５～３０ｗｔ％が好ましい。
　金属酸化物ゾルの濃度は、０．５～１６．７ｗｔ％が好ましい。金属酸化物ゾルの濃度が０．５ｗｔ％より低いと、被接着物間の接着強さが低くなる虞がある。また、金属酸化物ゾルの濃度が１６．７ｗｔ％より高くても、被接着物間の接着強さはそれ以上には増加し難い。
　ＰＶＡ樹脂と金属酸化物ゾルとの濃度比は３：１が好ましい。また、ＯＨ基を有する化合物の濃度は０．５～１０ｗｔ％が好ましい。 As described above, the adhesive or sizing agent according to the present invention is composed of one or more metal oxide sols, a compound containing one or more OH groups, and a PVA resin.
The concentration of these components is not particularly limited, but if the concentration of the adhesive or sizing agent is lower than a predetermined range, there is a possibility that adhesion / bonding may be unintentionally removed. Moreover, when the density | concentration of an adhesive agent or a sizing agent is higher than a predetermined range, there exists a possibility that it may become difficult for an adhesive agent or a sizing agent to osmose | permeate adherends, such as a rubber product and carbon fiber. Therefore, the concentration of each component of the adhesive or sizing agent according to the present invention has a preferred range as follows.
The concentration of the PVA resin is preferably 0.5 to 30 wt%.
The concentration of the metal oxide sol is preferably 0.5 to 16.7 wt%. When the concentration of the metal oxide sol is lower than 0.5 wt%, the adhesion strength between the adherends may be lowered. Further, even if the concentration of the metal oxide sol is higher than 16.7 wt%, the adhesion strength between the adherends hardly increases further.
The concentration ratio between the PVA resin and the metal oxide sol is preferably 3: 1. The concentration of the compound having an OH group is preferably 0.5 to 10 wt%.
　尚、本発明にかかる接着剤又はサイジング剤は、上記した構成成分以外にも、接着剤又はサイジング剤を改質するためにその他の添加物等を含有していてもよい。
　添加物としては、例えば、溶剤、粘着付与剤、可塑剤、硬化剤、架橋剤。希釈剤、充填剤、増粘剤、顔料等が挙げられるが、これに限定されず、接着剤又はサイジング剤の性質を改質するために通常用いられ、当業者に自明のものであれば、いかなるものでも用いることができる。 In addition, the adhesive agent or sizing agent concerning this invention may contain other additives etc. in order to modify | reform an adhesive agent or a sizing agent besides the above-mentioned structural component.
Examples of the additive include a solvent, a tackifier, a plasticizer, a curing agent, and a crosslinking agent. Examples include, but are not limited to, diluents, fillers, thickeners, pigments, etc., as long as they are commonly used to modify the properties of adhesives or sizing agents and are obvious to those skilled in the art. Anything can be used.
　また、本発明に係る接着剤又はサイジング剤が塗布される前、あるいは塗布された後の被接着物にコロナ放電及びプラズマ処理を施すことによって接着剤又はサイジング剤による接着・接合力をより高めることができる。
　被接着物に施すコロナ放電及びプラズマ処理の種類や条件等は特に限定されず、接着・接合力をより高めることができ、当業者に自明のものであれば、いかなるものでも用いることができる。 Further, by applying corona discharge and plasma treatment to the adherend before or after the adhesive or sizing agent according to the present invention is applied, the adhesion / bonding force by the adhesive or sizing agent is further increased. Can do.
There are no particular limitations on the types and conditions of corona discharge and plasma treatment applied to the adherend, and any adhesive or bonding force can be used, as long as it is obvious to those skilled in the art.
　加えて、本発明に係る接着剤又はサイジング剤を用いることで、ゴム材同士、炭素繊維同士等の同材質、あるいはゴム材と炭素繊維等の異種材質に対する、他の接着剤の接着力（はく離強度）を高めることができる。
　より具体的には、本発明に係る接着剤又はサイジング剤を、接着したい材質に塗布又は含浸させ、接着したい材質の表面に他の接着剤を塗布し、他の接着剤を介して接着したい材質の表面同士を密着させることで、これらの材質を接着・接合することができる。
　この効果は、本発明に係る接着剤又はサイジング剤のＯＨ基と他の接着剤が化学的に結合することにより生じる。 In addition, by using the adhesive or sizing agent according to the present invention, the adhesive strength (peeling) of other adhesives to the same material such as rubber materials, carbon fibers, or different materials such as rubber materials and carbon fibers. Strength) can be increased.
More specifically, the adhesive or sizing agent according to the present invention is applied or impregnated to the material to be bonded, the other adhesive is applied to the surface of the material to be bonded, and the material to be bonded via the other adhesive These materials can be bonded and bonded together by bringing the surfaces of them into close contact.
This effect is caused by chemically bonding the OH group of the adhesive or sizing agent according to the present invention with another adhesive.
　叙上の通り、本発明に係る接着剤又はサイジング剤を用いることで、他の接着剤の接着力（はく離強度）を増加させることができる。
　また、本発明に係る接着剤又はサイジング剤と他の接着剤を用いて、ゴム材同士、炭素繊維同士等の同材質、あるいはゴム材と炭素繊維等の異種材質を接着・接合した場合においても、６０℃乃至１８０℃の温度範囲でゴム材、６０℃乃至２６５℃の温度範囲で炭素繊維及びその他の有機物や無機物を容易に接着・接合することができる。
　加えて、他の接着剤により接着・接合したゴム材を６０℃乃至１８０℃の温度範囲で加温又は湯せんする、あるいは炭素繊維及びその他の有機物や無機物を６０℃乃至２６５℃の温度範囲で加温又は湯せんすることにより、接着したもの同士を容易にはく離することができる。
　それゆえに、他の接着剤により接着・接合したゴム材同士、炭素繊維同士等の同材質、あるいはゴム材と炭素繊維等の異種材質及びその他の有機物や無機物等を容易にリサイクルすることができる。 As described above, the adhesive force (peeling strength) of other adhesives can be increased by using the adhesive or sizing agent according to the present invention.
In addition, when the adhesive or sizing agent according to the present invention and other adhesives are used, the same materials such as rubber materials, carbon fibers, or different materials such as rubber materials and carbon fibers are bonded and joined. The rubber material can be easily bonded and bonded in the temperature range of 60 ° C. to 180 ° C., and the carbon fiber and other organic or inorganic materials can be easily bonded in the temperature range of 60 ° C. to 265 ° C.
In addition, the rubber material bonded / bonded with another adhesive is heated or heated in a temperature range of 60 ° C. to 180 ° C., or carbon fiber and other organic or inorganic materials are added in a temperature range of 60 ° C. to 265 ° C. By adhering to warm or hot water, the adhered objects can be easily separated.
Therefore, it is possible to easily recycle the same material such as rubber materials bonded to each other with another adhesive, carbon fibers or the like, or different materials such as rubber material and carbon fiber, and other organic or inorganic materials.
　尚、本明細書中において、他の接着剤とは、本発明に係る接着剤又はサイジング剤以外のあらゆる接着剤のことをいう。 In the present specification, the other adhesive means any adhesive other than the adhesive or sizing agent according to the present invention.
　以下、本発明に係る接着剤又はサイジング剤を用いた炭素繊維樹脂テープの製造方法の一例について詳述する。
　尚、以下に示す本発明に係る接着剤又はサイジング剤を用いた炭素繊維樹脂テープの製造方法は一例に過ぎず、これに限定されない。 Hereinafter, an example of the manufacturing method of the carbon fiber resin tape using the adhesive agent or sizing agent according to the present invention will be described in detail.
In addition, the manufacturing method of the carbon fiber resin tape using the adhesive agent or sizing agent which concerns on this invention shown below is only an example, and is not limited to this.
　本発明に係る接着剤又はサイジング剤を用いた炭素繊維樹脂テープの製造方法は、複数本の炭素繊維からなる炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、前記炭素繊維束を、本発明に係る接着剤又はサイジング剤に浸漬する第二工程と、前記炭素繊維束を乾燥させる第三工程とからなる。
　尚、炭素繊維樹脂テープに所望の特性を付加したい場合は、第三工程の後に、耐熱耐寒高強度粘着剤や紫外線防止塗料等の機能性物質を炭素繊維の表面に塗布する第四工程を備えていてもよい。 In the method for producing a carbon fiber resin tape using the adhesive or sizing agent according to the present invention, a carbon fiber bundle composed of a plurality of carbon fibers is immersed in reduced water having a negative oxidation-reduction potential, and the carbon fiber bundle is It consists of a first step of spreading flatly, a second step of immersing the carbon fiber bundle in the adhesive or sizing agent according to the present invention, and a third step of drying the carbon fiber bundle.
If you want to add the desired properties to the carbon fiber resin tape, after the third step, there is a fourth step of applying a functional substance such as a heat-resistant, cold-resistant, high-strength pressure-sensitive adhesive or an ultraviolet protection paint to the surface of the carbon fiber. It may be.
以下に、各工程の詳細を記載する。
＜第一工程＞
　炭素繊維束は、第１槽に貯留された水中に所定時間浸漬される。
　炭素繊維束としては、無撚炭素繊維の３Ｋ（３０００本束）、６Ｋ（６０００本束）、１２Ｋ（１２０００本束）等を例示することができる。 Below, the detail of each process is described.
<First step>
The carbon fiber bundle is immersed in the water stored in the first tank for a predetermined time.
Examples of the carbon fiber bundle include 3K (3,000 bundles), 6K (6000 bundles), 12K (12,000 bundles) and the like of untwisted carbon fibers.
　本発明において、第１槽に貯留された水は、負の酸化還元電位を有する還元水である。普通の水は正の酸化還元電位（水道水の場合：＋４００～＋６００ｍＶ程度）を有しているが、還元水は負の酸化還元電位を有しており、水分子クラスターが小さく、優れた浸透力を有している。炭素繊維束は、このような還元水中に浸漬されることによって、超音波等の物理的外力を作用させることなく自然に拡がる。
　尚、第１槽内に超音波発生装置を設置し、還元水中に浸漬された炭素繊維束に対して超音波を当てる方法を採用してもよい。この場合、還元水の開繊作用によって、超音波の出力を弱くしても充分な開繊が得られるため、繊維の損傷を確実に防ぎつつ、充分に拡がった帯状の平繊繊維束を効率良く製造することができるという効果を奏する。また、湿式方法の為に、環境にも非常に良いという利点がある。 In the present invention, the water stored in the first tank is reduced water having a negative redox potential. Ordinary water has a positive oxidation-reduction potential (in the case of tap water: about +400 to +600 mV), but reduced water has a negative oxidation-reduction potential, small water molecule clusters, and excellent penetration. Have power. The carbon fiber bundle is naturally expanded without being subjected to physical external forces such as ultrasonic waves by being immersed in such reduced water.
In addition, you may employ | adopt the method of installing an ultrasonic generator in a 1st tank and applying an ultrasonic wave with respect to the carbon fiber bundle immersed in reducing water. In this case, because the opening action of the reduced water allows sufficient opening even if the output of the ultrasonic wave is weakened, it is possible to efficiently prevent the damage of the fibers and efficiently expand the strip-like flat fiber bundle. There is an effect that it can be manufactured well. Also, because of the wet method, there is an advantage that it is very good for the environment.
　第一工程において用いられる還元水は、酸化還元電位が－８００ｍＶ以下のものとすることが好ましい。このような酸化還元電位が低い還元水を用いることにより、炭素繊維束を構成する炭素繊維を短時間で確実に平らに拡げて帯状の平繊繊維束を得ることが可能となる。また、得られた帯状の平繊繊維束が元に戻りにくいものとなる。 The reduced water used in the first step preferably has a redox potential of −800 mV or less. By using such reduced water having a low oxidation-reduction potential, the carbon fibers constituting the carbon fiber bundle can be surely spread flat in a short time to obtain a belt-like flat fiber bundle. Further, the obtained belt-like flat fiber bundle is difficult to return to its original state.
　本発明において用いられる還元水の製法は特に限定されるものではないが、例えば、ガスバブリング法、ヒドラジンの添加による方法、電気分解による方法等が用いられる。
　本発明においては、電気分解による方法により得られた還元水を用いることが好ましい。
　これは、電気分解による方法によれば、他の方法に比べて、より容易且つ確実に酸化還元電位が低く（－８００ｍＶ以下）、負の酸化還元電位を長時間にわたって維持できる還元水が得られるためである。
　尚、電気分解による方法を実施するための装置については、本出願人が特開２０００－２３９４５６号公報において開示しており、この開示内容に基づいて実施することが可能である。 The production method of the reduced water used in the present invention is not particularly limited, and for example, a gas bubbling method, a method by adding hydrazine, a method by electrolysis, or the like is used.
In the present invention, it is preferable to use reduced water obtained by a method by electrolysis.
This is because, according to the method by electrolysis, reduced water having a lower redox potential (−800 mV or less) and capable of maintaining a negative redox potential for a long time can be obtained more easily and reliably than other methods. Because.
An apparatus for carrying out the method by electrolysis is disclosed by the present applicant in Japanese Patent Application Laid-Open No. 2000-239456, and can be carried out based on this disclosure.
＜第二工程＞
　還元水に浸漬されることにより得られた平繊繊維束は、第２槽において６０℃乃至２６５℃の温度範囲で接着剤又はサイジング剤に浸漬される。
　尚、平繊繊維束を接着剤又はサイジング剤に浸漬する前に、平繊繊維束を、コロナ放電を用いて表面処理（いわゆるコロナ処理）することが望ましい。これにより、平繊炭素繊維束の表面粗さを増加させることができ、より容易に接着剤又はサイジング剤に含まれるＯＨ基が平繊炭素繊維束に結合し易くなる。
　このコロナ放電を用いる表面処理は、５Ｗ・ｍｉｎ／ｍ２～４００Ｗ・ｍｉｎ／ｍ２で行うことが好ましく、５０Ｗ・ｍｉｎ／ｍ２で行うことがより好ましい。 <Second step>
The flat fiber bundle obtained by being immersed in reducing water is immersed in an adhesive or a sizing agent in a temperature range of 60 ° C. to 265 ° C. in the second tank.
In addition, it is desirable to surface-treat (what is called corona treatment) a flat fiber bundle using corona discharge before immersing a flat fiber bundle in an adhesive agent or a sizing agent. Thereby, the surface roughness of the flat fiber carbon fiber bundle can be increased, and the OH group contained in the adhesive or the sizing agent can be easily bonded to the flat fiber carbon fiber bundle.
The surface treatment using corona discharge is preferably performed at 5 W · min / m 2 to 400 W · min / m 2 , and more preferably at 50 W · min / m 2 .
　このように、平繊繊維束が接着剤に浸漬されることにより、拡がった繊維と繊維の間に一種以上の金属酸化物ゾルと、一種以上のＯＨ基を含有する化合物と、ＰＶＡ樹脂とを含むサイジング剤が浸透する。
　尚、接着剤又はサイジング剤は、還元水に浸漬されることにより平らに拡げられた炭素繊維（平繊繊維束）に、霧状にして吹き付けてもよい。 In this way, the flat fiber bundle is immersed in the adhesive, so that one or more metal oxide sols, a compound containing one or more OH groups, and a PVA resin are provided between the spread fibers. Infiltrate sizing agent.
In addition, you may spray an adhesive agent or a sizing agent in the shape of a mist to the carbon fiber (flat fiber bundle) spread flatly by being immersed in reducing water.
＜第三工程＞
　接着剤又はサイジング剤に浸漬された後の拡がった炭素繊維束は、第２層から取り出された後、乾燥処理が施される。
　乾燥処理に用いる乾燥装置の種類は特に限定されず、ヒーター加熱装置、温風加熱装置、遠赤外線を利用した加熱装置等でもよい。また、乾燥装置を用いずに自然乾燥によって炭素繊維束を乾燥してもよい。
　なお、この第三工程の後に、炭素繊維樹脂テープをさらに水洗して余分な接着剤又はサイジング剤を除去し、乾燥させてもよい。余分な不純物が除去され、必要なＯＨ基を残すことによりはく離強度が向上する。 <Third step>
The spread carbon fiber bundle after being immersed in the adhesive or the sizing agent is taken out from the second layer and then subjected to a drying treatment.
The kind of drying apparatus used for the drying process is not particularly limited, and may be a heater heating apparatus, a hot air heating apparatus, a heating apparatus using far infrared rays, or the like. Moreover, you may dry a carbon fiber bundle by natural drying, without using a drying apparatus.
In addition, after this third step, the carbon fiber resin tape may be further washed to remove excess adhesive or sizing agent and dried. Excess impurities are removed and the peel strength is improved by leaving the necessary OH groups.
　接着剤又はサイジング剤に浸漬された後の炭素繊維束が乾燥することによって、拡がった繊維と繊維の間に浸透した一種以上の金属酸化物ゾルと、一種以上のＯＨ基を含有する化合物と、ＰＶＡ樹脂が固化する。
　このように、炭素繊維が平らに拡がった状態で接着剤又はサイジング剤により固められることにより、時間が経過しても炭素繊維が元に戻ることがなく、しかも高い機械的強度を有する炭素繊維樹脂テープが得られる。 The carbon fiber bundle after being dipped in the adhesive or sizing agent is dried, so that one or more metal oxide sols penetrated between the spread fibers and the fibers, and a compound containing one or more OH groups, PVA resin solidifies.
In this way, the carbon fiber is hardened with an adhesive or a sizing agent in a state where the carbon fiber spreads flat, so that the carbon fiber does not return to its original shape even after a long time, and has a high mechanical strength. A tape is obtained.
＜第四工程＞
　得られた炭素繊維樹脂テープに所望の特性を付加するために、第四工程を実施しても良い。
　前述の第三工程で得られた炭素繊維樹脂テープの一方の面から、例えば、耐熱性、耐寒性又は高強度のうちの一種以上の物理的特性を有する粘着剤を炭素繊維の表面に塗布する。耐寒性又は高強度のうちの一種以上の物理的特性を有する粘着剤として、例えば、ポリウレタン系接着剤、エポキシ樹脂接着剤、シリコーンゴム系接着剤、ポリテトラフルオロエチレン（ＰＴＦＥ）接着剤などが使用され得る。
　ついで他方の面に紫外線防止塗料を塗布し、乾燥させる。紫外線防止塗料として、例えば、シリコーン樹脂系塗料、アクリル樹脂系塗料、ウレタン樹脂系塗料、フッ素樹脂系塗料などが使用され得る。
　尚、上記した第四工程は一例であって、炭素繊維樹脂テープに所望の特性を付加することができる工程であれば、いかなるものであってもよい。 <Fourth process>
In order to add desired characteristics to the obtained carbon fiber resin tape, a fourth step may be performed.
From one surface of the carbon fiber resin tape obtained in the third step, for example, an adhesive having one or more physical properties of heat resistance, cold resistance or high strength is applied to the surface of the carbon fiber. . For example, polyurethane adhesives, epoxy resin adhesives, silicone rubber adhesives, polytetrafluoroethylene (PTFE) adhesives, etc. are used as pressure sensitive adhesives having one or more physical properties of cold resistance or high strength Can be done.
Next, an anti-ultraviolet paint is applied to the other surface and dried. For example, a silicone resin-based paint, an acrylic resin-based paint, a urethane resin-based paint, a fluororesin-based paint, or the like can be used as the ultraviolet ray preventing paint.
The fourth step described above is an example, and any step may be used as long as it can add desired characteristics to the carbon fiber resin tape.
　以上の通り、本発明に係る接着剤又はサイジング剤を用いた炭素繊維樹脂テープの製造方法の一例を示したが、本発明に係る接着剤又はサイジング剤を用いることにより、炭素繊維だけでなく、例えば、シリコーンゴム、スチレンブタジエンゴム（ＳＢＲ）、ニトリルゴム（ＮＢＲ）等のゴム製品やテフロン（登録商標）等、従来では化学的に接着・接合することができなかったものを容易に接着・接合することができる。
　加えて、本発明に係る接着剤又はサイジング剤を用いることにより、ゴム製品（ブチルゴム、ウレタンゴム、天然ゴム、ＳＢＲ、合成ゴム、あるいはシリコーンゴム等）や炭素繊維等の有機、無機物質材に、任意の添加剤や改質剤を接合・接着させることができる。 As described above, an example of a method for producing a carbon fiber resin tape using the adhesive or sizing agent according to the present invention was shown, but by using the adhesive or sizing agent according to the present invention, not only carbon fibers, For example, rubber products such as silicone rubber, styrene butadiene rubber (SBR), nitrile rubber (NBR), and Teflon (registered trademark), which could not be chemically bonded and bonded in the past, can be easily bonded and bonded. can do.
In addition, by using the adhesive or sizing agent according to the present invention, it can be applied to organic and inorganic materials such as rubber products (butyl rubber, urethane rubber, natural rubber, SBR, synthetic rubber, or silicone rubber) and carbon fiber. Arbitrary additives and modifiers can be bonded and adhered.
　まず、本発明に係る接着剤又はサイジング剤と従来の接着剤又はサイジング剤の比較試験を実施した。
　比較試験では、各接着剤又はサイジング剤のはく離強度を比較した。はく離強度試験は、ＪＩＳ　Ｋ　６８５４－１（ＩＳＯ　８５１０－１）に準拠し、９０°はく離試験を実施した。
　比較試験の結果、本発明に係る接着剤又はサイジング剤は、６０℃～１８０℃の温度範囲にてゴム材を接着・接合することができ、６０℃～２６５℃の温度範囲にて炭素繊維を接着・接合することができた。加えて、６０℃～１８０℃で加温することによりゴム材を、６０℃～２６５℃で加温することにより炭素繊維を夫々容易にはく離することができた。
　一方、従来のエポキシ樹脂を用いる接着剤又はサイジング剤では、６０℃～２６５℃の温度範囲では炭素繊維を接着・接合することができない、あるいは接着・接着接合できてもはく離強度が低かった。
　また、２６５℃以上に加熱し、炭素繊維を接着・接合したが、従来の接着剤又はサイジング剤で接着・接合された炭素繊維ははく離し難く、炭素繊維のリサイクルは困難であることがわかった。加えて、ゴム材は６０℃～１８０℃の温度で接着・接合することができたが、一度接着・接合したゴム材を６０℃～１８０℃で加温してもはく離し難く、ゴム材のリサイクルは困難であることが分かった。
　加えて、本発明に係る接着剤又はサイジング剤は、調製後２週間を経過してもはく離強度を維持しており、ゴム材や炭素繊維を容易に接着・接合及びはく離できたが、調製後２週間を経過した従来のエポキシ樹脂を用いる接着剤又はサイジング剤ははく離強度が大きく低下し、ゴム材や炭素繊維の接着・接合が困難であった。
　以下に、本発明に係る接着剤又はサイジング剤を用いたより具体的な実施例を記載する。 First, a comparative test of the adhesive or sizing agent according to the present invention and a conventional adhesive or sizing agent was performed.
In the comparative test, the peel strength of each adhesive or sizing agent was compared. The peel strength test was conducted according to JIS K 6854-1 (ISO 8510-1) and a 90 ° peel test.
As a result of the comparative test, the adhesive or sizing agent according to the present invention can adhere and bond the rubber material in the temperature range of 60 ° C. to 180 ° C., and the carbon fiber can be bonded in the temperature range of 60 ° C. to 265 ° C. We were able to bond and join. In addition, it was possible to easily separate the rubber material by heating at 60 ° C. to 180 ° C. and the carbon fiber by heating at 60 ° C. to 265 ° C.
On the other hand, conventional adhesives or sizing agents using epoxy resins cannot adhere or bond carbon fibers in the temperature range of 60 ° C. to 265 ° C., or have low peel strength even if they can be bonded and bonded.
In addition, heating and heating to 265 ° C or higher bonded carbon fibers, but it was found that carbon fibers bonded and bonded with conventional adhesives or sizing agents are difficult to peel off and it is difficult to recycle carbon fibers. . In addition, the rubber material could be bonded and bonded at a temperature of 60 ° C to 180 ° C. However, once the bonded and bonded rubber material was heated at 60 ° C to 180 ° C, it was difficult to peel off. Recycling proved difficult.
In addition, the adhesive or sizing agent according to the present invention maintains the peel strength even after 2 weeks from the preparation, and can easily bond, bond and peel rubber materials and carbon fibers. The adhesive or sizing agent using a conventional epoxy resin after two weeks has greatly deteriorated the peel strength, making it difficult to bond and join rubber materials and carbon fibers.
Below, the more concrete Example using the adhesive agent or sizing agent which concerns on this invention is described.
＜試験１＞
　本願発明に係る接着剤又はサイジング剤を用いてゴム材や炭素繊維を接着し、はく離強度試験を実施した。 <Test 1>
A rubber material or carbon fiber was bonded using the adhesive or sizing agent according to the present invention, and a peel strength test was performed.
　実施例１～３で用いた本発明に係る接着剤又はサイジング剤の成分及び各成分の濃度は以下の通りである。
　ＰＶＡ：５ｗｔ％
　ニオブの金属酸化物ゾル（バイラールＮｂ－Ｇ６０００）：１ｗｔ％
　過硫酸カリウム：１ｗｔ％
　水：９３ｗｔ％ The components of the adhesive or sizing agent according to the present invention used in Examples 1 to 3 and the concentration of each component are as follows.
PVA: 5 wt%
Niobium metal oxide sol (viral Nb-G6000): 1 wt%
Potassium persulfate: 1wt%
Water: 93wt%
　比較例１～３では、従来の接着剤として２液エポキシ接着剤（コニシ製、ボンドＥセット、Ａ剤；エポキシ樹脂１００％、Ｂ剤；変性ポリアミド１００％）を用いた。 In Comparative Examples 1 to 3, a two-component epoxy adhesive (manufactured by Konishi, Bond E set, A agent; epoxy resin 100%, B agent; modified polyamide 100%) was used as a conventional adhesive.
＜実施例１＞
　厚さ１ｍｍのゴム材（ノーブランドのゴム板、モノタロウで購入）に、本発明に係る接着剤又はサイジング剤をハケで均一に塗布した。　本発明に係る接着剤又はサイジング剤が塗布されたゴム材と、本発明に係る接着剤又はサイジング剤が塗布されていないゴム材を密着させ、フランジ（Φ５．５、厚み２ｃｍ、重さ２．３ｋｇ）で約２３Ｎの荷重をかけながら６０℃で２時間加熱し、ゴム材同士を接着した。
　接着したゴム材を用いて、ＪＩＳＫ６８５４－１（９０度はく離）に準じてはく離試験を実施した。
　加えて、接着したゴム材を８０℃のお湯に３０秒間浸漬（湯せん）させたものを用いて、ＪＩＳＫ６８５４－１（９０度はく離）に準じてはく離試験を実施した。尚、湯せんはＷａｔｅｒ　Ｂａｔｈ　ＢＭ１００（ヤマト科学株式会社製）を用い、はく離試験はＡＵＴＯＧＲＡＰＨ　ＡＧＳ－Ｘ　５０Ｎ（島津製作所製）を用いて実施した。
＜実施例２＞
　開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）同士を、実施例１と同じ本発明に係る接着剤又はサイジング剤を用いて、実施例１と同じ手順で接着し、実施例１と同様のはく離試験を実施した。
＜実施例３＞
　厚さ１ｍｍのゴム材（ノーブランドのゴム板、モノタロウで購入）と開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）を、実施例１と同じ本発明に係る接着剤又はサイジング剤を用いて、実施例１と同じ手順で接着し、実施例１と同様のはく離試験を実施した。 <Example 1>
The adhesive or sizing agent according to the present invention was uniformly applied by brush to a rubber material having a thickness of 1 mm (purchased from a non-brand rubber plate, Monotaro). The rubber material to which the adhesive or sizing agent according to the present invention is applied and the rubber material to which the adhesive or sizing agent according to the present invention is not applied are brought into close contact with each other, and a flange (Φ5.5, thickness 2 cm, weight 2. 3 kg) and heated at 60 ° C. for 2 hours while applying a load of about 23 N to bond the rubber materials together.
Using the bonded rubber material, a peel test was performed in accordance with JIS K6854-1 (90 degree peel).
In addition, a peel test was performed in accordance with JISK 6854-1 (90 degree peeling) using a bonded rubber material immersed in hot water at 80 ° C. for 30 seconds (water bath). Water bath BM100 (manufactured by Yamato Kagaku Co., Ltd.) was used as a hot water bath, and peeling test was carried out using AUTOGRAPH AGS-X 50N (manufactured by Shimadzu Corporation).
<Example 2>
Open carbon fibers (12K, 150 mm × 20 mm) are bonded to each other in the same procedure as in Example 1 using the same adhesive or sizing agent according to the present invention as in Example 1, and the same peel test as in Example 1 Carried out.
<Example 3>
A rubber material with a thickness of 1 mm (unbranded rubber plate, purchased as Monotaro) and spread carbon fiber (12K, 150 mm × 20 mm) were used with the same adhesive or sizing agent according to the present invention as in Example 1. Adhesion was carried out in the same procedure as in Example 1, and a peel test similar to that in Example 1 was performed.
＜比較例１＞
　厚さ１ｍｍのゴム材（ノーブランドのゴム板、モノタロウで購入）に従来の接着剤として２液エポキシ接着剤（コニシ製、ボンドＥセット、Ａ剤；エポキシ樹脂１００％、Ｂ剤；変性ポリアミド１００％）をハケで均一に塗布した。
　従来の接着剤が塗布されたゴム材と、従来の接着剤が塗布されていないゴム材を密着させ、約２３Ｎの荷重をかけながら６０℃で２時間加熱し、ゴム材同士を接着した。
　接着させたゴム材を用いて、ＪＩＳＫ６８５４－１（９０度はく離）に準じてはく離試験を実施した。
　加えて、接着させたゴム材を８０度のお湯に３０秒間浸漬（湯せん）させた後、ＪＩＳＫ６８５４－１（９０度はく離）に準じてはく離試験を実施した。
＜比較例２＞
　開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）同士を、比較例１と同じ手順で接着し、比較例１と同様のはく離試験を実施した。
＜比較例３＞
　厚さ１ｍｍのゴム材（ノーブランドのゴム板、モノタロウで購入）と開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）を、比較例１と同じ手順で接着し、比較例１と同様のはく離試験を実施した。 <Comparative Example 1>
Two-component epoxy adhesive (Konishi, Bond E set, A agent; epoxy resin 100%, B agent; modified polyamide 100) as a conventional adhesive to rubber material with a thickness of 1 mm (purchased as a non-brand rubber plate, monotaro) %) Was applied uniformly with a brush.
The rubber material to which the conventional adhesive was applied and the rubber material to which the conventional adhesive was not applied were brought into close contact with each other and heated at 60 ° C. for 2 hours while applying a load of about 23 N to bond the rubber materials to each other.
Using the bonded rubber material, a peeling test was performed in accordance with JIS K6854-1 (90 degree peeling).
In addition, the bonded rubber material was immersed in hot water of 80 degrees for 30 seconds (hot water bath), and then subjected to a peeling test according to JIS K6854-1 (90 degree peeling).
<Comparative example 2>
Open carbon fibers (12K, 150 mm × 20 mm) were bonded together in the same procedure as in Comparative Example 1, and the same peel test as in Comparative Example 1 was performed.
<Comparative Example 3>
A rubber material having a thickness of 1 mm (unbranded rubber plate, purchased with Monotaro) and spread carbon fiber (12K, 150 mm × 20 mm) are bonded in the same procedure as in Comparative Example 1, and the same peeling test as in Comparative Example 1 is performed. Carried out.
　実施例１～３及び比較例１～３のはく離試験の結果を表１に示す。 Table 1 shows the results of the peel tests of Examples 1 to 3 and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１のピーク点試験力において、実施例１～３は、はく離強度の値が約０．７～１．２前後であり、比較例１よりも低い値であるが、ゴム材同士を接着させるのに十分なはく離強度を備えており、且つ湯せんすることにより、そのはく離強度が半分以下になっていることがわかる。
　一方、比較例１および３は、湯せんしてもはく離強度はほとんど低下していないことがわかる。
　また、比較例２は、はく離強度の測定中に炭素繊維が破断したため、ピーク点試験力を測定することができなかった。加えて、湯せんした場合においても、はく離強度の測定中に炭素繊維が破断したため、ピーク点試験力を測定することができなかった。 In the peak point test force of Table 1, Examples 1 to 3 have a peel strength value of about 0.7 to 1.2, which is lower than that of Comparative Example 1, but the rubber materials are bonded to each other. It is clear that the peel strength is sufficient, and that the peel strength is reduced to half or less by boiling water.
On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used.
In Comparative Example 2, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength. In addition, even when the hot water bath was used, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
　表１の最大点試験力において、実施例１～３は、はく離強度の値が約３．７～４．５前後であり、比較例１および３よりも低い値であるが、炭素繊維同士を接着させるのに十分なはく離強度を備えており、且つ湯せんすることにより、そのはく離強度が半分以下になっていることがわかる。
　一方、比較例１および３は、湯せんしてもはく離強度はほとんど低下していないことがわかる。
　また、比較例２は、はく離強度の測定中に炭素繊維が破断したため、最大点試験力を測定することができなかった。加えて、湯せんした場合においても、はく離強度の測定中に炭素繊維が破断したため、最大点試験力を測定することができなかった。 In the maximum point test force of Table 1, Examples 1 to 3 have a peel strength value of about 3.7 to 4.5, which is lower than Comparative Examples 1 and 3, It can be seen that the peel strength is sufficient for bonding, and that the peel strength is reduced to half or less by boiling water.
On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used.
Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the maximum point test force could not be measured. In addition, even in the case of hot water bath, the maximum point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
　表１の平均試験力において、実施例１～３は、はく離強度の値が約２．２～３．７前後であり、比較例１および３よりも低い値であるが、ゴム材と炭素繊維を接着させるのに十分なはく離強度を備えており、且つ湯せんすることにより、そのはく離強度が半分以下になっていることがわかる。
　一方、比較例１および３は、湯せんしてもはく離強度はほとんど低下していないことがわかる。
　また、比較例２は、はく離強度の測定中に炭素繊維が破断したため、平均試験力を測定することができなかった。加えて、湯せんした場合においても、はく離強度の測定中に炭素繊維が破断したため、平均試験力を測定することができなかった。 In the average test force of Table 1, Examples 1 to 3 have a peel strength value of about 2.2 to 3.7, which is lower than Comparative Examples 1 and 3, but rubber materials and carbon fibers It can be seen that the peel strength is sufficient to bond the film, and that the peel strength is reduced to half or less by boiling water.
On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used.
Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the average test force could not be measured. In addition, even in the case of hot water bath, the average test force could not be measured because the carbon fiber broke during measurement of the peel strength.
　表１のはく離強度試験の結果より、本発明に係る接着剤又はサイジング剤は、ゴム材同士、炭素繊維同士、およびゴム材と炭素繊維を接着できることがわかった。
　加えて、本発明に係る接着剤又はサイジング剤は、一度接着したゴム材同士、炭素繊維同士、およびゴム材と炭素繊維を湯せんすることにより容易にはがすことができ、一度接着した材料を容易にリサイクルできることがわかった。
　一方、従来の接着剤は、ゴム材同士、炭素繊維同士、およびゴム材と炭素繊維を接着することはできるが、一度接着すると湯せんしてもはがすことが困難であることがわかった。そのため、従来の接着剤を用いると一度接着した材料のリサイクルが困難であることがわかった。 From the results of the peel strength test in Table 1, it was found that the adhesive or sizing agent according to the present invention can bond rubber materials to each other, carbon fibers to each other, and rubber materials to carbon fibers.
In addition, the adhesive or sizing agent according to the present invention can be easily peeled off by hot water bonding between the rubber materials once bonded, between the carbon fibers, and between the rubber material and the carbon fibers. I found out that it can be recycled.
On the other hand, it has been found that conventional adhesives can bond rubber materials to each other, carbon fibers to each other, and rubber materials to carbon fibers, but once bonded, it is difficult to remove even with a hot water bath. For this reason, it has been found that it is difficult to recycle a material once bonded using a conventional adhesive.
＜試験２＞
　本願発明に係る接着剤又はサイジング剤を塗布したゴム材や炭素繊維を、他の接着剤を用いて接着し、はく離強度試験を実施した。尚、試験２において使用した機器類は、試験１と同じものを用いた。 <Test 2>
The rubber material and carbon fiber which apply | coated the adhesive agent or sizing agent which concerns on this invention were adhere | attached using another adhesive agent, and the peeling strength test was implemented. The equipment used in Test 2 was the same as that used in Test 1.
　実施例４～６で用いた本発明に係る接着剤又はサイジング剤の成分及び各成分の濃度は以下の通りである。
　ＰＶＡ：５ｗｔ％
　ニオブの金属酸化物ゾル：１ｗｔ％
　過硫酸カリウム：１ｗｔ％
　水：９３ｗｔ％ The components of the adhesive or sizing agent according to the present invention used in Examples 4 to 6 and the concentration of each component are as follows.
PVA: 5 wt%
Niobium metal oxide sol: 1wt%
Potassium persulfate: 1wt%
Water: 93wt%
　本実施例では、他の接着剤として２液エポキシ接着剤（コニシ製、ボンドＥセット、Ａ剤；エポキシ樹脂１００％、Ｂ剤；変性ポリアミド１００％）を用いた。 In this example, a two-component epoxy adhesive (manufactured by Konishi, Bond E set, agent A; epoxy resin 100%, agent B; modified polyamide 100%) was used as another adhesive.
＜実施例４＞
　厚さ１ｍｍのゴム材（ノーブランドのゴム板、モノタロウで購入）に本発明に係る接着剤又はサイジング剤をハケで均一に塗布し、塗布した本発明に係る接着剤又はサイジング剤を乾燥させた。乾燥は６０℃で３０分間行った。尚、乾燥は、送風定温恒温器DN-42（ヤマト科学株式会社製）を用いて行った。
　本発明に係る接着剤又はサイジング剤を塗布したゴム材の表面に、他の接着剤を、ハケを用いて塗布した。
　本発明に係る接着剤又はサイジング剤が塗布されたゴム材同士を、他の接着剤を介して密着させ、約２３Ｎの荷重をかけながら６０℃で２時間加熱し、ゴム材同士を接着した。
　接着させたゴム材を用いて、ＪＩＳＫ６８５４－１（９０度はく離）に準じてはく離試験を実施した。
　加えて、接着させたゴム材を８０度のお湯に３０秒間浸漬（湯せん）させた後、ＪＩＳＫ６８５４－１（９０度はく離）に準じてはく離試験を実施した。
＜実施例５＞
　開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）同士を、実施例４と同じ手順で接着し、実施例４と同様のはく離試験を実施した。
＜実施例６＞
　厚さ１ｍｍのゴム材（ノーブランドのゴム板、モノタロウで購入）と開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）を、実施例４と同じ手順で接着し、実施例４と同様のはく離試験を実施した。 <Example 4>
The adhesive or sizing agent according to the present invention was uniformly applied by brush to a rubber material having a thickness of 1 mm (purchased from a non-brand rubber plate, monotaro), and the applied adhesive or sizing agent according to the present invention was dried. . Drying was performed at 60 ° C. for 30 minutes. In addition, drying was performed using ventilation constant temperature thermostat DN-42 (made by Yamato Scientific Co., Ltd.).
Another adhesive was applied to the surface of the rubber material coated with the adhesive or sizing agent according to the present invention using a brush.
The rubber materials coated with the adhesive or sizing agent according to the present invention were brought into close contact with each other through other adhesives, and heated at 60 ° C. for 2 hours while applying a load of about 23 N, thereby bonding the rubber materials together.
Using the bonded rubber material, a peeling test was performed in accordance with JIS K6854-1 (90 degree peeling).
In addition, the bonded rubber material was immersed in hot water of 80 degrees for 30 seconds (hot water bath), and then subjected to a peeling test according to JIS K6854-1 (90 degree peeling).
<Example 5>
Open carbon fibers (12K, 150 mm × 20 mm) were bonded together in the same procedure as in Example 4, and the same peel test as in Example 4 was performed.
<Example 6>
A rubber material having a thickness of 1 mm (unbranded rubber plate, purchased with Monotaro) and spread carbon fiber (12K, 150 mm × 20 mm) were bonded in the same procedure as in Example 4, and the same peel test as in Example 4 was performed. Carried out.
＜比較例１～３＞
　従来の接着剤を用いた比較例として、試験１と同様に比較例１～３を用いた。 <Comparative Examples 1 to 3>
As Comparative Examples using conventional adhesives, Comparative Examples 1 to 3 were used as in Test 1.
　実施例４～６及び比較例１～３のはく離試験の結果を表２に示す。 Table 2 shows the peel test results of Examples 4 to 6 and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２のピーク点試験力において、実施例４～６は、はく離強度の値が約２～３．５前後であり、比較例１および３よりも高い値であり、湯せんすることにより、そのはく離強度が大きく低下していることがわかる。
　一方、比較例１および３は、湯せんしてもはく離強度はほとんど低下していないことがわかる。
　また、比較例２は、はく離強度の測定中に炭素繊維が破断したため、ピーク点試験力を測定することができなかった。加えて、湯せんした場合においても、はく離強度の測定中に炭素繊維が破断したため、ピーク点試験力を測定することができなかった。 In the peak point test force of Table 2, Examples 4 to 6 have a peel strength value of about 2 to 3.5, which is higher than Comparative Examples 1 and 3. It can be seen that the strength is greatly reduced.
On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used.
In Comparative Example 2, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength. In addition, even when the hot water bath was used, the peak point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
　表２の最大点試験力において、実施例４～６は、はく離強度の値が約１１～１３前後であり、比較例１および３よりも高い値であり、湯せんすることにより、そのはく離強度が大きく低下していることがわかる。
　一方、比較例１および３は、湯せんしてもはく離強度はほとんど低下していないことがわかる。
　また、比較例２は、はく離強度の測定中に炭素繊維が破断したため、最大点試験力を測定することができなかった。加えて、湯せんした場合においても、はく離強度の測定中に炭素繊維が破断したため、最大点試験力を測定することができなかった。 In the maximum point test force of Table 2, in Examples 4 to 6, the peel strength value is about 11 to 13, which is higher than Comparative Examples 1 and 3, and the peel strength is increased by boiling water. It turns out that it has fallen greatly.
On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used.
Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the maximum point test force could not be measured. In addition, even in the case of hot water bath, the maximum point test force could not be measured because the carbon fiber broke during measurement of the peel strength.
　表２の平均試験力において、実施例１～３は、はく離強度の値が約７～１１前後であり、比較例１と同等であり、比較例３よりも高い値であり、湯せんすることにより、そのはく離強度が大きく低下していることがわかる。
　一方、比較例１および３は、湯せんしてもはく離強度はほとんど低下していないことがわかる。
　また、比較例２は、はく離強度の測定中に炭素繊維が破断したため、平均試験力を測定することができなかった。加えて、湯せんした場合においても、はく離強度の測定中に炭素繊維が破断したため、平均試験力を測定することができなかった。 In the average test force of Table 2, Examples 1 to 3 have a peel strength value of about 7 to 11, which is equivalent to Comparative Example 1, higher than Comparative Example 3, It can be seen that the peel strength is greatly reduced.
On the other hand, in Comparative Examples 1 and 3, it can be seen that the peel strength hardly decreases even when the hot water bath is used.
Moreover, since the carbon fiber broke during the measurement of the peeling strength in Comparative Example 2, the average test force could not be measured. In addition, even in the case of hot water bath, the average test force could not be measured because the carbon fiber broke during measurement of the peel strength.
　表２のはく離強度試験の結果より、本発明に係る接着剤又はサイジング剤は、従来の接着剤を介して、ゴム材同士、炭素繊維同士、およびゴム材と炭素繊維を接着させた場合、従来の接着剤の接着力を高めることができ、且つ湯せんすることにより、一度接着した材料をはく離できることがわかった。
　それゆえに、従来の接着剤で接着した場合よりも、より強固に材料を接着させることができ、且つ湯せんにより容易にはがすことができるため、一度接着した材料を容易にリサイクルできることがわかった。
　一方、従来の接着剤は、ゴム材同士、炭素繊維同士、およびゴム材と炭素繊維を接着することはできるが、一度接着すると湯せんしてもはがすことが困難であることがわかった。そのため、従来の接着剤を用いると一度接着した材料のリサイクルが困難であることがわかった。 From the results of the peel strength test in Table 2, the adhesive or sizing agent according to the present invention is conventional when the rubber materials, the carbon fibers, and the rubber material and the carbon fibers are bonded to each other through the conventional adhesive. It was found that the adhesive strength of the adhesive can be increased, and the material once adhered can be peeled off by hot water pouring.
Therefore, it was found that the material can be adhered more strongly than the case where it is adhered with a conventional adhesive, and can be easily peeled off with a hot water bath, so that the material once adhered can be easily recycled.
On the other hand, it has been found that conventional adhesives can bond rubber materials to each other, carbon fibers to each other, and rubber materials to carbon fibers, but once bonded, it is difficult to remove even with a hot water bath. For this reason, it has been found that it is difficult to recycle a material once bonded using a conventional adhesive.
＜試験３＞
　上記実施例２と比較例２を用いて、本発明に係る接着剤又はサイジング剤の安定性をはく離試験で確認した。はく離試験は、上記試験１と同じ方法で行い、ＪＩＳＫ６８５４－１（９０度はく離）に準じて行った。 <Test 3>
Using Example 2 and Comparative Example 2 above, the stability of the adhesive or sizing agent according to the present invention was confirmed by a peel test. The peeling test was performed in the same manner as in the above test 1, and was performed according to JISK6854-1 (90 degree peeling).
　実施例２－１：開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）に塗布する直前に調製した、本発明に係る接着剤又はサイジング剤を用いた。
　実施例２－２：開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）に塗布する２週間前に調製した、本発明に係る接着剤又はサイジング剤を用いた。 Example 2-1: An adhesive or sizing agent according to the present invention prepared immediately before application to a spread carbon fiber (12K, 150 mm × 20 mm) was used.
Example 2-2: An adhesive or sizing agent according to the present invention prepared two weeks before application to spread carbon fiber (12K, 150 mm × 20 mm) was used.
　比較例２－１：開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）に塗布する直前に調製した、従来の接着剤（２液エポキシ接着剤（コニシ製、ボンドＥセット、Ａ剤；エポキシ樹脂１００％、Ｂ剤；変性ポリアミド１００％））を用いた。
　比較例２－２：開繊炭素繊維（１２Ｋ、１５０ｍｍ×２０ｍｍ）に塗布する２週間前に調製した、従来の接着剤（２液エポキシ接着剤（コニシ製、ボンドＥセット、Ａ剤；エポキシ樹脂１００％、Ｂ剤；変性ポリアミド１００％））を用いた。 Comparative Example 2-1: Conventional adhesive (two-part epoxy adhesive (manufactured by Konishi, Bond E set, A agent; epoxy resin 100%) prepared immediately before application to spread carbon fiber (12K, 150 mm × 20 mm) , B agent; modified polyamide 100%)).
Comparative Example 2-2: Conventional adhesive (2-pack epoxy adhesive (Konishi, Bond E set, Agent A; epoxy resin) prepared two weeks before application to spread carbon fiber (12K, 150 mm × 20 mm) 100%, B agent; modified polyamide 100%)).
　はく離試験の結果、本発明に係る接着剤又はサイジング剤は、調製後２週間を経過してもはく離強度を維持しており、ゴム材や炭素繊維を容易に接着・接合及びはく離できたが、調製後２週間を経過した従来の接着剤は、はく離強度が大きく低下し、ゴム製品や炭素繊維の接着・接合が困難であった。
　はく離試験の結果より、本発明に係る接着剤又はサイジング剤は、従来の接着剤と比較して、優れた安定性を備えていることがわかった。 As a result of the peel test, the adhesive or sizing agent according to the present invention maintained the peel strength even after 2 weeks from the preparation, and was able to easily bond / bond and peel the rubber material and carbon fiber. Conventional adhesives that have passed 2 weeks after preparation have greatly reduced peel strength, making it difficult to adhere and bond rubber products and carbon fibers.
From the results of the peeling test, it was found that the adhesive or sizing agent according to the present invention has excellent stability as compared with conventional adhesives.
＜試験４＞
　本発明に係る接着剤又はサイジング剤を用いて製造した炭素繊維樹脂テープのはく離強度試験を実施した。
　はく離強度試験に使用した炭素繊維樹脂テープは、上記第一工程～第三工程により製造したものであり、１５０ｍｍ×２０ｍｍにカットしたものを用いた。
　尚、上記第２工程においてコロナ処理を行い、コロナ処理は５０Ｗ・ｍｉｎ／ｍ２で行った。
　下記の通り、接着剤又はサイジング剤に用いる金属酸化物ゾルの種類を変更し、夫々実施例７～１２とした。 <Test 4>
The peel strength test of the carbon fiber resin tape manufactured using the adhesive or sizing agent according to the present invention was performed.
The carbon fiber resin tape used for the peel strength test was manufactured by the above first to third steps, and was cut into 150 mm × 20 mm.
In the second step, corona treatment was performed, and the corona treatment was performed at 50 W · min / m 2 .
As described below, Examples 7 to 12 were used by changing the type of metal oxide sol used for the adhesive or sizing agent.
実施例７～１２で用いた接着剤又はサイジング剤の各成分の濃度は以下の通りである。
　ＰＶＡ：５ｗｔ％
　金属酸化物ゾル：１ｗｔ％
　過硫酸カリウム：１ｗｔ％
　水：９７ｗｔ％ The concentration of each component of the adhesive or sizing agent used in Examples 7 to 12 is as follows.
PVA: 5 wt%
Metal oxide sol: 1wt%
Potassium persulfate: 1wt%
Water: 97wt%
＜実施例７＞
　金属酸化物ゾル：アルミナ（アルミナゾル－１０Ａ（Ａｌ２Ｏ３換算重量％：９．８～１０．２、粒子の大きさｎｍ：５－１５、粘度２５℃，ｍＰａ／ｓ：＜５０、ｐＨ：３．４－４．２、川研ファインケミカル製））
＜実施例８＞
　金属酸化物ゾル：酸化スズ（セラメースＳ－８（ＳｎＯ２重量％：８、平均粒子径：８ｎｍ、ｐＨ：１０、多木化学製））
＜実施例９＞
　金属酸化物ゾル：酸化ジルコニウム（バイラールＺｒ－Ｃ２０（ＺｒＯ２重量％：２０、平均粒子径：４０ｎｍ、ｐＨ：８、多木化学製））
＜実施例１０＞
　金属酸化物ゾル：酸化チタン（タイノックＡ－６（ＴｉＯ２重量％：６、平均粒子径：２０ｎｍ、ｐＨ：１２、多木化学製））
＜実施例１１＞
　金属酸化物ゾル：酸化チタン（タイノックＡＭ－１５（ＴｉＯ２重量％：１５、平均粒子径：２０ｎｍ、ｐＨ：４、多木化学製））
＜実施例１２＞
　金属酸化物ゾル：酸化ニオブ（バイラールＮｂ－Ｇ６０００（Ｎｂ２Ｏ３重量％：６、平均粒子径：１５ｎｍ、ｐＨ：８、多木化学製）） <Example 7>
Metal oxide sol: Alumina (Alumina sol-10A (Al 2 O 3 equivalent weight%: 9.8 to 10.2, particle size nm: 5-15, viscosity 25 ° C., mPa / s: <50, pH: 3.4-4.2, manufactured by Kawaken Fine Chemicals))
<Example 8>
Metal oxide sol: Tin oxide (Cerames S-8 (SnO 2 wt%: 8, average particle size: 8 nm, pH: 10, manufactured by Taki Chemical))
<Example 9>
Metal oxide sol: Zirconium oxide (Viral Zr—C20 (ZrO 2 wt%: 20, average particle size: 40 nm, pH: 8, manufactured by Taki Chemical))
<Example 10>
Metal oxide sol: Titanium oxide (Tynoc A-6 (TiO 2 wt%: 6, average particle size: 20 nm, pH: 12, manufactured by Taki Chemical))
<Example 11>
Metal oxide sol: Titanium oxide (Tynoc AM-15 (TiO 2 wt%: 15, average particle size: 20 nm, pH: 4, manufactured by Taki Chemical))
<Example 12>
Metal oxide sol: Niobium oxide (Vialal Nb-G6000 (Nb 2 O 3 wt%: 6, average particle size: 15 nm, pH: 8, manufactured by Taki Chemical))
＜比較例４＞
　上記第二工程（開繊炭素繊維束を接着剤溶液に浸漬する工程）及びコロナ処理を行わず、上記第一工程及び第三～第四工程により製造した炭素繊維樹脂テープを比較例４とした。はく離試験では、１５０ｍｍ×２０ｍｍにカットした比較例４を用いた。 <Comparative example 4>
The carbon fiber resin tape produced in the first step and the third to fourth steps without performing the second step (step of immersing the opened carbon fiber bundle in the adhesive solution) and the corona treatment was used as Comparative Example 4. . In the peeling test, Comparative Example 4 cut to 150 mm × 20 mm was used.
　上記手順により製造した実施例７～１２及び比較例４に、アセトンを用いて５ｗｔ％になるように希釈した接着剤（コニシ株式会社製、ウルトラ多用途（登録商標））を塗布し、ステンレス板（ＳＵＳ板）と張り合わせ、６０℃の乾燥炉で４時間かけて完全硬化させた。
　サンプルは、各実施例及び比較例で３つずつ（Ｎ＝１～３）用意した。
　ＪＩＳ　Ｋ　６８５４－１（ＩＳＯ　８５１０－１）に準拠し、９０°はく離試験を実施した。
　はく離試験において、ピーク点試験力、最大点試験力、及び平均試験力を夫々確認した。尚、試験４において使用した機器類は、試験１と同じものを用いた。
　試験結果を下記表４～６に示す。 To Examples 7 to 12 and Comparative Example 4 manufactured by the above procedure, an adhesive diluted with acetone to 5 wt% (manufactured by Konishi Co., Ltd., Ultra Versatile (registered trademark)) was applied, and a stainless steel plate (SUS plate) was laminated and completely cured in a drying furnace at 60 ° C. for 4 hours.
Three samples (N = 1 to 3) were prepared for each example and comparative example.
A 90 ° peel test was performed in accordance with JIS K 6854-1 (ISO 8510-1).
In the peeling test, the peak point test force, the maximum point test force, and the average test force were confirmed. The equipment used in Test 4 was the same as that used in Test 1.
The test results are shown in Tables 4 to 6 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表４のピーク点試験力において、実施例７、実施例９、及び実施例１２は、はく離強度の値は低いが、各サンプル（Ｎ＝１～３）の数値のばらつきが小さく、安定したはく離強度を有していることがわかった。
　また、実施例８、実施例１０、及び実施例１１は、各サンプル（Ｎ＝１～３）の数値のばらつきが大きいが、平均して高いはく離強度を有していることがわかった。 In the peak point test force of Table 4, Example 7, Example 9 and Example 12 have low peel strength values, but the numerical values of each sample (N = 1 to 3) are small and stable peeling. It was found to have strength.
In addition, it was found that Example 8, Example 10, and Example 11 had a high peel strength on average, although the numerical value variation of each sample (N = 1 to 3) was large.
　表５の最大点試験力において、実施例８は、各サンプル（Ｎ＝１～３）の数値のばらつきが小さく、且つ高い値を有していた。
　また、実施例１２は、値は低いが、各サンプル（Ｎ＝１～３）の数値のばらつきが小さく、安定していた。 In the maximum point test force shown in Table 5, in Example 8, the numerical value variation of each sample (N = 1 to 3) was small and high.
In Example 12, although the value was low, the numerical value variation of each sample (N = 1 to 3) was small and stable.
　表６の平均試験力において、実施例８は、各サンプル（Ｎ＝１～３）の数値のばらつきが小さく、且つ高い値を有していた。 In the average test force shown in Table 6, in Example 8, the numerical value variation of each sample (N = 1 to 3) was small and had a high value.
　上記表４～６に示すはく離強度試験の結果より、接着剤溶液に用いる金属酸化物ゾルの種類を変更することで、炭素繊維樹脂テープのはく離強度が変化することがわかった。
　金属酸化物ゾルとして酸化スズを使用した場合、アルミナ、酸化ジルコニウム及び酸化ニオブを金属酸化物ゾルとして使用した場合よりも、２～３倍程度の試験力を得られることがわかった。
　加えて、実施例７～１２は、全ての試験（ピーク点試験力、最大点試験力及び平均試験力）において、比較例４よりも優れたはく離強度を有していることがわかった。
　それゆえに、開繊炭素繊維を接着剤に浸漬する第二工程及びコロナ処理は、優れたはく離強度を炭素繊維樹脂テープに付与することがわかった。 From the results of the peel strength tests shown in Tables 4 to 6, it was found that the peel strength of the carbon fiber resin tape was changed by changing the type of metal oxide sol used in the adhesive solution.
It has been found that when tin oxide is used as the metal oxide sol, a test force of about 2 to 3 times can be obtained as compared with the case where alumina, zirconium oxide and niobium oxide are used as the metal oxide sol.
In addition, Examples 7 to 12 were found to have better peel strength than Comparative Example 4 in all tests (peak point test force, maximum point test force and average test force).
Therefore, it was found that the second step of immersing the spread carbon fiber in the adhesive and the corona treatment impart excellent peel strength to the carbon fiber resin tape.
　実施例７～１２の中でも、実施例８は全ての試験力において高い数値を有していた。一般に、試験力が高いことは接着性が向上していることを示すので、接着性の観点からは、実施例８が最も優れていることがわかった。
　尚、実施例７において、アルミナゾルとしてＢＩＲＡＬ　Ａｌ－Ｌ７（多木化学株式会社製）を用いた場合の平均試験力は、３．０３３０７であり、アルミナゾルとしてＢＩＲＡＬ　Ａｌ－ＭＬ１５（多木化学株式会社製）を用いた場合の平均試験力は、９．８６２０３であった。このように、高い接着力を得る点において、アルミナゾルはＡｌ－Ｌ７あるいはＡｌ－ＭＬ１５を用いることが望ましい。
　これらの結果より、本発明に係る接着剤又はサイジング剤を用いて炭素繊維樹脂テープを製造することにより、炭素繊維樹脂テープに優れたはく離強度を付与できることがわかった。加えて、開繊炭素繊維を接着剤に浸漬する第二工程及びコロナ処理は、優れたはく離強度を炭素繊維樹脂テープに付与することがわかった。 Among Examples 7 to 12, Example 8 had high numerical values in all test forces. In general, a high test force indicates that the adhesiveness is improved, and thus it was found that Example 8 was most excellent from the viewpoint of adhesiveness.
In Example 7, the average test force when BIRAL Al-L7 (manufactured by Taki Chemical Co., Ltd.) was used as the alumina sol was 3.03307, and BIRAL Al-ML15 (manufactured by Taki Chemical Co., Ltd.) was used as the alumina sol. ), The average test force was 9.86203. Thus, it is desirable to use Al-L7 or Al-ML15 as the alumina sol in order to obtain a high adhesive strength.
From these results, it was found that excellent peel strength can be imparted to the carbon fiber resin tape by producing the carbon fiber resin tape using the adhesive or sizing agent according to the present invention. In addition, it has been found that the second step of immersing the opened carbon fiber in the adhesive and the corona treatment impart excellent peel strength to the carbon fiber resin tape.
　本発明に係る接着剤又はサイジング剤は、６０℃乃至１８０℃の温度範囲でゴム製品を容易に接着・接合することができ、６０℃乃至２６５℃の温度範囲で炭素繊維等のあらゆる被接着物を容易に接着・接合することができる。加えて、一度接着・接合されたゴム製品を６０℃～１８０℃で加温する、あるいは炭素繊維等を６０℃～２６５℃で加温及び湯せんすることにより夫々を容易にはく離することができるため、被接着物を容易にリサイクルすることができる。それゆえに、本発明に係る接着剤又はサイジング剤は、例えば、ゴム製品や炭素繊維等のあらゆる被接着物の接着・接合において好適に使用される。 The adhesive or sizing agent according to the present invention can easily bond and bond a rubber product in a temperature range of 60 ° C. to 180 ° C., and can be any adherend such as carbon fiber in a temperature range of 60 ° C. to 265 ° C. Can be easily bonded and bonded. In addition, the rubber products once bonded and joined can be easily separated by heating them at 60 ° C to 180 ° C, or by heating and hot watering carbon fibers at 60 ° C to 265 ° C. The adherend can be easily recycled. Therefore, the adhesive or sizing agent according to the present invention is suitably used for bonding / bonding all objects to be bonded such as rubber products and carbon fibers.

Claims (4)

  1. 　接着剤又はサイジング剤であって、
    　前記接着剤又はサイジング剤は、
    　酸化スズ、酸化チタン、酸化タンタル、酸化ニオブ、および酸化ジルコニウムの金属酸化物ゾルからなる群から選択される一種以上の金属酸化物ゾルと、
    　過硫酸カリウム、酢酸、安息香酸、フェニルホスホン酸、およびベンゾイルからなる群から選択される一種以上のＯＨ基を有する化合物と、
    　ＰＶＡ樹脂と
    から構成されていることを特徴とする、接着剤又はサイジング剤。     An adhesive or sizing agent,
    The adhesive or sizing agent is
    One or more metal oxide sols selected from the group consisting of metal oxide sols of tin oxide, titanium oxide, tantalum oxide, niobium oxide, and zirconium oxide;
    A compound having one or more OH groups selected from the group consisting of potassium persulfate, acetic acid, benzoic acid, phenylphosphonic acid, and benzoyl;
    An adhesive or sizing agent, characterized in that it is composed of PVA resin.
  2. 　前記金属酸化物ゾルが、酸化スズからなることを特徴とする、請求項１に記載の接着剤又はサイジング剤。 The adhesive or sizing agent according to claim 1, wherein the metal oxide sol is made of tin oxide.
  3. 　前記ＯＨ基を有する化合物が、過硫酸カリウムであることを特徴とする、請求項１又は２に記載の接着剤又はサイジング剤。 The adhesive or sizing agent according to claim 1 or 2, wherein the compound having an OH group is potassium persulfate.
  4. 　アルミナゾルをさらに含むことを特徴とする、請求項１乃至３のいずれか１項に記載の接着剤又はサイジング剤。 The adhesive or sizing agent according to any one of claims 1 to 3, further comprising alumina sol.
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